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OF COPPER SOLVENT
EXTRACTION
CONFIGURATIONS
Joseph Kafumbila
Design and optimization of copper solvent extraction configurations
2017 Joseph Kafumbila
jokafumbila@hotmail.com
https://www.researchgate.net/publication/321849653_Design_and_optimization_of_copper_so
lvent_extraction_configurations
1. INTRODUCTION..................................................................................................................... 4
REFERENCES ................................................................................................................................... 98
The Faradays law on the electrolysis of metals gives the quantity of material
deposited at the cathode as a function of time and the intensity of the electric
current. Faraday had found that there is a loss of the electric current. Tafel, in
studying the mechanism of metal deposition at the cathode, had found that the
loss of current is due to the electrical resistance of the circuit and to the over-
potential. Tafel had found the relationship between the current intensity and
the over-potential. In industrial practice the Faradays law continues to be used
since it is simple.
Copper production technology changes drastically in the last 25 years with introduction of
solvent extraction-electrowinning circuit as a copper production method. The technology of copper
solvent extraction produces the most economical copper from low-grade copper ore. Copper solvent
extraction technology consists of two circuits connected by a common organic phase. In the first step,
called extraction step, metal is extracted from aqueous phase by organic phase. In the second step, called
stripping step, metal is recovered from organic phase. The second aqueous phase is more pure and
concentrated.
At the beginning, copper solvent extraction configuration operating on dilute aqueous phases
were constituted with two stages respectively to extraction and stripping steps. Design of this 2Ex2S
configuration was simple and based on the value of copper transfer per extractant volume percentage of
0.22 (g/l/1% v/v). This value gives copper extraction efficiency greater than 98% and copper stripping
efficiency of 60%. Afterwards, understanding that copper extraction efficiency was not the most important
parameter than the cost of copper production plant, one stage of stripping step was removed and the
value of copper transfer was increased to 0.26 (g/l/1%V). Design of this 2Ex1S configuration was based
on the expected value of copper extraction efficiency of 90%.
MacCabe Thiele method was introduced in design of copper solvent extraction configuration
when copper solvent extraction technology started to be used for high-grade copper ore. A large number
of laboratory tests were required before obtaining the optimal configuration by using MacCabe Thiele
method. It was at this level that a simulation model of equilibrium line of extraction and stripping steps
was introduced.
Several simulation models of copper solvent extraction using chelating reagents were made.
There are three types of simulation models: empirical model, semi-empirical model and chemical model.
Empirical model is an extrapolation equation of the distribution isotherms. Semi-empirical model is the
extrapolation equation of the distribution ratio of copper between organic and aqueous phases. Chemical
empirical is based on mass-action equilibrium equations of intermediate chemical reactions.
The goal of this paper is to develop a semi-empirical model which is the extrapolation of
thermodynamic property of a global chemical reaction of copper solvent extraction. Equilibrium condition
of global chemical reaction is resulted on the assumption that chemical activity coefficients of species
change very little only in aqueous phase. On the other hand, chemical activity coefficients of species
change in organic phase. The semi-empirical model is developed using lix984N as copper extractant and
corrections between concentrations of copper in organic and aqueous are obtained. The simple procedure
which allows designers to quickly have a static modeling for complex configuration or new product that
have not yet simulation program developed by supplier is developed using the semi-empirical model.
Solvent extraction of metallic cation can be classified on process of extraction. There are four
types [1]:
Extraction by salvation
Extraction by cation exchange
Extraction by chelation
Extraction by anion exchange
Solute molecules are associated with the solvent molecules - this is known as salvation. In
extraction by salvation solvent molecules are directly involved in formation of the ion association
complex. In this case the extracted species is solvated with a certain number of solvent molecules on
condition that the extractant must be inert.
The extractant is an organic acid (HR) and can exchange hydrogen with cation. The extraction
will proceed with formation of a neutral uncharged species.
The cation forms first a complex in aqueous phase having negative charge. The extractant have
an anion which can be exchange with the aqueous cation complex. The extraction will proceed with
formation of a neutral uncharged species.
. The extractant exchanges cation with hydrogen ion as in extraction by cation exchange. In
additional the extractant have chelating ligand. The ligand with two or more points of attachments to
The organic phase is a mixture of extractant and diluent. Extractant is an organic compound
which extracts copper from aqueous phase. In industrial practices, Properties of extractant are: tailored
extractive strength, excellent Cu/Fe selectivity, fast kinetics, good stability, low crud formation and
excellent versatility [2]. There are three kinds of extractant:
Ketoximes: Ketoximes are moderately strong copper extractants which operate best when PLS is
relatively warm and pH is ~1.8 or above
Aldoximes: Modified aldoximes have good metallurgical properties even at low temperatures and
low pH
Mixture of ketoximes and aldoximes: Properties of aldoxime/ketoxime blends reflect ratio of
components
Diluent is an organic liquid in which extractant is dissolved. In general, diluent must allow
solubilisation of extractant. Diluent must have minimum surface tension to promote dispersion in mixer,
low volatility, and high ignition point. Diluent must be cheaper. Diluent is constituted with various
hydrocarbons. Kerosene is often used as a diluent [2].
In industrial practices, maximum value of extractant volume percent (v/v) is between 30 33%
[2]. Viscosity of organic phase increases with increasing extractant volume percent. Above this value, some
organic components must be added to organic phase to improve viscosity.
Extraction and strip isotherms are a graphical representation of the equilibrium copper
concentration in the aqueous and organic phases at different organic-to-aqueous (O/A) ratios. There are
two ways of determining the distribution isotherms for a particular operation: either by performing
laboratory-scale tests or by predicted distribution isotherms based on the extraction and stripping specific
conditions.
The theoretical prediction gives copper concentration in organic phase as a function of copper
concentration in aqueous phase. This function is called the model of distribution isotherm. There are three
types of distribution isotherm model: empirical model, semi-empirical model and chemical model [3].
The empirical model gives the equation that best matches the curve of equilibrium line. Due to
the absence of links with the modeled phenomenon, its extrapolation can be risky and its use is limited to
the field covered by the experimentation.
The empirical model has been developed for dynamic simulation of copper solvent extraction
plant [4]. The equation (1) gives the empirical model of extraction isotherm.
AX
Y = X+B (1)
Where Y is copper concentration in the organic phase, X is copper concentration in the aqueous phase.
A = a *ML (2)
(10pH )b
B= (d CuPLS + f* CuRaff ) (3)
MLc
Where ML is the maximum loading (g/L), is copper concentration in the PLS (g/L),
is copper concentration in the raffinate and pH of PLS and a, b, c, d and f are the constants.
Y = C*X +D (4)
Where Y is copper concentration in the organic phase and X is copper concentration in the aqueous phase.
C = g* ML (5)
hV%i
D= +m (6)
Acj
Where V% is the volume percent of extractant in the organic phase and Ac is the acid concentration of spent
electrolyte (g/L). g, h, i, j and m are the constants.
Just like the preceding one, it is based on an equation but which best fits the curve of distribution
ratio of copper. Semi-empirical model uses the overall solvent extraction reaction. If an aqueous phase
containing copper is contacted with an organic phase, than copper distributes between the aqueous and
organic phase according to equation (7).
Where is the distribution ratio of copper, is copper concentration in organic phase and is
copper concentration in aqueous phase.
It has been observed that the distribution ratio (D) is a function of free ligand concentration in
the organic phase [5]. Equation (8) gives the mathematical expression this observation.
Cu
DCu = Cuor = Do (Lt mCuor )n (8)
aq
Where is the distribution ratio of copper at trace concentrations, readily determined in the laboratory,
is the total ligand concentration in the extractant, m approximates the ratio of ligand molecules to extracted
molecules close to saturation, n approximates the ratio of ligand molecules to extracted molecules close to infinite
dilution.
It should be noted that m and n in equation (8) are sometimes equal, but often differ in
value, which underlines that fact that this equation has no theoretical basis. It is merely a convenient way
of representing much experimental data using three parameters that can readily be determined
experimentally.
Chemical model requires the knowledge of all intermediate chemical reactions of extraction
reaction. The first suggestion of intermediate chemical reactions for copper solvent extraction with oximes
based extractant involves the dissolution of extractant in aqueous phase [6]. Chemical reactions (c), (d),
(e), (f) and (g) give the intermediate chemical reactions:
HR or HR aq Step 1 (c)
+
HR aq Haq + Raq Step 2 (d)
Cu+2 +
aq + R aq CuR aq Step 3 (e)
The second suggestion of intermediate chemical reactions for copper solvent extraction with
oximes based extractant involves two forms of extractant molecule in the organic phase [7]. Chemical
reactions (h), (i) and (j) give the intermediate chemical reactions:
Cu+2 +
aq + 2 HR or CuR 2 or + 2 Haq (h)
Cu+2 +
aq + (HR)2 or CuR 2 or + 2 Haq (i)
(HR)2 or 2 HR or (j)
In the case of sulfate solution, the chemical reaction (k) must be taken into account.
HSO + 2
4 H + SO4 (k)
The modeling requires the knowledge of the corresponding mass-action equilibrium equations
for the chemical reactions listed above and the mass-balance of copper, ligand and hydrogen.
The mass-action equilibrium equations and the mass-balance of copper, ligand and hydrogen for
the second suggestion of intermediate chemical reactions are given by the equations (9), (10), (11), (12),
(13) and (14).
All models consider that the chemical activity coefficients of species in aqueous and organic
phases do not change.
Where [2 ] is the concentration of copper complex in the organic phase (mol/L), [] is the
concentration of the first molecule form of extractant in organic phase (mol/L), [()2 ] is the concentration of
the second molecule form off extractant in the organic phase (mol/L), [] is the total concentration of ligand
in the organic phase (mol/L), [+2 ] is the concentration of copper in aqueous phase, [+2 ] is the total
concentration of copper in aqueous and organic phases, [ + ] is the concentration of hydrogen ion in the feed
solution, [ +2 ] is the concentration of hydrogen ion in the aqueous phase, [ + ] is the concentration of
hydrogen ion in the initial aqueous phase and A is the ratio of organic phase volume on aqueous phase volume.
Extraction step is guided by thermodynamic disequilibrium between aqueous and organic phases.
Copper mass transfer is stopped when thermodynamic property reaches equilibrium condition in both
phases. Global copper solvent extraction chemical reaction with Lix984N extractant is followed chemical
reaction (l) [8]. LIX 984N reagent, a 1:1 volume blend of LIX 860N-I and LIX 84N-I, is a mixture of 5-
nonylsalicylaldoxime and 2-hydroxy-5-nonylacetophenone oxime.
where 2+ and + are copper and hydrogen ionic species in aqueous phase, HR is acid form of
Lix984N extractant, and 2 is copper complex form in organic phase
Thermodynamic equilibrium condition of global chemical reaction (l) is given by equation (15)
[9].
C (16)
= RTln( x x )
C0
where is standard-state activity of species and is a function of solvent nature and temperature, is
chemical activity coefficient of specie , is molar concentration of species , 0 is reference molar concentration
which by convention is 1 molar concentration, R is the perfect gas constant, and T is the temperature
The substitution of equation (16) for all species in equation (15) gives equation (17) which is the
thermodynamic equilibrium condition.
4.1.2.1. Definition
[Cue ]x[He ]2
e1 =[Cueor]x[HRaqe ]2 (18)
aq or
The values of copper molar concentrations at the steady-state in organic and aqueous phases are
respectively given by equations (19) and (20).
Cue
[Cueor ] = 63.55
or
(19)
Cue
aq
[Cueaq ] = 63.55 (20)
where and are respectively copper concentrations (g/L) in aqueous and organic phases
Vaq
Cueor = Cuior + (Cuiaq - Cueaq ) x V (21)
or
where and are respectively initial copper concentrations (g/L) in aqueous and organic phases.
and are respectively volumes of aqueous and organic phases.
The value of free extractant molar concentration in organic phase is given by equation (22).
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.
The value of hydrogen ion molar concentration in aqueous phase comes from sulfuric acid
dissociation reaction. Sulfuric acid dissociation reaction has followed chemical reactions (m) and (n).
H2 SO4 HSO
4 +H
+
K1ac = 104 (m)
HSO 2
4 SO4 + H
+
K ac
2 = 1.25 10
2 (n)
The corresponding mass-action equilibrium expressions for the chemical reactions (m) and (n)
are given by equations (23) and (24).
[HSO +
4 ][H ]
= K1ac = 104 (23)
[H2 SO4 ]
[SO2 +
4 ][H ]
= K ac
2 = 1.25 10
2 (24)
[HSO
4]
Where [4 ], [42 ], [2 4], and [ + ] are molar concentration of corresponding species in the aqueous
phase.
If C1 is free sulfuric acid molar concentration in aqueous phase and C2 is molar concentration of
anion SO2 4 associated with copper and buffers in aqueous phase at the initial state. Sulfuric acid
dissociation reaction (m) is complete because the value of chemical reaction equilibrium constant K1ac is
big. Following mass balance comes from sulfuric dissociation reaction (m).
H2 SO4 HSO
4 H+
Initial state C1 0 0
Final state -C1 C1 C1
Mass balance 0 C1 C1
Sulfuric acid dissociation reaction (n) is not complete because the value of chemical reaction
equilibrium constant K ac
2 is not big enough. Following mass balance comes from sulfuric acid dissociation
reaction (n). is molar concentration of anion HSO 4 which goes into dissociation.
Thermodynamic equilibrium condition of sulfuric acid dissociation reaction (n) given by equation
(24) is changed in equation (25). Resolution of the mathematical expression (25) gives second-degree
equation. Hydrogen ion molar concentration in aqueous phase is given by equation (26). The value of
molar concentration is given by equation (27) and the values of constants E and F are given by
equations (28) and (29).
(C2 +)(C1 +)
K ac
2 = (25)
(C1 )
e
[Haq ] = C1 + (26)
(E+ E2 4 x F)
= (27)
2
E = C1 + C2 + K ac
2 (28)
F = C1 x (C2 - K ac
2 ) (29)
From equation (27), the value of molar concentration becomes zero when the value of molar
concentration C2 is equal to the value of chemical reaction equilibrium constant K ac 2 . When the value of
molar concentration C2 is greater than the value of chemical reaction equilibrium constant K ac2 , the value
of molar concentration is lower than zero. In this condition, the value of molar concentration in
equation (26) is zero. When the value of molar concentration C2 is lower than the value of chemical
reaction equilibrium constant k ac
2 , the value of molar concentration is greater than zero.
4.1.3.1. Definition
Cu x HR 2 x HR 2
e2 = 2 x Cu (30)
CuR2 x H CuR2 x H 2
Depending on molar concentrations of species in aqueous phase, three cases are possible [1]:
Aqueous phase very diluted. In this condition, the values of chemical activity coefficients
tend to 1.
Ionic strength in aqueous phase varies very little. In the condition, the value of ratio of
chemical activity coefficients is a constant.
Ionic strength in aqueous phase varies. In this condition, the value of ratio of chemical
activity coefficients is a variable.
The assumption is that ionic strength varies very little. So, ratio of chemical activity coefficients is
a constant in aqueous phase.
In organic phase, the study done on the extractant Kelex 100, which is chelating copper solvent
extraction reagent, shows that ratio of chemical activity coefficients of species in organic phase is a
function of copper concentration in organic phase [9].
The assumption is that this thermodynamic property is also true for chelating copper extractant.
4.1.4. Observations
[Cueor ]x[Heaq ]2
[Cueaq ]x[HReor ]2
= f([Cueor ]) (31)
Test conditions of lab test 1 done with pure copper sulfate aqueous phase are the following:
Table (1) gives equilibrium line data of lab test 1 from which the values of thermodynamic
equilibrium condition 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 e1 versus the values of copper concentration in organic
phase.
Figure 1: Values of e1 versus values of copper concentrations in organic phase of lab test 1
The values of thermodynamic equilibrium condition e1 are not the same for steady-state
positions of equilibrium line.
The value of thermodynamic equilibrium condition e1 is a linear function of the value of
copper concentration in organic phase.
The values of line slope are not the same in the ranges (0.8 to 5.75 g/L Cu) and (5.75 to
10.8 g/L Cu) where molar concentration is greater or lower than zero respectively.
Test conditions of lab test 2 done with industrial copper sulfate aqueous phase are the following:
Elements grade of industrial copper sulfate aqueous phase is given in Table (2).
Extractant: Lix984N.
Extractant volume percentage in the organic: 18%.
Table 2: Element concentrations of industrial copper sulfate aqueous phase of lab test 2
Cu Co Al Fe Mg Mn Zn Ni Acid
g/l g/l g/l g/l g/l g/l g/l g/l g/l
5.23 4.40 0.50 0.82 1.40 1.59 0.43 .0.27 5.20
Table (3) gives equilibrium line data from which the values of thermodynamic equilibrium
condition e1 of each steady-state position are calculated. Figure (2) gives the values of thermodynamic
equilibrium condition e1 versus the value of copper concentration in organic phase.
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 is lower than zero.
The value of thermodynamic equilibrium condition e1 also is a linear function of the
value of copper concentration in organic phase.
Figure 2: Values of e1 versus values of copper concentration in organic phase of lab test 2
4.1.5.3. Observations
In order to get closer to industrial conditions, only the range where molar concentrations are
lower than zero will be taken in static model. In this condition hydrogen ion concentration in aqueous
phase is given now by equation (32). Equation (33) gives sulfuric acid concentrations in aqueous phase at
steady state.
e ACeaq
[Hor ]= (32)
98
e i
Acaq = Acaq + (Cuiaq - Cueaq ) x 1,54 (33)
The substitution of equations (19), (20), (22) and (32) in equation (18) gives equation (34) which
gives the value of thermodynamic equilibrium condition 1e1 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
1e1 = aq
* [3.3030 V%3.0842 = G * Cueorg + H (34)
Cueaq Cue
org ]2
The value of thermodynamic equilibrium condition 1e1 obtained from the equation (34) is
plotted versus the values of copper concentration in organic phase in the range where the value of molar
concentration is lower than zero using pure copper sulfate aqueous phases. Table (4) gives equilibrium
line data of lab test 1, 3, 4 and 5 (value in blue color). Figure (3) gives the value of thermodynamic
equilibrium condition 1e1 versus the values of copper concentration in organic phase.
The values of constants G and H for different concentration of free acid in the feed solution
are given in Table (5)
Results in Table (5) shows that initial free acid concentration of feed solution does not affect the
values of constants G and H.
The value of thermodynamic equilibrium condition 1e1 obtained from the equation (34) is
plotted versus the values of copper concentration in organic phase in the range where the value of molar
concentration is lower than zero using pure copper sulfate aqueous phases. Table (6) gives equilibrium
line data of lab test 1, 6 and 7 (value in blue color). Figure (4) gives the value of thermodynamic
equilibrium condition 1e1 versus the values of copper concentration in organic phase. Results show that:
The values of constants G and H for different extractant volume percent in organic phase
are given in Table (7)
The values of constants G and H are only function of extractant volume percentage.
Equilibrium condition on extraction step is given by equation (35) in the range from 8 to 32% of
extractant volume percent.
Cueorg [Aceaq ]2
Cueaq
* [3.3030 V%3.0842 Cue ]2
=(-25.698 * v%(1.704) ) Cueor+ 10.663 * v%(0.608) (35)
org
Table (8) gives the experimental data and data from extraction step equilibrium condition
equation for lab test (1)(pure sulfate solution) and lab test (2) (industrial solution). Results show that:
For lab test (1), the gap between the values of copper concentration in the organic phase
of experimental and model data is around 5.02% in the range where the value of is
greater than zero (red color in Table (8)).
For lab test (1), the gap between the values of copper concentration in the organic phase
of experimental and model data is around 0.30% in the range where the value of is
less than zero (blue color in Table (8)).
Stripping step is guided by thermodynamic disequilibrium between aqueous and organic phases.
Copper mass transfer is stopped when thermodynamic property reaches equilibrium condition in both
phases. Copper stripping chemical reaction with Lix984N extractant is followed chemical reaction (p)
which is the reverse reaction of copper extraction chemical reaction.
[Cueor ] x [Heaq ]2 Cu x HR 2 x HR 2
[Cueaq ] x [HReor ]2
= 2 x Cu = s (36)
CuR2 x H CuR2 x H 2
Thermodynamic equilibrium condition of extraction and stripping steps are similar. Equilibrium
condition equation of extraction step is used to simulate equilibrium line of stripping step. Test conditions
of lab test 8 of stripping step are the following:
Table (9) gives equilibrium line data and the values of copper concentration in organic phase
from model of extraction step. Figure (5) gives the graphical representation of results of Table (9).
Results show that there is a gap between the values of copper concentration from experimental
data and data of extraction step model. Results show that the stripping step has a similar model because
experimental and model data have the same profile. The gap between the experimental and model data is
due to the difference of ion strength of the solutions of extraction and stripping steps. The ratios of
chemical activity coefficients in aqueous phase are not the same for PLS solution and spent electrolyte.
Table (10) gives equilibrium line data and the values of thermodynamic equilibrium condition
s1 of lab test 8. Figure (6) gives the value of thermodynamic equilibrium condition s1 versus the values
of copper concentration in organic phase.
Figure 6: Values of s1 versus the values of copper concentration in organic phase of lab test 8
Results show that value of s1 is linear function of the concentration of copper in the organic
phase. Value of s1 is affected only by the extractant volume percent in organic phase. Equation (37)
gives the mathematical expression of equilibrium condition of stripping step in the range from 8 to 32% of
extractant volume percent.
The second semi-empirical model of extraction step using Lix984N as extractant is given by the
equation (35). Equation (33) gives the concentration of free acid at equilibrium.
Cueorg (Aceaq )2
x =(-25.698 * v%(1.704) ) Cueor + 10.663 * v%(0.608) (35)
Cueaq (3.3030 x V%3.0842 x Cueorg )2
e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (33)
Where is the concentration of copper in the PLS (g/L) and is the concentration of free acid in
the PLS (g/L).
i
Acaq = 98* 10(pH) (38)
e
The value of Acaq in equation (35) is replaced by the equation (33), it appears equation (39).
The new designations are introduced and equation (40) becomes equation (41).
Y = Cueor
X = Cueaq
Y (a +b X)2
* ex ex = eex *Y + fex (41)
X (c +d Y)2
ex ex
i
aex =Acaq + 1.54 * Cuiaq (42)
Equation (41) becomes equation (48) after placing Y on one side and X on other side.
The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.
Equation (48) becomes equation (50) after introducing equation (49) where values of constants
ex , ex and ex are given by equations (51), (52) and (53) respectively.
f (cex )2
ex = (dex (53)
2
ex ) eex
ex
Y = t ex - (54)
3
Equation (50) becomes equation (55) after replacing the variable Y by equation (54). Equations
(56) and (57) give the values of constants pex and q ex .
t 3 +pex *t +q ex =0 (55)
(ex )2 (56)
pex = ex - 3
ex ex 2 (57)
q ex = ex - + 27* (ex )3
3
Equation (55) has a form of Cardan formula (three degree equation). The value of t ex is given
by the equation (58).
1 1 1 1
qex 1 4 qex 1 4
t ex = [ 2
2 ((qex )2 + 27 (pex )3 )(2) ](3) + [ 2
+ 2
((qex )2 + 27 (pex )3 )(2) ](3) (58)
1
( )
hex 2aex bex ((hex )2 4aex bex hex ) 2 (61)
X= 2(bex )2
The second semi-empirical model of stripping step using Lix984N as extractant is given by the
equation (37). Equation (33) gives the concentration of free acid at equilibrium.
e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (33)
Where is the concentration of copper in the spent electrolyte (g/L) and is the concentration of free
acid in the spent electrolyte (g/L).
e
The value of Acaq in equation (37) is replaced by the equation (33), it appears equation (62).
The new designations are introduced and equation (63) becomes equation (64).
Y = Cueor
X = Cueaq
Y (a +b X)2
* st st = est *Y + fst (64)
X (c +d Y)2st st
Equations (65), (66), (67), (68), (69) and (70) give the values of ast , bst , cst , dst , est ,
and fst .
i
ast =Acaq + 1.54 * Cuiaq (65)
The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.
Equation (71) becomes equation (73) after introducing equation (72) where values of constants
st , st and st are given by equations (74), (75) and (76) respectively.
f (cst )2
st = (dst (76)
2
st ) est
st
Y = t st - (77)
3
Equation (73) becomes equation (78) after replacing the variable Y by equation (77). Equations
(79) and (80) give the values of constants pst and q st .
t 3 +pst *t +q st =0 (78)
(st )2 (79)
pst = st - 3
st st 2 (80)
q st = st - + 27* (st )3
3
1 1 1 1
qst 1 4 qst 1 4
t st = [ 2
2 ((qst )2 + 27 (pst )3 )(2) ](3) + [ 2
+ 2
((qst )2 + 27 (pst )3 )(2) ](3) (81)
1
( )
hst 2ast bst ((hst )2 4ast bst hst ) 2 (84)
X= 2(bst )2
Table (11) gives example of extraction isotherm from laboratory scale test [10]. PLS contains 2.5
g/L of copper and 1.3 g/L of iron at pH 1.8. The organic phase contains 1.8 g/L of copper and 8.7% of
Lix984N as extractant.
The predicted extraction isotherm is obtained by using the procedure explained in chapter
(4.3.1.). Table (12), as it appears on the Excel spreadsheet, gives the predicted extraction isotherm. The
Figure (7) gives graphical representation of laboratory scale test and semi-empirical model results.
A B C D E F G H I J
1
2 Table 12 Semi-empirical model predicted extraction isotherm
3 V% 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7
4 CuPLS (g/L) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
5 AcPLS (g/L) 1.553 1.553 1.553 1.553 1.553 1.553 1.553 1.553
6 Cueaq (g/L) 2.5 1.94 1.24 0.51 0.26 0.17 0.09 0.07
7 Cueor (g/L) 4.414 4.356 4.188 3.662 3.146 2.786 2.223 2.000
8 aex 5.403 5.403 5.403 5.403 5.403 5.403 5.403 5.403
9 bex -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54
10 cex 28.736 28.736 28.736 28.736 28.736 28.736 28.736 28.736
11 dex -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842
12 eex -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644
13 fex 2.862 2.862 2.862 2.862 2.862 2.862 2.862 2.862
14 g ex 0.965 3.007 9.842 41.808 96.254 155.48 307.93 400.36
15 ex -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078
16 ex 169.76 170.10 171.21 176.43 185.32 194.98 219.86 234.98
17 ex -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71
18 pex -7.761 -7.428 -6.312 -1.095 7.791 17.458 42.340 57.458
19 q ex 9.788 12.353 20.934 61.068 129.43 203.79 395.19 511.49
20 t ex -3.278 -3.336 -3.505 -4.031 -4.547 -4.907 -5.469 -5.692
21
aex = C8 = C5+1,54*C4
bex = C9 = -1.54
cex = C10 = 3,303*C3
dex = C11 = -3.0842
eex = C12= -25.698*C3^-1,704
fex = C13 = 10.663*C3^-0,608
One excel formula of excel cell C are set up, the excel cells ranged from C7 to C20 are
copied and passed to others column.
The gap on the concentration of copper in the organic phase obtained for the low values of
concentration of copper in the aqueous phase is due to the presence of iron in the PLS.
Table (13) gives example of stripping isotherm from laboratory scale test [10]. Spent electrolyte
contains 30.7 g/L of copper and 190 g/L of free acid. The loaded organic phase contains 3.9 g/L of
copper and 8.7% of Lix984N as extractant.
The predicted stripping isotherm is obtained by using the procedure explained in chapter (4.3.2.).
Table (14), as it appears on the excel spreadsheet, gives the predicted stripping isotherm. The Figure (8)
gives graphical representation of laboratory scale test and semi-empirical model results.
ast = C8 = C5+1,54*C4
b = C9 = -1.54
cst = C10 = 3,303*C3
dst = C11 = -3.0842
est = C12= 5,11*10^-3*C3-0,194
fst = C13 = 12,81*C3^-0,901
g st = C14 = (C8+C9*C6)^2/C6
st = C15 = (2*C10*C11*C12+C11^2*C13)/(C11^2*C12)
st = C16 = (2*C10*C11*C13+C10^2*C12-C14)/(C11^2*C12)
st = C17 = (C13*C10^2)/(C11^2*C12)
pst = C18 = C16-(C15^2)/3
q st = C19 = C17-C15*C16/3+2/27*C15^3
t st = C20 = (-C19/2-(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)+
(-C19/2+(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)
e
Cuor = C7 = C20-C15/3
One excel formula of excel cell C are set up, the excel cells ranged from C7 to C20 are
copied and passed to others column.
Figure (9) gives scheme of stage of rank n of extraction step in counter current
n1
configuration. Stage of rank n of extraction step receives aqueous phase Eaq from stage of rank
n+1
n-1 and organic phase Eor from stage of rank n+1. Stage of rank n produces aqueous phase
n n
Eaq and organic phase Eor .
MacCabe Thiele diagram of stage of rank n of extraction step is shown in Figure (10).
The Point E gives feed coordinates, the Point B gives outlet coordinates and the Point D
gives outlet equilibrium coordinates. Triangle ABC gives MacCabe Thiele diagram of stage
of rank n of extraction step.
Y Y
Slope AC = XA XC (85)
A C
Y Y Y Y Y Y
Slope BE = XBX C = X DXC = XD XB = - Slope AC (86)
C A D A D B
Figure (11) gives scheme of stage of rank n of stripping steps in cascade configuration.
n+1
Stage of rank n of stripping step receives aqueous phase Saq from stage of rank n+1 and
n1 n
organic phase Sor from stage of rank n-1. Stage of rank n produces aqueous phase Saq and
n
organic phase Sor .
Y Y
Slope AC = XA XB (87)
B C
Y Y Y Y Y Y
Slope EB = XAX C = XAXD = XB XD = -slope AC (88)
C B C D B D
Copper solvent extraction unit process consists of two circuits coupled with common
organic phase. Figure (13) gives common Leach/solvent extraction/electrowinning circuit. On
extraction step, copper is extracted from the copper rich solution called Pregnant Leach
Solution by copper poor organic phase called stripped organic. Extraction step produces acid
rich solution called Raffinate and copper rich organic phase called Loaded organic. On
stripping step, copper is recovered from the copper rich organic phase by acid rich electrolyte
called spent electrolyte coming from the copper electrowinning unit process. Stripping step
produces copper rich electrolyte called advance electrolyte and the copper poor organic phase.
The organic phase of copper solvent extraction technology is a mixture of extractant and diluent.
Extraction and stripping steps are carried out at industrial scale with mixersettlers. In mixer, one
phase is dispersed into a second phase to provide interface contact for mass transfer and in a
settler mixture of aqueous and organic phase is decanted to allow phases to coalesce and separate.
Consequently, leaching unit process must be designed to allow the extraction of copper on
organic phase and copper electrowinning unit process must be designed to allow stripping of
copper from the organic phase.
In the laboratory scale test, the maximum loading is determined by the following
procedure:
a. Prepare PLS with concentrations of copper and free acid after data correction
and mass balance operation;
b. Combine prepared PLS and stripped organic with an O/A ratio of 1:1;
c. Agitate for 5 minutes and allow the phases to separate;
d. Repeat steps b and c until pH does not change, each time with fresh
prepared PLS;
e. The copper tenor in the organic after iterations is the maximum loading.
The absolute maximum loading (AMLL ) is determined following the same procedure
with the synthetic solution (6 g/L Cu at pH 1.8) in place of prepared PLS (Cognis procedure).
Reagent suppliers have developed simulation computer model which can help to
determine the maximum loading.
In case of the new semi-empirical model using Lix984N as extractant, the value of ML
following the procedure explained in chapter (4.3.1.). The equilibrium concentration of copper in
aqueous phase is the concentration of copper in the PLS.
ML
ML = t ML - (89)
3
1 1 1 1
qML 1 4 qML 1 4
t ML = [ ((qML )2 + (pML )3 )(2) ](3) + [ + ((qML )2 + (pML )3 )(2) ](3) (90)
2 2 27 2 2 27
(ML )2 (91)
pML = ML - 3
ML ML 2 (92)
q ML = ML - + 27* (ML )3
3
f (cex )2
ML = (dex (95)
2 e
ex ) ex
Equations (96), (97), (98), (99), (100), (101), and (102) give the values of aex , bex ,
cex , dex , eex , fex , and g ML .
In this paper the predicted absolute maximum loading (AMLP ) is the maximum loading
when the concentration of free acid in the PLS is zero.
In case of the second semi-empirical model using Lix984N as extractant, equation (103)
gives the value of predicted absolute maximum loading.
Joseph kafumbila Page 44
AMLP = 0.415 * V%(1.096) (103)
The absolute maximum loading depends only on the value of the extractant volume
percent.
Figure (14) gives a graphical representation of loaded organic, maximum loading and
predicted absolute maximum loading.
During extended tests in both laboratory and industry, there are diluent evaporation and
extractant degradation. It is therefore necessary to regularly check the effective concentration of
extractant.
The procedure for determining the effective extractant volume percent is the following:
Joseph kafumbila Page 45
Determine the absolute maximum loading using the laboratory scale test method
with a fresh organic phase containing 10% of extractant (AML1L ).
Determine the absolute maximum loading using the laboratory scale test method
with plant stripped organic ((AML2L ).
AML2
V% = 10 * AMLL1 (104)
L
Observing equation (103), the predicted absolute maximum loading is not a linear
function of the extractant volume percent. By using the equation (104) for determining the
extractant volume percent, the gap between the effective extractant volume percent and the value
calculated from equation (104) will increase with increasing the value of extractant volume
percent. The new method consists to determine the absolute maximum loading using laboratory
scale test with fresh organic phase having extractant volume percent ranged from 5 to 35% and
to determining the extrapolation equation of the function V%=f(AMLL ).
In the case of Lix984N is used as extractant, equation (105) gives the value of extractant
volume percent ranged from 2.5 to 32%.
CuLO CuSO
NetCu = (106)
V%
Where NetCu is the copper net transfer ((g/L)/1Vol %), is the copper tenor in loaded
organic (g/L), is the copper tenor in stripped organic (g/L), and V% is the extractant
volume percent (%).
CuLO
%ML = x100 (107)
ML
Where %ML is percentage of maximum loading (%), is copper tenor in loaded organic
(g/L), and ML is maximum loading (g/L).
Equations (108) and (109) give respectively copper recovery on extraction and stripping
steps.
CuPLS CuRaf
RCuex = x 100 (108)
CuPLS
CuLO Cu
RCust = x 100 (109)
CuSO
Figure (15) gives scheme of solvent extraction stage. The scheme shows mixer and
settler of copper solvent extraction installation. Mixer receives a mixture of fresh and recycle
aqueous phases which have volume flowrates, respectively of a and c m3/h and a mixture of
fresh and recycle organic phases which have volume flowrates, respectively of b and d m 3/h.
Advance ratio (O/A) is ratio of the organic phase flowrate on aqueous phase flowrate, which are
fed to stage. Operating ratio (O/A) is ratio of the organic phase flowrate on aqueous phase
flowrate into the mixer.
Equations (110) and (111) give respectively values of operating and advance ratios
(O/A) determined with stream flowrates.
(b+d)
O/AOPF = (110)
(a+c)
Equations (112) and (113) give the value of the advance ratio (O/A) as a function of the
concentration of copper in aqueous and organic phases before and after extraction respectively
on extraction and stripping steps.
CuIaq CuO 1
O/Aex aq
ADA = = (112)
CuO I
or Cuor Slope "AC"
CuO I
aq Cuaq 1
O/Ast
ADA = = Slope "AC" (113)
CuIor CuO
or
Where and are concentrations of copper respectively in inlet and outlet aqueous phases on
a stage and and are concentrations of copper respectively in inlet and outlet organic phases
on a stage.
When operating ratio (O/A) is greater than 1.1/1, aqueous phase is dispersed in the
organic phase and mixer works in organic continuity regime. On the other side, when operating
ratio (O/A) is lower than 1/1.1, organic phase is dispersed in the aqueous phase and mixer works
in aqueous continuity regime. Between the two values of the operating ratio (O/A) there is a
transition zone where continuity regime changes constantly. When mixer works in organic
continuity regime organic entrainment in the aqueous phase is low. On the other hand, when
mixer works in aqueous continuity regime aqueous entrainment in organic phase is low. In the
The copper recovery on extraction step is improved when two stages at least are used.
The stage configuration can be counter current cascade (Figure 16) or parallel cascade (Figure
17). The counter current cascade is called also series.
Figure 16: Scheme of counter current cascade on extraction step with two stages
Figure 17: Scheme of parallel cascade configuration on extraction step with two stages
Figures (18), (19) and (20) give MacCabe Thiele diagrams having respectively one stage,
two stages in series and two stages in parallel on extraction step. The aqueous phase contains 7
g/L of copper and 2 g/L of free acid. The extractant volume percent is 20% (v/v) (Lix984N
extractant). Stripped organic contains 2 g/L of copper. For one stage, values of advance and
operating ratios are 1/1.
Figure 18: MacCabe Thiele diagrams having two stages in series with aqueous phase (7 g/L of
copper and 2 g/L of free acid), stripped organic phase (2 g/L of copper), extractant
volume percent (20% v/v Lix984N) and advance and operating ratios (O/A) 1/1.
For two stages in series, values of advance and operating ratios are 1/1 on each stage.
For two stages in parallel, values of advance and operating ratios are 2/1 on each stage. In all
cases, the total flowrate of aqueous phase and the total flowrate of organic phase are the same.
The copper concentration in raffinate of one stage is greater than copper concentration
in global raffinate of two stages in series and in parallel.
The copper concentration in global raffinate of two stages in parallel is greater than
copper concentration in global raffinate of two stages in series.
The use of two stages in parallel is based on the desire to reduce the capital cost of
copper solvent extraction plant.
Figure (21) gives the exiting configurations of extraction step of copper solvent
extraction.
In the industrial practices counter current configuration usually used on stripping step
has either one stage or two stages in series. In the case of two stages in series, first stage receives
loaded organic and second stage receives spent electrolyte. Figure (22) gives a scheme of
stripping step having two stages in series. Notice that the copper recovery increases with
increasing the number of stages in series.
Residence time into the mixer: stage efficiency increases with increasing of mixer residence
time. In industrial practice residence time is ranged from 2 to 3 minutes.
Number of mixing stages: stage efficiency increases with increasing number of mixing stages.
In modern copper solvent extraction installation number of mixing stages is 2.
Viscosity of solution: stage efficiency decreases with increasing solution viscosity (presence of
impurities as Al and Mg).
Operating ratio O/A: stage efficiency decreases with increasing of operating ratio (O/A)
(mixing is non-homogenous).
Energy input and type of impeller: stage efficiency increases with increasing of intensity of
agitation. Notice that intense agitation can produce a mixture of aqueous and organic
phases which needs a long separation phases time.
Co-extraction of impurities: stage efficiency decreases with increasing of co-extraction of
impurities (iron)
According to Figures (10) and (12), equations (114) and (115) give the stage efficiencies
calculated with the concentrations of copper in organic and in aqueous respectively on extraction
step. Equations (116) and (117) give the stage efficiencies calculated with the concentrations of
copper in organic and in aqueous respectively on stripping step.
e XB XA
Effaq = 100 x (115)
XB XD
s YB YA
Effor = 100 x (116)
YB YD
s XB XA
Effaq = 100 x (117)
XD XA
In copper solvent extraction plant having extraction step containing at least two stages
and stripping step containing one or two stages, equilibrium constraints between extraction and
stripping steps are given by equations (118) and (119).
The optimum value of advance ratio O/A of the extraction step must give the smallest
size of copper solvent extraction configuration.
The organic loss in aqueous phase is low when the mixer works in organic phase
continuity regime. Operating ratio O/A of the last stage on extraction step and the first stage on
stripping step must be 1.25/1 to have organic continuity regime to reduce loss of organic phase.
In this continuity regime organic phase tenor in raffinate is around 50 ppm. Recovery of organic
phase in pre-settler raffinate pond and in advance electrolyte coalescing tank are respectively 30
and 75%.
Loss of organic phase increases with increasing of crud formation. Crud is a solid
formed by mixing aqueous phase containing fine suspended solids with organic phase. Crud is a
thin and compact layer of solid around 50% organic by weight in organic-aqueous interface in
settler, which is stabilized emulsion. Solid particles that give emulsion stability are typically
demonstrated as silica, but any fine solid (<2 micron) that passes thickeners can cause crud
formation. Clays, iron precipitate, gypsum, quartz, and micas have all been linked to the crud
formation in copper solvent extraction. Silica is always present in PLS as fine silica particles and
dissolved silica. Dissolved silica precipitates and polymerizes as chains of colloidal silicon, which
absorbs organic. It has been observed that running organic continuous decreased silica tenor in
high acid strip where silica precipitation is most prevalent [12-13]. Crud formation linked to iron
precipitate is due to high pH in PLS. Hydrolysis and polymerization reactions of ferric are
formed at pH greater than 2 [13]. Coagulants are used to remove silica gel in PLS and also Crud
treatment such as centrifugation or clay application is commonly used to recover the organic
phase [14]. The second possibility is to add a stage before the first stage on extraction step. This
new stage is contained only diluent which turns around on a stage. Silica gel is dissolved in diluent
and is removed from PLS before copper solvent extraction. Clay treatment is applied on diluent
of new stage to remove silica gel. First test results show that around 50% of silica gel has been
removed from PLS.
It has been observed that the stage efficiency on extraction step is greater when the
organic phase continuity regime is used [11].
6.2.2.5. Actions
Therefore, all mixers on extraction and stripping steps must work in organic continuity
regime with value of the operating ratio (O/A) of 1.25/1. In this condition, value of the advance
ratio O/A that gives the smallest size of copper solvent extraction is equal to value of operation
ratio O/A of 1.25/1 on extraction step. On stripping step, value of the advance ratio (O/A) is
depended on the copper mass transferred to stripping step and values of copper tenors in
advance and spent electrolyte.
Joseph kafumbila Page 55
6.2.3. Copper concentration in spent electrolyte
6.2.3.1. Constraint
In the copper electrowinning unit process, anodes are lead alloys because are cheaper.
Observations of operations of copper electrolysis show that corrosion of lead anodes increases
with increasing of current density. There are many scientific explanations of this phenomenon.
Simpler way to explain is that [15]:
First step lead anodes are in contact with copper electrolyte: free acid attacks lead and
forms PbSO4 in the form of scales on anode surface.
Second step current is applied to copper electrowinning: water decomposition takes
place on a lead alloy between PbSO4 scales producing oxygen gas and acid. Oxygen
oxidizes PbSO4 into PbO2. Oxygen evolution on anodes removes lead oxide because it
takes place between scales.
Once lead oxides are removed from anode surface, the second step starts again. This
phenomenon corrodes anodes. Removal of lead oxide by oxygen gas evolution increases
with increasing of current density of copper deposition.
Presence of cobalt in copper electrolyte decreases the corrosion rate because cobalt
oxides precipitate between lead oxides scales and oxygen evolution takes place on cobalt
oxides.
6.2.3.2. Actions
In industrial practices maximum value of operating current density is 400 A/m2 to have
anode lifetimes around 7 years. The value of design current density is 300 A/m2 [16]. The
minimum value of copper concentration in spent electrolyte must be 30 g/L to have a compact
copper deposit at design current density (general rule in copper electrowinning for obtaining a
compact copper deposit is: ratio of the operating current density (A/m2) on copper tenor in
spent electrolyte (g/L) must be less than 10) [17]. Optimum copper tenor in spent electrolyte is
35 g/L for operating current density ranged 280 320 A/m2.
6.2.4.1. Constraint
The maximum value of free acid concentration in spent electrolyte is also fixed by lead
anode behaviour. Initially, lead anodes used for direct copper electrowinning unit process were
lead 6-10% antimony. High strength antimony rich eutectic phase of 6-10% Sb lead alloys
Early 1980 rolled Pb-Ca-Sn alloys anodes have been introduced in the copper
electrowinning unit process to improve lead alloys corrosion behaviour due to free acid. The
corrosion rate of Pb-Ca-Sn alloys anodes is lower than that of Pb-Sb. Anode corrosion due to
high level of the free acid tenor in spent electrolyte for Pb-Ca-Sn alloys takes place in another
form. Free acid breaks contact between lead oxides and lead alloys [15].
6.2.4.2. Actions
Today, copper electrowinning circuit coupled to copper solvent extraction unit process
uses Pb-Ca-Sn anode and maximum value of the free acid concentration in spent electrolyte is
190 g/L which gives anode lifetime of 7 years.
6.2.5.3. Actions
2Ex2S configuration is simulated with new reagent (Lix984N) using the new semi-
empirical method. The parameters of simulation are the following:
Figure (23) gives copper extraction recovery, percentage to maximum loading, and
copper net transfer versus stripping recovery.
Copper extraction recovery increases with decreasing of stripping recovery. The minimum
value of stripping recovery is 60%, from which the increase of copper extraction recovery
is negligible with decreasing stripping recovery. Value of extraction recovery is 98% at
stripping recovery of 60%.
Copper net transfer increases with increasing of stripping recovery. The value of copper
net transfer is 0.215 (g/L)/1Vol% at stripping recovery of 60%. In old papers, the average
value of copper net transfer was 0.220 (g/L)/1Vol% for old extractants at stripping
recovery of 60%.
Because of copper extraction recovery is near about 100% at stripping recovery of 60%,
approximate value of extractant volume percent has been given by equation (120).
CuPLS (120)
V% = 0.220
Where is copper tenor in PLS (g/L), V% is extractant volume percent (%), and
0.220 is copper net transfer ((g/L)/1Vol %).
Observation of operations of copper solvent extraction in the heap leaching circuit was
shown that copper extraction recovery was not the important parameter. The most important
parameter was capital cost of copper solvent extraction circuit in all capital cost of the production
plant. The capital cost of copper solvent extraction circuit increases with increasing of flowrate of
PLS and number of stages of extraction and stripping steps. The capital cost of copper solvent
extraction decreases with increasing of copper concentration in PLS. The increase of copper
concentration in PLS increases copper net transfer at the same value of copper concentration in
stripped organic.
Copper solvent extraction configuration has been changed from 2Ex2S to 2Ex1S to reduce
the number of stages because copper concentrations in PLS are low (less than 5 g/L).
Value of copper net transfer must be high (good use of organic phase). In industrial practices
value of copper net transfer with Lix984N reagent range from 0.24 to 0.30 (g/L)/1vol% for
2Ex1S configuration [10].
Size of copper solvent extraction must be the smallest (values of advance and operating
ratios (O/A) are the same on extraction step).
2Ex1S configuration is simulated with Lix984N reagent using the new semi-empirical
method. The parameters of simulation are the following: Copper concentration in PLS from heap
leaching of low grade oxide ores was around 4 g/L at pH 1.8.
Table (15) gives values of %ML versus the values of copper net transfer. Results show
that the values of %ML on boundaries of the good use zone of organic phase range from 77.92
to 95%.
%ML % 75 77.92 80 85 90 95
Copper net transfer (g/L)/1%(v/v) 0.228 0.24 0.248 0.267 0.286 0.302
It has been observed that ferrous and ferric are transferred to copper electrowinning
circuit by physical entrainment. In addition, ferric is transferred by chemical entrainment [18].
Solvent extraction reagents, capable to extract selectively copper, were characterized on the
selectivity of Cu extraction against ferric contaminant. The test shows that the extraction of
Ferric begins at pH around 1.5 [19] lower than leaching pH of copper oxide ores of 1.8.
The most important parameter is not the ratio of Cu/Fe in loaded organic phase, but
the ratio of Cu/Fe transferred to electrowinning unit process. Table (16) gives simulation results
made by Cognis Corporation Isocalc computer program to predict performance of 2Ex2S and
3Ex1S configurations [21]. Simulations have been made using organic phase containing 0.296
molar of 5-nonyl-2-hydrxyacetophenone oxime (ketoxime) and 0.0964 molar of 5-
nonysalicyladoxime (aldoxime). Cu/Fe transferred is (Loaded organic Cu Stripped organic
Cu)/loaded organic Fe.
Ratio Cu/Fe in loaded organic phase is bigger than ratio Cu/Fe transferred to copper
electrowinning unit process.
Cu/Fe transferred decreases with increasing of copper stripping recovery.
6.2.6.4. Actions
Loaded organic phase is saturated with copper. The optimum value of %ML, which gives
the ratio Cu/Fe value of around 1000, is greater than 80% [22]. In industrial practice %ML
values depends on the PLS copper tenor and the copper solvent extraction recovery. The
copper solvent extraction recovery must be greater than 90%.
Washing step is added between extraction step and stripping step. In this condition capital
cost of copper solvent extraction increases. Wash stage uses an aqueous solution at pH of 2.
Advance ratio (O/A) is around 50/1. In industrial practice iron stripping efficiency is around
50% and copper recycle from wash stage represent 0.5 % of copper transferred [18].
6.2.7.1. Nitrate
Constraint
Actions
In any plant with potential for nitrate ions to enter the PLS it is important to choose an
appropriate organic extractant [23].
Constraint
Actions
Wash stage is applied for avoiding excessive chloride tenor in the electrolyte.
6.2.7.3. Manganese
Constraint
Actions
Wash stage is applied for avoiding excessive Mn tenor in the electrolyte. Electrolyte
must contain au minimum 1 g/L of iron giving solution potential less than 600 mV (Ag/AgCl).
7.1. Concept
Mass balance defines an engineering problem where parameters between unit operations
are partly known. The purpose of mass balance is to mathematically examine the known
parameters to solve for the unknown parameters. Two main types of mass balances are
commonly made: design mass balance and operating plant mass balance. The design mass
balance is typically faced during plant design when the test work results and a flowsheet diagram
are the only known parameters. Design mass balance purpose is to find values for the unknown
parameters. A static modelling is developed for copper solvent extraction plant design using
Lix984N as extractant. The most important feature of this program is that the percentage to
maximum loading (saturation ratio) which is the important parameter for iron rejection
determines the value of the extractant volume percent.
7.2.1. General
In this paper for good understanding, static modelling program will be made step by
step for a conventional configuration containing two stages in counter current on extraction step
and two stages in counter current on stripping step as an example.
. Table (17) gives data of chosen example for explanation of modelling program
conception. Unlike classical static modelling where the value of extractant volume percent in the
organic phase is a datum, in this static modelling the value of extractant volume percent is found
from the value of percentage to maximum loading.
Extraction step
Data
- In the excel cell C6 (PLS flowrate), type number 400 in red color.
- In the excel cell C7 (PLS copper concentration), type number 7 in red color.
- In the excel cell C8 (PLS acid concentration), type number 1.96 in red color.
- In the excel cell C9 (%ML), type number 80 in red color.
- In the excel cell C10 (advance ratio O/A), type number 1.25 in red color.
- In the excel cell C11 (stage efficiency stage 1), type number 95 in red color.
- In the excel cell C12 (stage efficiency stage 2), type number 95 in red color.
- In the excel cell F6 (PLS flowrate), type number 400 in blue color.
- In the excel cell F7 (PLS copper concentration), type number 7 in blue color.
- In the excel cell F8 (PLS acid concentration), type number 1.96 in blue color.
- In the excel cell F9 (%ML), type number 80 in blue color.
The starting value of extractant volume percent is random number between 1 and 32%.
The starting value of extractant volume percent is used in all equations of extraction step as
extraction volume percent data. For this case, chosen starting value is 25%.
- In the excel cell C15 (extractant volume percent), type number 25 in blue color.
Constants
General
Extraction stage 1
The value of YD1 is a solver variable. Starting value is random number between ML
and YA1. The stating value is 11.
Extraction stage 2
The value of YD2 is a solver variable. Starting value is random number between YD1
and YA2. The stating value is 7.
Performance
Stripping step
Data
- In the excel cell C50 (spent electrolyte copper concentration), type number 35 in red
color.
- In the excel cell C51 (spent electrolyte acid concentration), type number 190 in red
color.
- In the excel cell C52 (advance electrolyte copper concentration), type number 50 in red
color.
- In the excel cell C53 (stage efficiency stage 1), type number 98 in red color.
- In the excel cell C54 (stage efficiency stage 2), type number 98 in red color.
- In the excel cell F50 (spent electrolyte copper concentration), type number 35 in blue
color.
- In the excel cell F51 (spent electrolyte acid concentration), type number 190 in blue
color.
- In the excel cell F52 (advance electrolyte copper concentration), type number 50 in blue
color.
- In the excel cell F53 (stage efficiency stage 1), type number 98 in blue color.
- In the excel cell F54 (stage efficiency stage 2), type number 98 in blue color.
- In the excel cell I50 (spent electrolyte copper concentration), type =F50-C50 in green
color.
- In the excel cell I51 (spent electrolyte acid concentration), type =F51-C51 in green
color.
- In the excel cell I52 (advance electrolyte copper concentration), type =F52-C52 in
green color.
- In the excel cell I53 (stage efficiency stage 1), type =F53-C53 in green color.
- In the excel cell I54 (stage efficiency stage 2), type =F54-C54 in green color.
General
Stripping stage 1
The value of YD1 is a solver variable. Starting value is random number less than
YA1. The stating value is ML * 0.5 = 5.63.
- In the excel cell D69 (YD1 ), type number 5.63 in blue color.
- In the excel cell F69 (hst ), type =(G57*D69+G58)*(E57+E58*D69)^2/D69.
- In the excel cell C69 (XD1 ),
type =(F69-2*C57*C58-(F69^2-4*C57*C58*F69)^(1/2))/(2*C58^2).
The starting value of YD1 is changed manually until the value of XD1 is between
XA1 and XA1 +1. The new value of the starting value of YD1 is 4.00.
- In the excel cell D67 (YB1 ), type =D69-(C67-C69)/C61 equations (88) and (113).
- In the excel cell D68 (YC1), type =D67.
- In the excel cell C68 (XC1 ), type =C67-C61*(D66-D67) equations (87) and (113).
- In the excel cell H69 (organic stage efficiency), type =(D66-D67)/(D66-D69)*100
- In the excel cell I69 (solver constraint), type =H69-F53 in green color.
Stripping stage 2
The value of YD2 is a solver variable. Starting value is random number less than
YD1 . The stating value is YD1 * 0.5 = 2.0.
- In the excel cell D76 (YD2 ), type number 2.0 in blue color.
- In the excel cell F76 (hst ), type =(G57*D76+G58)*(E57+E58*D76)^2/D76.
- In the excel cell C76 (XD2 ),
type =(F76-2*C57*C58-(F76^2-4*C57*C58*F76)^(1/2))/(2*C58^2).
The starting value of YD2 is changed manually until the value of XD2 is between
XA2 and XA2 +1. The new value of the starting value of YD1 is 2.3.
- In the excel cell D74 (YB2 ), type =D76-(C74-C76)/C61 equations (88) and (113).
- In the excel cell D75 (YC2), type =D74.
- In the excel cell C75 (XC2 ), type =C74-C61*(D73-D74) equations (87) and (113).
- In the excel cell H76 (organic stage efficiency), type =(D73-D74)/(D73-D76)*100
- In the excel cell I76 (solver constraint), type =H76-F54 in green color.
Performance
Set objective
Equation (119)
- In the excel cell I84 (set objective), type =D75-D39.in green color.
1) On the Data, in the Analysis group click solver (if the solver command is not
available, you must activate the solver add-in).
2) In the Set objective box, enter the cell reference I84 of simulation program constraint.
3) Click Value of and then type the number 0 in the box.
8.1. Concept
Operating plant mass balance is tried to have a large amount of data from operating plant.
Operating plant mass balance purpose is to produce a picture of the state of an operating plant. Static
simulation program has been developed to give a picture of copper solvent extraction plant using Lix984N
as extractant [26]. The main problem of this program is to consider that the measurements of stream
flowrates and concentration of copper in the streams are correct. In reality, operating plant mass balance
requires data correction and copper mass balance between extraction and stripping steps. This step
requires always human reasoning. In most cases the advance ratio O/A calculated with the stream
flowrates is generally different from that calculated with the concentrations of copper in the streams.
The objective of this chapter is to give a simple method for data correction operation. This
method is applied to all copper extraction reagents. After this data correction operation, the main
parameters of SX plant optimization can be determined: advance ratio O/A, maximum loading, extractant
volume percent, copper recovery, copper net transfer, percentage to maximum loading and stage
efficiencies. These parameters are calculated regularly and give the performances of copper solvent
extraction plant.
Figure (24) gives a MacCabe-Thiele diagram on extraction step having two stages in counter
current configuration. Points A, B and C must be on the straight line. Otherwise the data of Points
A, B and C must be changed to be on the straight line. Equation (121) gives the mathematical
expression of straight line passing through points A, B and C.
The value of (slope) is known and equation (122) gives the value of the slope. The
unknown value is .
The values of and are unknown.
1
= O/A (122)
ADF
Where / is the advance ratio O/A (ratio organic flowrate on PLS flowrate)
In this case, the regression line has a value of which is the average value of A , B and
C of straight passing through points A, B and C. The new position can take any position on the
straight line. The approximation to get the new data of points is that: the new position of point is the
interception of the straight line with the line perpendicular to the straight line AC and passing through
the old position of point.
Figure (25) gives an example of regression line. The value of the slope of straight line is known.
Joseph kafumbila Page 76
Figure 25: Regression line with known value of the slope
The concentrations of copper in the aqueous phase are accurate. In this case the
concentrations of copper in the organic phase are changed by finding the least squares
regression line (Cuor = f(Cuaq ).
The concentrations of copper in the organic phase are accurate. In this case the
concentrations of copper in aqueous phase are changed by finding the least squares
regression line (Cuaq = f(Cuor ).
The concentrations of copper in the organic and the aqueous phases are not accurate. In
this condition, the change in concentrations of copper in organic and aqueous can take
several directions. The approximation is that this change takes the orthogonal direction
on the orthogonal regression line.
Figure (26) gives an example of the three possibilities of changes of X and Y coordinates. On
Figure (26) there are three points A, B and C having the coordinates X and Y. The three points
must be on the same straight line.
Points in red color changes the position to points in green color when the least squares
regression line Y=f(X) is used.
Points in red color changes the position to points in violet color when the least squares
regression line X=f(Y) is used.
Points in red color changes the position to points in blue color when the orthogonal
regression line is used.
Plant data
Figure (27) gives an example of copper solvent extraction plant having triple series configuration
on extraction step and series configuration on stripping step [22].
Table (29) gives the coordinates of A1, C1, C2 and C3 on the extraction step and the
coordinates of points A1, C1 and C2 on the stripping step.
Figures (28) and (29) present respectively the coordinates in form of graphic on extraction and
stripping step. The points are not on the straight line on extraction and stripping steps.
Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 39.00 12.30 55.60 12.30
C1 29.00 10.00 43.80 6.00
C2 15.70 7.80 42.00 5.30
C3 10.00 5.30
Extraction step
Table (30), as it appears on the Microsoft Excel spreadsheet, gives data correction of extraction
step. The explanation of the procedure for obtaining the new coordinates is the following:
- On Table (30) the maximum number of data that can be corrected is five (four stages in counter
current configuration).
- The excel cells ranged from B5 to B9 give the designation of points
- In excel cells ranged from C5 to C9, type the concentrations of copper in aqueous (g/L) (if there
is not value to type in the cell at the end of the range, the excel cell must be empty).
- In excel cells ranged from D5 to D9, type the corresponding concentration of copper in the
organic (g/L). (If there is not value to type in the cell at the end of the range, the excel cell must be
empty).
Figure (30) present the new coordinates of points on extraction step on a graph.
Stripping step
Table (31) gives the new coordinates on stripping step using the procedure explained in chapter
(extraction step).
A B C D E F G H
1
2 Table 31 New coordinates of points stripping step
3 Old coordinates New coordinates
4 Cuaq Cuor Cuaq Cuor
5 A1 55.60 12.30 -23.091 54.85 12.78
6 C1 43.80 6.00 -21.880 44.00 5.87
7 C2 42.00 5.30 -21.435 42.55 4.95
8 C3 0.00 0.00 0.00
9 C4 0.00 0.00 0.00
10
11 -66.604
12 O/AADF 1.571
13 n 3
14 0.637
15 -22.153
Figure (31) present the new coordinates of points on stripping step on a graph.
Extraction step
Table (32), as it appears on the Microsoft Excel spreadsheet, gives new coordinates of points on
extraction step. The explanation of the procedure for obtaining the orthogonal regression line is the
following:
- On Table (32) the maximum number of data that can be corrected is five (four stages in counter
current configuration).
- The excel cells ranged from B6 to B10 give the designation of points.
- In excel cells ranged from C6 to C10, type the concentrations of copper in aqueous (g/L) (if
there is not value to type in the cell at the end of the range, the excel cell must be empty).
- In excel cells ranged from D6 to D10, type the corresponding concentration of copper in the
organic (g/L). (if there is not value to type in the cell at the end of the range, the excel cell must be
empty)
- In the excel cells ranged from E6 to E10, type:
o E6=IF(C6=0,0,C6*D6)
o E7=IF(C7=0,0,C7*D7)
o E8=IF(C8=0,0,C8*D8)
o E9=IF(C9=0,0,C9*D9)
o E10=IF(C10=0,0,C10*D10)
Equation (123) gives the mathematical expression of Cuor = f(Cuaq ) regression line.
Equation (124) gives the mathematical expression of Cuaq = f(Cuor ) regression line.
Equation (126) gives the advance ratio O/A obtained with the concentrations of copper in the
streams.
Joseph kafumbila Page 87
1
O/AADA = (126)
3
Where / is the advance ratio obtained with the concentrations of copper in the streams.
Stripping step
Table (32) gives the new coordinates on stripping step using the procedure explained in chapter
(extraction step). Figure (33) present the new coordinates of points on stripping step.
A B C D E F G H I J
1
2 Table 33 Orthogonal regression coordinates on stripping step
3
4 Table A =f( ) Table B =f( )
5 Cuaq Cuor Cuaq *Cuor [Cuaq ]2 Cuor Cuaq Cuaq *Cuor [Cuor ]2
6 A1 55.60 12.30 683.88 3091.36 12.30 55.60 683.88 151.29
7 C1 43.80 6.00 262.80 1918.14 6.00 43.80 262.80 36.00
8 C2 42.00 5.30 222.60 1764.00 5.30 42.00 222.60 28.09
9 C3 0.00 0.00 0.00 0.00 0.00 0.00
10 C4 0.00 0.00 0.00 0.00 0.00 0.00
11
12 Cuaq Cuor Cuaq *Cuor [Cuaq ]2 Cuor Cuaq Cuaq *Cuor [Cuor ]2
13 141.40 23.60 1169.28 6773.8 23.60 141.40 1169.28 215.38
14
15 n 3 n 3
16 Max 55.60 Max 12.30
17
18 Y=f(x) coefficients X=f(Y) coefficients
19 1 0.522 2 1.915
20 1 -16.719 2 32.067
21
22 Table C Orthogonal coefficients
23 3 0.522
24 3 -16.731
25
26 Table D New coordinates
27 Y=f(x) X=f(Y) Orthogonal
28 Cuaq Cucor Cucaq Cuor Cucaq Cucor
29 A1 55.60 12.28 55.62 12.30 55.61 12.29
30 C1 43.80 6.13 43.56 6.00 43.68 6.06
31 C2 42.00 5.19 42.22 5.30 42.11 5.24
32 C3 0.00 0.00 0.00 0.00 0.00 0.00
33 C4 0.00 0.00 0.00 0.00 0.00 0.00
34
35 O/AADA 1.916
Observation
By observing the results after data correction, the regression line having the value of slope
coming from the advance ratio O/AADF is far from coincide with the regression line whose slope comes
from the advance ratio O/AADA . This means that the flowrate measurement is not correct. In this
condition, the orthogonal regression line is adopted as the method for data correction.
8.2.2.1. Concept
After data correction operation, the values of copper concentrations in loaded organic and
stripped organic remain the measurement values. Equations (127), (128), (129) and (130) give the new
concentrations of copper in the PLS, raffinate, advance electrolyte and spent electrolyte with the
measurement values of copper concentrations in the loaded organic and stripped organic. Notice that
when the stripping step has one stage, the values of and are given by mathematical expression of
straight line passing through points A and B having measurement coordinates.
CuM
LO
CuPLS = (127)
CuM
SO
CuRaf = (128)
CuM
SO
CuSE = (130)
Where and are respectively the measurement values of concentrations of copper in loaded and
stripped organic.
Table (34) gives the new concentrations of copper in the streams after data correction with the
orthogonal regression line method. Table (35) gives the new concentrations of copper in the streams after
mass balance operation.
Table 34: Coordinates of points after correction with orthogonal regression line
Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 38.72 12.36 55.61 12.29
C1 28.74 10.06 43.68 6.06
C2 17.33 7.42 42.11 5.24
C3 9.21 5.55
Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 38.45 12.30 55.63 12.30
C1 28.74 10.06 43.68 6.06
C2 17.33 7.42 42.22 5.30
C3 8.12 5.30
8.3.1. Concept
There are a number of solvent plant parameters which help to evaluate the performance of
copper solvent extraction and can be determined after data correction and copper mass balance
operations. These parameters are determined in a regular basis in copper solvent extraction plant. These
parameters are:
Maximum loading, extractant volume percent, copper recovery, copper net transfer and
percentage to maximum loading can be determined by using explanation described in chapter (612).
Determining of stage efficiencies requires the first getting the coordinates of the equilibrium points.
8.3.2.1. Concept
The concentrations of copper in the outlet aqueous and organic of stage approach equilibrium,
but it do not reach it because of residence time, present of impurities, impeller power and impeller type.
The stage efficiencies are used to measure how close to equilibrium each stage gets.
The next step is determining the concentrations of copper in organic and aqueous of points D
(Figures (10) and (12)) for each stage. Point D is the intercession of the line having the slope - and
passing through point B and the distribution isotherm line.
According to Figures (10) and (12), equations (131) and (132) give the mathematical expressions
of the straight line passing through point B and having the slope - respectively on extraction and
stripping steps.
In this case there is not a computer program, PLS and spent electrolyte solutions having
concentrations of copper and free acid after data correction and mass balance operations are prepared.
Extraction and stripping isotherms are constructed using the laboratory scale test method using Plant
The extrapolation curves of extraction and stripping isotherms are obtained using equations (133)
and (134) respectively.
The extraction and stripping isotherms are constructed using the concentrations of copper and
free acid in PLS and spent electrolyte after data correction and mass balance in form of point coordinates.
The extrapolation curves of extraction and stripping isotherms are obtained using equations (133) and
(134) respectively.
The explanation of the procedure for determining stage efficiencies is done through an example.
Figure (34) gives a flow diagram of pilot plant with data. The configuration of copper solvent extraction is
triple series with two stages on stripping step.
Figure (35) gives pilot plant flow diagram with after data correction and mass balance. Table (36)
gives the concentrations of copper in organic and aqueous of extraction isotherm. The extraction isotherm
is obtained using method explained in chapter (4.3.) and data from Figure (35). Table (37) gives the
concentrations of copper in organic and aqueous of stripping step isotherm. The stripping isotherm is
obtained using method explained in chapter (4.3.) and data from Figure (35).
Cueaq (g/L) 4.321 2.880 1.920 0.960 0.480 0.240 0.120 0.060
Cueor (g/L) 11.231 10.885 10.333 9.108 7.677 6.140 4.600 3.190
Figure 35: Flow diagram of copper solvent extraction of pilot plant after correction of data
Equations (135) and (136) give extrapolation curves obtained using Excel trendline program on
extraction and stripping steps.
Cueor = -1.130 * 105 * [Cueaq ]2 + 7.667 * 102 * Cueaq + 3.590 * 102 (136)
Table (38), as it appears on Microsoft Excel spreadsheet, gives the stage efficiencies on extraction
and stripping steps.
A B C D E F G H
1
2 Table 38 Stage efficiencies
3
4 Extraction step
5 1.654
6 Cuaq Cuor
e
7 A1 4.321 9.722 Effaq -1 73.10 %
e
8 C1 2.839 7.272 Effaq -2 80.01 %
e
9 C2 1.013 4.251 Effaq -3 94.49 %
10 C3 0.158 2.838
11
12 Cueaq Cueor-1 Cueor-2 constraints
13 D1 2.294 10.62 10.62 0.000
14 D2 0.556 8.03 8.03 0.000
15 D3 0.108 4.33 4.33 0.000
16
17 Stripping step
18 0.768
19 Cuaq Cuor
e
20 A1 39.40 9.722 Effaq -1 79.33 %
e
21 C1 32.64 4.527 Effaq -2 85.61 %
22 C2 30.44 2.838
23
24 Cueaq Cueor-1 Cueor-2 constraints
25 D1 41.17 3.17 3.17 0.000
26 D2 33.01 2.55 2.55 0.000
27
Extraction step
- In the excel cell C13 (solver variable), type number 2.839 (starting value - Aqueous copper
concentration of point C1).
- In the excel cell C14 (solver variable), type number 1.013 (starting value - Aqueous copper
concentration of point C2).
- In the excel cell C15 (solver variable), type number 0.158 (starting value - Aqueous copper
concentration of point C3).
- In the excel cell D13, type =-C$5*C13+(D7+C$5*C8) (Equation (93) of stage 1).
- In the excel cell D14, type =-C$5*C14+(D8+C$5*C9) (Equation (93) of stage 2).
- In the excel cell D15, type =-C$5*C15+(D9+C$5*C10) (Equation (93) of stage 3).
- In the excel cell F13, type =D13-E13 (solver constraint of stage 1).
- In the excel cell F14, type =D14-E14 (solver constraint of stage 2).
- In the excel cell F15, type =D15-E15 (solver constraint of stage 3).
Stripping step
- In the excel cell C25 (solver variable), type number 39.40 (starting value - Aqueous copper
concentration of point A1).
- In the excel cell C26 (solver variable), type number 32.64 (starting value - Aqueous copper
concentration of point A2).
- In the excel cell F25, type =D25-E25 (solver constraint of stage 1).
- In the excel cell F26, type =D25-E25 (solver constraint of stage 2).
Solver program
1) On the Data, in the Analysis group click solver (if the solver command is not available, you
must activate the solver add-in).
2) In the Set objective box, enter the cell reference F13 of simulation program constraint.
3) Click Value of and then type the number 0 in the box.
4) In the By Changing Variable Cells box, enter the reference (C13, C14, C15, C25 and C26)
for each solver variable (blue color). Separate the references with commas (English version).
5) In the Subject to the constraints box, enter solver constraints by doing the following:
a. In the Solver Parameters dialog box, click Add.
b. In the Cell Reference box, enter the cell reference F14 solver constraint (green color).
c. Click the relationship =, in the Constraint box, type the number 0.
d. In the Solver Parameters dialog box, click Add.
e. In the Cell Reference box, enter the cell reference F15 solver constraint (green color).
f. Click the relationship =, in the Constraint box, type the number 0.
g. In the Solver Parameters dialog box, click Add.
h. In the Cell Reference box, enter the cell reference F25 solver constraint (green color).
i. Click the relationship =, in the Constraint box, type the number 0.
j. In the Solver Parameters dialog box, click Add.
k. In the Cell Reference box, enter the cell reference F26 solver constraint (green color).
l. Click the relationship =, in the Constraint box, type the number 0.
m. Click OK to return to Solver Parameters dialog box.
6) Click Solve. To keep the solution values on the worksheet, in the Solver Results dialog box,
click Keep solver solution.
Figures (36) and (37) give MacCabe-Thiele diagram on extraction and stripping steps after data
correction and mass balance operations.
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