Data Correction and Copper Mass Balance Before Evaluation of Copper Solvent Extraction Performance

Joseph Kafumbila
DATA CORRECTION
AND COPPER MASS
BALANCE
OPERATIONS
BEFORE
EVALUATION OF
COPPER SOLVENT
EXTRACTION PLANT
PERFORMANCE
2017
Data correction and copper mass balance before evaluation of copper solvent extraction plant
performance
© Joseph Kafumbila - November 2017
jokafumbila@hotmail.com
Joseph Kafumbila Page 1

0. Contents
0. CONTENTS 2
1. INTRODUCTION 3
2. CHEMISTRY OF SOLVENT EXTRACTION 4
2.1. CLASSIFICATION OF METAL SOLVENT EXTRACTION 4
2.1.1. Extraction by salvation 4
2.1.2. Extraction by cation exchange 4
2.1.3. Extraction by anion exchange 4
2.1.4. Extraction by chelation 4
2.2. CHEMISTRY OF COPPER SOLVENT EXTRACTION 5
3. DATA CORRECTION AND MASS BALANCE 6

3.1. DATA CORRECTION 6
3.1.1. Problem description 6
3.1.2. Application to SX plant 9
3.2. COPPER MASS BALANCE 21
3.2.1. Concept 21
3.2.2. Application to SX plant 22
4. CONSTRUCTION OF DISTRIBUTION ISOTHERMS 23

4.1. LABORATORY-SCALE TEST 23
4.2. PREDICTED DISTRIBUTION ISOTHERMS 23
4.2.1. Classification of predicted distribution isotherms 23
4.2.2. Comparison between results from laboratory test and model 34
5. SOLVENT EXTRACTION PLANT PARAMETERS 41

5.1. MAXIMUM LOADING AND EXTRACTANT VOLUME PERCENT 41
5.1.1. Laboratory scale test 41
5.1.2. Predicted isotherms 42
5.2. COPPER RECOVERY 43
5.3. COPPER NET TRANSFER 43
5.4. PERCENTAGE OF MAXIMUM LOADING 43
5.5. STAGE EFFICIENCIES 44
5.5.1. Concept 44
5.5.2. Determining of stage efficiencies 45
6. REFERENCES 51

1. Introduction
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 program has been developed for copper solvent
extraction plant design [1]. Lix984N is used as extractant in this static simulation because it is the most
used in our country. 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. This program can simulate eighteen configurations of copper solvent
extraction. In the same context, a PDF e-book has been published to set the copper solvent extraction
operation in its position in the copper production circuit [2]. This e-book gives design criteria to apply to
copper solvent extraction plant and configuration of copper solvent extraction in case of heap leaching
circuit, conventional circuit and split circuit.
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 [1]. 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 calculated with the stream flowrates is
generally different from that calculated with the concentration of copper in the stream.
The objective of this paper is to give a simple method for data correction operation. This method
is applied to all copper extraction reagents. After this data correction operation, this paper explains how to
determine advance ratio, 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.

2. Chemistry of solvent extraction
2.1. Classification of metal solvent extraction
Solvent extraction of metallic cation can be classified on process of extraction. There are four
types [3]:
 Extraction by salvation
 Extraction by cation exchange
 Extraction by chelation
 Extraction by anion exchange
2.1.1. Extraction by salvation
Solute molecules are associated with the solvent molecules - this is known as salvation. In
extraction by salvation solvent molecules are directly involved in formation of the ion association
complex. In this case the extracted species is solvated with a certain number of solvent molecules on
condition that the extractant must be inert.
2.1.2. Extraction by cation exchange
The extractant is an organic acid (HR) and can exchange hydrogen with cation. The extraction
will proceed with formation of a neutral uncharged species.
2.1.3. Extraction by anion exchange
The cation forms first a complex in aqueous phase having negative charge. The extractant have
an anion which can be exchange with the aqueous cation complex. The extraction will proceed with
formation of a neutral uncharged species.
2.1.4. Extraction by chelation
. The extractant exchanges cation with hydrogen ion as in extraction by cation exchange. In
additional the extractant have chelating ligand. The ligand with two or more points of attachments to

metal atoms are called chelating ligands. The substance which brings about chelation is called chelating
agent and the product is called chelate.
2.2. Chemistry of copper solvent extraction
In case of copper solvent extraction, the extraction is typically achieved by an oxime-based

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

3. Data correction and mass balance
3.1. Data correction
3.1.1. Problem description
Figure (1) 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 (1) gives the mathematical
expression of straight line passing through points “A”, “B” and “C”.
Figure 1: MacCabe-Thiele diagram on extraction step having two stages
Cuor = ε * Cuaq + λ (1)
Where “ε” and “λ” are constant values.

There are two possibilities for copper solvent extraction configuration:
 The value of “ε” (slope) is known and equation (2) gives the value of the slop. The
unknown value is “λ”.
 The values of “ε” and “λ” are unknown.
1
ε = O/A (2)
AF
Where “𝑂/𝐴𝐴𝐹 ” is the advance ratio O/A (ratio organic flowrate on PLS flowrate)
3.1.1.1. Known slope value
In this case, the regression line has a value of “λ” which is the average value of “λA ”, “λB ” and
“λC ” 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 (2) gives an example of regression line. The value of the slope of straight line is known.
Figure 2: Regression line with known value of the slope

3.1.1.2. Unknown value of the slope
In this case there are three types of regression line:
 The concentrations of copper in the aqueous phase are accurate. In this case the
concentrations of copper in the organic phase are changed by finding the least squares
regression line (Cuor = f(Cuaq ).
 The concentrations of copper in the organic phase are accurate. In this case the
concentrations of copper in aqueous phase are changed by finding the least squares
regression line (Cuaq = f(Cuor ).
 The concentrations of copper in the organic and the aqueous phases are not accurate. In
this condition, the change in concentrations of copper in organic and aqueous can take
several directions. The approximation is that this change takes the orthogonal direction
on the orthogonal regression line.
Figure (3) gives an example of the three possibilities of changes of X and Y coordinates. On
Figure (3) there are three points “A”, “B” and “C” having the coordinates X and Y. The three points must
be on the same straight line.
Figure 3: Regression lines with unknown value of slope

There are three possibilities:
 Points in red color changes the position to points in green color when the least squares
regression line Y=f(X) is used.
 Points in red color changes the position to points in violet color when the least squares
regression line X=f(Y) is used.
 Points in red color changes the position to points in blue color when the orthogonal
regression line Y=f(X) is used.
3.1.2. Application to SX plant
3.1.2.1. Plant data
Figure (4) gives an example of copper solvent extraction plant having triple series configuration
on extraction step and series configuration on stripping step [4]. Figures (5) and (6) give respectively the
MacCabe-Thiele on extraction and stripping steps. Figures (5) and (6) give the designation of points on the
MacCabe-Thiele diagram.
Figure 4: Data of copper solvent extraction plant
Table (1) gives the coordinates of “B1”, “A1”, “A2” and “A3” on the extraction step and the
coordinates of points “B1”, “A1” and “A2” on the stripping step.
Figures (7) and (8) 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.
Table 1: coordinates of points of Figure 4
Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
B1 39.00 12.30 55.60 12.30
A1 29.00 10.00 43.80 6.00
A2 15.70 7.80 42.00 5.30
A3 10.00 5.30
Figure 5 : MacCabe-Thiele diagram – one stage on extraction step
Figure 6 : MacCabe-Thiele diagram – one stage on stripping step

Figure 7: Point coordinates on extraction step for Figure (4)
Figure 8: Point coordinates on stripping step for Figure (4)

3.1.2.2. Known values of slope
3.1.2.2.1. Extraction step
Table (2), 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 (2) the maximum number of data that can be corrected is five (four stages in
counter current configuration).
A B C D E F G H
1
2 Table 2 New coordinates of points extraction step
3 Old coordinates New coordinates
4 Cuaq Cuor 𝜆𝑛 Cuaq Cuor
5 B1 39.00 12.30 1.664 37.58 12.69
6 A1 29.00 10.00 2.091 28.36 10.18
7 A2 15.70 7.80 3.518 17.68 7.26
8 A3 10.00 5.30 2.491 10.39 5.28
9 A4 0.00 0.00 0.00
10 Σ𝜆𝑛
11 9.764
12 O/AAF 3.667
13 n 4
14 ε 0.273
15 λ 2.441
- The excel cells ranged from “B5” to “B9” give the designation of points following
MacCabe-Thiele diagrams on figure (5).
- 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).
- In the excel cells ranged from “E5” to “E9”, type:

o E5= if(C5=0,0,D5-D$13*C5)
o E6= if(C6=0,0,D6-D$13*C6)
o E7= if(C7=0,0,D7-D$13*C7)
o E8= if(C8=0,0,D8-D$13*C8)
o E9= if(C9=0,0,D5-D$13*C9)
- In the excel cells ranged from “F5” to “F9”, type:

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

o F5= if(C5=0,0,(D$14+D5+D$13*C5)/2)
o F6= if(C6=0,0,(D$14+D6+D$13*C6)/2)
o F7= if(C7=0,0,(D$14+D7+D$13*C7)/2)
o F8= if(C8=0,0,(D$14+D8+D$13*C8)/2)
o F9= if(C9=0,0,(D$14+D9+D$13*C9)/2)
- In the excel cell “E11”, type “=SUM(E5:E9)”.

- In the excel cell “D12”, type number “3.667” the advance ratio on extraction step.
- In the excel cell “D13”, type “=COUNT(C5:C9)”.
- In the excel cell “D14”, type “=1/D12”.
- In the excel cell “D15”, type “=E11/D13”.
Figure (9) present the new coordinates of points on extraction step on a graph.
Figure 9: Point new coordinates on extraction step of Table (3)

3.1.2.2.2. Stripping step
Table (3) gives the new coordinates on stripping step using the procedure explained in chapter
(3.1.2.1.2).
A B C D E F G H
1
2 Table 3 New coordinates of points stripping step
3 Old coordinates New coordinates
4 Cuaq Cuor 𝜆𝑛 Cuaq Cuor
5 B1 55.60 12.30 -23.091 54.85 12.78
6 A1 43.80 6.00 -21.880 44.00 5.87
7 A2 42.00 5.30 -21.435 42.55 4.95
8 A3 0.00 0.00 0.00
9 A4 0.00 0.00 0.00
10 Σ𝜆𝑛
11 -66.604
12 O/AAF 1.571
13 n 3
14 ε 0.637
15 λ -22.153
Figure (10) present the new coordinates of points on stripping step on a graph.
Figure 10: Point new coordinates on stripping step of Table (3)

3.1.2.3. Unknown values of slope
Table (4), 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 (4) 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 following
MacCabe-Thiele diagrams of extraction and stripping steps on figures (10) and (11).
Small Table (A)
- In excel cells ranged from “C6” to “C10”, type the concentrations of copper in aqueous
(g/L) (if there is not value to type in the cell at the end of the range, the excel cell must be
empty).
- In excel cells ranged from “D6” to “D10”, type the corresponding concentration of
copper in the organic (g/L). (if there is not value to type in the cell at the end of the
range, the excel cell must be empty)

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)

o F6= C6^2
o F7= C7^2
o F8= C8^2
o F9= C9^2
o F10= C10^2
- In the excel cell “C13”, type “=SUM(C6:C10)”.

- In the excel cell “D13”, type “=SUM(D6:D10)”.
- In the excel cell “E13”, type “=SUM(E6:E10)”.
- In the excel cell “F13”, type “=SUM(F6:F10)”.
- In the excel cell “D15”, type “=COUNT(C6:C10)”.

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

A B C D E F G H I J
1
2 Table 4 Orthogonal regression coordinates on extraction step
3
4 Table A 𝐂𝐮𝐨𝐫 =f(𝐂𝐮𝐚𝐪 ) Table B 𝐂𝐮𝐚𝐪 =f(𝐂𝐮𝐨𝐫 )
5 Cuaq Cuor Cuaq*Cuor [Cuaq ]2 Cuor Cuaq Cuaq *Cuor [Cuor ]2
6 B1 39 12.3 479.70 1521.00 12.30 39.00 479.70 151.29
7 A1 29 10 290.00 841.00 10.00 29.00 290.00 100.00
8 A2 15.7 7.8 122.46 246.49 7.80 15.70 122.46 60.84
9 A3 10.3 5.3 54.59 106.09 5.30 10.30 54.59 28.09
10 A4
11
12 ΣCuaq ΣCuor ΣCuaq*Cuor Σ[Cuaq ]2 ΣCuor ΣCuaq ΣCuaq *Cuor Σ[Cuor ]2
13 94.00 35.40 946.75 2714.58 35.40 94.00 946.75 340.22
14
15 n 4 n 4
16 Max 39.00 Max 12.30
17
18 Y=f(x) coefficients X=f(Y) coefficients
19 ε1 0.227 ε2 4.265
20 λ1 3.512 λ2 -14.243
21
22 Table C Orthogonal coefficients
23 ε3 0.231
24 λ3 3.426
25
26 Table D New coordinates
27 Y=f(x) X=f(Y) Orthogonal
28 Cuaq Cucor Cucaq Cuor Cucaq Cucor
29 B1 39.00 12.37 38.21 12.30 38.723 12.364
30 A1 29.00 10.10 28.40 10.00 28.741 10.060
31 A2 15.70 7.08 19.02 7.80 17.326 7.425
32 A3 10.30 5.85 8.36 5.30 9.210 5.552
33 A4
34
35 O/AAA 4.332
- In the excel cell “D19” (ε1), type “=(D15*E13-C13*D13)/(D15*F13-C13^2)”.

- In the excel cell “D20” (λ1), type “=(D13*F13-C13*E13)/(D15*F13-C13^2)”.
Equation (3) gives the mathematical expression of Cuor = f(Cuaq ) regression line.
Cuor = ε1 * Cuaq + λ1 (3)
Small Table (B)

o G6=D6
o G7=D7
o G8=D8
o G9=D9
o G10=D10
- In the excel cells ranged from “H6” to “H10”, type:

o H6=C6
o H7=C7
o H8=C8
o H9=C9
o H10=C10

o I6= IF(G6=0,0,G6*H6)
o I7= IF(G7=0,0,G7*H7)
o I8= IF(G8=0,0,G8*H8)
o I9= IF(G9=0,0,G9*H9)
o I10= IF(G10=0,0,G10*H10)
- In the excel cells ranged from “J6” to “J10”, type:

o J6= G6^2
o J7= G7^2
o J8= G8^2
o J9= G9^2
o J10= G10^2
- In the excel cell “G13”, type “=SUM(G6:G10)”.

- In the excel cell “H13”, type “=SUM(H6:H10)”.
- In the excel cell “I13”, type “=SUM(I6:I10)”.
- In the excel cell “J13”, type “=SUM(J6:J10)”.
- In the excel cell “H15”, type “=D15”.

- In the excel cell “H16”, type “=MAX(G6:G10)”.
- In the excel cell “H19” (ε2), type “=(H15*I13-G13*H13)/(H15*J13-G13^2)”.

- In the excel cell “H20” (λ2), type “=(H13*J13-G13*I13)/(H15*J13-G13^2)”.
Equation (4) gives the mathematical expression of Cuaq = f(Cuor ) regression line.
Cuaq = ε2 * Cuor + λ2 (4)
Small Table (C)
- In the excel cell “E23” (ε3), type “=(D19*H19+1)/(2*H19)”.

- In the excel cell “E24” (λ3), type “=(D20*H19-H20)/(2*H19)”.
Equation (5) gives the mathematical expression of orthogonal regression line.
Cuor = ε3 * Cuaq + λ3 (5)
Small Table (D)
- In the excel cells ranged from “C29” to “C33”, type:

o C29=if(C6=0,0,C6)
o C30= if(C7=0,0,C7)
o C31= if(C8=0,0,C8)
o C32= if(C9=0,0,C9)
o C33= if(C10=0,0,C10)
- In the excel cells ranged from “D29” to “D33”, type:

o D29= if(C29=0,0,C29*D$19+D$20)
o D30= if(C30=0,0,C30*D$19+D$20)
o D31= if(C31=0,0,C31*D$19+D$20)
o D32= if(C32=0,0,C32*D$19+D$20)
o D33= if(C33=0,0,C33*D$19+D$20)

o F29=if(D6=0,0,D6)
o F30= if(D7=0,0,D7)
o F31= if(D8=0,0,D8)
o F32= if(D9=0,0,D9)
o F33= if(D10=0,0,D10)

o E29= if(F29=0,0,F29*H$19+H$20)
o E30= if(F30=0,0,F30*H$19+H$20)
o E31= if(F31=0,0,F31*H$19+H$20)
o E32= if(F32=0,0,F32*H$19+H$20)
o E33= if(F33=0,0,F33*H$19+H$20)

o G29= if(C6=0,0,(D6+E$23*C6-E$24)/(2*E$23))
o G30= if(C7=0,0,(D7+E$23*C7-E$24)/(2*E$23))
o G31= if(C8=0,0,(D8+E$23*C8-E$24)/(2*E$23))
o G32= if(C9=0,0,(D9+E$23*C9-E$24)/(2*E$23))
o G33= if(C10=0,0,(D10+E$23*C10-E$24)/(2*E$23))
- In the excel cells ranged from “H29” to “H33”, type:

o H29= if(C6=0,0,(E$24+D6+E$23*C6)/2)
o H30= if(C7=0,0,(E$24+D7+E$23*C7)/2)
o H31= if(C8=0,0,(E$24+D8+E$23*C8)/2)
o H32= if(C9=0,0,(E$24+D9+E$23*C9)/2)
o H33= if(C10=0,0,(E$24+D10+E$23*C10)/2)
- In the excel cell “H35”, type “=1/E23”.
Figure (11) present the new coordinates of points on extraction step on a graph (Table 4).
Figure 11: Graphic representation of Table (4) results
Equation (6) gives the advance ratio O/A obtained with the concentrations of copper in the
streams.
1
O/AAA =𝜀 (6)
3
Where “𝑂/𝐴𝐴𝐴 ” is the advance ratio obtained with the concentrations of copper in the streams.
Table (5) gives the new coordinates on stripping step using the procedure explained in chapter
(3.1.2.2.1). Figure (12) present the new coordinates of points on extraction step on a graph (Table 5).

A B C D E F G H I J
1
2 Table 5 Orthogonal regression coordinates on stripping step
3
4 Table A 𝐂𝐮𝐨𝐫 =f(𝐂𝐮𝐚𝐪 ) Table B 𝐂𝐮𝐚𝐪 =f(𝐂𝐮𝐨𝐫 )
5 Cuaq Cuor Cuaq*Cuor [Cuaq ]2 Cuor Cuaq Cuaq *Cuor [Cuor ]2
6 B1 55.60 12.30 683.88 3091.36 12.30 55.60 683.88 151.29
7 A1 43.80 6.00 262.80 1918.14 6.00 43.80 262.80 36.00
8 A2 42.00 5.30 222.60 1764.00 5.30 42.00 222.60 28.09
9 A3 0.00 0.00 0.00 0.00 0.00 0.00
10 A4 0.00 0.00 0.00 0.00 0.00 0.00
11
12 ΣCuaq ΣCuor ΣCuaq*Cuor Σ[Cuaq ]2 ΣCuor ΣCuaq ΣCuaq *Cuor Σ[Cuor ]2
13 141.40 23.60 1169.28 6773.8 23.60 141.40 1169.28 215.38
14
15 n 3 n 3
16 Max 55.60 Max 12.30
17
18 Y=f(x) coefficients X=f(Y) coefficients
19 ε1 0.522 ε2 1.915
20 λ1 -16.719 λ2 32.067
21
22 Table C Orthogonal coefficients
23 ε3 0.522
24 λ3 -16.731
25
26 Table D New coordinates
27 Y=f(x) X=f(Y) Orthogonal
28 Cuaq Cucor Cucaq Cuor Cucaq Cucor
29 B1 55.60 12.28 55.62 12.30 55.61 12.29
30 A1 43.80 6.13 43.56 6.00 43.68 6.06
31 A2 42.00 5.19 42.22 5.30 42.11 5.24
32 A3 0.00 0.00 0.00 0.00 0.00 0.00
33 A4 0.00 0.00 0.00 0.00 0.00 0.00
34
35 O/AAA 1.916

Figure 12: Graphic representation of Table (5) results
3.1.2.4. Observation
By observing the results after data correction, the regression line having the value of slope
coming from the advance ratio O/AAF is far from coincide with the regression line whose slope comes
from the advance ratio O/AAA . This means that the flowrate measurement is not correct. In this
condition, the orthogonal regression line is adopted as the method for data correction.
3.2. Copper mass balance
3.2.1. Concept
There are two cases:
 The stripping step has one stage. The new concentration of copper in the loaded organic
is the average value of corrected concentration of copper in loaded organic on extraction
step and the measurement concentration of copper in the loaded organic. The same
procedure is applied on the concentration of copper in the stripped organic.
 The stripping step has two stages. The new concentration of copper in the loaded organic
is the average value of corrected concentration of copper in loaded organic on extraction
step and the corrected concentration of copper in the loaded organic on stripping step.
The same procedure is applied on the concentration of copper in the stripped organic.

Equations (7), (8), (9) and (10) give the new concentrations of copper in the PLS, raffinate,
advance electrolyte and spent electrolyte with the average value of loaded organic and stripped organic.
Notice that when the stripping step has one stage, the values of “𝜀3𝑠 ” and “𝜆3𝑠 ” are given by mathematical
expression of straight line passing through points “A” and “B” having measurement coordinates.
Cuav e
LO −λ3
CuPLS = (7)
εe3
Cuav e
SO −λ3
CuRaf = (8)
εe3
Cuav s
LO −λ3
CuAD = (9)
εs3
Cuav s
SO −λ3
CuSE = (10)
εs3
𝑎𝑣 𝑎𝑣
Where “𝐶𝑢𝐿𝑂 ” and “𝐶𝑢𝑠𝑂 ” are respectively the average values of concentrations of copper in loaded and stripped
organic.
3.2.2. Application to SX plant
Table (6) gives the new concentrations of copper in the streams after data correction with the
orthogonal regression line method. Table (7) gives the new concentrations of copper in the streams after
mass balance operation.
Table 6: Coordinates of points after correction with orthogonal regression line
Extraction Strip
B1 38.72 12.36 55.61 12.29
A1 28.74 10.06 43.68 6.06
A2 17.33 7.42 42.11 5.24
A3 9.21 5.55
Table 7: Coordinates of points after mass balance
Extraction Strip
B1 38.57 12.33 55.68 12.33
A1 28.74 10.06 43.68 6.06
A2 17.33 7.42 42.40 5.40
A3 8.54 5.40

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

 Measure the initial concentration of copper and free acid (PLS for extraction isotherm or
spent electrolyte for stripping isotherm);
 Combine aqueous feed (PLS for extraction and spent electrolyte for stripping) with
previously stripped organic for extraction isotherm or loaded organic for stripping
isotherm at the specified O/A ratio;
 Agitate mixture for a minimum 5 minutes and allow to settle;
 Once settled, sample and measure the concentrations of copper and free acid in aqueous
phase;
 For each O/A point, perform a mass balance to determine the equilibrium copper
concentration in the organic phase or the organic can also be analyzed to verify the mass
balance points
4.2. Predicted distribution isotherms
4.2.1. Classification of predicted distribution isotherms
The theoretical prediction gives copper concentration in organic phase as a function of copper
concentration in aqueous phase. This function is called the model of distribution isotherm. There are three
types of distribution isotherm model: empirical model, semi-empirical model and chemical model [5].

4.2.1.1. Empirical model
The empirical model gives the equation that best matches the curve of equilibrium line. Due to
the absence of links with the modeled phenomenon, its extrapolation can be risky and its use is limited to
the field covered by the experimentation.
4.2.1.1.1. First model
The first model of empirical model has been developed for dynamic simulation of copper solvent
extraction plant [6]. The equation (11) gives the empirical model of extraction isotherm.
A∗X
Y = X+B (11)
Where “Y” is copper concentration in the organic phase, “X” is copper concentration in the aqueous phase.
Values of “A” and “B” are given by the equations (12) and (13).
A = a *ML (12)
(10−pH )b
B= (d ∗ CuPLS + f* CuRaff ) (13)
MLc
Where “ML” is the maximum loading (g/L), “𝐶𝑢𝑃𝐿𝑆 ” is copper concentration in the PLS (g/L), “𝐶𝑢𝑟𝑎𝑓𝑓 ”
is copper concentration in the raffinate and pH of PLS and “a”, “b”, “c”, “d” and “f” are the constants.
The equation (14) gives the empirical model of stripping isotherm.
Y = C*X +D (14)
Where “Y” is copper concentration in the organic phase and “X” is copper concentration in the aqueous phase.
Values of “C” and “D” are given by the equations (15) and (16).
C = g* ML (15)
h∗V%i
D= +m (16)
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.

4.2.1.1.2. Second model
The data from laboratory scale test or a computer program given distribution isotherms data in
form of coordinates obtained in specific conditions can be extrapolated. Equations (17) and (18) give the
form of extrapolation curves of the extraction and stripping isotherms.
 Extraction isotherm
Ln(Cueor ) = Δ * [ln⁡(Cueaq )]2 + Ω * ln(Cueaq )+ ρ (17)
Where “Δ”, “Ω” and “ρ” are the constants.
 Stripping isotherm
Cueor = δ * [Cueaq ]2 + θ * Cueaq + φ (18)
Where “δ”, “θ” and “φ” are the constants.
4.2.1.2. Semi-empirical model
Just like the preceding one, it is based on an equation but which best fits the curve of a parameter
of either the thermodynamic property of an overall chemical reaction or distribution isotherm. Semi-
empirical model uses the overall solvent extraction reaction.
4.2.1.2.1. Parameter of distribution isotherm
If an aqueous phase containing copper is contacted with an organic phase, than copper
distributes between the aqueous and organic phase according to equation (19).
Cu
DCu = Cuor (19)
aq
Where “𝐷𝐶𝑢 ” is the distribution ratio of copper, “𝐶𝑢𝑜𝑟 ” is copper concentration in organic phase and “𝐶𝑢𝑎𝑞 ” is
copper concentration in aqueous phase.
It has been observed that the distribution ratio (D) is a function of free ligand concentration in
the organic phase [7]. Equation (20) gives the mathematical expression this observation.
Cu
DCu = Cuor = Do ∗ (Lt − mCuor )n (20)
aq
Where “𝐷𝑜 ” is the distribution ratio of copper at trace concentrations, readily determined in the laboratory, “𝐿𝑡 ”
is the total ligand concentration in the extractant, “m” approximates the ratio of ligand molecules to extracted

molecules close to saturation, “n” approximates the ratio of ligand molecules to extracted molecules close to infinite
dilution.
It should be noted that “m” and “n” in equation (20) 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. If the extractant is the mixture of two extractants as Lix984N, the distribution ratio must
be defined for each extractant.
4.2.1.2.2. Parameter of the thermodynamic property
A. Concept
In 1976, Gerald L. Bauer and Thomas W. Chapman observed that ratio of chemical activity
coefficients in organic phase is a function of copper tenor in organic phase at steady state when copper is
extracted with kelex 100 solvent extractant [8]. This observation is applied to copper solvent extraction
equilibrium condition with Lix984N extractant [1]. Equation (21) gives the equilibrium condition on the
extraction and stripping steps.
Cueorg (Ace )2
aq
* (3.3030∗⁡V%−3.0842∗⁡Cu = E * Cueorg + F (21)
Cueaq e
org ⁡)
2
Where “E” and “F” are function of extractant volume percent. The concentrations of copper is expressed in (g/L)
Extraction step
Equations (22) and (23) give the values of “Ee ” and “Fe ”.
Ee = -25.698 * V%(−1.704) (22)
Fe = 10.663 * V%(−0.608) (23)
Stripping step
Equations (24) and (25) give the values of “Es ” and “Fs ”.
Es = 5.11 * 10(−3) * V% - 0.194 (24)
Fs = 12.81 * V%(−0.901) (25)
Where “V%” is the extractant volume percent.

Equations (22), (23), (24) and (26) have been slightly improved.
B. Resolution of equations of equilibrium conditions
Extraction step
The second semi-empirical model of extraction step using Lix984N as extractant is given by the
equation (26). Equation (27) gives the concentration of free acid at equilibrium.
Cueorg (Ace )2
Cueaq
aq
x (3.3030⁡x⁡V%−3.0842⁡x⁡Cue 2 =(-25.698 * v%(−1.704) ) ∗ ⁡Cueor + 10.663 * v%(−0.608) (26)
org ⁡)
e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (27)
𝑖 𝑖
Where “𝐶𝑢𝑎𝑞 ”is the concentration of copper in the PLS (g/L) and “𝐴𝑐𝑎𝑞 ” is the concentration of free acid in
the PLS (g/L).
Equation (30) gives the concentration of free acid as function of pH.
i
Acaq = 98* 10(−pH) (30)
e
The value of “Acaq ” in equation (26) is replaced by the equation (27), it appears equation (31).
Cueorg (Aci +(Cui −Cue )∗1.54)⁡2

Cueaq
aq aq aq
x (3.3030∗⁡V%−3.0842∗⁡Cue 2 =(-25.698 * v%(−1.704) ) ∗ ⁡Cueor + 10.663 * v%(−0.608) (31)
org ⁡)
After arrangement equation (31) becomes equation (32).
Cueorg ((Aciaq +1.54∗Cuiaq )−1.54∗Cueaq ))⁡2

Cueaq
x (3.3030∗⁡V%−3.0842∗⁡Cueorg ⁡)2
=(-25.698 * v%(−1.704) ) ∗ ⁡Cueor + 10.663 * v%(−0.608) (32)
The new designation is introduced and equation (32) becomes equation (33).
 Y = Cueor
 X = Cueaq
Y (a+b∗X)2
* = e*Y + f (33)
X (c+d∗Y)2
Equations (34), (35), (36), (37), (38) and (39) give the values of “a”, “b”, “c”, “d”, “e” and “f”.
i
a =Acaq + 1.54 * Cuiaq (34)

b = −1.54 (35)
c = 3.303*V% (36)
d = −3.0842 (37)
e = −25.698 * V%(−1.704) (38)
f = 10.663 * V%(−0.608) (39)
Equation (33) becomes equation (40) after placing “Y” on one side and “X” on other side.
(a+b∗X)2 (e∗Y+f)∗(c+d∗Y)2
= (40)
X Y
Known value of concentration of copper in aqueous
The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.
Equation (41) gives the value of constant “g”.
(a+b∗X)2 (41)
g= X
Equation (40) becomes equation (42) after introducing equation (41)
(d2 *e)*Y 3 + (2*c*d*e + d2 *f)*Y 2 +(2*c*d*f+c 2 *e-g)*Y + c 2 *f =0 (42)
Equation (42) becomes equation (43) after introducing equations (44), (45) and (46).
Y 3 + α*Y 2 +β*Y +γ =0 (43)
2∗c∗d∗e+d2 ∗f (44)
α= d2 ∗e
2∗c∗d∗f⁡+⁡c2 ∗e⁡−⁡g (45)

β= d2 ∗e
f∗c2 (46)
γ = d2 ∗e
Equation (47) gives the value of variable “Y” as a function of variable “t”.

𝛼
Y=t-3 (47)
Equation (47) becomes equation (48) after replacing the variable “Y” by equation (47). Equations
(49) and (50) give the value of constant “p” and “q”.
t 3 +p*t +q =0 (48)
𝛼2 (49)
p=β- 3
α∗β 2 (50)
q=γ- + 27* α3
3
Equation (48) has a form of Cardan formula (three degree equation). The value of “t” is given by
the equation (51).
1 1 1 1
q 1 2 4 3 (2) (3) q 1 2 4 3 (2) (3)
t = [− − ∗ (q + ∗p ) ] + [− + ⁡ ∗ (q + ∗p ) ] (51)
2 2 27 2 2 27
Known value of concentration of copper in organic
Equation (52) gives the value of constant “h”.
(e∗Y+f)∗(c+d∗Y)2 (52)
h= Y
Equation (40) becomes equation (53) after introducing equation (52).
b2 *X 2 + (2*a*b-h)*X + a2 = 0 (53)
Equation (54) gives the value of concentration of copper in aqueous phase.
1
( )
h−2∗a∗b−(h2 −4∗a∗b∗h) 2 (54)
X= 2∗b2
Stripping step
The second semi-empirical model of stripping step using Lix984N as extractant is given by the
equation (55). Equation (27) gives the concentration of free acid at equilibrium.
Cueorg (Ace )2
Cueaq
aq
x (3.3030⁡x⁡V%−3.0842⁡x⁡Cue 2 =(5.11 * 10−3 * v% - 0.194) x Cueor + 12.81 * v%(−0.901) (55)
org ⁡)
e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (27)

𝑖 𝑖
Where “𝐶𝑢𝑎𝑞 ”is the concentration of copper in the spent electrolyte (g/L) and “𝐴𝑐𝑎𝑞 ” is the concentration of free
acid in the spent electrolyte (g/L).
e
The value of “Acaq ” in equation (55) is replaced by the equation (27), it appears equation (56).
Cueorg ((Aciaq +1.54∗Cuiaq )−1.54∗Cueaq ))⁡2

Cueaq
x (3.3030∗⁡V%−3.0842∗⁡Cueorg ⁡)2
=(5.11 * 10−3 * v% - 0.194) x Cueor + 12.81 * v%(−0.901) (56)
The new designation is introduced and equation (56) becomes equation (57).
 Y = Cueor
 X = Cueaq
Y (a+b∗X)2
* = i*Y + j (57)
X (c+d∗Y)2
Equations (34), (35), (36), (37), (58) and (59) give the values of “a”, “b”, “c”, “d”, “i” and “j”.
i
a =Acaq + 1.54 * Cuiaq (34)
b = −1.54 (35)
c = 3.303*V% (36)
d = −3.0842 (37)
i = 5.11*10(−3) *V%- 0.194 (58)
j = 12.81 * V%(−0.901) (59)
Equation (57) becomes equation (60) after placing “Y” on one side and “X” on other side.
(a+b∗X)2 (e∗Y+f)∗(c+d∗Y)2
= (60)
X Y
Known value of concentration of copper in aqueous
The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.
Equation (41) gives the value of constant “g”.

(a+b∗X)2 (41)
g= X
Equation (60) becomes equation (61) after introducing equation (41)
(d2 *i)*Y 3 + (2*c*d*i + d2 *j)*Y 2 +(2*c*d*j+c 2 *i-g)*Y + c 2 *j =0 (61)
Equation (61) becomes equation (62) after introducing equations (63), (64) and (65).
Y 3 + µ*Y 2 +η*Y +π =0 (62)
2∗c∗d∗i+d2 ∗j (63)
µ= d2 ∗i
2∗c∗d∗j⁡+⁡c2 ∗i−g (64)

η= d2 ∗i
j∗c2 (65)
π = d2 ∗i
Equation (66) gives the value of variable “Y” as a function of variable “w”.
µ
Y=w-3 (66)
Equation (62) becomes equation (67) after replacing the variable “Y” by equation (66). Equations
(68) and (69) give the value of constant “m” and “n”.
w 3 +m*w +n =0 (67)
µ2 (68)
m=η- 3
µ∗η 2 (69)
n=π- + 27* µ3
3
Equation (67) has a form of Cardan formula (three degree equation). The value of “w” is given
by the equation (70).
1 1 1 1
n 1 2 4 3 (2) (3) n 1 2 4 3 (2) (3)
w = [− − ∗ (n + ∗m ) ] + [− + ⁡ ∗ (n + ∗m ) ] (70)
2 2 27 2 2 27
Known value of concentration of copper in organic
Equation (71) gives the value of constant “r”.
(i∗Y+j)∗(c+d∗Y)2 (71)
r= Y

Equation (60) becomes equation (72) after introducing equation (71).
b2 *X 2 + (2*a*b-r)*X + a2 = 0 (72)
Equation (73) gives the value of concentration of copper in aqueous phase.
1
( )
r−2∗a∗b−(r2 −4∗a∗b∗r) 2 (73)
X= 2∗b2
4.2.1.3. Chemical model
Chemical model requires the knowledge of all intermediate chemical reactions of extraction
reaction. The first suggestion of intermediate chemical reactions for copper solvent extraction with oximes
based extractant involves the dissolution of extractant in aqueous phase [9]. Chemical reactions (c), (d),
(e), (f) and (g) give the intermediate chemical reactions:
HR or ⁡ ↔ HR aq Step 1 (c)
The step 1 involves the dissolution of extractant in the aqueous phase.
+
HR aq ⁡ ↔ Haq + R−aq Step 2 (d)
The step 2 involves the dissociation of extractant in the aqueous phase.
Cu+2 − +
aq + R aq ↔ CuR aq Step 3 (e)
The step 3 the first ligand is added to copper in aqueous phase.
CuR+aq + R−aq ↔ CuR 2 aq Step 4 (f)
The step 4 the second ligand is added to copper in aqueous phase.
CuR 2 aq ↔ CuR 2 or Step 5 (g)
The step 5 the copper complex is absorbed by the organic phase.
The second suggestion of intermediate chemical reactions for copper solvent extraction with
oximes based extractant involves two forms of extractant molecule in the organic phase [10]. 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 case where the extractant is the mixture of two extractants as Lix984N, the intermediate
chemical reaction will be defined for each extractant.
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 expressions
for the chemical reactions listed above and the mass-balance of copper, ligand and hydrogen.
The mass-action equilibrium expressions and the mass-balance of copper, ligand and hydrogen
for the second suggestion of intermediate chemical reactions are given by the equations (74), (75), (76),
(77), (78) and (79).
All models consider that the chemical activity coefficients of extractant and copper complex in
the organic phase are the constants.
[Cu+2 ]aq ∗[HR]2or

[CuR 2 ]or = K1 * (74)
[H+ ]2aq
[Cu+2 ]aq ∗[(HR)2 ]or

[CuR 2 ]or = K 2 * (75)
[H+ ]2aq
[(HR)2 ]ot = K 3 * [HR]2or (76)
[Cu+2 ]taq = [Cu+2 ]aq + A * CuR 2 or (77)
[HR]tor = [HR]or + 2* [(HR)2 ]or+ 2* [CuR 2 ]or (78)
[H +2 ]aq = [H + ]iaq + 2* A* [CuR 2 ]or (79)

Where [𝐶𝑢𝑅2 ]𝑜𝑟 is the concentration of copper complex in the organic phase (mol/L), [𝐻𝑅]𝑜𝑟 is the
concentration of the first molecule form of extractant in organic phase (mol/L), [(𝐻𝑅)2 ]𝑜𝑟 is the concentration of
the second molecule form off extractant in the organic phase (mol/L), [𝐻𝑅]𝑡𝑜𝑟 is the total concentration of ligand
in the organic phase (mol/L), [𝐶𝑢+2 ]𝑎𝑞 is the concentration of copper in aqueous phase, [𝐶𝑢+2 ]𝑡𝑎𝑞 is the total
concentration of copper in aqueous and organic phases, [𝐻 + ]𝑖𝑎𝑞 is the concentration of hydrogen ion in the feed
solution, [𝐻 +2 ]𝑎𝑞 is the concentration of hydrogen ion in the aqueous phase, [𝐻 + ]𝑖𝑎𝑞 is the concentration of
hydrogen ion in the initial aqueous phase and “A” is the ratio of organic phase volume on aqueous phase volume.
4.2.2. Comparison between results from laboratory test and model
4.2.2.1. Empirical model
The empirical model seems to be simple but it uses under certain conditions. The first empirical
model is used in the dynamic modelling of copper solvent extraction. The first empirical model needs a
computer program to be used. The second empirical model is easy to use on the Microsoft Excel
spreadsheet. The second empirical model is adopted for the purpose of this paper.
Table 8 gives example of extraction isotherm from laboratory scale test [11]. 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.
Table 8: Laboratory scale test - extraction isotherm
O/A Organic phase Aqueous phase

Cu (g/L) Cu (g/L)
10/1 2.04 0.07
5/1 2.28 0.09
2/1 2.96 0.17
3/2 3.26 0.26
1/1 3.70 0.51
1/2 4.19 1.24
1/5 4.35 1.94
Equation (80) gives the empirical model obtained using Excel trendline program. Figure (13)
gives graphical representation of the laboratory scale test and empirical extraction isotherms.
Ln(Cueor ) = -6.284 * 10−2 * [ln⁡(Cueaq )]2 + 9.600 * 10−2 * ln(Cueaq )+ 1.423 (80)

Figure 13: Laboratory scale test and empirical model extraction isotherms
Table 9 gives example of stripping isotherm from laboratory scale test [11]. 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.
Table 9: Laboratory scale test - stripping isotherm
O/A Organic phase Aqueous phase

Cu (g/L) Cu (g/L)
10/1 1.76 51.3
5/1 1.38 43.2
2.5/1 1.21 37.7
1/1 1.07 33.8
1/2 1.01 32.3
1/4 0.98 31.2
Equation (81) gives the empirical model obtained using Excel trendline program. Figure (14)
gives graphical representation of the laboratory scale test and empirical extraction isotherms.
Cueor = 4.767 * 10−4 * [Cueaq ]2 – 9.826 * 10−4 * Cueaq + 0.5513 (81)

Figure 14: Laboratory scale test and empirical model stripping isotherms
4.2.2.2. Semi-empirical model
The semi-empirical model based on the assumption that the distribution ratio is a function of the
concentration of the free ligand in the organic phase need the lab test with high accuracy to find the value
of the distribution ratio of copper at trace concentrations (𝐷𝑜 ). The first semi-empirical model can take
into account the effect of the impurities. The second semi-empirical model, based on the observation that
the ratio of chemical activity coefficients of species in the organic phase is function of the concentration
of copper in the organic phase, is easy to establish and gives the equations of distributions lines easy to
resolve on Microsoft Excel spreadsheet. This second semi-empirical model does not take into account the
effect of the impurities.
Data of laboratory scale test are given in Table (8). The predicted extraction isotherm is obtained
by using the procedure explained in chapter (4.2.1.2.2.). Table (10), as it appears on the Excel spreadsheet,
gives the predicted extraction isotherm. The figure (15) 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 10 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
e
7 Cuaq(g/L) 4.414 4.356 4.188 3.662 3.146 2.786 2.223 2.000
8 a 5.403 5.403 5.403 5.403 5.403 5.403 5.403 5.403
9 b -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54
10 c 28.736 28.736 28.736 28.736 28.736 28.736 28.736 28.736
11 d -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842
12 e -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644
13 f 2.862 2.862 2.862 2.862 2.862 2.862 2.862 2.862
14 g 0.965 3.007 9.842 41.808 96.254 155.48 307.93 400.36
15 α -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078
16 β 169.76 170.10 171.21 176.43 185.32 194.98 219.86 234.98
17 γ -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71
18 p -7.761 -7.428 -6.312 -1.095 7.791 17.458 42.340 57.458
19 q 9.788 12.353 20.934 61.068 129.43 203.79 395.19 511.49
20 t -3.278 -3.336 -3.505 -4.031 -4.547 -4.907 -5.469 -5.692
21
The excel formula of the excel column “C” are the following:
 a = C8 = C5+1,54*C4
 b = C9 = -1.54
 c = C10 = 3,303*C3
 d = C11 = -3.0842
 e = C12= -25.698*C3^-1,704
 f = C13 = 10.663*C3^-0,608
 g = C14 = (C8+C9*C6)^2/C6
 α = C15 = (2*C10*C11*C12+C11^2*C13)/(C11^2*C12)
 β = C16 = (2*C10*C11*C13+C10^2*C12-C14)/(C11^2*C12)
 γ = C17 = (C13*C10^2)/(C11^2*C12)
 p = C18 = C16-(C15^2)/3
 q = C19 = C17-C15*C16/3+2/27*C15^3
 t = 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 15: Laboratory scale test and semi-empirical model extraction isotherms
The gap on the concentration of copper in the organic phase obtained for the low values of
concentration of copper in the aqueous phase is due to the presence of iron in the PLS.
Data of laboratory scale test are given in Table (9). The predicted stripping isotherm is obtained
by using the procedure explained in chapter (4.2.1.2.2.). Table 11, as it appears on the excel spreadsheet,
gives the predicted stripping isotherm. The Figure (16) gives graphical representation of laboratory scale
test and semi-empirical model results.
The excel formula of the excel column “C” are the following:
 a = C8 = C5+1,54*C4
 b = C9 = -1.54
 c = C10 = 3,303*C3
 d = C11 = -3.0842
 i = C12= 5,11*10^-3*C3-0,194
 j = C13 = 12,81*C3^-0,901
 g = C14 = (C8+C9*C6)^2/C6

A B C D E F G H I
1
2 Table 11 Semi-empirical model – predicted stripping isotherm
3 V% 8.7 8.7 8.7 8.7 8.7 8.7
4 CuSE (g/L) 30.7 30.7 30.7 30.7 30.7 30.7
5 AcSE (g/L) 190.0 190.0 190.0 190.0 190.0 190.0
e
6 Cuaq (g/L) 51.3 43.2 37.7 33.8 32.3 31.2
e
7 Cuaq (g/L) 1.76 1.43 1.217 1.072 1.018 0.978
8 a 236.20 236.20 236.20 236.20 236.20 236.20
9 b -1.54 -1.54 -1.54 -1.54 -1.54 -1.54
10 c 28.736 28.736 28.736 28.736 28.736 28.736
11 d -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842
12 i -0.150 -0.150 -0.150 -0.150 -0.150 -0.150
13 j 1.824 1.824 1.824 1.824 1.824 1.824
14 g 481.70 666.40 841.77 1003.27 1076.36 1134.65
15 µ -30.832 -30.832 -30.832 -30.832 -30.832 -30.832
16 η 652.74 782.58 905.86 1019.39 1070.78 1111.76
17 π -1098.88 -1098.88 -1098.88 -1098.88 -1098.88 -1098.88
18 m 335.86 465.71 588.99 702.52 753.91 794.88
19 n 3478.45 4812.90 6079.88 7246.71 7774.82 8195.95
20 w -8.517 -8.847 -9.060 -9.205 -9.260 -9.299
21
 µ = C15 = (2*C10*C11*C12+C11^2*C13)/(C11^2*C12)
 η = C16 = (2*C10*C11*C13+C10^2*C12-C14)/(C11^2*C12)
 π = C17 = (C13*C10^2)/(C11^2*C12)
 m = C18 = C16-(C15^2)/3
 n = C19 = C17-C15*C16/3+2/27*C15^3
 w = 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 16: Laboratory scale test and semi-empirical model stripping isotherms

5. Solvent extraction plant parameters
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;
 Organic net transfer;
 Percentage of maximum loading;
 Mixer efficiencies.
5.1. Maximum loading and extractant volume percent
5.1.1. Laboratory scale test
5.1.1.1. Maximum loading
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” five times, each time with fresh prepared PLS; and,
e. The copper tenor in the organic after five 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).
5.1.1.2. Extractant volume percent
Reagent suppliers use the absolute maximum loading obtained from laboratory scale test with a
synthetic PLS to have the approximate extractant volume percent [12]. Equation (82) gives the
approximate extractant volume percent.
AMLL
V% = (82)
U
Where “U” is the constant ranged from 0.52 to 0.54.
5.1.2. Predicted isotherms
5.1.2.1. Maximum loading
The value of equilibrium concentration of copper in the organic phase when the equilibrium
concentration of copper in the aqueous is the concentration of copper in prepared PLS is called the
maximum loading (ML).
In case of the second semi-empirical model using Lix984N as extractant, the value of ML
following the procedure explained in chapter (4.2.2.2.1.). the equilibrium concentration of copper in
aqueous phase is the concentration of copper in the PLS.
In this paper the predicted absolute maximum loading (AMLP ) is the maximum loading when the
concentration of free acid in the PLS is nil.
In case of the second semi-empirical model using Lix984N as extractant, equation (83) gives the
value of predicted absolute maximum loading.
AMLP = 0.415 * V%(1.1) (83)
Where “𝐴𝑀𝐿𝑃 ” is the predicted absolute maximum loading (g/L).
The absolute maximum loading depends only on the value of the extractant volume percent.
5.1.2.2. Extractant volume percent
In the case of Lix984N is used as extractant, equation (84) gives the value of extractant volume
percent ranged from 2.5 to 32%.
V% = 2.238 * AMLL (0.912) (84)
Where “V%” is in percentage and “𝐴𝑀𝐿𝐿 ” is absolute maximum loading obtained in laboratory with the
synthetic PLS (6 g/L of copper at pH 1.8) (g/L).

5.2. Copper recovery
The copper recovery is calculated in the two steps of copper solvent extraction plant after data
correction and mass balance operations: extraction step and stripping steps. The copper recoveries on the
extraction and stripping steps are given respectively by equations (85) and (86).
CuPLS −Curaf
Rcuex = 100 x (85)
CuPLS
CuLO −CuSO
Rcuor = 100 x (86)
CuLO
Where “𝑅𝑐𝑢𝑒𝑥 ” is the copper recovery on extraction step (%), “𝑅𝑐𝑢𝑜𝑟 ” is the copper recovery on the stripping
step (%), “𝐶𝑢𝑃𝐿𝑆 ” is the concentration of copper in the PLS (g/L), “𝐶𝑢𝑟𝑎𝑓 ” is the concentration of copper in
the raffinate, “𝐶𝑢𝐿𝑂 ” the concentration of copper in the loaded organic (g/L) and “𝐶𝑢𝑆𝑂 ” is the concentration of
copper in the stripped organic.
5.3. Copper net transfer
The copper net transfer is given by equation (87) after data correction and mass balance
operations.
CuLO −CuSO
NTor = (87)
V%
Where “𝑁𝑇𝑜𝑟 ” is the organic net transfer ((g/L)/1V%).
5.4. Percentage of maximum loading
The percentage of maximum loading (or saturation ratio “Sr”) is given by equation (88) after data
correction and mass balance operation.
CuLO
%ML or “Sr” = 100 x (88)
ML
Where “%ML” is the percentage of maximum loading (%) and “Sr” is the saturation ratio.

5.5. Stage efficiencies
5.5.1. Concept
The concentrations of copper in the outlet aqueous and organic of mixers 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.
According to Figures (5) and (6), equations (89) and (90) give the stage efficiencies calculated
with the concentrations of copper in organic and in aqueous respectively on extraction step. Equations
(91) and (92) give the stage efficiencies calculated with the concentrations of copper in organic and in
aqueous respectively on stripping step.
e YB −YA
Effor = 100 x (89)
YD −YA
e XB −XA
Effaq = 100 x (90)
XB −XD
s YB −YA
Effor = 100 x (91)
YB −YD
s XB −XA
Effaq = 100 x (92)
XD −XA
The next step is determining the concentrations of copper in organic and aqueous of points “D”
(Figures (5) and (6)) for each stage. Point “D” is the intercession of the orthogonal regression line having
the slope “-ε3 ” and passing through point “C” and the distribution isotherm line.
5.5.1.1. Straight line passing through points D and C
According to Figures (5) and (6), equations (93) and (94) give the mathematical expressions of
the straight line passing through point “C” and having the slope “-ε3 ” respectively on extraction and
stripping steps.
Cuor = - εe3 * Cuaq + (YB + εe3 * XA ) (93)
Cuor = - εs3 * Cuaq + (YA + εs3 * XB ) (94)

5.5.1.2. Distribution isotherms
5.5.1.2.1. Without computer program
In the 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
stripped organic on extraction step and plant loaded organic on stripping step. The maximum loading
using the prepared PLS must be obtained during the laboratory scale test on extraction step.
The second-empirical models are stablished on extraction and stripping steps. The maximum
loading must be taken account during the construction of the second-empirical model on the extraction
step.
5.5.1.2.2. With computer program
The extraction and stripping isotherms are constructed using the concentrations of copper and
free acid in PLS and spent electrolyte after data correction and mass balance in form of point coordinates.
The second-empirical models are stablished on extraction and stripping steps with point coordinates
obtained with computer program. The maximum loading must be taken account during the construction
of the second-empirical model on the extraction step.
In the case where the extractant volume percent is unknown, extractant volume percent is
determined using reagent suppliers method or equation (97) in case where Lix984N is used as extractant.
5.5.2. Determining of stage efficiencies
The explanation of the procedure for determining stage efficiencies is done through an example.
Figure (17) gives a flow diagram of pilot plant with plant data. The configuration of copper solvent
extraction is triple series with two stages on stripping step.
Figure (18) gives pilot plant flow diagram with after data correction and mass balance. Table (12)
gives the concentrations of copper in organic and aqueous of extraction isotherm. The extraction isotherm
is obtained using method explained in chapter (4.2.2.2.) and data from Figure (18). Table (13) gives the
concentrations of copper in organic and aqueous of stripping step isotherm. The stripping isotherm is
obtained using method explained in chapter (4.2.2.2.) and data from Figure (18).
Table 12: Predicted Extraction isotherm
Cueaq (g/L) 4.350 2.900 1.933 0.957 0.483 0.242 0.121 0.060
Cueor (g/L) 11.231 10.884 10.331 9.104 7.671 6.133 4.593 3.183

Table 13: Predicted stripping isotherm
Cueaq (g/L) 43.00 40.00 37.00 34.00 31.00 28.00

Cueor (g/L) 3.313 3.086 2.859 2.631 2.403 2.175
Equations (95) and (96) give second-empirical models obtained using Excel trendline program on
extraction and stripping steps.
Ln(Cueor ) = -0.0583 * [ln⁡(Cueaq )]2 + 0.2133 * ln(Cueaq ) + 2.2254 (95)
Cueor = -1.146 * 10−5 * [Cueaq ]2 + 7.671 * 10−2 * Cueaq + 3.599 * 10−2 (96)
Table (14), as it appears on Microsoft Excel spreadsheet, gives the stage efficiencies on extraction
and stripping steps.
Figure 17: Flow diagram of copper solvent extraction of pilot plant

Figure 18: Flow diagram of copper solvent extraction after data correction and mass balance
A B C D E F G H
1
2 Table 14 Stage efficiencies
3
4 Extraction step
5 εe3 1.654
6 Cuaq Cuor
e
7 B1 4.350 9.770 Effaq -1 74.42 %
e
8 A1 2.839 7.272 Effaq-2 80.13 %
e
9 A2 1.013 4.251 Effaq -3 96.83 %
10 A3 0.136 2.802
11
12 Cueaq Cueor-1 Cueor-2 constraints
13 D1 2.319 10.63 10.63 0.000
14 D2 0.560 8.02 8.02 0.000
15 D3 0.107 4.30 4.30 0.000
16
17 Stripping step
18 εs3 0.768
19 Cuaq Cuor
e
20 B1 39.47 9.770 Effaq -1 79.55 %
e
21 A1 32.64 4.527 Effaq-2 87.35 %
22 A2 30.39 2.802
23
24 Cueaq Cueor-1 Cueor-2 constraints
25 D1 41.22 3.18 3.18 0.000
26 D2 32.96 2.55 2.55 0.000
27

The data in red color come from Figure (18). The data in blue color are the solver variables. The
procedure of determining the stage efficiencies is the following:
Extraction step
- In the excel cell “C13” (solver variable), type number “2.839” (starting value - Aqueous
copper concentration of point “A1”).
- In the excel cell “D13”, type “=-C$5*C13+(D7+C$5*C8)” (Equation (93) of stage 1).
- In the excel cell “E13”, type “=EXP(-0,0583*(LN(C13))^2+0,2133*LN(C13)+2,2254)”

(Equation (95) of stage 1).
- In the excel cell “F13”, type “=D13-E13” (solver constraint of stage 1).
- In the excel cell “G7”, type “=(C7-C8)/(C7-C13)*100” (equation (90) - efficiency of stage1).
- In the excel cell “G8”, type “=(C8-C9)/(C8-C14)*100” (equation (90) - efficiency of
stage2).
stage3).
Stripping step
copper concentration of point “B1”).
copper concentration of point “B2”).
- In the excel cell “D25”, type “=-C$18*C25+(D21+C$18*C20)” (Equation (94) – stage 1).
- In the excel cell “D36”, type “=-C$18*C26+(D22+C$18*C21)” (Equation (94) - stage 2).

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

stage 1).
stage 2).
Solver program
Excel solver program execution is as follows:
1) On the ‘Data’, in the ‘Analysis group’ click solver (if the solver command is not available, you
must activate the solver add-in).
2) In the ‘Set objective’ box, enter the cell reference ‘F13’ of simulation program constraint.
3) Click ‘Value of’ and then type the number ‘0’ in the box.
4) In the ‘By Changing Variable Cells’ box, enter the reference (C13, C14, C15, C25 and C26)
for each solver variable (blue color). Separate the references with commas (English version).
5) In the ‘Subject to the constraints’ box, enter solver constraints by doing the following:
a. In the ‘Solver Parameters’ dialog box, click ‘Add’.
b. In the ‘Cell Reference’ box, enter the cell reference “F14” solver constraint (green color).
c. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
d. In the ‘Solver Parameters’ dialog box, click ‘Add’.
e. In the ‘Cell Reference’ box, enter the cell reference “F15” solver constraint (green color).
f. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
g. In the ‘Solver Parameters’ dialog box, click ‘Add’.
h. In the ‘Cell Reference’ box, enter the cell reference “F25” solver constraint (green color).
i. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
j. In the ‘Solver Parameters’ dialog box, click ‘Add’.
k. In the ‘Cell Reference’ box, enter the cell reference “F26” solver constraint (green color).
l. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
m. Click ‘OK’ to return to ‘Solver Parameters’ dialog box.
6) Click ‘Solve’. To keep the solution values on the worksheet, in the ‘Solver Results’ dialog box,
click ‘Keep solver solution’.
Figures (19) and (20) give MacCabe-Thiele diagram on extraction and stripping steps after data
correction and mass balance operations.

Figure 19: MacCabe-Thiele diagram on extraction step
Figure 20: MacCabe-Thiele diagram on stripping step
The maximum loading is the concentration of copper in organic for 4.35 g/L of copper in the
aqueous (Table 12) – ML=11.231 g/L. The value of percentage to maximum loading is 86.99%. The value
of extraction recovery is 96.88%. The value of stripping recovery is 71.32%. The value of copper net
transfer is 0.342 (g/l)/1V%.

6. References
1. K. Kafumbila, Static simulation program of copper solvent extraction configurations using excel
solver, researchgate, 2017.
https://www.researchgate.net/publication/314519885_STATIC_SIMULATION_PROGRAM_OF_CO
PPER_SOLVENT_EXTRACTION_CONFIGURATIONS_USING_MICROSOFT_EXCEL_SOLVE
R
2. K. Kafumbila, Pre-feasibility studies of copper hydrometallurgical plant, 2017.
http://www.youscribe.com/catalogue/documents/savoirs/techniques/pre-feasibility-studies-of-copper-
hydrometallurgical-plants-2866594
3. AIDI AMEL, Etude thermodynamique de l’extraction des métaux de transition par

Salicylidèneaniline, Thèse, Université Mohamed Khider, 2013.
4. N.B. du Preez and J.J. Taute, Evaluation of copper solvent extraction circuit data and performance,
SAIMM, Zambia, 2015.
5. Pierre-Antoine Noirot, Logiciels d’étude et de prévision des extractions par solvants : application à la
valorisation des solutions de chlorure de Nickel, Thèse, Université des sciences et techniques de Lille,
1985.
6. C.M. Moreno, J.R. Pérez-correa, A. Otero, Dynamic modelling of copper solvent extraction mixer-
settler units, Minerals Engineering, 2009.
7. Philip J.D. LLOYD, solvent extraction principles and practice-Second Edition, Taylor & Francis
Group, 2004.
8. Gerald L. BAUER and Thomas W. CHAPMAN, Measurement and correlation of solvent extraction
Equilibria. The extraction of copper by Kelex 100, Metallurgical Transaction, 1976.
9. D.B. Dreisinger, Solvent extraction kinetic of divalent metals with organophorus acids using the
rotating diffusion cell technique, ISEC’88 volume II, USSR, 1988.
10. F.J. Alguacif, Modelling copper solvent extraction from acidic sulphate solution using MOC 45, Rev.
Metal. Madrid, 1998.
11. BASF, Redbook Mining solutions.
12. O. Tinkler, D. Shiels, and M. Soderstrom, The ACORGA OPT series: comparative studies against
aldoxime: ketoxime reagents, SAIMM, 2009.

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Data Correction and Copper Mass Balance Before Evaluation of Copper Solvent Extraction Performance

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Joseph Kafumbila

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3. DATA CORRECTION AND MASS BALANCE 6

4. CONSTRUCTION OF DISTRIBUTION ISOTHERMS 23

5. SOLVENT EXTRACTION PLANT PARAMETERS 41

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2.1. Classification of metal solvent extraction

2.1.1. Extraction by salvation

2.1.2. Extraction by cation exchange

2.1.3. Extraction by anion exchange

2.1.4. Extraction by chelation

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2.2. Chemistry of copper solvent extraction

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

CuSO4 + 2*HR → CuR2 + H2SO4 (a)

CuR2 + H2SO4 → CuSO4 + 2*HR (b)

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

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3.1. Data correction

3.1.1. Problem description

Figure 1: MacCabe-Thiele diagram on extraction step having two stages

Cuor = ε * Cuaq + λ (1)

Where “ε” and “λ” are constant values.

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3.1.1.1. Known slope value

Figure 2: Regression line with known value of the slope

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In this case there are three types of regression line:

Figure 3: Regression lines with unknown value of slope

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3.1.2. Application to SX plant

3.1.2.1. Plant data

Figure 4: Data of copper solvent extraction plant

Figure 5 : MacCabe-Thiele diagram – one stage on extraction step

Figure 6 : MacCabe-Thiele diagram – one stage on stripping step

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Figure 8: Point coordinates on stripping step for Figure (4)

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3.1.2.2.1. Extraction step

- In the excel cells ranged from “E5” to “E9”, type:

- In the excel cells ranged from “F5” to “F9”, type:

- In the excel cells ranged from “G5” to “G9”, type:

- In the excel cell “E11”, type “=SUM(E5:E9)”.

Figure 9: Point new coordinates on extraction step of Table (3)

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Figure 10: Point new coordinates on stripping step of Table (3)

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3.1.2.3.1. Extraction step

Small Table (A)

- In the excel cells ranged from “E6” to “E10”, type:

- In the excel cells ranged from “F6” to “F10”, type:

- In the excel cell “C13”, type “=SUM(C6:C10)”.

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

Joseph Kafumbila Page 15

- In the excel cell “D19” (ε1), type “=(D15*E13-C13*D13)/(D15*F13-C13^2)”.

Cuor = ε1 * Cuaq + λ1 (3)

Small Table (B)

- In the excel cells ranged from “G6” to “G10”, type:

- In the excel cells ranged from “H6” to “H10”, type:

- In the excel cells ranged from “E6” to “E10”, type:

- In the excel cells ranged from “J6” to “J10”, type:

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

- In the excel cell “H15”, type “=D15”.

- In the excel cell “H19” (ε2), type “=(H15*I13-G13*H13)/(H15*J13-G13^2)”.

Cuaq = ε2 * Cuor + λ2 (4)

- In the excel cell “D19” (ε1), type “=(D15E13-C13D13)/(D15*F13-C13^2)”.

- In the excel cell “H19” (ε2), type “=(H15I13-G13H13)/(H15*J13-G13^2)”.

- In the excel cell “E23” (ε3), type “=(D19H19+1)/(2H19)”.

(d2 e)Y 3 + (2cde + d2 f)Y 2 +(2cdf+c 2 e-g)Y + c 2 *f =0 (42)

Y 3 + αY 2 +βY +γ =0 (43)

i = 5.1110(−3) V%- 0.194 (58)