MODELING OF SOLVENT EXTRACTION

OF COPPER FROM SULPHATE

SOLUTIONS WITH D2EHPA
Clenilson Sousa Junior (IFRJ/EQ-UFRJ)
Marisa Nascimento (CETEM)
Ldia Yokoyama (EQ-UFRJ)
Osvaldo Galvo da Cunha (EQ-UFRJ)
1. INTRODUCTION
2. THEORETICAL
3. EXPERIMENTAL
4. RESULTS
4.1. Equilibrium constant and metal complex determination
4.2. Thermodynamic model
5. CONCLUSIONS
SUMMARY
1. INTRODUCTION
Solvent extraction is an important economical, practical and
clean hydrometallurgical process and the technique is one of
the most versatile methods used for the removal, separation
and concentration of metallic species from aqueous media. In
the hydrometallurgy, the organic extractant Di-(2-ethylhexyl)
phosphoric acid (D2EHPA or HA) has been used successfully to
extract many divalent metal ions in sulfate media, in the
extraction of Cu
2+,
Co
2+
and Ni
2+
, particularly, at equilibrium by
D2EHPA has been reported.
Shibata et al., 1982; Owusu, 1998; Gajda et al., 2007.
1. INTRODUCTION
Thermodynamic and kinetics parameters were investigated by
Haghshenas Fatmehsari et al. (2009), Simonin et al. (2003),
Zhang et al. (2001) and Darvishi et al. (2005), that determined
parameters such as rate constant, pH, distribution
coefficients, equilibrium constant and composition of
extracted species in different conditions.
In the specific case of this work, the objective was to obtain a
thermodynamic model for extraction of Cu(II) in sulfuric acid
media by D2EHPA in Isoparaffin (17/21).
1. INTRODUCTION
Reaction Equilibrium constant
H
2
O = H
+
+ OH
-
K
1
= 1.00 x 10
-14
H
+
+ SO4
2-
= HSO
4
-
K
2
= 9.85 x 10
1
Cu
2+
+ SO
4
2-
= CuSO
4(aq)
K
3
= 251.2
Cu
2+
+ HSO
4
-
= CuHSO
4
+
K
4
= 229.1
Cu
2+
+ OH
-
= CuOH
+
K
5
= 5.01 x 10
7
Cu
2+
+ 2OH
-
= Cu(OH)
2
K
6
= 1.58 x 10
16
Equilibrium mass
[Cu]
i
=[Cu
2+
]+[CuSO
4
]+[CuHSO
4
+
]+[CuOH
+
]+[Cu(OH)
2
]+(V
org
/V
aq
) [CuH
2x
A
2+2x
]
Charge balance
[H
+
] +[CuHSO
4
+
]+ [CuOH
+
] + 2[Cu
2+
] = [OH
-
] + [HSO
4
-
] + 2 [SO
4
2-
]
Table 1: Chemical reaction equilibrium mass and charge balance equations for copper species.
2. THEORETICAL
On account of the dimerization of acid phosphoorganic extractants, it
is adopted in scientific reports that in the formation of complexes with
Cu
2+
ions. The reaction of extraction with D2EHPA can be written as :
The model used the logarithm of activity coefficient of ( i) for a single
ion is described and presents validity similar to the model of Pitzer,
though with a much simpler mathematical formulation. The Equation
is a modification of the Daviess equation.
Fu and Golding, 1987; Biswas et al, 2000; Swain, et al., 2006; Samson et al., 1999.
) ( ) ( 2 2 2 ) ( 2 2
2
) (
2 ) 1 (
aq or x x or aq
H A CuH A H x Cu
1000
) 2 , 0 ) 10 17 , 4 ((
) 10 3 ( 1
ln
2 15
10
2
I Az I x
I B x
I Az
i i
i
2. THEORETICAL
For to represent the equilibrium constant for the reaction of
extraction (K
eq
), we used this equation:
) , (
2
) , ( 2 2 2
] [
] [
t aq
t or x x
Cu
A CuH
D
] )[ 1 ( 2 ] [ ] [
2 2 2 2 2 2 2 x x inicial
A CuH x A H A H
eq x x inicial
K A CuH x A H x pH LogD log ]} )[ 1 ( 2 ] log{[ ) 1 ( 2
2 2 2 2 2
) 1 (
2
2 2
2 2
2
2 2 2
.
.
log log ] log[ ) 1 ( 2
x
A H
Cu
H
A CuH
eq
x x
K A H x pH LogD
) 1 (
2
) 1 (
2 2
2
2
2 2 2
2 2
2
2 2 2
.
.
] ].[ [
] ].[ [
x
A H
Cu
H
A CuH
x
x x x x
x
A H Cu
H A CuH
Keq
3. EXPERIMENTAL
0.0075M; 0.015M e 0.03M
CuSO
4
.5H
2
O
pH = 2.5; 3.5 e 4.5
0.05M; 0.10M e 0.20M
D2EHPA in
isoparaffin
5 min.
25.00 mL
40 min.
25.00 mL
Reexctracion
Atomic Abs.
Org.
pH
Aq.
4. Results
The Quasi-Newton method of non-linear regression estimation was
applied and the results of the copper extraction and x (1.231) and
K
eq
(2.10x10
-1
) were found, with a correlation coefficient R equal to
0.9439. As a result, the reaction of Cu extraction by D2EHPA can
finally be represented as:
) (
) (
4 . 4 4 . 2 ) ( 2 2
2
) (
2 2 . 2
aq
or or aq
H A CuH A H Cu
4.1. Equilibrium constant and metal complex determination
4. Results
For the model the number of solutes in the aqueous phase before
extraction , is ten (Cu
2+
, CuSO
4
, CuHSO
4
+
, Cu(OH)
+
, Cu(OH)
2
, H
+
, OH
-
,
SO
4
2-
, HSO
4
-
and H
2
O). First, we considered the activity of water equal
to 1 as an approximation. Second, the activity of hydrogen was
obtained from the initial pH value. The activity of the eight remaining
solutes was calculated by solving the six chemical equilibria, one
mass balance and one balance of charges.
4.2. Thermodynamic model
4. Results
4. Results
CuSO4
CuHSO4(+)
SO4(2-)
HSO4(-)
0
10
20
30
40
50
60
70
80
90
100
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
P
e
r
c
e
n
t
a
g
e
m

o
f

s
u
l
f
a
t
e

s
p
e
c
i
e
s
pH
Cu(2+)
CuSO4
CuHSO4(+)
CuOH(+)
Cu(OH)2
0
10
20
30
40
50
60
70
80
90
100
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
P
e
r
c
e
n
t
a
g
e
m

o
f

c
o
p
p
e
r

s
p
e
c
i
e
s
pH
Figure 1. Copper metal species .
Figure 2. Sulphate species.
4. Results
The chemical species after extraction with D2EHPA are twelve
Cu
2+
, CuSO
4
, CuOH
+
, Cu(OH)
2
, H
+
, OH-, SO
4
2-
, HSO
4
-
, H
2
O, H
2
A
2
,
Cu
2.4
A
24.4
and diluent.
4. Results
y = 1,0837x + 0,0761
R = 0,9855
-1,30
-1,10
-0,90
-0,70
-0,50
-1,30 -1,10 -0,90 -0,70 -0,50
L
o
g

D

c
a
l
c
Log D exp.
y = 1,0617x - 0,0678
R = 0,9611
1,00
1,10
1,20
1,30
1,40
1,50
1,60
1,70
1,80
1,00 1,20 1,40 1,60 1,80
p
H

c
a
l
c
.
pH exp.
Figure 3. Log D calc x Log Dexp. Figure 4. pH calc x pH exp.
5. Conclusions
The studies show that the copper aqueous species extracted
was CuH
2.4
A
4.4
, and the equilibrium constant for the reaction of
extraction, obtained by nonlinear regression of experimental
data, was 2.52x10
-1
.
The thermodynamic data calculated by the Cu
2+
proposed
model had a satisfactory fit when compared to those obtained
experimentally.
Acknowledgements
cjunior@cetem.gov.br or clenilson.sousa@ifrj.edu.br
Thank You! Obrigado! Muchas Gracias!