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ABSTRACT
Caravaca, C. and Alguacil, F.J., 1991. Study of the ZnSO4-Cyanex 302 extraction equilibrium system.
ttydrometallurgy, 27: 327-338.
The application of the new extractant Cyanex 302 (Cyanamid), bis (2,4,4-trimethylpentyl) mon-
othiophosphinic acid, as an extraction agent of zinc(II) from sulphate medium is studied. The ex-
traction system is studied as a function of several variables, such as the diluent of the organic phase,
temperature, metal concentration in the aqueous phase, etc., along with the zinc (II) stripping stage
by sulphuric acid. The behaviour of Cyanex 302 has been studied with respect to other organophos-
phorous extractants and also the selectivity of the reagent in the system zinc ( II ) versus iron ( III ).
INTRODUCTION
For many years the production of zinc (II) has been carried out by a com-
bination of pyrometallurgy and hydrometallurgy from which zinc can be
recovered from aqueous solutions by solvent extraction followed by an elec-
trowinning step. It is known that solvent extraction has a number of features
that makes it a very useful and widespread technique in hydrometallurgy, al-
though it has not been so much used in zinc industrial processes in compari-
son to other metals such as uranium and copper.
In some cases solvent extraction has been used to recover zinc directly from
solutions and in others as a m e d i u m to purify aqueous solutions ready for
electrowinning [ 1-5 ]. The extraction of zinc from chloride [ 6-10 ], sulphate
[ 11-14), nitrate [ 15-16 ] and perchlorate [ 13,17 and 18 ] media has been
widely studied.
With respect to sulphate media it seems that the organophosphorous deriv-
ative extractants and especially DEHPA (di (2-ethylhexyl) phosphoric acid ),
are the most accepted reagents in this particular field, DEHPA is the most
widely used reagent although it has a number of disadvantages. Zinc is ex-
tracted from aqueous solution at a pH value higher than 1.5 and, most im-
portant, iron (III) is extracted with preference to zinc at pH 1.5.
In the present work the extraction of zinc (II) from aqueous solution in a
sulphate medium is studied by means of a new reagent, bis (2,4,4-trimethyl-
pentyl) monothiophosphinic acid, commercial name (Cyanamid) Cyanex
302. This is a new contribution in the understanding of zinc extraction from
aqueous solutions by organophosphorous derivatives and offers new possibil-
ities in zinc recovery by solvent extraction.
EXPERIMENTAL
S
\\ p//
/ \
R OH
TABLE 1
In most solvent extraction systems the characteristics and type of the di-
luent in the organic phase may influence metal extraction [20-22 ]. In the
present work the use of various diluents for the Cyanex 302-zinc sulphate
extraction system was investigated for extractions carried out with aqueous
solutions of 1.0 g/l zinc and organic solutions of 20% v / v Cyanex 302. The
main properties of the diluents are shown in Table 2.
The results obtained are shown in Fig. 2 in which per cent of zinc extracted
is plotted against pH of the aqueous phase. The results obtained for the pres-
ent extraction system show that the change of the diluent influences zinc ex-
traction by Cyanex 302 since the pH50 values vary from 1.2 for Solvesso 150
to 1.0 for n-dodecane. Accordingly it can be deduced that in the present sys-
330 C. CARAVACAAND F.J. ALGUACIL
TABL E 2
n.a. = n o t applicable.
IOO
J
9O
80
a
uJ
I-- 70
,3
r,- KEROSENE
I- 60 "
x A EXXOL D-IO0
Y
uJ
SOLVESSO 150
5O
o ESCAtD I00
40 x n- DODECAN
(,3
z
30
2O
IO
I I I
0.5 I 1.5 2
pH
Fig. 2. Influence of the diluent of the organic phase on the extraction of zinc by Cyanex 302.
Organic phase 20% v/v extractant in each diluent; aqueous phase 1.0 g/l zinc (II); temperature
50C.
tern the best extraction results were obtained when mainly aliphatic type di-
luents were employed.
The influence of the initial zinc concentration in the extraction of this metal
by Cyanex 302 was investigated. This study was carried out at 50C, by shak-
ing aqueous phases which contained various zinc concentrations and organic
ZnSO4-CYANEX302 SYSTEM 331
I00
90
80
70 0.1 g/l Zn
W 0.5 g/[ Zn
I-"
0 60 X I.O g / l Zn
rr 2.0 g/[ Zn
X 50
Ld
4-0
0
Z
a 30
20
I0 I
I I I L
0,5 I 1.5 2
pH
Fig. 3. Effect of varying zinc (II) concentration on the metal extraction by Cyanex 302. Organic
phase 20% v / v extractant in kerosene; temperature 50C.
TABLE 3
Influence of the variation of zinc concentration on the extraction at constant pH by Cyanex 302
0. l 0.065 0.035 65
0.5 0.24 0.27 48
1.0 0.46 0.54 46
2.0 0.87 1.13 43.5
phases o f 20% v / v Cyanex 302 in kerosene. The results are shown in Fig. 3 in
which the percentage o f zinc extracted is plotted against the pH of the aqueous
phase. This shows that the variation o f the initial zinc concentration has little
influence on the pHso value, although it appears that the best results are ob-
tained when the initial zinc concentration is low.
The influence of the initial zinc concentration on the extraction of the metal
at a constant pH value was also studied. The experiments were carried out
332 C. CARAVACAAND F.J. ALGUACIL
with various zinc concentrations and 20% v / v Cyanex 302 in kerosene. The
extraction pH was fixed at 1.1 + 0.02. The results obtained (Table 3) show
that when the extraction is carried out at a constant pH values, the per cent
of zinc extracted decreases if the initial metal concentration increases, and
this variation is substantial if very low zinc concentrations are used.
IOO
9o
80 CYANEX502 5% v/v
/// /
F-
,b..I
X 50
~ 40
Ri 3O
~ 20
[ I ~( dI"~I I I
0.5 I 1.5 2
pH
Fig. 4. Zinc (II) sulphate extraction by various Cyanex 302 concentrations in kerosene. Aqueous
phase 2.0 g/l zinc(II); temperature 50C.
ZnSO4-CYANEX 302 SYSTEM 333
5
CYANEX 302 5% v/v /
X CYANEX 302 IO/o v/v /
CYANEX 302 20/0 v/v / /
LL3 4 /
<~
n-
o
z 3
rY
0
J
2 / x/
-2 /fx IA ~
t 1 I I I I L I I I ill I I L 1 I I
I 2 3 4 5 6 7 8 9 I0 12 13 14 15 16 17
ZINC (11) G / L AQUEOUS PHASE
Fig. 5. Equilibrium loading isotherms for zinc(II) extraction by Cyanex 302. Effect of extrac-
rant concentration. Aqueous phase: aqueous solutions containing varying concentrations of
ZnSO4. Temperature 50C; ratio A:O 1 : 1.
TABLE 4
1 mol of sulphuric acid is liberated for 1 mol of zinc (II) extracted by Cyanex
302 as shown by the experimental values (Table 4) for 5% v/v Cyanex 302
in kerosene.
According to the experimental data, the following extraction reaction for
zinc (II) sulphate by Cyanex 302 is suggested:
2HRo~g + ZnSO4aq ~ Z n R 2 o r g 4- H2 SO4aq (1)
3,34 C. CARAVACA A N D F.J. A L G U A C I L
I00
90
Zn (II]
Fe (III) /
BO ?i
Q 70
b.I
I--
(0 6O
/
F-
X 50
W
..J
40
I,m
IE
30
I0 /
Y ~ I
I 2
pH
Fig. 6. Extraction of zinc (II) and iron (III) sulphate media by Cyanex 302. Organic phase 20%
v / v extractant in kerosene; aqueous phase 1.0 g/1 of the metal; temperature 50C.
ZnSO4-CYANEX 302 SYSTEM 335
The behaviour of the system Cyanex 302-zinc was compared to other zinc
extraction systems with organophosphorous derivatives such as DEHPA and
Cyanex 272 (di-2,4,4-trimethylpentyl phosphinic acid). Experiments were
carried out by shaking organic solutions of the extractant at 20% v / v in ker-
osene and aqueous solutions of 1.0 g/l zinc. The experimental results are
shown in Fig. 7, where the percentage of zinc extracted is represented versus
aqueous pH value for the three extractants tried. The figure shows that zinc
is extracted from the most acidic pH by means of Cyanex 302, although the
difference between the pHso values of this extractant and of DEHPA is small;
the overall zinc extraction order appears to be Cyanex 302 >/DEHPA > Cyanex
272.
It is interesting to note that the substitution of the oxygen in the P=O bond
by a sulphur atom in the phosphinic derivatives displaces the zinc pHso value
appreciably to the left, thus allowing zinc extraction from more acidic
solutions.
I00
A
90 CYANEX 302
DEHPA
80 X CYANE 2 7 2
70 /
laJ X
I-"
r~
F-
60 /
x 50
~J
"I
#0
X
Z
N 30
20
i Xj l
I 2 3 _u
rn 4
<[
~-J 12
0
Z
Fig. 8. Distribution o f z i n c ( I I ) between an organic phase and aqueous sulphuric acid solutions
at 50C.
ZnSO4-CYANEX302 SYSTEM 337
CONCLUSIONS
ACKNOWLEDGEMENTS
The authors wish to thank Miss M.P. Santamaria and Miss I. Rubio for
efficient typewriting work.
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