Hydrometallurgy, 27 ( 1991 ) 327-338 327

Elsevier Science Publishers B.V., Amsterdam

Study of the ZnSO4-Cyanex 302 extraction

equilibrium system

C. Caravaca and F.J. Alguacil

Centro Nacional de Investigaciones Metalurgicas, Avda. Gregorio del Amo, 8, Ciudad Universitaria,
28040 Madrid, Spain
(Received October 26, 1990; revised version accepted April 27, 1991 )

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-

0304-386X/91/$03.50 1991 Elsevier Science Publishers B.V. All rights reserved.

328 C. CARAVACA AND F.J, ALGUACIL

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

The reagent Cyanex 302 (registered name of American Cyanamid), was

kindly supplied by Cyanamid Ib6rica, S.A. Its composition is C~6H34PSOH,
the molecular weight is 306 [ 19] and density (experimental at 20C) is 943
kg/m 3. This extractant is a phosphinic derivative of phosphoric acid, where
one sulphur atom replaces one of the oxygen atoms bonded to the phosphorus
according to the structure given in Fig. 1, where R represents alkyl chains
linked to the phosphorus atom. The reagent Cyanex 272 was kindly supplied
by Cyanamid Ib6rica, S.A., and the DEHPA was supplied by Daihachi.
As diluent of the organic phases, kerosene, supplied by CAMPSA, was used
with the following specifications: boiling point 200-260 C flash; point 60 C;
aromatic content 10%. The other diluents were kindly supplied by Exxon
Chemical Iberia, except n-dodecane from Merck.
Extractions were carried out by the following procedure: equal volumes of
organic and aqueous phases were placed in separation funnels, heated to a
thermostatically controlled temperature and mechanically shaken at the tem-
perature for the time required. The aqueous solutions were prepared from
ZnSO4-7H20 for Fe2 (SO4)3-9H20. The zinc and iron were analyzed by
atomic absorption spectrometry whereas the acidity of the organic and
aqueous phases were determinated by titration with standard sodium hydrox-
ide solution.

RESULTS AND DISCUSSION

Some solutions of Cyanex 302 diluted in kerosene were prepared from

commercially available reagent to determine the concentration of the organic
phase accurately. This was done by diluting the samples with ethanol and

S
\\ p//
/ \
R OH

Fig. 1. The structure of Cyanex 302.

ZnSO4-CYANEX302 SYSTEM 329

TABLE 1

Experimental values of Cyanex 302 extractant concentration

Organic phase Theoretical Experimental Ratio

extractant concentration concentration (%)
(/0 v / v ) (M) (m)

2.5 0.077 0.067 87.6

5 0.154 0.135 87.6
10 0.308 0.257 83.4
20 0.616 0.514 83.4
Average 85.5

titrating with sodium hydroxide using Bromothymol Blue as indicator. The

results obtained are shown in Table l, in which theoretical and experimental
molar concentrations are compared. In all cases the experimental values are
lower than theoretical values, meaning that the commercial reagent has an
average of 85% active c o m p o u n d for the extraction with respect to the theo-
retical concentration.
Experiments on the influence of agitation time and temperature on zinc
extraction have been carried out by shaking at 20C or 50C for various
lengths of time aqueous solutions of 2.0 g/l zinc and organic phases of 5% v/
v Cyanex 302 in kerosene. Equilibrium is reached after 1 min of shaking, with
no change in zinc concentration in the organic phase when the longer agita-
tion time was used. In addition, the relationship between zinc extracted into
the organic phase and the extraction temperature were studied, the organic
and aqueous phases used being the same as above. The results show that, in
the range of temperatures used (from 20 C to 60 C ), there is little influence
on zinc extraction; in all cases phase disengagement was good.

Organic phase diluent influence

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

Characteristics of the diluents used in zinc extraction by Cyanex 302

Diluent Aromatics Boiling point Flash point Density

(%) (C) (C) ( k g / m 3)

Kerosene 10 260 60 785

ExxolD-10 0.9 264 102 816
Solvesso 150 99.6 208 68 901
Escaid 100 24 237 81 805
n-Dodecane 0 216 n.a. 749

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.

Influence of zinc concentration

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

[Zn ] initial [Zn ] organic [Zn ] aqueous Extraction

aqueous phase phase phase (%)
(g/l) (8/1) (8/1)

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

Organic phase 20% v / v Cyanex 302 in kerosene.

pH extraction 1.1 _+0.02.
Temperature 50 C.
RatioA:O 1: 1.

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.

Reagent concentration dependence

In Fig. 4 the variation in the percentage of zinc extracted against pH at

various extractant concentrations is shown. Experiments were carried out by
shaking at 50 C equal volumes of an aqueous solution of 2.0 g/l zinc (II) and
organic solutions of Cyanex 302 5, 10 and 20% v / v in kerosene for 5 min.
This was long enough to reach equilibrium in all cases. Figure 4 shows that
the variation in the initial extractant concentration has a significance influ-
ence on zinc extraction and that under the experimental conditions used it
was possible to reach zinc pHs0 values of near 1.0.
Several zinc extraction equilibrium isotherms were obtained by shaking at
50C equal volumes of organic phases of Cyanex 302, 5, 10 and 20% v / v in
kerosene and aqueous phases which contained different zinc concentrations.
The results obtained are shown in Fig. 5.
Sulphuric acid titration of the equilibrated aqueous phases showed that

IOO

9o

80 CYANEX502 5% v/v
/// /

CYANEX 502 IO/o v/v )(lw.~ i

C' 60
W
<0I--- 70 CYANEX30220/0v/v / T A/ I ,

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

Experimental values of sulphuric acid liberated by the extraction of zinc (II)

[Zn[II) ] o r g [H2SO4]aq [Zn (II) ]org/[ HzSO4].q

(mM) (mM)

6.73 6.53 1.03

10.2 10.2 1.0
18.13 17.6 1.04
19.6 20.4 0.96
20.') 21.1 0.99
23.6 24.0 0.98

Organic phase 5% v/v Cyanex 302 in kerosene.

Temperature 50 C.
Ratio A:O 1: 1.

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

where HR represents the simplified reactant formula. Thus, according to this

suggested mechanism, as the reagent concentration increases the zinc concen-
tration in the organic phase increases at more acidic pH values, because the
extraction equilibrium is shifted to the right; this is in agreement with the
experimental results shown in Fig. 4.

Selectivity of the system Cyanex 302-zinc(II) versus iron(III)

One of the main problems in zinc(II ) extraction by DEHPA is that at acidic

pH values iron (III) is extracted preferably to zinc (II) [ 23,24 ], which means
that it is necessary to eliminate iron (III) prior to zinc extraction.
The extraction of these two metals by the new extractant Cyanex 302 was
studied by shaking equal volumes of an organic phase of 20% v/v Cyanex 302
in kerosene and an aqueous phase which contained 1.0 g/1 of zinc(II) or
iron (III) in sulphate media. The results obtained are shown in Fig. 6, where
the percentage of metal extracted is plotted against the equilibrium pH.
Under the experimental conditions used, zinc (II) was extracted in prefer-
ence to iron(III) at a pH value of near 1.05, and better separations are
obtained between these two metals at pH values near 1.6. This behaviour pro-
vides a new approach to the application of the solvent extraction technique

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

using organophosphorous derivatives in the recovery of zinc as this metal can

be extracted in the presence of iron (III).

Behaviour of the Cyanex 302 extractant with respect to other

organophosphorous reagents

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

Fig. 7. Extraction of zinc(II) by various organophosphorous derivatives. Organic phase: 20%

extractants in kerosene; aqueous phase 1.0 g/l zinc; ratio A: O 1 : 1.
336 C. CARAVACA A N D F.J. A L G U A C I L

Zinc stripping with sulphuric acid

In hydrometallurgical processes for zinc, the metal is obtained by a final

electrowinning step from acidic solutions of sulphuric acid. This is because
this acid is the only one used in all zinc stripping stages, no matter what the
initial leaching medium and the solvent extraction reagent. In order to study
the stability of the new Cyanex 302 reagent in sulphuric acid solutions, exper-
iments were carried out with organic phases of 5% and 10% v/v Cyanex 302
in kerosene and an aqueous phase of 200 g/1 sulphuric acid. The organic and
aqueous phases were contacted at 30 C for 500 h and the corresponding acid-
ity of both phases was controlled, taking samples and analyzing the acidic
content by titration with sodium hydroxide.
The results obtained from these experiments show that, under the experi-
mental conditions used, the degradation, if any, of the extractant is almost
negligible, thus indicating that this reagent is hydrolytically stable in sul-
phuric acid solutions and, consequently, in a stripping stage using this acid.
Zinc stripping experiments were carried out using an organic phase of 10%
v/v and 20% v/v of Cyanex 302 in kerosene loaded with 3.0 and 5.9 g/1 zinc
and aqueous phases of 150 g/l and 200 g/1 of sulphuric acid, respectively.
Contact time in all experiments was 10 rain, enough to reach equilibrium.
and various A: O ratios were used.
The results obtained are shown in Fig. 8. Sulphuric acid is an efficient strip-
ping agent for zinc. The initial sulphuric acid concentration appears not to
have a great influence on metal stripping Under these conditions it is possible
to reach concentrations in the aqueous phase of about 25 g/1 zinc, while the

ORGANIC PHASE AQUEOUS PHASE

LU A CVANEX302 10% V/V 200 G/L H2SO4
U')
<I CYANEX302 20% V/V 200 GIL H2SO4
~2/-, "CVANEX302 20IoV/V 150GIL H2SOz,
n
U')
20
UJ

<[
~-J 12

0
Z

0.1 0.2 0.3 0Y-, 0.5

ZINC(II) G/L ORGANIC PHASE

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

metal concentration in the organic phase can be reduced to values of near

0.01 g/1.

CONCLUSIONS

The results obtained show that the extractant bis(2,4,4-trimetylpentyl)

monothiophosphinic acid, commercial name Cyanex 302, can be used as an
extraction reagent for zinc in sulphate media from acidic solutions since it is
a stronger extractant for this metal than other organophosphorous derivatives.
The extraction mechanism corresponds to Cyanex 302 acting as a cationic
liquid ion exchanger, that is, an acidic extractant, by the formation of what
appears to be a R2Zn species in the organic phase and liberation of 1 mol of
sulphuric acid for 1 mol of metal extracted. The diluent used has some influ-
ence on zinc extraction.
One of the most notable features of Cyanex 302 is that from a relatively
acidic pH value, near 1.0, zinc (II) is extracted preferably to iron (III). This
is an advantage over other organophosphorous reagents and it is possible to
extract zinc directly at lower aqueous pH values.
With Cyanex 302 extractant, sulphuric acid can be used as an effective
stripping agent for zinc allowing metal concentrations in the stripped organic
phase as low as 0.01 g/l to be obtained. The extractant is also extremely hy-
drolytically stable in the presence of high sulphuric acid concentrations.

ACKNOWLEDGEMENTS

The authors wish to thank Miss M.P. Santamaria and Miss I. Rubio for
efficient typewriting work.

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