Hydrometallurgy, 32 ( 1993 ) 365-372 365

Elsevier Science Publishers B.V., Amsterdam

Cobalt-nickel separation: the extraction of

cobalt (II) and nickel (II) by Cyanex 301, Cyanex
302 and Cyanex 272

Brian K. Tait
Process Chemistry Division, Mintek, PrivateBag .¥3015, Randburg 2125, South ~{frica
(Received February 20, 1992; revised version accepted May 19, 1992 )

ABSTRACT

Tait, B.K., 1993. Cobalt-nickel separation: the extraction of cobalt (II) and nickel (II) by Cyanex
301, Cyanex 302 and Cyanex 272. Hydrometallurgv 32: 365-372.

Cyanex 301, Cyanex 302 and Cyanex 272 were used to extract cobalt(II) and nickel(II) from a
sulphate medium in order to elucidate any separation properties these phosphinic acid extractants
display. All the reagents extracted cobalt selectively, Cyanex 302 exhibiting better separation charac-
teristics than Cyanex 272, which in turn showed a higher selectivity than did Cyanex 301. The sepa-
ration (PHo.5-pHo.5)
Ni Co found for Cyanex 302 was 2.6 pH units, compared to 1.7 pH units for Cyanex
272 and 1.1 pH units for Cyanex 301. Based on these results and the fact that Cyanex 301 would need
strong acid to strip it, an experiment was conducted using Cyanex 302 and Cyanex 272 to separate
cobalt(II) and nickel(II) from a solution containing 100 g/l NiSOa'6H20 and 2 g/l COSO4" 7H20
with favourable results.
Vapour pressure osmometry was used to determine the degree of aggregation of the extractants in
toluene. Both Cyanex 272 and Cyanex 302 are dimeric and Cyanex 30l exists as a monomer. Slope
analysis methods were used to determine the nature of the cobalt(ll) and nickel(ll) complexes
extracted.

INTRODUCTION

A number of years ago, the separation of cobalt and nickel presented prob-
lems because of the similar physical and chemical properties of these metals.
Much work was performed in the field of solvent extraction to develop ex-
tractants that are selective for one of the metal ions. Although reagents have
been developed that selectively extract nickel (II) over cobalt (lI) [ 1,2 ], the
more usual route is to extract cobalt (II), leaving nickel (II) in the aqueous
phase. It is this route that has found application in nickel refineries such as
INCO, Outokumpu and Matthey Rustenburg.

Correspondence to." B.K. Tait, Process Chemistry Division, Mintek, Private Bag X3015, Rand-
burg 2125, South Africa.

0304-386X/93/$06.00 © 1993 Elsevier Science Publishers B.V. All rights reserved.

366 B.K. TAIT

The following extractants have been widely studied with respect to cobalt-
nickel selectivity in a sulphate medium: di(2-ethylhexyl)phosphoric acid
(D2EHPA), 2-ethylhexyl 2-ethylhexylphosphonic acid (PC-88A or Ionquest
801 ) and bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272 ).
Rickelton et al. [ 3 ] have reported the cobalt-nickel separation factors, de-
fined as the ratio between the cobalt and nickel extraction coefficients, which
are given in Table 1. This trend, that is, phosphoric <phos-
phonic < phosphinic acids, under comparable conditions, has been confirmed
by others [ 4,5 ].
The poor cobalt-nickel selectivity exhibited by D2EHPA often requires that
some form of pre-concentration technique is employed to increase the co-
bait:nickel ratio. Although the cobalt-nickel selectivity displayed by PC-88A
is significantly better than D2EHPA, both these extractants are active cal-
cium extractants. This is particularly deleterious in sulphate circuits, where
the formation of gypsum cruds can result in serious solvent losses. Cyanex
272 shows the best cobalt-nickel selectivity and the ability to reject calcium.
However, it is relatively expensive.
Recently Cyanamid introduced two thiophosphinic acid extractants, Cy-
anex 301 (bis (2,4,4-trimethylpentyl) dithiophosphinic acid ) and Cyanex 302
(bis(2,4,4-trimethylpentyl) monothiophosphinic acid). These two extrac-
rants differ with respect to the anionic donor atom which facilitates extrac-
tion: sulphur in the case of Cyanex 301 and oxygen in the case of Cyanex 302.
The structures are given in Table 2. This paper investigates the extraction of
cobalt (II) and nickel (II) individually from a sulphate medium by Cyanex
301, Cyanex 302 and Cyanex 272 and presents data on cobalt-nickel separa-
tion using Cyanex 302 and Cyanex 272.

EXPERIMENTAL

Cyanex 301, Cyanex 302 and Cyanex 272 were kindly supplied by Cy-
anamid and used without further purification. The samples were equilibrated
at 25 + 1 °C for 10 min. It was ascertained in a preliminary experiment that

TABLE 1

Cobalt-nickel separation factors as given in [3]

Medium Co/Ni
separation
factor

D2EHPA 14
PC-88A 280
Cyanex 272 7000
E X T R A C T I O N O F C o ( I I ) A N D Ni ( I1 ) BY C Y A N E X 301. CYANEX t02 A N D CYANEX 272 367

TABLE 2

The structures of Cyanex 272, Cyanex 301 and Cyanex 302

R O
/
Cyancx 272 P
R OH

R S
Z
P
Cyanex 301
R SH

R S
,/
P
Cyanex 302
R OH

CH3
R = CH3--C-- CH2--CH - - CH 2-
CH s CH3

this time is sufficient to ensure complete equilibration. The phases were al-
lowed to separate and were filtered prior to analysis.
The extractants were dissolved in toluene to the required concentration.
The organic-to-aqueous phase volume ratio was unity. The metal ions were
analysed by titration against EDTA or by atomic absorption spectroscopy.
The extractants were analysed by titration in ethanolic medium against so-
dium hydroxide.
The vapor pressure osmometry readings were taken at 35 °C using toluene
as the solvent. Benzophenone was used as the calibration standard.

RESULTS AND DISCUSSION

Vapour pressure osmomelry

It is generally accepted that monobasic organophosphorus acid extractants

are dimeric in solvents of low polarity [6 ]. The dimer arises from strong in-
termolecular hydrogen bonding. Cote and Bauer [7 ] have reported that di-
thiophosphoric acids are monomeric, whereas monothiophosphoric acids are
usually dimeric. Sulphur can act as a proton acceptor; however it is a weaker
368 B.K, TAIT

acceptor than oxygen. This, and the relatively poor proton donor properties
of the S-H group, could explain the absence of aggregation for dithio acids.
Vapour pressure osmometry was used to determine the aggregation of the ex-
tractant in toluene for Cyanex 301 and Cyanex 302 and to confirm that Cy-
anex 272 is indeed dimeric. The results are given in Table 3. Considering that
the extractants are 80-85% pure, it can be assumed that Cyanex 302 and Cy-
anex 272 are dimeric and Cyanex 301 exists as a m o n o m e r in toluene.

Extraction of cobalt(II) and nickel(II)

The extraction of cobalt (II) and nickel (II) from 1.0 M a m m o n i u m sul-
phate solutions by Cyanex 301, Cyanex 302 and Cyanex 272 is presented in
Fig. 1. All the extractants function efficiently for both cobalt and nickel. Co-
balt (II) is extracted in preference to nickel (II) by any given extractant. This
can be explained in terms of the geometric differences between the cobalt ( II )
and nickel(II) extracted complexes. Complexes of cobalt (II) with organo-

TABLE 3

Vapor pressure osmometry results for 0.2 M and 0.4 M Cyanex 301, Cyanex 302 and Cyanex 272 in
loluene

Extractant MM* MM* MM*

Theoretical 0.2 M 0.4 M

Cyanex 301 322 338 334

Cyanex 302 306 523 530
Cyanex 272 290 527 502

*MM = molecular mass in g/mol

100

80

60

40

20

0
0 2 4 6 8 10
pH

Fig. 1. The effect of pH on the extraction of 0.02 M cobalt(II) (solid symbols) and 0.02 M
nickel (II) (open symbols) individually from 1.0 M ammonium sulphate solutions by Cyanex
301 (square), Cyanex 302 (triangle) and Cyanex 272 (circle). Extractant concentrations were
0.25 M in toluene.
EXTRACTION OF Co( 11) AND Ni( I1 ) BY CYANEX 301, CYANEX 302 AND ( YANEX 272 369

phosphorus acids are tetrahedral, whereas the nickel (II) complexes are octa-
hedral, with the general formula [ 5 ] :Ni (HAp) 2(HpAp)~ (H20) 2- ~, x = 0,1,
2, p = 1,2.
Cyanex 301 is the most efficient extractant for cobalt (II) and nickel (II),
although their separation with this reagent is more critically dependent on pH
than is the case with Cyanex 302 and Cyanex 272. Since Cyanex 301 contains
only sulphur donor atoms, it tends to form more stable complexes with diva-
lent 3d transition metal ions such as cobalt (II) and nickel (II) than Cyanex
302 and Cyanex 272, which contain oxygen donor atoms. Thus, Cyanex 301
is able to effect extraction at lower pH values than Cyanex 302 and Cyanex
272.
The pH values at which 50% extraction of cobalt (II) occurs (pHo.5) are
1.3, 4.0 and 5.3 for 0.25 Msolutions of Cyanex 301, Cyanex 302 and Cyanex
272 in toluene, respectively. The pH0.5 values for nickel(II) are 2.4, 6.6 and
7.0 for Cyanex 301, Cyanex 302 and Cyanex 272, respectively. This trend in
extractability, that is, Cyanex 301 > Cyanex 302 > Cyanex 272, can be corre-
lated with the strength of the acid. Rickelton and Boyle [8 ] have reported
pKa values of 2.61, 5.63 and 6.37 for Cyanex 301, Cyanex 302 and Cyanex
272, respectively. This series also conforms with the decreasing number of
sulphur donor atoms in the extractant molecule, which could explain the trend
in relative acidities.
Cyanex 301, Cyanex 272 and Cyanex 302 can all, in theory, be used to
separate cobalt from nickel. The separation (pHo.5-pHo.5)
N~ Co is 1.1, 1.7 and 2.6
pH units, respectively. These separations indicate that Cyanex 302 is a better
reagent for cobalt-nickel separation than Cyanex 272 which, in turn, is a bet-
ter reagent than Cyanex 301. A further disadvantage of Cyanex 301 is that it
extracts cobalt at low pH, which means that it will require a strong acid for
stripping.

Determination of the nature of the extracted complexes

The nature of the complexes extracted was elucidated by a slope analysis

method. Consider the general extraction equation:
K
M 2+ +n(HA)p--~MAnpHnp_ 2 + 2 H + ( 1)
By taking logarithms and rearranging:
log D - 2 p H = l o g K + nlog [ (HA)p] (2)
where D is the distribution coefficient.
Thus, a plot of log D - 2 pH against log [ (HA)p] should be a straight line
with slope n. All the plots were straight lines (correlation coefficient 0.98 or
better) over the extractant concentration range 0.05-0.5 M. The metal ion
370 B.K. T A I T

log D 2 pH
-

i r i

o ° \ •

"0

P
0

Fig. 2. Slope analysis plots. Dots: Cyanex 272-Co (II), slope = 2; circles: Cyanex 272-Ni (II)
slope=3: solid squares: Cyanex 301-Co(II) slope=2; open squares: Cyanex 301-Ni(II)
slope = 2: solid triangles = Cyanex 302-Co (II) slope = 4; open triangles: Cyanex 302-Ni (II)
slope = 4.

concentration was 0.02 M in 1.0 M a m m o n i u m sulphate. The slopes were 1.9

for the extraction of cobalt (II) and 2.1 for the extraction of nickel (II) by
Cyanex 301, 3.9 for the extraction of cobalt (II) and 3.9 for the extraction of
nickel (II) by Cyanex 302, and 2.0 for the extraction of cobalt (II) and 3.1 for
the extraction of nickel(II) by Cyanex 272. The plots are shown in Fig. 2.
Visible spectroscopy was used to confirm the tetrahedral symmetry of co-
balt (II) and the octahedral symmetry of nickel (II). Using the vapour pres-
sure osmometry results, the following extracted complexes are proposed: CoA2
and NiA2 (H20)2 for Cyanex 301; Co (HA2)2 (H2A2)2 and Ni(HA2)2 (H2A2)2
or Ni (HA2) 2 (H2A2) 2 (H20) 2 for Cyanex 302; and Co (HA2) 2 and Ni (HA2) 2
(HzA2) (H20) for Cyanex 272
There is some uncertainty as to the nature of the nickel (II) extracted com-
plex for Cyanex 302. The slope of 4 for cobalt (II) extraction by Cyanex 302
indicates that the extracted complex is solvated by two dimer molecules, since
the symmetry is tetrahedral. This may also be the case with nickel(II) and
thus two water molecules are required to preserve the octahedral symmetry.
However, the two dimer molecules may be coordinated to the nickel (II) ion
giving rise to octahedral symmetry without any water molecules in the pri-
mary coordination sphere.

Separation of cobalt(II) from nickel(II)

In view of the superior separation characteristics of Cyanex 302 and Cy-

anex 272 over Cyanex 301 demonstrated in a previous section, an experiment
was conducted using these reagents to extract cobalt (II) from a mixture of
cobalt(II) and nickel(II). The aqueous phase consisted of 100 g/l
EXTRACTION OF Co (I1) AND Ni (ll) BY CYANEX 301, CYANEX 302 AND CYANEX 272 371

100
/

80

60

40 /
///

20 / A/ /

2 3 4 5 6
pH

Fig. 3. The effect o f p H on the extraction of cobalt(II) (solid symbols) and nickel(lI) (opcn
symbols) from a solution containing 100 g/1 NiSO4-6H20 and 2 g/I COSO4"7H20 by Cyanex
302 (triangles) and Cyanex 272 (circles). The extractant concentration was 5% v/v in toluene.

NiSO4" 6HzO and 2 g/1 Co804 °7HzO dissolved in water and the organic phase
was a 5% solution of the extractant in toluene. The contact time was 5 min-
utes at 25 °C. The results are presented in Fig. 3.
Figure 3 shows that Cyanex 302 displays better separation properties than
Cyanex 272 and that very good separations are possible, even when nickel (II)
is present in about 50 times excess over cobalt(II). The separation factors,
flcyo=Dco/DNi, at pH 6.0 are 53 for Cyanex 272 and 126 for Cyanex 302 un-
der the experimental conditions used. These separation factors are much
smaller than those reported before [ 3 ], which were obtained under different
conditions. Larger separation factors will be obtained at lower pH values, but
pH 6.0 was chosen for comparison of Cyanex 302 and Cyanex 272 since the
more substantial degree of extraction of nickel (II) allows greater accuracy.

CONCLUSIONS

Cyanex 302 is a more effective separation reagent for cobalt and nickel than
either Cyanex 272 or Cyanex 301. All these reagents are available from Cy-
anamid Canada Inc. and are of the same cost. At least four plants that use
Cyanex 272 are operating. Cyanex 301 and Cyanex 302 are not yet being used
in a full scale commercial plant, but several pilot plants are operating with
these reagents, particularly Cyanex 302. It is clear that further work needs to
be done in this area in order to assess the suitability of Cyanex 301 and Cy-
anex 302 for practical applications. The author is currently running continu-
ous counter-current mini-plant tests on Cyanex 272 and Cyanex 302 for co-
bait-nickel separation and will communicate the results of this study in the
future.
372 B.K. TAIT

ACKNOWLEDGEMENTS

The author wishes to thank Mrs A.C. du Preez for performing the vapour
pressure osmometry measurements and Dr J.S. Preston for his useful com-
ments. This paper is published by permission of Mintek.

REFERENCES

1 Preston, J.S., J. S. Aft. Inst. Min. Metall., 83 ( 1983): 126-132.

2 Preston, J.S., Hydrometallurgy, 11 (1983): 105-124.
3 Rickelton, W.A., Flett, D.S. and West, D.W., Solvent Extr. Ion Exch., 2 ( 1984): 815-838.
4 Danesi, P.R., Reichley-Yinger, L., Mason, G., Kaplan, L., Horwitz, E.P. and Diamond. H.,
Solvent Extr. Ion Exch., 3 ( 1985): 435-452.
5 Preston, J.S., Solvent Extraction of colbalt and nickel by organophosphorus acids. I. Com-
parison of phosphoric, phosphonic and phosphinic acid systems. Hydrometallurgy, 9 ( 1982):
115-133.
6 Marcus, Y. and Kertes, A.S., Ion Exchange and Solvent Extraction of Metal Complexes.
Wiley-Interscience, New York (1969) p. 528, and references therein.
7 Cote, G. and Bauer, D., Chem. Ind. (London), 22 ( 1986): 780-784.
8 Rickelton, W.A. and Boyle, R.J., Solvent Extr. Ion Exch., 8 ( 1990): 783-797.