Physicochemical Problems of Mineral Processing, 39 (2005), 117-128

Fizykochemiczne Problemy Mineralurgii, 39 (2005), 117-128

Leszek GOTFRYD*

SOLVENT EXTRACTION OF NICKEL(II) SULPHATE

CONTAMINANTS
Received March 15, 2005; reviewed; accepted May 15, 2005

Potentials of the solvent extraction method for separation of contaminants, especially Co(II),
from nickel(II) sulphate solutions have been reviewed. Properties of most important and
commercially available organic preparations, making extractive separation of these elements
possible, have been shortly characterized.
On the basis of laboratory investigations, behaviour of cationic liquid ion exchangers, Cyanex
272 and Cyanex 302, used for Co(II) and Ni(II) separation, has been compared. Co-extraction
isotherms of most important contaminants, including Zn(II), Cu(II) and Co(II), with Cyanex 272,
from solutions of nickel(II) sulphate have been examined. Next, the extractant has been applied to
purification of the so called crude nickel(II) sulphate or CNS from the contaminants.
The CNS, a commercial product of technical grade, produced by Polish copper smelters, had been
previously, before its further extractive purification treatment, prepared by leaching and dissolution
in deionised water and by preliminary hydrometallurgical (oxy-hydrolytic) purification from iron(II),
iron(III), arsenic(III), arsenic(V) and similar elements.
Pilot apparatus with continuous flow of all media, applied to the CNS purification, consisted of 5
extractors of the mixer-settler type, joined together to make adequate counter-current system 1-2-0-2.
Washing of the organic phase had not been applied because of purposeful preparation of the system
merely for common, not selective, collecting of all metal ions, contaminating CNS.
The system has reached an excellent purification level of nickel(II) sulphate. Obtained, as an
additional product, the cobalt(II) sulphate concentrate (stripped solution) was almost totally
neutralised (pH > 3.5).

Key words: solvent extraction, Co/Ni separation, Cyanex 272, Cyanex 302, nickel(II) sulphate,
cobalt(II) sulphate, solution purification

INTRODUCTION

The Polish copper smelters currently produce an electro-refinery by-product, called

the crude nickel(II) sulphate or CNS. The CNS is a technical grade commercial
product sold for its nickel value. It would be economically much more justified to

*
Institute of Non-Ferrous Metals; Sowinskiego 5; 44-101 Gliwice; Poland, phone: (+ 048 32) 2 380 387;
e-mail: [email protected]
118 L. Gotfryd

separate pure NiSO4 from contaminants, typically zinc(II), iron(II), copper(II) and
cobalt(II) and make a further use of both nickel(II) and cobalt(II) sulphate
concentrates obtained, to produce pure nickel(II) and pure cobalt(II) salts on the
premises.
The goal of this work was to obtain Ni(II) and Co(II) concentrates from the CNS
by solvent extraction technique. Features of this technique, when liquid cationic ion
exchangers are used, create possibilities for sequential separation of the heavy metal
simple ions in aqueous solution of their salts, for example sulphates, nitrates or diluted
chlorides. They can be separated using the step by step approach or in bulk in
arbitrarily limited extent (e.g. sole Zn(II) or Zn(II) with Cu(II) or Zn(II) with Cu(II)
and Co(II)) from the rest of heavy metal ions present and from a bulk of common
lighter cations such as sodium(I), potassium(I), magnesium(II), ammonium(I) and
similar. Additionally, all anionic contaminants (chlorides/sulphates, fluorides,
cyanides, arsenates and further) are fully rejected, being completely ignored by
extractant of a cationic type.
This author, following recent achievements of the hydrometallurgy, has applied
solvent extraction of metals, to investigate and solve the basic aim – transformation of
the CNS technical product into pure NiSO4 without loosing the chance to recover the
remaining valuable metal salts.

SELECTIVE EXTRACTION OF COBALT(II) IN THE PRESENCE OF NICKEL(II)

First suggestion of extractive power of di(2-etylheksyl)phosphoric acid (DEHPA)

for Co(II)/Ni(II) separation has been made by Ritcey and Ashbrook in 1966 (Ritcey
1969). A few years later, working for Eldorado Nuclear Ltd. and Canadian
Department of Energy, Mines and Resources (further known as CANMET) they
worked out a viable technology for Co(II)/Ni(II) separation using the mentioned
extractive system. It was quite sophisticated, involving 8 stages of extraction and 4
stages of stripping at elevated temperatures. A few plants had been operated on this
technological basis.
In the middle seventies of the XX century a second separation process, called
Falconbridge, has been developed. It was based on extractive properties of aliphatic
amines (trioctylamine), which extract anionic forms of cobalt(II) - e.g. CoCl4-2 from
chloride aqueous solutions with a high selectivity. This idea was applied as a
background of the SMMC Process (Sumitomo Metal Mining Co., Japan). Here, the
nickel(II) and cobalt(II) chloride solutions, being the feed for selective extraction of
Co(II), are obtained and preliminary purified from most of the contaminants by their
common extraction from the sulphate solutions with the Versatic 911 (Shell Chemicals
Co.) extractant. In those years Nippon Mining Co., within their NMC Process,
exploiting initially the DEHPA (known in Japan as DP-8R, according to Daihachi
Chemical Ind.), has changed it into Daichachi’s PC-88A. This preparation (about 20-
 Solvent extraction of nickel(II) sulphate contaminants 119

fold more selective for Co/Ni separation) was based on alkyl-phosphinic acid. After
short period, Shell Chemicals (SME 418 or earlier as RD 577) and Albright & Wilson
(Ionoquest 801) have developed their own preparations for the same purpose and with
similar formula. The main ingredient of all those was mono-2-etylhexyl(2-
etylhexyl)phosphonic acid (Agatzini-L. 1997; Sole 1992; Tait 1993).
Nowadays, all mentioned reagents have been replaced with the Cyanex series (Am.
Cyanamid Co. products): Cyanex 272, 302 and 301, distributed in Europe by Cytec
Industries Ltd., France. The most important of them is Cyanex 272 – containing
mainly bis(2,4,4-trimethylpentyl)phosphinic acid (76 %). Cyanex 302 and Cyanex 301
are its monothio- and dithio- derivatives. The last two, especially Cyanex 301, are not
very stable in contact with Cu(II), Cd(II) and common oxidants. Table 1 illustrates
great advantages of Cyanex 272 over earlier extractants (Preston 1983; Rickelton
1984). Additionally, Cyanex 272 almost does not extract calcium at the optimal for
Co(II) extraction conditions (pH 5.0-5.5). This allow to avoid gypsum crystallisation
in stripping-electrowinning circuits.

Table 1. Comparison of Co(II)/Ni(II) separation coefficients for various extractants

pH of optimal ∆pH50%Ni-Co
Extractant βCoNi
Co extraction
(20 oC) (50 oC)
DEHPA 14 3.6-3.8 0.35 0.70
PC-88A 280 5,0 1.21 1.48
Cyanex 272 7000 5.3-5.5 1.58 1.94

βCoNi = coefficient of Co(II)/Ni(II) separation = D(Co)/D(Ni); D(M) = coefficient of metal ion (M)
distribution = concentration of M in organic phase divided by concentration of M in aqueous phase;
∆pH50%Ni-Co = pH50%Ni - pH50%Co; pH50%M – so called “pH of half extraction of ion M” ; that means for
D(M) = 1.

Parameters β are not absolute and they depend on the pH value but they are useful
for comparison of the abilities of extractants at fixed (individually optimal) conditions.
Further physical and chemical data of the most important Co(II) extractants, are
gathered and compared in Table 2 (Rickelton 1991; Rickelton 1992; Szymanowski
1997; Booklets)
Alkyl phosphonic and alkyl phoshinic acids as Co(II) extractants have one
common and important disadvantage. If saturated to the level of 15-20 g/dm3 Co(II)
they highly increase their viscosity to over 150 cSt (even to 400 cSt). At such
conditions mixing and pumping can be almost impossible. Maximal concentrations of
extractants, and consequently of Co(II) extracted, should be limited to medium levels
and/or elevated temperature should be applied to avoid problems of too high viscosity.
The elevated temperature is moreover advantageous because the selectivity increases
with rising of temperature.
120 L. Gotfryd

Table 2. Physico-chemical parameters of bis(alkyl)phosphinic acids and DEHPA [20 oC]

Temp. [oC] of... Solub.

Main Molar Density Viscosity
Extractant pKa in H2O
ingredient weight [g/cm3] [cP] melt. boil. ign. [mg/dm3]
Cyanex 272 R2PO(OH) 290 6.37 0.91 142 -32 >300 108 16
Cyanex 302 R2PS(OH) 306 5.63 0.93 195 -20 205 96 3
Cyanex 301 R2PS(SH) 322 2.61 0.95 78 -34 220* 74 7
DEHPA (R’O)2PO(OH) 322 3.95 0.97 56 -60 - 171 < 10

* - boiling with decomposition

R = 2,4,4-trimethylpentyl: CH3C(CH2)2CH2CH(CH3)CH2- ;R’ = 2-ethylhexyl: CH3(CH2)3CH(C2H5)CH2-
, pKa = - log Ka (Ka – equilibrium constant of acidic dissociation).

There is a number of examples of extractant applications for Co(II)/Ni(II)

separation in US patents issues (Patents) and in commercial brochures of Cytec
Industry Ltd. (Booklets).
The solvent extraction technique for Co(II)/Ni(II) separation has been successfully
applied in a few industrial plants, e.g. Matthey Rustenburg Refiners Ltd. (Transvaal,
South Africa); Hitachi (Japan), Sudbury (International Nickel Co., Canada) /with the
use of DEHPA at the beginning/; INCO, Outokumpu (Cyanex 272), SMMC Plant
(Japan) (versatic acids and tertiary amines).

METHOD AND MATERIALS

The purpose of the work was to develop viable extractive system for purification of
the CNS, to the maximal extent, from the Zn, Cu, Co and similar element mixtures. To
achieve this, it was necessary to select best extractants and check extractive features of
the elements (selective and collective), especially at the quasi-industrial conditions.
That has meant quite wide spread preliminary screening investigations. The method
involved identification of individual extraction and their dependencies on pH, their
mutual comparative assessment and then more detailed studies on extraction isotherms
for selected extractants at a constant pH of their optimal extraction as well as studies
identifying isotherms of stripping. On this basis, the best extractant had been selected
and counter-current extractive system has been designed. At the last stage, this
extractive system has been evaluated on the pilot scale in a set of mixer-settlers type
extractors. Each of them had 2.2/5.5 dm3 of mixer/settler individual capacity.
 Solvent extraction of nickel(II) sulphate contaminants 121

PERCENT OF EXTRACTION VS. PH AND CLASSICAL EXTRACTION ISOTHERMS

Typical conditions of extraction were as follows:

• pure metal salt concentration – 0.02 to 0.10 M,
• neutralizing agent – 5.0 M NaOH pure solution,
• ambient temperature (about 20 oC),
• time of stirring - 10 minutes, also after each dose of NaOH solution added.
The percent of extraction measurements were performed by mixing a quite large
volume sample of single metal sulphate solution with an equal sample of extractant
(typically 0.350:0.350 dm3/dm3 at the beginning), then a sequential adding of small
volumes of neutralizing agent (1.0 cm3) and taking aliquot samples (25 cm3) of both
phases at every extraction equilibrium stage obtained.
To explore extraction and stripping isotherms, reacting phases were mixed together
at a few various organics (O) to aqueous (A) volume ratios (typically from O:A = 10:1
to 1:10), to pick up a range of data: pairs of metal ion concentrations in both phases at
consecutive extraction equilibria. If extraction itself was investigated, additionally, in
all cases, small amounts of concentrated neutralizing agent were added to reach
desired equilibrium pH level. For the stripping isotherm, the organic phase
(extractant), was preliminary loaded with the metal ion at their individual optimal
conditions, and then it was contacted with the solution of the chosen acid (H2SO4)
with an arbitrary fixed initial concentration (typically 1.0 or 2.0 M).
CROSS-CURRENT EXPERIMENTS ON THE LABORATORY SCALE

The step by step investigation of extractive process should cover, as the next stage,
laboratory experiments of chosen character (typically counter-current one). Details of
such type of experiment could be found in literature (Gotfryd and Szymanowski
2004). Here, because of the simplicity of the extractive conditions, they were
substituted by simpler cross-current ones, bearing information useful enough to design
the pilot step of the counter-current experiment. They were performed under typical
conditions of mixing time and temperature. Details are described in Results section.
COUNTER-CURRENT (C-C) EXPERIMENTS ON PILOT SCALE

A real C-C experiment of continuous character has been performed using a pilot
plant equipment, consisting of a train of mixer-settler type extractors, arranged to
exercise an optimal extractive system, developed in the previous laboratory steps of
investigations. This was a configuration of the 1-2-0-2 type, consisting of one stage of
extractant conditioning, two stages of extraction and two stages of stripping (without
scrubbing). The reactors had the 2.2/5.5 dm3 mixer/settler individual capacity. The
value of pH was maintained automatically at the desired levels of 5.0-5.5 by
controlled addition of 2.5 M NaOH solution.
122 L. Gotfryd

MATERIALS

A series of extractants has been examined: DEHPA, Cyanex 272, Cyanex 302,
Cyanex 301, LIX 54-100 (1-phenylnonandione-1,3), LIX 64N (2-hydroxy-5-
nonylbenzophenone oxime), LIX 84-I (2-hydroxy-5-nonylacetophenone oxime) and
also DIPSA (di(3,5-isopropyl)salicylic acid) / Cyanex 471X (tributylphosphine
sulphide) combination. They were used as 0.2 M solution in kerosene-like dissolvents
(Escaid 110 or Escaid 120 /Exxon/).
Preliminary experiments (pH dependencies and extraction/stripping isotherms)
were performed using individual synthetic solutions of Zn(II), Cd(II), Cu(II), Co(II)
and Ni(II) sulphates (pure). Main pilot trials of technological character were
performed with a real CNS solution. It was prepared by leaching/dissolution of the
technical CNS in hot deionised water and oxy-hydrolytic purification from iron,
manganese, arsenic and further similar elements. The chemical compositions of the
CNS and prepared nickel solutions are shown in Table 3.

Table 3. Crude nickel(II) sulphate (CNS) and its preliminary purified feed solutions (1, 2),
directed to further extractive purification

Element Ni Co Cu Zn Pb Ca Mg Fe As H2O
CNS % 29,4 0,52 0,58 0,15 0,012 1,19 0,080 0,60 0,075 3,02
1 74.3 1.14 0.90 0.27 0.0033 0.64 0.20 < 0.001 0.0007 -
g/dm3
2 72.0 1.3 1.48 0.34 0.011 0.50 0.21 0.36 <0.005 -

RESULTS AND ANALYSES

EXTRACTION VERSUS pH

Typical results of extraction versus pH measurements are presented on Figure 1,

showing selected metal extraction curves obtained for Cyanex 272.
The horizontal line at the level of 50 % extraction cuts the isotherm curves and
indicates the individual values of pH50% for each metal cation extracted, a parameter
characterising the extractant-metal mutual behaviour. All of the values obtained during
investigation with a few selected cations extracted from sulphate solutions with
various 0.2 M extractants, are gathered in Table 4.
Treating the value of ∆pH50% = pH50%(Ni) - pH50% (Co) as an indicator of impurities
vs. Ni(II) separation ability, it was easy to state, that the optimal extractant, with
characteristics suitable for the Ni(II) purification from Co(II) (∆pH50% = 1.7), Zn(II)
and Cu(II), is Cyanex 272. The next ones, but less effective, can be Cyanex 302 (0.8),
Cyanex 301 (0.7) and DEHPA (0.6). All three LIX and DIPSA/Cyanex 272
combinations were eliminated as potential extractants of Ni(II) contaminants, as
having too high pH50% level of the Zn(II) extraction.
 Solvent extraction of nickel(II) sulphate contaminants 123

Fig. 1. Extraction of metal cations with 0.2 M Cyanex 272. Dissolvent - Escaid 110 (Exxon); temp. 20
o
C; mixing time – 10 min.; metal salts conc. as indicated in table 4 and Pb2+ as 0.05 M lead(II) nitrate

Table 4. Equilibrium pH of 50 % extraction of metal cations

Salt conc.
Extractants pH50% ∆pH50%
[mol/dm3]
(concentration - 0.2 M) (sulphates) Zn Cd Cu Co Ni Ni-Co
Cyanex 272 0.10 2.75 5.9 3.3 5.0 6.7 1.7
Cyanex 302 0.02 1.4 0.5 - 3.4 4.2 0.8
Cyanex 301 0.10 -0.5 1.3 <1.0 0.7 1.4 0.7
DEHPA 0.10 1.8 3.1 3.1 3.6 4.2 0.6
DIPSA/Cyanex 471X* 0.05 5.1 4.3 3.8 - - -
LIX 54-100 0.05 6.32 - - - - -
LIX 64N 0.05 5.92 - - - - -
LIX 84-I 0.05 6.13 - - - - -

* - dissolved in Solvesso 150 (Exxon)

ISOTHERMS OF EXTRACTION OF CO(II) AND OTHER CNS CONTAMINANTS

Cyanex 272 and Cyanex 302 were proven as the Co(II) extractants by comparing
their extraction (from 0.1 M CoSO4 pure solutions) and stripping (with 2 M H2SO4
pure solution) isotherms. They showed, by comparison of the McCabe-Thiele
124 L. Gotfryd

constructions, plotted for the counter-current extractive systems, that Cyanex 272 is
the more effective extractant, especially from the stripping conditions point of view. A
number of counter-current stages necessary to obtain almost total solution purification
and complete Co(II) stripping had been found. They are as follows: 2/3 for Cyanex
302 and 2/2 for Cyanex 272 (extraction/stripping). The last system has been fixed as a
basic one for the execution of the next steps of investigations, covering real
continuous experiments, performed on a small pilot plant installation.
ISOTHERMS OF COMMON EXTRACTION VS. pH

The first step of investigation on the natural solution of a semi-industrial origin

were measurements of common extraction isotherms of all important impurities. The
results in Table 5 illustrate characteristic behaviour of the contaminants of the crude
nickel sulphate. All of them are step-by-step eliminated from the NiSO4 solution with
rising pH, and there is seen their characteristic sequence: Zn(II) > Fe(II) > Cu(II) >
Co(II).
A perfect repetition of this experiment with solution 2, having a decreased level of
the initial Fe(II) concentration to 0.08 g/dm3, has led to almost the same result without
any physical difficulties. Separation of reacting phases was also good.
Table 5. Extraction of CNS contaminants versus equilibrium pH

pH Concentrations in aqueous solution [g/dm3]

- Co(II) Cu(II) Fe(II) Zn(II)
1 2.13 1.21 1.44 0.24 0.28
2 2.92 1.21 1.41 0.033 0.044
3 3.91 1.18 1.16 0.065 0.0018
4 4.95 0.49 0.10 0.02 < 0.0002
5 6.05 0.033 0.007 < 0.001 < 0.0001

Stationary experiments on solution 2 (table 3; Ni = 72 g/dm3); 0.2 M Cyanex 272/Escaid 110;

O:A volumetric ratio = 1:1; time of mixing - 10 min.; temperature - 20 oC; 25 % NH3 as neutralising
agent; “lazy” phases disengagement

CLASSICAL ISOTHERMS OF COMMON EXTRACTION OF ALL IMPORTANT

CONTAMINANTS OF CNS

The investigations were performed on the purified CNS solution 2 (Table 3) by the
method described in the Procedures section. The results are shown on Figure 2.
The presence of Zn(II) and Fe(II) depresses extraction of Cu(II) and Co(II) but all
of them can be extracted commonly when proper values of pH and organic-to-aqueous
ratio is maintained, covering a necessary capacity to contain all of them. As
previously, the presence of Fe(II) was the reason of some problems with phase
separations, therefore it should be removed before extraction.
 Solvent extraction of nickel(II) sulphate contaminants 125

Fig. 2. Isotherms of common extraction of CNS contaminants. Vertical lines indicate initial levels of
contaminants (solution 2 - table 3); temp. 20 oC; mixing time - 10 min.

CROSS-CURRENT LABORATORY EXPERIMENTS

Instead of rather laborious counter-current extractive experiments (described in

details by Gotfryd and Szymanowski, 2004), simple laboratory tests of the cross-
current character confirmed possibilities of easy common extraction of all the CNS
contaminants. The extractant was preliminary prepared by contact with the Na2SO4
solution and adjusting pH with 5.0 M NaOH solution to the level of 7.0 and then
contacted one, two or three times with the solution 1 (Table 3). The results and other
conditions are shown in Table 6.

COUNTER-CURRENT EXPERIMENTS

A laboratory step of counter-current extraction of CNS contaminants was skipped,

basing on the results shown in Table 6. An experiment using the pilot counter-current
equipment, consisting of five mixer-settler type extractors, was performed.
126 L. Gotfryd

Table 6. Cross-current extraction of CNS contaminants

Step I II III I II III Last step
O:A Co (A)
equilibrium pH
No. phase ratios [dm3/dm3] [g/ dm3]
1 1:2 - - 4.8-5.0 - - 0.1-0.2
2 1:2 1:2 - 4.8-5.0 5.2-5.4 - 0.017-0.020
3 1:2 1:1 - 4.8 5.45 - 0.008
4 1:2 1:2 1:2 4.9 5.0 5.1 < 0.001
5 1:1 1:1 - 4.8 5.4 - < 0.001
Extractant: 0.2 M Cyanex 272 / Escaid 110; feed: solution 1 (table 3); temperature - 20 oC; time of
mixing – 10 min.; pH regulated with 2.5 M NaOH.

Fig. 3. Continuous counter-current extractive system designed for CNS purification. Extractant: 0.2 M
Cyanex 272 / Escaid 110; feed: solution 1 (table 3)

They were arranged into the 1-2-0-2 counter-current system. The figures designate
numbers of necessary extractive stages for all extractive processes, contributing to the
whole procedure, consisting of conditioning – extraction itself - washing – stripping.
A scheme of the designed extractive system is shown Figure 3. As the feed Solution 1
(Table 3) was used.
 Solvent extraction of nickel(II) sulphate contaminants 127

After reaching and stabilizing the optimal conditions, the level of Co(II) in the
purified NiSO4 solution was as low as < 0.01 g/dm3 and concentrate of metals was
totally neutralized. The compositions of the both resulting solutions are shown in
Table 7.
Table 7. Composition of the samples of stripped solution (Co concentrate) and Ni rafinate,
taken at optimal conditions of pilot plant extractive experiment
Co(II) Cu(II) Ni(II) Zn(II) Mg(II) Ca(II) pH
Co concentrate 27.2 18.3 6.0 5.5 1.8 0.7 3 3.5
g/dm
Ni rafinate 0.005 < 0.001 72 < 0.001 - 0.2 5.2

DISCUSSION AND CONCLUSIONS

The obtained results confirmed an expectation, that Cyanex 272 is the most
adequate extractant for the purpose for which the investigations had been carried out –
that’s to find an extractive purification method for crude nickel(II) sulphate, enabling
its most common contaminants (Zn(II), Cu(II) and Co(II)) removal. 0.2 M Cyanex 272
in Escaid 110 (Exxon) has been used for all further investigations.
The presence of Fe(II) is the reason of important physical disturbances at the phase
border of the reacting media and additionally, taking into account that Fe(III) is
known as being extracted very strongly, both cationic forms of iron should be
removed from solutions directed to the extractive purification. The oxy-hydrolysis
seems to be a good enough method for their removal (along with manganese and
arsenic) before applying the solution to further purification by extraction. Ammonia
could be used as a neutralizing agent in diluted Ni(II) solutions. To avoid the
precipitation of mixed Ni(II)/NH4(I) sulphates, the concentrated (2.5-5 molar) solution
of NaOH should be chosen for more concentrated solutions of NiSO4.
The shapes of extraction isotherms, analysed by the McCabe-Thiele pattern, and
results of simplified laboratory cross-counter experiments has led to designing an
extractive system, consisting of one-step extractant conditioning, two steps of
extraction (without washing) and two steps of stripping (1-2-0-2 type of counter-
current system). This has been successfully examined on pilot scale apparatus, giving
purified NiSO4 solution and Co(II) concentrate suitable for further extractive
purification.

ACKNOWLEDGEMENTS

Investigations had been partially performed due to a Polish Committee of Scientific Research grant
No. 1020/T08/2004/27.

REFERENCES

AGATZINI-LEONARDOU S. AND TSAKIRIDIS P., (1997); Simultaneous Cobalt and Magnesium

Extraction from Nickel Sulphate Solutions; Proc. of the XX IMPC - Aachen, 1997, September 21-26.
128 L. Gotfryd

BOOKLETS: I) Cyanex 272 Extractant; II) Cyanex 302 Extractant; III) Cyanex 301 Extractant;
IV) Cyanex Extractants – Solvent Extraction Reagents; American Cyanamid Company - Phosphine
Chemicals Division (ed.); V) DEHPA - Di(2-ethylhexyl) Phosphoric Acid - Metal Extractant -
Rhodia Phosphorus Specialties - Product Information (www.rhodia-ppd.com).
GOTFRYD L., SZYMANOWSKI J., (2004): Recovery of zinc(II) from acidic sulfate solutions. Simu-
lation of counter-current extraction-stripping process; Physicochem. Probl. Min. Proc., 38 p.113-
120.
OGATA T., NAMIHISA S., FUDJII T.: US Patent No. 4 246 240: Process for Separating Cobalt and
Nickel from a Solution Containing Cobalt and Nickel.
PATENTS (USA): 4 196 076; 4 242 314; 4 348 367; 4 353 883; 4 382 016; 4 600 435; 5 028 403.
PRESTON J. S., (1983): Recent Developments in the Separation of Nickel and Cobalt from Sulphate
Solutions by Solvent Extraction; J. S. Afr. Inst. Min. Metall.; June.
RICKELTON W. A., (1992): Novel uses for thiophosphinic acids in solvent extraction, J. Met., 5 p.52-54
RICKELTON, W. A., BOYLE R. J., (1991): The selective recovery of zinc with new thiophosphinic
acids, Solvent Extr. Ion Exch. 9 p. 73-8.4
RICKELTON W. A., FLETT D. S., WEST D. W., (1984) Solvent Extr. Ion Exch. 2 p. 815-838.
RITCEY,G.M., ASHBROOK,A.W. (1969): Separation of Nickel and Cobalt in Ammoniacal Solution by
Liquid-Liquid Extration; Trans. Instn. Min. Metall. (Sect. C.: Mineral Process. Extr. Metall.) 78 p.
C5-63.
SOLE K. C. AND HISKEY J. B., (1992): Solvent Extraction Characteristics of Thiosubstituted
Organophosphinic Acid Extractants; Hydrometallurgy 30 p. 345-365.
SZYMANOWSKI J., COTÉ G., BLONDET I., BOUVIER C., BAUER D., SABOT J. L., (1997):
Interfacial activity of bis(2-ethylhexyl)phosphoric acid in model liquid-liquid systems;
Hydrometallurgy 44 p. 163-178.
TAIT B. T., (1993): Cobalt-nickel Separation: the Extraction of Cobalt (II) and Nickel (II) by Cyanex
301, Cyanex 302 and Cyanex 272 ; Hydrometallurgy 32 p. 365-372.

Gotfryd L., Rozpuszczalnikowa zanieczyszczeń siarczanu niklu(II), Physicochemical Problems of

Mineral Processing, 39 (2005) 117-128 (w jęz. ang).

Dokonano przeglądu literaturowego potencjalnych metod ekstrakcyjnego oddzielania

zanieczyszczeń, w szczególności Co(II), z roztworów siarczanu niklu(II). Krótko scharakteryzowano
właściwości ważniejszych dostępnych na rynku preparatów organicznych, umożliwiających ekstrakcyjne
oddzielanie tychże zanieczyszczeń. Na podstawie badań laboratoryjnych porównano zachowanie się
ciekłych wymieniaczy jonowych, Cyanexu 272 oraz Cyanexu 302, wobec Co(II) i Ni(II). Wykorzystując
Cyanex 272 zbadano izotermy współekstrakcji najważniejszych zanieczyszczeń, w tym Zn(II), Cu(II) i
Co(II), z bogatych roztworów siarczanu niklu(II). Następnie, ekstrahent ten został zastosowany do
głębokiego oczyszczenia surowego siarczanu niklu(II) (SSN), od tych zanieczyszczeń. SSN jest
technicznej jakości produktem handlowym, produkowanym przez polskie huty. Przed obróbką
ekstrakcyjną, został wstępnie przygotowany poprzez roztworzenie w gorącej wodzie zdemineralizowanej
i hydrometalurgiczne (oksyhydrolityczne) oczyszczenie od żelaza(II), żelaza(III), arsenu(III), arsenu(V),
itp.
Aparatura pilotowa, o ciągłym przepływie mediów roboczych, zastosowana do oczyszczania SSN,
składała się z 5 ekstraktorów typu mieszalnik-odstojnik, połączonych w odpowiedni układ
przeciwprądowy typu 1-2-0-2. Nie zastosowano przemywania fazy organicznej ekstrahenta ze względu
na świadome przygotowanie systemu wyłącznie do wspólnego, nie selektywnego, oddzielenia
wszystkich jonów, zanieczyszczających SSN. Uzyskano znakomity poziom oczyszczenia siarczanu
niklu(II). Pozyskany ponadto dodatkowy produkt, koncentrat siarczanu kobaltu(II) (roztwór
poreekstrakcyjny) był niemal całkowicie neutralny (pH > 3,5).