Minerals Engineering 23 (2010) 454–456

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Minerals Engineering
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Technical Note

Separation of nickel from copper in ammoniacal/ammonium carbonate solution

using ACORGA M5640 by selective stripping
Vaishnavi Sridhar a,*, J.K. Verma a, Nyoti S. Shenoy b
a
Inorganic Research Laboratory, K.J. Somaiya College of Science and Commerce, Vidyavihar, Mumbai 400 077, India
b
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India

a r t i c l e i n f o a b s t r a c t

Article history: Separation of nickel from copper in ammoniacal/ammonium carbonate solution using ACORGA M5640 by
Received 9 September 2009 selective stripping was carried out. The influence of equilibration time, equilibrium pH and extractant
Accepted 12 December 2009 concentration on the extraction of both the metals was studied. It was found that the copper extraction
Available online 22 January 2010
equilibrium was reached in a shorter time than the nickel extraction equilibrium. Nickel extraction
decreases above an equilibrium pH of 9.0, while the extraction of copper remains unaffected by the
Keywords: changes in the equilibrium pH range of 7–10. Co-extraction, ammonia scrubbing and the selective strip-
Solvent extraction
ping of copper and nickel were performed for a solution containing 3 g/l each of copper and nickel and
Non-ferrous metallic ores
Hydrometallurgy
60 g/l ammonium carbonate. The extraction and the percentage stripping of copper and nickel were
Co-extraction almost quantitative.
Selective stripping Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction solution. According to Caron’s process, ammoniacal leaching of lat-

Copper and nickel bearing ores are subjected to appropriate
technological processes (De Graff, 1980a,b; Gupta and Mukherjee,
1990; Caron, 1950) for the separation and recovery of their metal
values. Ammoniacal leaching is one such method in which the me-
tal values are brought into solution as their ammine complexes.
The technique of solvent extraction is employed successfully for
the recovery and separation of various metals and thus play an
important role in the field of hydrometallurgy. A number of com-
mercially available extractants particularly the hydroxyoximes
such as LIX 64N (Bhaskara Sarma et al., 1987), LIX 87QN (Sandhi-
bigraha and Bhaskara Sarma, 1997), LIX 973N (Alguacil and Cobo,
1999), LIX 984N (Vaishnavi Sridhar et al., 2009), and ACORGA
PT5050 (Alguacil and Cobo, 1998a) are used for the co-extraction
and selective stripping of copper and nickel from ammoniacal solu-
tions by solvent extraction. The present work deals with the co-
extraction of copper and nickel from an ammoniacal solution using
ACORGA M5640, followed by ammonia scrubbing and the selective
stripping of both metals from the loaded organic phase using acid.
2. Materials and methods
Copper and nickel solutions were prepared by dissolving their
corresponding sulfate salts in an ammonium carbonate aqueous
* Corresponding author. Tel.: +91 22 25115919; fax: +91 22 25115918.
E-mail address: bonjugs@rediffmail.com (V. Sridhar).
erite ores convert nickel and copper into ammines, while iron and
cobalt are oxidized by passing air. Cobalt in +3 state is not ex-
tracted and remains in the raffinate. Similarly, the leach solutions
are obtained from copper converter slag by acid leaching. These
solutions contain copper and other components like iron, silica, co-
balt and other impurities. After leaching the clear solutions were
obtained by filtration in both the cases. Thus for the experimental
purpose, a typical leach solution containing 3 g/l each of nickel and
cobalt in 60 g/l of ammonium carbonate is synthetically prepared
with pH 9.2.
The chelating extractant ACORGA M5640 (Cox, 1992; Szyma-
nowski, 1993; Alguacil and Cobo, 1998b), a salicylaldoxime deriv-
ative in solvent mixture, obtained from Cytec-Metal Extraction
products, Australia Holdings, was diluted in deodorized kerosene
(b.p. 160–200 °C) and used.
The kinetics of copper and nickel extraction was studied by con-
tacting equal volume of the aqueous solution (pH 9.2) containing
3 g/l each of copper and nickel in ammonium carbonate with the or-
ganic phase of 1% (v/v) ACORGA M5640 in kerosene for various peri-
ods of time. The influence of equilibrium pH on the co-extraction of
copper and nickel was studied over the pH range of 7–10, using equal
volume of the aqueous and organic phase equilibrated for 10 min at
room temperature. Metal concentrations were determined using a
Chemito AA 201 atomic absorption spectrophotometer.
In order to determine the number of solvent extraction stages
required at a chosen volume phase ratio, the extraction isotherm
was obtained with 15% (v/v) ACORGA M5640 in kerosene. Scrub-
bing tests were carried out at an 1:1 volume phase ratio with scrub

0892-6875/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2009.12.001
 V. Sridhar et al. / Minerals Engineering 23 (2010) 454–456 455

solutions of different pH (adjusted with sulfuric acid). The raffi- Table 1

nates were analysed for copper, nickel and ammonia. The ammonia Influence of extractant concentration on metal extraction.

concentration was estimated by Indophenol procedure (Mar- Extractant concentration Copper in organic Nickel in organic
czenko, 1976). The ammonia free loaded organic phase obtained (% v/v) phase (g/l) phase (g/l)
by this method was used to carry out selective nickel stripping 1 2.321 0.111
with aqueous solutions, whose pH was adjusted to 0.5, 1.0, 1.5 5 2.948 0.550
(with sulfuric acid) at a 1:1 volume pase ratio. This is followed 10 2.992 2.909
15 2.998 2.990
by copper stripping using an aqueous solution of 180 g/l sulfuric
acid. Single stage stripping experiments were carried out at an A/ Organic phase: ACORGA M5640 in kerosene.
O volume phase ratio of 1 at room temperature. Aqueous feed: solution containing 3 g/l each of copper and nickel, 60 g/l ammonium
carbonate, pH 9.2, A/O = 1.
Contact time: 10 min at room temperature.
3. Results and discussion

increasing the extractant concentration in the organic phase.

3.1. Kinetics of copper and nickel extraction, equilibrium pH and
Extraction of both copper and nickel increases with increase in
extractant concentration in the organic phase
extractant concentration. However at lower extractant concentra-
tions there is preferential extraction of copper, and at higher
Fig. 1 reveals that copper equilibrium is reached quicker than
extractant concentrations there is an excess of extractant that al-
nickel extraction equilibrium.
low more nickel to be extracted.
As seen from Fig. 2, a constant copper extraction of 3 g/l is
maintained in the pH range of 7–10 using ACORGA M5640. How-
ever, the nickel extraction decreased above an equilibrium pH of 3.2. Extraction isotherm
9.0.
As observed from Table 1, nickel extraction is approximately Almost complete extraction of both copper and nickel is possi-
37% when 1% (v/v) ACORGA M5640 was used as the organic phase. ble in a single stage when the volume phase ratio is unity or in two
An increased percentage nickel extraction can be achieved by stages when the A/O volume phase ratio is 1.5.

100 3.3. Ammonia scrubbing, selective nickel stripping and copper

stripping
90
80 The ammonia present in the loaded organic phase should be re-
moved before attempting nickel stripping because, the oxime picks
70
Extraction (%)

up some ammonia (Flett and Melling, 1979). As shown in Table 2,

60
copper when a scrub solution of initial pH 3.0 was used for removing
50 nickel ammonia, at an equilibrium pH of 7.4, most of the ammonia is re-
moved in a single stage with negligible loss of both copper and
40 nickel.
30 The results of the selective nickel stripping experiments are
shown in Table 3. There was some copper stripping with nickel as
20 the aqueous pH was decreased from 1.5 to 0.5. Nickel stripping
10 was low, when an aqueous phase of pH 1.5 was used, but increased
sharply at a pH of 1.0. Copper stripping from the nickel-free organic
0
0 10 20 30 40
Table 2
Time (min) Ammonia scrubbing of the loaded organic phase.

Initial Equilibrium Ammonia Copper Nickel

Fig. 1. The kinetics of copper and nickel extraction at room temperature.
pH pH scrubbed (%) scrubbed (%) scrubbed (%)
2.0 2.3 Quantitative 2.00 20.22
3.0 7.4 Quantitative 0.05 0.12
4 4.0 8.0 30.0 0.00 0.00
Metal g/l, organic phase

Organic feed: 15% (v/v) ACORGA M5640 in kerosene loaded with copper, nickel and
ammonia.
3 Aqueous phase: 3 g/l each of copper and nickel, 60 g/l ammonium carbonate,
pH 9.2.
Contact time: 10 min at room temperature.

2
Cu Table 3
Ni Nickel stripping at various pH values.
1
Initial pH Equilibrium pH Copper stripping (%) Nickel stripping (%)
0.5 1.0 36.7 99.5
1.0 1.5 2.1 98.3
0 1.5 2.0 1.0 59.9
7 7.5 8 8.5 9 9.5 10
Organic phase: 15% (v/v) ACORGA M5640 in kerosene loaded with copper and
Equilibrium pH nickel.
Aqueous phase: sulfuric acid of 0.5, 1.0, 1.5 pH, A/O = 1.
Fig. 2. Effect of pH on copper and nickel extraction. Contact time: 10 min at room temperature.
456 V. Sridhar et al. / Minerals Engineering 23 (2010) 454–456
phase using an aqueous solution of sulfuric acid was almost 99%
efficient. From Table 3, it is clear that selective stripping of the me-
tal values using sulfuric acid is more quantitative and the principle
of selective extraction or stripping in sulfuric acid had been demon-
strated in the literature (Nan et al., 2006).
4. Conclusions
ACORGA M5640 is capable of extracting both copper and nickel
from ammoniacal solutions. By using an appropriate concentration
of the extractant, both metals are quantitatively extracted from an
aqueous solution containing 3 g/l each of copper and nickel and
60 g/l ammonium carbonate.
The ammonia from the loaded organic phase is removed by a
single stage pH controlled scrubbing with no loss of either metals.
Selective nickel stripping from the ammonia free organic phase
was achieved by using aqueous solution of pH 1.0 followed by cop-
per stripping using 180 g/l of sulfuric acid in order to remove cop-
per quantitatively. Thus the separation of the two metals was
accomplished.
Acknowledgements
We would like to thank Dr. Vijay Joshi, Principal, K. J. Somaiya
College of Science and Commerce, Dr. Usha Mukundan, Principal,
and Professor V. B. Kulkarni, HOD, Chemistry Department, R. J. Col-
lege, Mumbai, for their constant encouragement to carry out this
work.
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