Hydrometallurgy 52 Ž1999.

55–61

Recovery of copper from ammoniacalrammonium

carbonate medium by LIX 973N
F.J. Alguacil
´
Centro Nacional de InÕestigaciones Metalurgicas (CSIC), AÕda. Gregorio del Amo 8, Ciudad UniÕersitaria,
28040 Madrid, Spain

Received 30 April 1998; received in revised form 14 December 1998; accepted 16 January 1999

Abstract

The extraction–stripping reactions of copper with LIX 973N in Iberfluid have been studied.
The effect of equilibration time, temperature, ammonium carbonate concentration, aqueous pH,
extractant and strip solution concentrations as well as the loading capacity of the reagent were
investigated. The loaded organic was found to pick up some ammonia, which has been selectively
stripped at controlled pH. The number of stages required for the extraction and stripping of copper
was also evaluated. The results are used to assess the conditions for purification of ammoniacal
industrial waste solutions containing copper. q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Copper; LIX 973N; Iberfluid

1. Introduction

Nowadays, there is general concern to minimize the discharge or disposal of effluents

containing hazardous metals. In some cases, such effluents contain valuable metals, thus,
there is also an economic interest in their recycle for the recovery of these values. This
is the case for a number of liquid effluents. Precipitation techniques are often used for
the removal of metallic species from such liquid effluents, despite that the operation lead
to the generation of, e.g., sludges Žthat need to be disposed andror processed. and the
products obtained are not always of the required quality. Accordingly, there is a search
for new technologies which allow the treatment of such effluents. Solvent extraction
processing seems to be promising due to its versatility in the removal, separation and
concentration of metal ions and also due to its capacity for the relatively fast treatment
of large volumes of solutions.

0304-386Xr99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X Ž 9 9 . 0 0 0 1 2 - 2
56 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61

In the case of the treatment of copper-ammoniacal pregnant solutions or effluents,

solvent extraction has been used for a number of years Že.g., in the processing of printed
circuit board etchants. w1–4x. On the other hand, new extractants are being introduced to
the market and, as in the case of LIX 973N, few data are available in the literature about
its use in the solvent extraction operation and, particularly with this reagent, in its
application to the extraction of copper from non-acidic solutions Že.g., ammoniacal
aqueous media..
In the present work, the extraction of copper by LIX 973N from aqueous ammonia-
calrammonium carbonate medium of various pH was studied under equilibrium condi-
tions. The results are applied in simulated counter-current extraction to investigate the
efficiency of such a system in the recovery of copper from ammoniacal waste solutions
in practical operations.

2. Experimental

LIX 973N ŽHenkel. is a mixture of 5-nonylsalicylaldoxime and 2-hydroxy-5-nonyl-

acetophenone oxime, the salicylaldoxime being in excess with respect to the former
component w5x. The reagent was used as received from the manufacturer by diluting in
Iberfluid Ža kerosene type reagent, boiling range 210–2848C, flash point 968C, - 2%
aromatic content, density 785 kgrm3 Ž208C... All other chemicals were of AR grade.
Copper extractionrstripping experiments were carried out by mechanical shaking of
the appropriate aqueous and organic phases in thermostatted separatory funnels, for the
time and temperature required.
Copper was analyzed by AAS. The content of ammonia was estimated using the
Indo-phenol procedure w6x.

3. Results and discussion

The reaction which governs the extraction of copper from ammoniacal solutions by
oximes is known and can be described by:
2q
2HR org q Cu Ž NH 3 . 4 aq ° CuR 2 org q 2NHq
4 aqq 2NH 3 aq Ž 1.
where HR represents the oxime molecule, and aq and org are the respective aqueous and
organic phases. No data are available in the literature about how LIX 973N performs in
alkaline solutions.

3.1. Effect of pH

The effect of pH on copper extraction has been determined using an aqueous solution
of 3 grl Cu and 60 grl ammonium carbonate and an organic solution of 10% vrv LIX
973N in Iberfluid. The aqueous pH was adjusted to values between 8.5 and 10.5 and
extractions have been carried out at equal phase ratios, 208C and 10 min of contact time.
 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61 57

The results obtained showed that there is near copper quantitative extraction Žpercentage
values exceeding 99.5. within the pH range studied.

3.2. Effect of ammonium carbonate

The effect of the presence of ammonium carbonate in the aqueous phase on copper
extraction has been studied by varying its concentration between 10 and 100 grl. In all
these experiments, the equilibrium pH was 9.5 " 0.05. The organic and aqueous phases
were of 10% vrv LIX 973N in Iberfluid and 3 grl copper, respectively, and extractions
were carried out at O:A ratio of 1, 208C and 10 min. The results show that the presence
of ammonium carbonate in the aqueous phase has only a small effect on copper
extraction. The percentage of extraction decreased from 99.7 Ž10 grl ammonium
carbonate. to 97.4 Ž100 grl ammonium carbonate..

3.3. Kinetics of copper extraction

The experiments were carried out by contacting at 208C, for time periods ranging
between 1 min and 60 min, an aqueous phase of 3 grl Cu, 60 grl ammonium carbonate
at pH 9.5 and an organic solution of 10% vrv LIX 973N in Iberfluid; O:A phase ratio
was 1. The analysis of the equilibrated aqueous solutions indicated that copper kinetics
are fast since equilibrium is attained within 2.5 min.

3.4. Effect of temperature

This influence was studied using the same organic and aqueous solutions as described
above, 10 min of contact time, O:A phase ratio of 1 and temperatures ranging from 20 to
608C. The results obtained showed that there is no influence of temperature on copper
extraction from ammoniacal solutions using LIX 973N within the present experimental
conditions, the percentages of copper extraction exceeding 99%.

3.5. Loading capacity

The loading capacity of LIX 973N has been determined by two procedures. First by
contacting an organic phase of 20% vrv LIX 973N and an aqueous phase ŽpH 9.5.
containing 3 grl Cu, 60 grl ammonium carbonate at 1:1 phase ratio, 208C and 10 min.
By repeated contact of the organic solution with fresh aqueous phases the loaded organic
was found to contain 12.2 grl copper after six cycles.
The second procedure used an organic solution of 5% vrv LIX 973N and the same
aqueous phase and conditions as described above except that various O:A phase ratios
Ž3:1 to 1:4. were employed. Experimental results showed that the loaded organic
solution contained around 3 grl Cu. This value is consistent with the results obtained
above and with that obtained with other LIX reagents.

3.6. Influence of extractant concentration

Experiments were carried out using various extractant concentrations in Iberfluid and
an aqueous solution of 3 grl copper, 60 grl ammonium carbonate at various pH.
58 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61

Table 1
Influence of LIX 973N concentration on copper extraction
pH eq 2.5% vrv 5% vrv 10% vrv 20% vrv
9.0 47.3 93.7 Quantitativea Quantitativea
9.9 48.7 92.9 Quantitativea Quantitativea
10.2 48.8 94.6 Quantitativea Quantitativea
a
Copper in the raffinate less than 0.01 grl.

Temperature was 208C, equilibration time 10 min and O:A phase ratio of 1. Results
obtained are presented in Table 1; using 10 and 20% vrv extractant in Iberfluid
quantitative copper extraction Žless than 0.001 grl copper in the raffinate. can be
obtained, in the case of 5% solutions an average 94% copper extraction was reached
within the pH range studied.

3.7. The processing of a copper ammoniacalr ammonium carbonate solution

For a solution of pH 9.5 containing 3 grl Cu, 60 grl ammonium carbonate,

conditions for extraction and selective ammoniarcopper stripping were established.

3.7.1. Extraction
To determine the number of stages for a given phase ratio, the copper loading
isotherm has been obtained using the aqueous solution described above and an organic
phase of 5% vrv LIX 973N in Iberfluid at various O:A phase ratios ŽFig. 1.. Copper
extraction is possible in two stages at an A:O phase ratio of 1. To confirm these results a
simulation experiment has been carried out for a 10-cycle operation. The results

Fig. 1. Copper extraction isotherm.

 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61 59

Table 2
Ammonia selective stripping
pH init pH eq % NH 3 stripped
6.0 8.48 30.1
4.0 8.47 33.6
3.0 8.05 70.1
2.5 3.94 97.2
2.0 3.04 99.9

obtained by analysis of the loaded organic solutions and the raffinates shown an average
of 99.8% copper extraction efficiency; these results confirm the values obtained from
Fig. 1 for the extraction of copper under counter-current conditions.
It is known that oxime extractants pick up ammonia w7,8x; in the present case the
loaded organic solution contained near 0.2 grl ammonia. The value is not high, possibly
because the system operates at a near maximum copper loading which should inhibit the
loading of ammonia, but needs to be eliminated to avoid the build-up of undesirable
products due to reaction, in the stripping operation, with the spent electrolyte.

3.7.2. Ammonia stripping

The ammonia selective stripping has been studied using aqueous solutions of various
pH Žadjusted with sulphuric acid. and organic solutions loaded with 0.2 grl ammonia
and 3 grl copper. Results are shown in Table 2; ammonia removal from the organic
phase is possible in a single stage at 1:1 phase ratio and 208C using an aqueous phase of
initial pH value near 2.5. The stripping of copper is negligible under these experimental
conditions.
A new approach Žcircuit with internal ammonia recycling. for the treatment of
copperrammonia loaded organic solutions obtained in the solvent extraction operation
of ammoniacal etchant solutions has been described w4x but it has not yet been
experimentally tested using LIX 973N. Experiments are to be conducted in this
laboratory to compare its performance against the conventional procedure described in
this work.

3.7.3. Copper stripping

Once the loaded organic phase was made ammonia free, the stripping of copper was
studied using aqueous solutions which represented the main elements and concentrations
of a typical spent electrolyte from an electrowinning operation.

Table 3
Copper stripping
Stage % Cu stripped
1 84.0
2 11.5
3 3.8
60 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61

Fig. 2. Copper stripping isotherm. Temperature 408C.

The organic solution containing 3 grl copper was contacted with an aqueous phase of
24 grl copper and 180 grl sulphuric acid at 408C, O:A ratio of 1 and 10 min of
equilibration time Žsufficient to achieve equilibrium.. The procedure was repeated three
times on the same organic solution. The results obtained are shown in Table 3; it can be
observed that copper can be stripped under these conditions to an extent of around
99.3%.
A stripping isotherm has been obtained for the 3 grl copper loaded organic solution
and the aqueous phase of 24 grl Cu and 180 grl sulphuric acid, various O:A ratios
were used. Fig. 2 shows that it is possible to obtain near 3 grl copper in the aqueous
phase in two stages at an O:A ratio of 1. The unloaded organic solution still contains
near 0.02 grl copper, although it can be recycled with no problem.

4. Conclusions

The results obtained show that the commercially available extractant LIX 973N can
be used as a reagent for copper extraction in ammoniacalrammonium carbonate media.
In the present experimental conditions, neither aqueous equilibrium pH nor ammo-
nium carbonate concentration nor temperature influenced copper extraction. The extent
of copper concentration can be regulated with the initial extractant concentration in the
organic solution. For a typical aqueous solution Ž3 grl copper, 60 grl ammonium
carbonate at pH 9.5. the process is optimized with: Ži. near complete extraction possible
in two stages at A:O ratio of 1; Žii. the loaded organic picking up ammonia which could
be selectively stripped in a single stage pH controlled operation; and Žiii. near complete
copper stripping possible in two stages at an O:A ratio of 1 using a make-up spent
electrolyte solution Ž24 grl copper and 180 grl sulphuric acid..
 F.J. Alguacilr Hydrometallurgy 52 (1999) 55–61 61

Acknowledgements

We would like to thank the CSIC ŽSpain. for support to carry out this work and Dr.
Schawb ŽHenkel, Germany. for supply of a sample of LIX 973N reagent.

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