SOLVENT EXTRACTION OF COPPER FROM

HIGH CONCENTRATION PRESSURE ACID LEACH LIQUORS

Kathryn C. Sole

Anglo American Research Laboratories (Pty) Ltd, Johannesburg, South Africa

Hydrometallurgical processes for the recovery of copper from sulphide concentrates are
under evaluation for the Konkola Deeps project in Zambia and for a copper-gold ore deposit.
The process flowsheets involve copper dissolution from the concentrate by pressure leaching
in sulphuric acid, followed by purification of the leach liquor by solvent extraction, and metal
recovery by electrowinning. The autoclave discharge liquors contain 50 to 90 g/l Cu and,
under appropriate operating conditions, minimal residual free acid. The choice of extractants
and operating conditions for the recovery of copper from such solutions is discussed, and
selected results from laboratory and pilot-scale studies are presented.

INTRODUCTION

Pressure acid leaching (PAL) can offer technical and economic advantages in base metal
flowsheets and is now being considered for the treatment of sulphide concentrates [1].
Flowsheets that integrate PAL with solvent extraction (SX) for the downstream processing of
autoclave discharge liquors present interesting opportunities for efficient metal recovery.

Significant advances in copper SX have been made over the past thirty years [2], with almost
30% of world copper production today via this route. Most applications involve the relatively
dilute liquors (1 to 4 g/l Cu) arising from the dump or heap leaching of low-grade material. In
contrast, autoclave discharge liquors from the partial or total oxidation of copper sulphides
have tenors ranging from 50 to 90 g/l Cu.

Modern copper extractants (HA) employ the hydroxyoxime functionality for the complexation
of copper, the schematic reaction for which can be written:
Cu2+ + 2 HA ' CuA2 + 2 H+.
The reaction stoichiometry shows that 1.54 g H2SO4 is generated per g Cu extracted. The
purification of leach liquors with high copper concentrations provides challenges in designing
flowsheets to accommodate the substantial quantities of acid produced by the extraction
reaction. Limited studies on the processing of such liquors have been documented [3].

This paper examines two case studies (the recovery of copper from a copper-gold deposit
and the hydrometallurgical option for the Konkola Deep expansion project in Zambia) in
which these challenges are met by innovative process integration. The choice of extractants
and operating conditions for the purification of copper from the high-concentration PAL
liquors are discussed, and selected results from laboratory and pilot-scale studies presented.

Proceedings of the International Solvent Extraction Conference, ISEC 2002

Edited by K. C. Sole, P. M. Cole, J. S. Preston and D. J. Robinson
 South African Institute of Mining and Metallurgy, Johannesburg, 2002
Produced by Document Transformation Technologies, Published by Chris van Rensburg Publications (Pty) Ltd

1033
 SELECTION OF EXTRACTANTS

Simulation Modelling
Potential extractant systems for achieving the high copper transfers required (∆Cu = 50 g/l)
for the processing of PAL pregnant leach solutions (PLS) were identified using the Isocalc
(Cognis) and MEUM (Avecia) simulation models. There was excellent agreement between
experimental data and the model predictions, confirming the validity of using modelling for
the preliminary selection of extractant compositions and operating conditions.

Selected results are presented in Table 1. Various combinations of circuit configurations and
organic-to-aqueous (O:A) flowrate ratios will achieve similar objectives; the particular choice
of conditions will be governed by capital and operating costs, as well as by site-specific
considerations.

Table 1. Modelling of copper extraction from high-concentration liquors.

Concn. PLS Cu Circuit Advance Raffinate ∆Cu*
Extractant
(vol.%) (g/l) configuration O:A Cu (g/l) (g/l)
LIX 984N 32 60 3E, 2S** 4.2 8.8 51.2
2E, 2S 5.5 9.88 50.1
80 2E, 2S 6 30.0 50.0
3E, 1S 6 28.7 51.3
LIX 664N 32 60 3E, 2S 6 8.47 51.5
3E, 2S 5 10.0 50.0
Acorga 32 60 4E, 2S 4.5 9.1 50.9
M5640 3E, 2S 3.76 15.0 45.0
70 3E, 2S 5 15.2 54.8
6 12.6 57.4
Acorga 32 70 3E, 2S 5 15.8 54.2
M5774 6 13.3 56.6
35 70 3E, 2S 5 14.1 55.9
6 12.4 57.6
* PLS acid: 5 g/l H2SO4; SE: 35 g/l Cu, 180 g/l H2SO4; AE: 45 g/l Cu; Mixer efficiency: 98%
** 3E, 2S ≡ three extraction stages, two stripping stages

Extraction Isotherms
The extractants chosen for the experimental study are described in Table 2. The partially
aromatic diluent was Shellsol 2325, supplied by Shell Chemicals.

Table 2. Copper extractants.

Supplier Extractant Functionality Modifier
Avecia Acorga M5640 aldoxime ester
Acorga M5774 aldoxime ester
Cognis LIX 664N aldoxime ester
LIX 84-I ketoxime none
LIX 984N 50:50 aldoxime:ketoxime none
LIX 973N 70:30 aldoxime:ketoxime none

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 Figure 1 shows the extraction of copper from an autoclave discharge liquor containing 70 g/l
Cu. Both Acorga extractants, LIX 664N and LIX 984N will produce a raffinate of < 10 g/l Cu
under appropriate operating conditions. LIX 84-I and LIX 973N were also tested, but their
extraction capability dropped significantly in the presence of too much acid, so they are not
suitable for the treatment of autoclave discharge liquors. In general, aldoximes have a
higher loading capacity for copper than ketoximes, but, since they form stronger complexes,
are typically less readily stripped; hence the need to include a stripping modifier in the
formulation of aldoximes.

The effect of extractant concentration is shown in Figure 2. Higher concentrations increase

copper transfer due to higher loadings, thereby reducing the equipment size for a given PLS
throughput. Higher concentrations usually require higher temperature operation due to
viscosity and settling limitations, however even at ambient temperature, the use of 48 vol.%
extractant did not pose visible problems, and loadings up to 25 g/l Cu were measured.

20 30

16 25
[Cu]org (g/l)

[Cu]org (g/l)
20
12
15
8 M5774
30 vol.%
LIX 664N 10
4 LIX 984N 40 vol.%
5
M5640 48 vol.%
0 0
0 20 40 60 80 0 20 40 60 80
[Cu]aq (g/l) [Cu]aq (g/l)
Figure 1. Extraction of copper from PAL Figure 2. Effect of extractant concentration
liquor (70 g/l Cu, 2.8 g/l Fe, 6 g/l H2SO4) on copper extraction from PAL liquor by
by 32 vol.% extractant in Shellsol 2325. Acorga M5774 in Shellsol 2325.

RECOVERY OF COPPER FROM A COPPER-GOLD DEPOSIT

A hydrometallurgical process is under development for the recovery of copper from a copper-
gold deposit. Copper is liberated from the finely ground concentrate by pressure leaching
under conditions that minimise the free acid and iron in solution. The clarified leach solution
contains 60 g/l Cu which is treated by SX to maximise copper recovery. The raffinate,
containing significant quantities of acid liberated in the extraction reaction, is recycled to the
leach. The flowsheet also includes a second conventional SX circuit to recover copper from
the filtrate wash water. A single electrowinning (EW) circuit provides a recycle of electrolyte
between the two SX strip circuits. Gold is recovered from the leach residue.

Following modelling simulations and initial screening of extractants, LIX 984N and Acorga
M5774 were chosen for further evaluation using leach liquor generated from the pressure
leaching testwork. The SX performance of the high-tenor circuit (32 vol.% extractant) is
summarised in Table 3.

Table 3. Extraction and stripping performance of the high-tenor SX circuit.

Stream Acorga M5774 LIX 984N
Stripped organic (SO) (g/l Cu) 3.58 3.94
Loaded organic (LO) (g/l Cu) 18.58 16.18

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McCabe-Thiele constructions were used to determine the staging requirements and
operating conditions for the high-tenor SX circuit (Figure 3). An advance O:A of 5.4 will
produce a raffinate of 10 g/l Cu in three extraction stages from a PLS containing 60 g/l Cu at
pH 1.4. Using a spent electrolyte (SE) of 35 g/l Cu and 180 g/l H2SO4, a stripping ratio of O:A
= 1.1 will upgrade the advance electrolyte (AE) to 45 g/l Cu in two stages.

20 55

16 50
AE
[Cu]org (g/l)

[Cu]aq (g/l)
12 45
1 1
8 O:A = 5.4 40
2 2 O:A = 1.1
3 SE
4 Stripped organic 35
Raffinate PLS SO LO
0 30
0 10 20 30 40 50 60 70 0 3 6 9 12 15
[Cu]aq (g/l) [Cu]org (g/l)
Figure 3. McCabe-Thiele constructions for (a) extraction and (b) stripping of copper
in the high-tenor SX circuit (32 vol.% Acorga M5774 in Shellsol 2325).

KONKOLA DEEPS EXPANSION PROJECT

A hydrometallurgical flowsheet (Figure 4) for the combined treatment of the Konkola Deeps
sulphide deposit and Chingola refractory ore (CRO) has been proposed. The sulphide
concentrate (40-45% Cu) is pressure leached under conditions that maximise recovery of
copper and cobalt while rejecting iron as hematite. The autoclave discharge contains 60 g/l
Cu and the acid tenor is minimised to 5 g/l, allowing the liquor to be purified directly by SX.
The high-tenor SX1 circuit removes the bulk of the copper, the extraction of 50 g/l Cu
generating a raffinate containing ~80 g/l H2SO4. This acid is used to leach copper from the
CRO, the aggressive conditions necessitated by the high aluminium, magnesium, and
calcium oxides and carbonates in this material. The atmospheric leach liquor is treated for
copper recovery in the low-tenor SX2 circuit. Both SX circuits are integrated with EW to
produce a high-grade copper cathode product.
Konkola concentrate CRO ore

High pressure First-stage

acid leach atmospheric leach

U/F O/F
Thickener Thickener

O/F U/F
Raffinate Second-stage
High tenor SX
atmospheric leach

Low tenor SX CCD

Filtration
Copper EW

Residue
Copper cathode

Figure 4. The hydrometallurgical flowsheet for the Konkola project.

1036
This flowsheet capitalises on the synergy between the leaching of the sulphide concentrate
(acid producing) and the oxide ore (acid consuming), which provides a convenient way of
‘transferring acid’ from the sulphide to the oxide circuit. Key to the concept is the high copper
transfer (∆Cu = 50 g/l) of the SX1 circuit which generates a raffinate of sufficient acid
strength to leach the refractory CRO minerals. SX1 maximises copper extraction using a high
extractant concentration and high O:A; SX2 generates a low copper raffinate (< 0.5 g/l).
Pilot-Plant Evaluation
An eight-week, integrated pilot-plant campaign producing 24 kg/h cathode copper was
carried out at AARL [4]. The pilot plant treated 27 tons of CRO and 2.5 tons of Konkola
concentrate, and produced 940 kg of LME Grade A copper cathode.

Both SX circuits comprised three extraction and two strip stages, configured for counter-
current flow. Two extractants were tested: Acorga M5640 and LIX 984N. The diluent was
Shellsol 2325. The operating conditions are shown in Table 4.
Table 4. Konkola pilot-plant SX operating conditions.
Parameter SX1 SX2
Extractant concentration (vol.%) 32 16
PLS Clarified autoclave discharge Clarified CRO liquor
PLS composition 60 g/l Cu, 6.5 g/l H2SO4 5.3 g/l Cu, 2.7 g/l H2SO4
Extraction advance O:A 4.9 1.0
Target extraction ∆Cu (g/l) 50 4.8
Strip advance O:A 0.91 1.76
Strip liquor (SE) 37 g/l Cu, 170 g/l H2SO4 37 g/l Cu, 170 g/l H2SO4
Loaded strip liquor (AE) 46.1 g/l Cu, 156 g/l H2SO4 45.4 g/l Cu, 157 g/l H2SO4

SX1 consistently achieved copper extractions of 50 g/l. SX2 exceeded the performance
specifications, with average raffinates of 0.25 g/l Cu. Typical results are shown in Table 5.
Comparison of the plant data with laboratory isotherms generated from the plant solutions
showed excellent correlation (Figure 5), indicating optimal operation of both SX circuits. Both
extractants performed well and little differentiation of metallurgical performance could be
quantified under the pilot-plant operating conditions. LME Grade A copper was produced
throughout the campaign, with all cathodes meeting the BSI standard 6017:1981.
Table 5. Typical performance of SX circuits during the Konkola pilot-plant campaign.
Element SX1 SX2
(g/l) PLS1 LO1 SO PLS LO SO
Cu 59.29 15.6 6.2 5.81 8.85 3.8
Co 1.23 < 0.001 < 0.001 0.61 < 0.001 < 0.001
Fe 1.22 < 0.001 < 0.001 1.77 < 0.001 < 0.001
Al 1.12 < 0.001 < 0.001 1.31 < 0.001 < 0.001
Mg 7.95 < 0.001 < 0.001 6.83 < 0.001 < 0.001
Ca 0.65 < 0.001 0.001 0.69 < 0.001 < 0.001
Mn 1.31 < 0.001 < 0.001 1.22 < 0.001 < 0.001
Zn 0.10 0.001 < 0.001 0.05 < 0.001 0.001

CONCLUSIONS
Pressure leaching technologies currently under development for the treatment of copper
sulphide concentrates yield leach liquors that contain 50 to 90 g/l Cu. Purifying such liquors
by SX requires an integrated flowsheet in which the large quantities of acid produced by the
extraction reaction can be accommodated. This work has demonstrated that extractant

1037
concentrations up to 45 vol.% can achieve copper transfers of 50 g/l in three stages.
Adequate stripping is achieved in two stages with a conventional SE composition, producing
an AE from which LME Grade A copper cathode can be electrowon.
Extraction SX1 Stripping SX1
25 70

20 Maximum loading
60
[Cu]org (g/l)

[Cu]aq (g/l)
15 AE
50
10 O:A = 4.90
SE O:A = 0.78
Stripped organic
40
5
Raffinate PLS SO LO
0 30
0 10 20 30 40 50 60 70 0 4 8 12 16
[Cu]aq (g/l) [Cu]org (g/l)

Extraction SX2 Stripping SX2

10 70

8 Maximum loading
60 AE
[Cu]org (g/l)

[Cu]aq (g/l)

6
50
O:A = 1.06
4
SE O:A = 3.11
Stripped organic 40
2
Raffinate PLS SO LO
0 30
0 1 2 3 4 5 6 0 2 4 6 8 10
[Cu]aq (g/l) [Cu]org (g/l)
Figure 5. Comparison of laboratory extraction and stripping isotherms (solid lines)
with typical pilot-plant operating conditions (▲ and dotted lines) for SX1 and SX2.
The performance of conventional extractants and circuit configurations for transferring such
high amounts of copper has not been previously documented for continuous trials. The
successful completion of the Konkola pilot plant demonstrated that existing extractants can
be used in non-traditional applications without problems.

ACKNOWLEDGEMENTS
The extractants and modelling packages were kindly made available by Avecia and Cognis.
Anglo Base are thanked for permission to discuss details of the two development projects.
This paper is published by permission of Anglo American Research Laboratories (Pty) Ltd.

REFERENCES
1. R. McElroy, W. Young (1999), Copper Leaching, Solvent Extraction and Electrowinning,
G. V. Jergensen (ed.), Society for Mining, Metallurgy and Exploration, Littleton, pp. 29-40.
2. G. Kordosky (2002), Proc. International Solvent Extraction Conference ISEC 2002, South
African Institute of Mining and Metallurgy, Johannesburg, pp. 853-862.
3. T. Moore, B. Townson, C. Maes, O. Tinkler (1999), ALTA 1999 Copper Hydrometallurgy
Forum, ALTA Metallurgical Services, Melbourne.
4. R. M. Whyte, N. Schoeman, K. G. Bowes (2001), Copper, Cobalt, Nickel and Zinc
Recovery, South African Institute of Mining and Metallurgy, Johannesburg, 15 pp.

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