Professional Documents
Culture Documents
ABSTRACT
Copper SX/EW plants often bleed part of their electrowinning electrolyte to control
impurities and maintain consistent cathode quality. Depending on the specific situation at
each site, the bleed is either returned to raffinate, to an SX extraction stage, to an SX wash
stage, or to the PLS pond, to avoid losing the copper in the bleed. This practice can have
undesirable effects on the overall process. An alternative is to electrowin all or most of the
copper in the bleed, thus avoiding the recirculation of the copper in the bleed. In this manner,
the bleed is converted to metallic copper without interfering with the SX circuit. This in turn
reduces the copper concentration in the raffinate, improving global copper recovery because
of improved leaching conditions.
INTRODUCTION
The main objective of an electrowinning tankhouse is to produce the largest possible
amount of copper while maintaining high cathode quality. Achieving a high copper
production implies applying a high current to the electrowinning cells. However, if the
current density is increased beyond a certain point, undesirable reactions begin to occur,
such as the degradation of organic carried over from the SX stage or the degradation of
Galactosol (guar) that is usually added to the electrolyte to improve copper deposit quality.
These reactions result in imperfections in the deposit and therefore lower copper quality.
Additionally, depending on each site, chemical impurities begin to accumulate in the
electrolyte, causing other problems such as those shown in Table 1:
Contaminant
Cl
Fe
Mn
% of Total
20
20
20
13.3
10
10
6.7
100
DISCUSSION
175 to 210
36 42 g/L
4 60 ppm
13 36 ppm
120 250 ppm
40 60 ppm
1 1.2 g/L
10 160 ppm
3 to 10
Table 6 shows the results of several runs where copper cathode was harvested at the
end of each run. Different runs used varying copper concentration, varying current density
and varying process flow rate. The first four runs were performed on the same electrolyte
recirculating from a closed process tank. For the first run, the initial copper concentration
was 39 grams per liter, and the copper concentration at the first copper harvest was 29 grams
per liter. A current density of 560 ampere per square meter was maintained constant for the
first run. After the first harvest, a second run was performed on the same solution at a lower
current density, 417 ampere per square meter, and the copper concentration at the second
harvest was 18.8 grams per liter. This procedure was repeated until a copper concentration of
0.8 grams per liter was achieved, with a total of four interruptions to harvest the accumulated
copper. Runs 6 to 9 and 11 to 14 were carried out in a similar fashion.
No.
1
2
3
4
5
6
7
g/T
O2
40.4
67.5
89.2
208.5
46.0
47.9
68.2
47
64
71
146
70
62
37
39.0
29.0
18.8
11.4
38.9
40.4
32.2
29.0
18.8
11.4
0.8
30.6
32
24.0
2.4
2.4
2.2
2.0
3.7
3.3
2.8
559
417
282
188
891
825
614
120
120
120
120
120
120
200
13.3
16.6
14.2
20.6
23.5
22.5
23.9
91
91
86
81
88
87
88
2
3
3
3
9
3
2
31
38
42
41
39
22
29
8
9
10
11
12
13
14
15
65.5
61.0
59.2
17.1
37.5
45.9
53.5
33.8
23.9
13.3
37.2
31.4
28.4
20.6
9.7
38.4
13.5
1.9
19.6
28.6
22.5
10.2
1.9
32.3
2.8
2.7
2.7
4.7
3.9
2.7
2.4
3.8
605
528
664
1130
850
460
303
1100
200
200
200
200
200
200
200
200
22.8
20.6
21.4
11.4
19.4
12.7
9.4
19.4
89
98
84
89
93
93
89
80
2
15
2
7
7
2
11
8
22
32
60
53
49
23
62
125
43
710
51
110
82
96
140
101
For each harvest, an analysis of impurities was carried out on the harvested copper.
Table 6 also shows the levels of sulphur, carbon and oxygen for the harvested cathodes.
With these results, a graph of copper concentration and sulphur content versus current
density can be constructed, which is shown in Figure 1. Each bar on the graph shows the
initial and final copper concentration for a particular run at a given current density, and the
number inside the bar shows the sulphur content of the copper harvested for that run.
Figure 1 Sulphur levels in Copper Cathodes produced at a given Current density and
within a given Copper concentration range.
With the help of this graph, the ideal working conditions to assure the production of
Grade A copper from EW bleed streams can be defined for any concentration of copper in
the bleed stream, in the range of 36 grams per liter of copper to 2 grams per liter of copper.
It is seen that at high copper concentrations, above 30 grams per liter, a very high current
density of 800 ampere per square meter can be used and the resulting copper will be of high
purity, Grade A. In contrast, if the copper concentration is low, for example 4 grams per
liter, a current density no greater than 250 ampere per square meter should be used if Grade
A copper is desired as a product. Therefore, the optimum configuration of a plant to treat an
EW bleed streams should consider at least two different electrowinning stages, one operating
at a very high current density where most of the copper is produced, and one operating at a
more modest current density. The conclusion is that as copper concentration decreases,
current density must be decreased in order to maintain high copper quality.
Enami Salado Tests:
Similar tests as those described above for Codelco Norte were carried out at the
ENAMI El Salado plant. The composition of the electrolyte used was very similar to that of
Codelco Norte shown in Table 5. The results of the Enami Salado work are shown in Tables
7 and 8 below. Table 7 shows the operational parameters for each run and Table 8 shows the
chemical analysis of the impurities in the copper harvested for each run:
Table 7 Experimental Results for Enami Salado Bleed
Run Current
Flow Concentration Voltage Mass
Density
Cu gpl Cu gpl Volts
Cu
(amp/m2 ) (m3/h) Initial Final
(Kg)
1
450
9
33.0
18.2
2.4
19.9
2
350
9
18.2
7.0
2.2
15.4
3
580
9
35.3
14.8
2.6
32.0
4
300
9
14.8
3.0
2.2
22.8
5
700
9
34.2
22.0
2.8
16.4
8
600
9
39.1
22.3
2.6
34.0
10
350
9
22.3
3.71
2.25 25.3
11
800
10
42.78 28.13
2.9
19.4
The results obtained for the bleed stream are shown below in Tables 9 and 10:
2
300
9
13.1
3.6
2.4
241
255
143
24
93
2.1
Raffinate Results
Tests were also conducted at Collahuasi using EMEW powder cells on Raffinate
having the composition shown in Table 11:
Table 11. Collahuasi Raffinate
Parameter Concentration
Cu
1.46 gpl
H2SO4
20 gpl
Total Fe
18 gpl
+2
Fe
16 gpl
Table 12 shows the operational conditions used for the runs using EMEW powder
cells with Raffinate at low copper concentrations. The applied current density was 600
Ampere /m2, the flowrate was 2.5 m3/h and cell voltage was 3.8 volt.
Table 12. Powder Results with EMEW cells on Raffinate
Run Number
5
6
7
8
9
2
Current Density, Ampere/m
600
600
600
600
600
Flowrate, m3/h
2.5
2.5
2.5
2.5
2.5
Initial Copper, gpl
1.46
0.5
0.34
0.23
0.17
Final Copper, gpl
0.5
0.34
0.23
0.17
0.13
Voltage, V
3.7
3.9
3.9
3.8
3.8
Run time, Hr.
8
5
15
16
28
From Table 12 it can be seen that the copper concentration in the Raffinate is
reduced from 1.46 grams per liter to 130 ppm over 5 consecutive runs on the same
electrolyte. The change in the copper concentration for the first run is larger than the change
in copper concentration for the following runs, suggesting that a practical limit for the
depletion of copper in the Raffinate is on the order of 200 ppm, as further run time produces
a relatively small change in copper concentration. These results show that another way to
reduce copper concentration in the Raffinate is to electrowin copper directly from the
Raffinate using EMEW powder cells, which is a direct method, as compared to the method
discussed above, which is an indirect reduction of copper concentration by electrowinning
copper from the EW bleed using EMEW plating cells.
Due to indications of ferrous oxidation from earlier evidence gathered in laboratory
work and field tests, a separate run was performed on the Raffinate after the copper was
depleted to the 130 ppm level to examine the change in the distribution of Ferrous / Ferric
concentration, as shown in Table 13:
13.6
2.7
110
117
103
23
94%
2.4
4
2.4
117
135
119
19
90%
2.3
CONCLUSIONS
A tool is available that allows for the recovery of copper contained in Electrowinning
bleed streams. By removing this copper, the recirculation of the bleed stream to other
parts of the circuit and the problems that this practice causes can be avoided.
It is shown that EMEW technology can produce high quality copper cathodes with
high current efficiencies from Electrowinning bleed streams, and that copper can be
depleted (while maintaining high copper quality) to concentration levels that
conventional technology has difficulty achieving.
By allowing for a larger bleed without the potential for loss of copper, the electrolyte
quality in the existing electrowinning circuit can be improved, thus increasing the
percentage of high quality cathode copper produced in the existing circuit and
decreasing the percentage of copper not meeting quality specifications.
The capacity of the SX stage is slightly increased because copper is not recirculated,
so that SX capacity is increased in an amount equal to the copper contained in the
bleed, which can be greater than 4% for some copper producers.
The use of this method allows for a reduction of Raffinate copper concentration.
From the results, it can be estimated that a typical reduction of copper concentration
in the Raffinate is on the order of 200 ppm.
The method allows for a plant expansion of the same magnitude as the copper
contained in the bleed at a comparatively low cost, because it is not necessary to
improve upon the SX stage facilities, the investment is reduced to adding enough
electrowinning capacity to treat the bleed. This is true however, if and only if the
mine can produce and the leaching facilities can process the additional ore needed.
The copper concentration in the raffinate can be reduced directly with EMEW
powder cells. In this case however, the product is copper powder and not grade A
cathode.
Ferrous ion in the Raffinate can be oxidized to Ferric ion with reasonable
efficiencies. It is likely that simultaneous copper depletion and Ferrous oxidation to
produce a low copper, high Ferric Raffinate can be achieved.
For the production of cathode copper from electrolyte bleed streams and from waste
stream, the energy use is on the order of 2.2 KwHr per kilo of copper deposited, and
the electrical efficiency is on the order of 94%.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the valuable contributions of Vernica Escobar
(Codelco Norte), David Olgun (Enami El Salado), and Rodrigo Valds (Enami El Salado).
REFERENCES
1. Robinson T., Sandoval S., and Cook P., (2003), World Copper Solvent Extraction
Plants: Practices and Design, JOM, Volume 55, Number 7, 1 July 2003, pp. 2426(3).
2. Escobar, V., Treasure, P.A., and Dixon, R.E., (2003). High Current Density
EMEW Copper Electrowinning, Hydrometallurgy 2003, Volume 2:
Electrometallurgy and Environmental Hydrometallurgy, Edited by C.A. Young,
A.M. Alfantazi, C.G. Anderson, D.B. Dreisinger, B. Harris and A. James, TMS,
Vancouver, 2003, pp. 1369 1380.
3. Dixon S., (2004). "Definition of Economic Optimum for the Leaching of High Acid
Consuming Copper Ores". Minerals and Metallurgical Processing 21(4), pp. 198-201.
4. Dixon, D.G., Tshilombo, A.F., (2005), Leaching Process for Copper Concentrates,
United States Patent Application 20050269208, December 8, 2005.
5. Aguad, J.S., Jordn, H.D., Vargas, T., (2000), Lixiviacin de Minerales Oxidados
de Cobre con Soluciones Acidas de Alta Carga Inica, Revista Ciencia Abierta,
Nmero 12, 7, 2000.
6. C.A.Garca, J.Campos, J. Cruz, D. Garca, G. Rodrguez, J.D. Miller , (2002)
"Lixiviacin de minerales sulfurados de Cobre" Hydromet 2002, Antofagasta,
Octubre 2002.
7. C.A.Garca, J.D. Miller, (2005) "Fundamentos, Resultados y Evaluacin Econmica
del Remining en Pilas de Lixiviacin" II Encuentro Internacional de
Hidrometalurgia, Antofagasta, Chile, Mayo 2005.