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ADDING VALUE TO LIX / SX / EW OPERATIONS BY

RECOVERING COPPER FROM BLEED, RAFFINATE AND OTHER PLANT


STREAMS
Richard E. Dixon
HATCH Associates
Av. El Bosque 500, 12th Floor
Santiago Chile
rdixon@hatch.cl
Rudi Fester, Carlos Garca, Carlos Contreras, Fernando Romero
Compaa Minera Doa Ins de Collahuasi
Baquedano 902, Iquique-Chile
Ian D. Ewart
Electrometals Technologies, Ltd.
206 3711 Delbrook Avenue
North Vancouver BC V7N 3Z4

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

Table 1 Electrolyte Contaminant Issues


Typical range Potential Problems at Higher Concentrations
10 50 ppm
Cathode Stripping Problems
1-3 g/L
Current Efficiency loss (2% to 3% per g/L of Fe)
10 500 ppm Faster degradation of Lead Anodes

Because of these problems, many electrowinning tankhouses bleed a portion of their


electrolyte in order to reduce the concentration of contaminants and to reach a steady state
for the concentration of impurities that allows for acceptable operating conditions.
There is significant variability in this practice, as some tankhouses practically do not
bleed any electrolyte and others bleed large amounts, as can be seen in Tables 2, 3 and 4, in
which data are summarized for 30 Copper EW Tankhouses around the world from data
compiled by Robinson [1] on SX/EW plants.
Table 2 Typical Copper Electrowinning Bleed Volumes
Bleed Amount (as % of total annual Cu production)
Number of Plants
0 to 0.2%
6
0.2 to 0.4%
6
0.4 to 1%
6
1 to 2%
4
2 to 3%
3
3 to 4%
3
Over 4%
2
Total
30

% of Total
20
20
20
13.3
10
10
6.7
100

Table 3 Reason for Bleeding


Contaminant
Number of Plants
% of Total
Fe
7
35
Fe + Cl
1
5
Fe + Mn
4
20
Cl
4
20
Cl + Mn
3
15
Mn
1
5
Total
20
100

Table 4 Destination of the EW Bleed


Destination
Number of Plants
% of Total
E1
9
41
PLS
2
9
SX Wash
4
18
Raffinate
7
32
Total
22
100
It is noted that the total number of plants reporting is different in each table because
information is not available for all plants about all aspects of their operation.
Recirculating the bleed has deleterious effect on the LiX SX EW operation. If the
bleed is sent to the Raffinate pond, the increased concentration of copper in the raffinate
causes a decrease in the leaching power of the raffinate (because the chemical potential of
the leaching reaction decreases), which results in a lower recovery of copper from the heap.
If the bleed is returned to an extraction stage, the copper and acid concentrations are
increased. As a result, the recovery in the SX stage is reduced, which is normally
compensated for by increasing the extractant concentration, which in turn results in
increased carryover and loss of organic.
If the bleed is sent to an SX wash stage, the acid concentration is increased and a
loss of copper occurs, because the wash stage behaves like a stripping stage. In this case, the
bleed also increases the amount of impurities, thus decreasing the efficiency of the wash
stage.
Finally, if the bleed is sent to the PLS pond, the copper concentration entering the
SX stage is increased, which means that it is necessary to increase the concentration of
extractant, causing increased organic carryover and loss.

To avoid recirculating the electrolyte bleed, it would be necessary to remove most of


the copper in the bleed. However, this is not common practice, because conventional
electrowinning cells do not produce high quality copper when the copper concentration in
the electrolyte is low, so that the bleed is not processed to remove copper and is instead
recirculated to another part of the plant.
This paper describes a way to avoid recirculating the bleed by using EMEW
electrowinning cells to remove the copper from the bleed. Earlier work by Escobar et al. [2]
has shown that EMEW technology allows for the production of high purity copper from
dilute copper solutions, maintaining Grade A quality copper down to copper concentrations
of around 3 grams per liter. EMEW technology has important process advantages compared
to traditional electrowinning technology, because it is not necessary to heat the copper
electrolyte, or to add any chemical additives to the electrolyte. Additionally, there are
Environmental advantages because the cells are closed and acid mist is not emitted to the
atmosphere inside the electrowinning facility, thus avoiding the use of specialized clothing,
respirators, and acid mist handling equipment.
In order to evaluate the feasibility of the concept of eliminating the recirculation of
the EW bleed streams, the following results from pilot programs using EMEW technology
carried out at Codelco Norte (Radomiro Tomic), Enami Salado, and Cia. Minera Doa Ins
de Collahuasi results are presented.
EXPERIMENTAL
Pilot tests were carried out with an EMEW plant containing six full-scale EMEW
plating cells and four full-scale EMEW powder cells. The cylindrical plating cells are 150
mm in diameter and 1500 mm in length. The internal DSA cylindrical anodes for plating
cells are 50 mm in diameter. EMEW powder cells have a smaller electrode gap than plating
cells to compensate for the lower conductivity of the electrolytes used with powder cells,
which typically are run at a maximum copper concentration of 2500 ppm and a minimum
copper concentration of 100 ppm. Powder cells are similar to plating cells, except that
cathode diameters are 200 mm and DSA anode diameters are 180 mm. Current densities
ranging from 200 to 1000 ampere per square meter were used. Copper concentrations varied
between 45 and 2 grams per liter for runs using plating cells, and between 3000 and 100 ppm
for runs using powder cells. Harvested copper cathode weights were between 12 and 30
kilos, which were analyzed to determine their level of impurities.

DISCUSSION

Codelco Norte Tests


Pilot tests were carried out at Codelco Norte using an EW bleed electrolyte with the
following typical initial composition:
Table 5 Codelco Norte Electrolyte Composition
H2SO4
Cu
HNO3
Cl
Co
Al
Fe
Fe ++
Mn

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

Table 6 Experimental Results for Codelco Norte Bleed


Time Cu ini Cu end Volts Dens Flow Kg Effic g/T g/T
Hrs
g/l
g/l
A/m2 l/min cathode %
S
C

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

Table 8 Cathode quality from Enami Salado Bleed


Run Current
Flow
Concentration
S O2
Current
Density
Cu g/L Cu g/L
Efficiency
(amp/m2 ) (m3/h) Initial
Final
g/T g/T
%
1
450
9
32.95
18.2
8 120
94
2
350
9
18.2
6.95
4 170
94
3
580
9
35.3
14.78
5 30
92
4
300
9
14.78
3.02
5 150
93
5
700
9
34.18
22.03
1 20
97
8
600
9
39.1
22.3
2 15
94
10
350
9
22.3
3.71
2 40
91
11
800
10
42.78
28.13
2 20
95
Cia. Minera Doa Ins de Collahuasi Tests:
Three different substrates were used for EMEW trials at Collahuasi. The first was
Electrowinning bleed, similar to that presented above for Codelco Norte and Enami Salado,
the second was raffinate, and the third was an effluent from the SX/EW plant, combining
cell cleaning effluent, spills, etc.
Electrowinning Bleed
For the tests carried out at the Oxides plant at Compaa Minera Doa Ins de
Collahuasi, the bleed electrolyte used with the EMEW pilot plant had the composition
shown in Table 8:
Table 8 Collahuasi Electrolyte Composition
Parameter Concentration
Cu
36 gpl
H2SO4
200 gpl
Fe
1.3 gpl
Mn
30 ppm
Al
150 ppm
Cl
20 ppm
Co
140 ppm

The results obtained for the bleed stream are shown below in Tables 9 and 10:

Table 9 Experimental Results for Collahuasi Bleed


Run
1
Current Density, Amp/m2
400
Flow, m3/h
9
Initial Copper, gpl
33.1
Final Copper, gpl
13.1
Voltage ,V
2.6
Initial Acid, gpl
199
Final Acid, gpl
241
Run Time, h
121
Cathode Mass, Kg
28
Current Efficiency, %
96
Conversion Energy, Kwh/Kg Cu
2.2

2
300
9
13.1
3.6
2.4
241
255
143
24
93
2.1

Table10 Experimental Results (Analytical) for Collahuasi Bleed


Element
Ag As
Bi
Cd Co Cr
Fe Mn Ni
P
ppm ppm Ppm ppm ppm ppm ppm ppm Ppm ppm
Concentration < 0.2 < 0.1 < 0.1 < 0.2 < 0.8 < 1 < 0.8 < 0.5 < 0.8 < 1
Element
Sb
Se
Si
Te Zn Sn
O
Cl
C
S
ppm Ppm Ppm ppm ppm ppm ppm ppm Ppm ppm
Concentration < 0.2 < 0.1 < 5 < 0.1 < 2 < 0.2 85 < 5 20
5
The results for Codelco Norte, Collahuasi and Salado show that it is possible to
electrowin the copper concentration to values below 4 grams per liter and obtain high quality
copper at good efficiencies. For the Collahuasi case, if one considers that the Raffinate
flowrate in the plant is on the order of 1000 m3/h and that the feed to an EMEW plant to
remove copper from the bleed would be approximately 6 m3/h at 36 grams per liter of
Copper, then the production of copper cathodes from the EMEW circuit would be on the
order of 150 Kg/h. Therefore, the reduction of the copper concentration in the Raffinate
would be approximately 0.2 gpl. This means that if the current concentration of copper in the
Raffinate were 500 ppm, the copper concentration in the Raffinate would drop to 300 ppm if
the EW bleed were treated using EMEW cells. This has important effects on the overall
copper recovery, because a lower Raffinate copper concentration improves leaching
conditions and allows for a greater global recovery of copper from the leach pads, as shown
by Dixon et al. [3], Dixon et al. [4], Aguad et al. [5], Garca et al. [6] and Garca et. al. [7].

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:

Table 13. Change in the Distribution of Fe (II) / Fe (III) in the Raffinate


t Fe t Fe II Fe III
(h) (gpl) (gpl) (gpl)
0 18
16
2
31 17
13
4
44 16
13
4
55 18
13
5
The results in Table 13 show that the concentration of Ferric ion increases and that
the concentration of Ferrous ion decreases with consecutive runs. In a similar fashion than
what happens with the copper concentration in the Raffinate as discussed above, the initial
change in Ferric concentration is greater than the change at the end of the sequence of runs.
These results show that EMEW cells could be used to produce ferric ion to improve leaching
conditions at plants that need greater concentrations of Ferric ion to leach copper or other
metals. A calculation using data obtained from the run indicates that the energy needed to
produce one kg of Ferric ion starting from a Ferrous solution is on the order of 1.8 Kw Hr.,
which would allow for an economical production of Ferric ion. The results with Raffinate
indicate that it may be possible to simultaneously deplete copper and oxidize ferrous to ferric
in Raffinate streams via direct electrowinning of the Raffinate, thus providing a large
increase in Raffinate leaching power by having a low copper, high ferric Raffinate returning
to the heap leaching operation.
Effluent Results
Two runs were performed on a mixture of effluents from the Collahuasi plant. The
solution contained effluents from EW cell cleaning, electrolyte spills, and other streams from
the SX plant. This solution was analyzed for copper and acid only.
Table 14. Collahuasi Effluent
Parameter
Concentration
Cu
21.7 gpl
H2SO4
110 gpl
Tables 15 and 16 show the operational parameters and the analysis of impurities in
the harvested cathodes for EMEW plating runs on Collahuasi Effluent:
Table 15. Parameters for Copper recovery from Effluent with EMEW plating cells
Run
3
4
Current Density, Ampere /m2
400
300
Flow Rate, m3/h
9
9
Initial Cu Concentration, gpl
21.7
13.6

Final Cu Concentration final, gpl


Initial Voltage, V
Initial Acid, gpl
Final Acid, gpl
Run Time, h
Cathode Weight, Kg.
Current Efficiency, %
Energy Use, KWh/Kg Cu

13.6
2.7
110
117
103
23
94%
2.4

4
2.4
117
135
119
19
90%
2.3

Table 16. Analysis of impurities in Copper harvested from Collahuasi Effluent


Element
Ag
As
Bi
Cd
Co
Cr
Fe
Mn
Ni
P
ppm ppm ppm ppm ppm Ppm ppm ppm ppm ppm
Results
< 0.2 < 0.1 < 0.1 < 0.2 < 0.8 < 1 < 0.8 < 0.5 < 0.8 < 1
Element
Sb
Se
Si
Te
Zn
Sn
O
Cl
C
S
ppm ppm ppm ppm ppm Ppm ppm ppm ppm ppm
Results
< 0.2 < 0.1 < 5 < 0.1 < 2 < 0.2 N/A < 5
20
5
These results show that EMEW plating cells can be used to produce high-grade
copper from electrolytes that are contaminated as compared to the cleaner electrolytes
normally used in copper electrowinning.

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.

It is suggested that by using this method, operational conditions of existing Solvent


Extraction / Electrowinning circuits can be improved. This is because it is likely that
by truly purging the Electrowinning bleed stream, with no indirect returns, the
system impurity level is lowered, which would allow the existing EW stage to
operate at a higher current and increase the production of copper while maintaining
quality.

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.

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