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Possible role of copper species

in enhanced chalcopyrite
dissolution
PhD. Cynthia Torres Godoy

TEAM

Cynthia Torres
Maria Elisa Taboada
Tefilo Graber
Osvaldo Herreros
Pa Hernandez
Helen Watling
Denis Shiers

OUTLINE

RELEVANCE OF THIS RESEARCH


OBJECTIVES
EXPERIMENTAL PROCEDURE
RESULTS AND CONCLUSIONS

RELEVANCE OF THIS RESEARCH

In recent years several processes have been proposed for leaching


of chalcopyrite concentrates in chloride media.

However, there is very little information in the public domain


about the role of copper species in enhanced chalcopyrite
dissolution.

Focused studies simulating different unit processes will become


the foundation for optimising those processes and/or describing
the possible role of copper species for the chalcopyrite
concentrate study.

KEY OBJECTIVE

The primary goal of this research is to understand the


formation of chlorocomplexes mechanisms (the
concentration of copper monochloride ion (+1) (CuCl+)
correlated directly with extraction.

EXPERIMENTAL EQUIPMENTS

Shaker

Shaker with temperature control

Leaching reactors

METHODOLOGY

In the present study, copper extraction from chalcopyrite


concentrate was investigated using:
A suite of solutions acidified with H2SO4 and encompassing
five chloride concentrations,
three cupric ion concentrations and,
two initial solution pH set points.
Soluble copper was measured during the leaching
experiments.
The extraction data were analysed in respect of the roles of
major copper species present in initial acidified leach media.

INFORMATION OF CPY CONCENTRATE


Table Mineralogical analysis of chalcopyrite concentrate [%]
Mineral phase

Content Ideal formula

Mineral phase

Content Ideal formula

Chalcopyrite

74

CuFeS2

Hematite

Fe2O3

Melanterite

FeSO4.7H2O

Bernalite

Fe(OH)3

MgFe3+2O4

Calcite

4.5

CaCO3

Magnesioferrite

Quartz

2.5

SiO2

Siderite

0.5

FeCO3

K-Jarosite

2.5

KFe3(SO4)2(OH)6

Ferrihydrite

0.5

Fe5O3(OH)9

Pentlandite

(Fe,Ni)9S8

Talc

0.5

Mg3(Si2O5)2(OH)2

Rmerite

Fe3(SO4)4.14H2O

Dwornikite

0.5

NiSO4.H2O

Pyrite

FeS2

Magnesite

0.5

MgCO3

Table Chemical analysis of chalcopyrite concentrate [%]


Cu

Fe

As

Si

24.5

25.9

28.6

0.126 5.19

Na

Al

Mg

Zn

Pb

0.036 <0.05 0.323 0.950 0.106 0.094

RESULTS AND CONCLUSIONS


Estimated Cu extraction [%]

100
Cu 0.0234 M pH 1

80

Cu 0.0234 M pH 2

60

Cu 0.0391 M pH 1

40

Cu 0.0391 M pH 2
20
0
0

50

100

150

Time [hours]

Effect of initial solution pH on copper extraction.


The media were 0.143 M chloride.

Copper extraction was faster in chloride media initially pH 1 compared with pH 2.


The results are consistent with those of Velsquez-Yvenes et al. (2010) who reported that extraction
rates are almost independent of pH in the range 0.5-2.0, but that a fairly low pH is necessary to keep
iron(III) in solution.

RESULTS AND CONCLUSIONS


Estimated Cu extraction [%]

100
Cu 0.0078 M

80
60

Cu 0.0234 M

40
Cu 0.0391 M

20
0
-20
0

50

100

150

Cu 0.0078 M
adjusted f or
adsorption

Time [hours]

Initial copper concentration effect in leach medium on


copper extraction. The media were 0.2 M chloride at pH 1.

While an initial copper concentration 0.0078 M was limiting, copper extractions were not affected
greatly at higher initial copper concentrations.
Thus the presence of cupric ions is necessary for accelerated chalcopyrite dissolution,
but above the limiting concentration, rates of dissolution are not enhanced for increased copper
concentration.

RESULTS AND CONCLUSIONS


Estimated Cu extraction [%]

100
80
60

Cl 0 M
Cl 0.143 M

40

Cl 0.200 M
Cl 0.286 M

20
0
0

50

100

150

Time [hours]

Effect of chloride concentration on copper extraction from


chalcopyrite. Initial copper concentration was 0.0391 M in media at pH
1.

The presence of chloride in the initial leach medium resulted in increased copper extraction,
compared with the chloride-free medium.
However, the rate of chalcopyrite dissolution is not greatly affected by the chloride concentration

RESULTS AND CONCLUSIONS


Reaction

G (kJ/mol)

-2.198

K1=2.426

CuCl+ + Cl CuCl2(aq)

6.653

K2=0.068

CuCl3

9.131

K3=0.025

13.142

K4=0.005

Cu2+ + Cl CuCl+
CuCl2(aq) +

Cl

CuCl3 + Cl CuCl42

Predicted copper speciation [M] as a function of chloride


concentration. Initial copper concentration was 0.0234 M in media pH
1.

A model of copper speciation in the experimental range predicted that, increased Cl concentration,
Cu+2 concentration decreased significantly while the chlorocomplex species CuCl+ concentration
increased

Table 4. Copper extraction [%] at pH 1 correlated with predicted copper speciation at different chloride
and copper concentrations.
Total Cl
[M]

Total Cu
[M]

Cu+2
[M]

CuCl+
[M]

Extraction
[%]

0
0
0
0.143
0.200
0.286
0.143
0.200
0.286
0.143
0.200
0.286

0.0078
0.0234
0.0391
0.0078
0.0078
0.0078
0.0234
0.0234
0.0234
0.0391
0.0391
0.0391

0.0078
0.0234
0.0391
0.0058
0.0053
0.0046
0.0176
0.0159
0.0139
0.0295
0.0267
0.0234

0
0
0
0.0020
0.0025
0.0032
0.0058
0.0074
0.0093
0.0095
0.0122
0.0153

16
24
30
39
55
57
60
67
67
57
58
57

SUMMARY AND CONCLUDING REMARKS


At low initial copper concentration and pH 1, copper was removed from solution in
the first 24 hours of leaching. This could be due to adsorption of cupric ions or the
formation of a disordered bornite-like phase on the chalcopyrite surface.
This phenomenon was not discerned at pH 2 or in higher-concentration copper
solutions.
An increase in the initial copper concentration resulted in increased copper
extraction from chalcopyrite. Copper extraction was faster in media initially pH 1
compared with pH 2.
Copper extraction increased with increase chloride concentration but chloride itself
was not the key component.
Using a thermodynamic model, it was predicted that CuCl+ was the dominant copper
species in the system at the concentrations studied

ACKNOWLEDGEMENTS
The authors are grateful for the financial support provided by CICITEM R04I1001,
CSIROChile International Centre of Excellence, and CONICYT through Fondecyt
Project 1140169 (Director: Maria Elisa Taboada)