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Preg-Robbing Phenomena in The Cyanidation of Sulphide Gold Ores
Preg-Robbing Phenomena in The Cyanidation of Sulphide Gold Ores
Preg-Robbing Phenomena in The Cyanidation of Sulphide Gold Ores
6180
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Abstract
The ability of pyrite and chalcopyrite to adsorb gold was examined. Experiments were conducted in cyanide deficient
solutions with and without activated carbon. Chalcopyrite was shown to be very strongly preg-robbing. It competed with
activated carbon to remove the majority of gold from solution. Pyrite was also strongly preg-robbing, and in cyanide
deficient solutions adsorbed the majority of the gold in preference to activated carbon. The degree of adsorption onto the ore
or the activated carbon was a function of the kinetics of the adsorption process.
The role of the cyanide complexes of copper, silver, zinc, nickel and iron was also examined. It was found that these
complexes counteract preg-robbing, and serve to stabilise the aurocyanide complex by precipitating prior to gold
precipitation. When cyanide or cyanide-species were present in solution, the adsorption onto activated carbon was found in
general to take preference to the adsorption onto the minerals. The ability of a sulphide ore to adsorb AuCN.y
2 from
solution was found to be a function of how rapidly the ore consumed cyanide and precipitated metalcyanide complexes.
A mechanism was proposed where the gold is reduced at the chalcopyrite surface through the formation of an adsorbed
intermediate. The gold was reduced, along with the oxidation of chalcopyrite to form coppercyanide complexes in solution.
Reduction of gold on the pyrite was observed to occur with the release of zinc as an impurity into solution, and a mechanism
for this reaction was proposed. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Preg-robbing; Gold; Reduction; Pyrite; Chalcopyrite
1. Introduction
Preg-robbing is the phenomenon whereby the gold
cyanide complex, AuCN.y
2 , is removed from solution by the constituents of the ore. The preg-robbing
components may be the carbonaceous matter present
in the ore, such as wood chips, organic carbon, or
other impurities, such as elemental carbon. The aurocyanide complex may also be removed from solution
)
Corresponding author.
E-mail address: jsj.van deventer@chemeng.unimelb.edu.au
J.S.J. van Deventer..
0169-4332r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 1 3 1 - 6
62
63
2. Experimental methods
2.1. Ore characterisation
A flotation feed, pyrite concentrate and a chalcopyrite concentrate were used for the preg-robbing
experiments. These were obtained from the Telfer
Gold Mine, Australia, and are the feed and product
of a two-stage sequential flotation sequence. Goldfree samples of pyrite and chalcopyrite were obtained from Geological Specimen Supplies, Australia. These gold-free mineral samples were crushed
in a rolls crusher to y2 mm and milled in a ball mill
to 80% passing 75 mm. The copper concentrate and
flotation feed had a particle size distribution of 80%
64
Table 1
Quantitative XRD analysis of sulphide mineral samples mass percent.
Mineral
Copper concentrate
Chalcopyrite sample
Pyrite concentrate
Pyrite sample
Flotation feed
Albite
Arsenopyrite
Calcite
Chalcopyrite
Dolomite
Gypsum
Pyrite
Quartz
Muscovite
Sphalerite
5.6
0.8
0.0
46.7
16.5
0.0
24.3
5.9
0
0
0
0
0
65.0
0
0
31.2
0
0
3.5
6.2
0.1
0.4
0.7
3.4
0.8
79.2
9.0
0
0
0
0
0
0
0
0
100.0
0
0
0
23.5
0.1
1.1
0.7
13.8
0
5.4
48.1
6.6
0
Table 2
Elemental analysis of sulphide minerals, as determined by ore digestion
Element
Copper concentrate
Chalcopyrite sample
Pyrite concentrate
Pyrite sample
Flotation feed
Cu %.
Fe %.
S %.
Sulphide sulphur %.
C %.
Organic carbon %.
Au ppm.
Ag ppm.
Ni ppm.
Zn ppm.
24
25
29
25.1
1.5
0.18
225
72
250
440
21
34
39.2
37.6
0.05
0.03
0.2
205
47
47,000
0.9
36
40
37.5
0.6
0.01
23.5
6
600
3
0.04
49
51.5
48.2
0.04
0.03
0
7
29
420
6.6
4.8
4
3.3
1.8
0.04
6.6
2.2
64
24
65
analysed for Au, Ag, Fe, Cu, Ni, Zn, Ca, Mg and S.
Standards were created using stock cyanide solutions. Activated carbon was analysed by ashing the
carbon at 7508C for 6 h. The ash was then digested
using aqua regia and analysed by ICP in 10% HCl.
Fire assay of the ores and mineral samples was
performed by Genalysis Laboratory Services WA..
Cyanide concentration was determined by performing a silver nitrate titration, using rhodanine as
an indicator. For some of the experiments performed,
the level of copper in solution was high, so the
titration was not an accurate indicator of the actual
level of free cyanide. This was due to the dissociation of copperI. cyanide complexes during the titration. Copper cyanide complexes with three or four
ligands dissociate, and a significant amount of the
cyanide bound in these complexes is titrated, giving
higher results for free cyanide.
This problem may be overcome by the use of an
ion-chromatographic method to determine the concentration of free cyanide in solution and the concentration of metalcyanide complexes w16,17x. However, this was not used here, as it was only desired to
understand the trend of the cyanide consumption for
the different ores and not the absolute value of free
cyanide in solution. Therefore, whenever free cyanide
concentrations are reported throughout this paper, the
figure given is only indicative of the actual free
cyanide concentration, which would be lower than
reported when copper cyanide complexes were present in solution.
3. Results and discussion
3.1. Preg-robbing behaiour by ores at low cyanide
concentrations
Initially, experiments were performed with five
different ores. These five ores consisted of two oxide
ores, which contained mainly silicate and clay-type
minerals. A sulphide ore was also studied, which
was the feed to a flotation plant. Pyrite and chalcopyrite were the main sulphide minerals in this ore.
A pyrite concentrate and copper concentrate produced from this feed were also investigated.
A 1000 ppm stock solution of gold was prepared
by adding KAuCN. 2 powder to distilled water at
pH 10.5. Five milliliters of this stock solution was
66
copyrite consumed all of the gold almost immediately at zero cyanide conditions, while the pyrite
concentrate adsorbed over half the gold. The flotation feed showed a reduced adsorptive capacity. This
ore had a low pyrite and chalcopyrite concentration,
yet still showed the ability to adsorb gold.
Under zero-cyanide conditions the gold that is
adsorbed may be reduced at the surface of the minerals in an oxidationreduction reaction. Zhang et al.
w18x showed that gold will precipitate in cyanide
deficient solutions if the solution conditions are not
sufficiently oxidising. An indication of the oxidising
potential of the slurries was gained by measuring the
Eh . This was found to be similar for the oxide and
sulphide slurries, at approximately 300 mV vs.
SHE..
The preg-robbing of the sulphide ores could not
solely be the result of a deficit of free cyanide, or
preg-robbing would have been observed for the oxide ores. The AuCN.y
2 complex was found to be
stable in the oxide ore slurries. There may have been
a lack of sites on these ores to which the gold could
adsorb or reduce. The sulphide ores did possess such
reactive sites however, and preg-robbing was observed. From Fig. 1, chalcopyrite was clearly a much
stronger adsorber of gold than pyrite.
In order to investigate the competitiveness of the
adsorption onto the ore, an experiment was per-
y
Fig. 1. Kinetics of preg-robbing by different ores from a solution initially containing 5 ppm Au, as AuCN.y
2 , and no free CN .
% Au in
solution
% Au
on ore
% Au on
carbon
Flotation feed
Pyrite concentrate
Copper concentrate
0.0
2.6
1.4
4.6
12.5
74.8
95.4
84.9
23.8
67
Fig. 2. Relationship between preg-robbing, cyanide concentration and copper concentration for the pyrite concentrate in the absence of
dissolved oxygen.
68
contrast with the results found for the flotation concentrates. The pyrite is 100% pure however, and may
be more active. Hausen and Bucknam w1x demonstrated that preg-robbing to pyrite increased as the
relative amount of pyrite in the sample was increased. Here it is possible that the stronger pregrobbing of the pyrite sample compared with the
chalcopyrite sample is related to the lower cyanide
concentration in solution. Fig. 3 shows that the pyrite
sample consumes the free cyanide more quickly than
does the chalcopyrite. For the pyrite mineral sample
the cyanide is consumed rapidly through the formation of FeCN. 64y. This is a very stable complex and
does not act to stabilise the gold in solution, as it
also precipitates rapidly, as shown in Section 3.3.
Therefore, the preg-robbing of gold at this pyrite
surface is very rapid. The copper complexes formed
by the chalcopyrite sample are less stable than gold,
and slowly precipitate, with the release of cyanide,
prior to gold precipitation. Therefore, less preg-robbing is observed for this sample.
When both activated carbon and cyanide were
present with the gold-free mineral samples, Table 4
shows that preg-robbing on the mineral surface was
virtually undetectable. When there was no free
cyanide both mineral samples adsorbed a large fraction of the gold from the solution. However, the
kinetics of the preg-robbing for the pyrite sample
was much faster than for the chalcopyrite sample,
although this is not shown here. When 4 g of activated carbon was present, both mineral samples
competed strongly for the adsorption of the gold
Table 4
Preg-robbing and adsorption onto 4 g activated carbon from a 5 ppm AuCN.y
2 solution at different initial cyanide concentrations after 24 h
Mineral sample
Initial cyanide
concentration ppm.
Final cyanide
concentration ppm.
Mass activated
carbon g.
% Au in
solution
% Au on
mineral sample
% Au on
carbon
Pyrite
Pyrite
Pyrite
Pyrite
Pyrite
Pyrite
Chalcopyrite
Chalcopyrite
Chalcopyrite
Chalcopyrite
Chalcopyrite
Chalcopyrite
0
300
2000
0
300
2000
0
300
2000
0
300
2000
0
0
180
0
0
125
0
0
120
0
0
70
0
0
0
4
4
4
0
0
0
4
4
4
1.6
23.2
96.0
2.6
1.0
1.0
3.2
86.5
100
0.5
3.8
12.7
98.4
76.8
4.0
94.2
0
0
96.8
13.5
0
44.0
0
0
3.2
99
99
55.5
96.2
87.3
69
onto activated carbon. Table 4 shows that the presence of cyanide enhanced the loading of gold onto
the activated carbon rather than the mineral sample.
It is known that adsorption onto carbon occurs without chemical change w20,21x. Therefore, the adsorption of the gold without chemical change is favoured
over the reduction at the mineral surface in the
presence of cyanide due to the faster kinetics of the
adsorption onto activated carbon.
To test the reversibility of preg-robbing, activated
carbon was added to a fresh slurry made up using the
mineral samples. The samples were previously loaded
with gold from a solution containing 5 ppm Au. Any
gold that was pulled from the mineral onto the
Table 5
Transfer of gold adsorbed on pyrite and chalcopyrite samples to 4 g activated carbon after 24 h
Mineral sample
Initial cyanide
concentration ppm.
Final cyanide
concentration ppm.
Pyrite
Pyrite
Pyrite
Chalcopyrite
Chalcopyrite
Chalcopyrite
0
300
2000
0
300
2000
0
0
155
0
0
90
98.4
76.8
4.0
96.8
13.5
0
70.9
28.5
2.0
96.4
6.7
0
70
Table 6
Percentage of Au preg-robbed by ore from a 5 ppm gold solution after 24 h
Ore
No free cyanide
Copper concentrate
Chalcopyrite sample
Pyrite concentrate
Pyrite sample
0
13.5
0
76.8
97
93.6
13.2
100
99
100
55
98.4
71
Fig. 4. Preg-robbing and iron precipitation from copper concentrate. No free cyanide was present.
72
Fig. 5. a. Preg-robbing and iron precipitation from pyrite concentrate; b. preg-robbing and iron precipitation from pyrite sample. No free
cyanide was present.
gold-free pyrite sample had the same crystal structure, therefore the difference in adsorption cannot be
accounted for by differences in the pyrite crystallinity. XRD analysis of the copper concentrate and
chalcopyrite mineral sample also gave similar patterns.
It was expected that the differences in adsorption
observed could be due to the different levels of
73
74
Fig. 7. a. Cyanide consumption for pyrite concentrate and mineral sample from a 2000 ppm CNy solution; b. cyanide consumption for
copper concentrate and chalcopyrite mineral sample from a 2000 ppm CNy solution.
75
Fig. 8. The kinetics of gold and copper leaching and precipitation for the gold-free chalcopyrite sample following contact with a 50 ppm
solution of Au, Cu, Ag, Ni, Zn and Fe with 300 ppm free cyanide.
76
Fig. 9. The kinetics of iron, nickel, silver and zinc leaching and precipitation for the gold-free chalcopyrite sample following contact with a
50 ppm solution of Au, Cu, Ag, Ni, Zn and Fe with 300 ppm free cyanide.
Stability log b .
AuCN.y
2
AgCN.y
2
y
CuCN. 2
CuCN. 32y
CuCN.43y
FeCN. 64y
FeCN. 63y
NiCN.42y
ZnCN.42y
39.3
20.5
16.3
21.7
23.1
35.4
43.6
30.2
19.6
77
Fig. 10. Kinetics of gold and copper leaching and precipitation for the gold-free chalcopyrite sample. The solution initially contained 50
ppm Au in the form of AuCN.y
2 and no free cyanide.
Fig. 11. Kinetics of gold and zinc leaching and precipitation for the pyrite concentrate. The solution initially contained 5 ppm Au in the form
of AuCN.y
2 and no free cyanide.
78
z Au CN. q CN
q e z Au CN .
z Au q CN
y
2
Au CN . ads
ads
y
ads
Au CN . ads
1.
2.
z Au q 2CN
0
CuFeS 2
z Cu
2q
Fe 2q 2S 0 q 4ey
5.
Insufficient free cyanide is available for the formation of ferrocyanide complexes. The iron released by
the oxidation of chalcopyrite must therefore form
FeOH. 2 at the pH and E h used in the experiments.
The copperII. formed in Eq. 5. reacts with the
cyanide ions released by the gold reduction to form
copperI. and cyanogen according to the following
reaction w29,30x. The level of free cyanide could also
be reduced by reaction with the elemental sulphur
formed in Eq. 5..
z Cu CN.
Cu2q 3CNy
y
2 q 0.5
CN. 2
6.
3.
ions. The sulphide formed can be oxidised to sulphate, which is the thermodynamically stable species
w25x though the reaction is slow. Any iron and copper
ions released into solution are likely to precipitate as
a hydroxide under cyanide deficient conditions.
However, ion-chromatographic analysis has shown
that residual free cyanide is present after gold adsorption w13x. It was shown in Fig. 10 that 1 mol of
copper was released into solution as a cyanide species
for every 1.5 mol of gold reduced. Clearly copper
cyanide complexes are forming as the gold is reduced at the chalcopyrite surface. A mechanism is
suggested from the evidence presented in this paper,
where the gold is reduced with the corresponding
oxidation of chalcopyrite.
Following the argument Quach et al. w12x made
for the reduction of gold by pyrrhotite, the chalcopyrite can be oxidised either by the oxidation of ferrous
to ferric ions, or sulphide to sulphur ions. As the
potential of the solutions used was always below 300
mV vs. SHE., Fe 2q is the stable form of iron, so
the oxidation must occur through the formation of
sulphur. Therefore, the oxidation of chalcopyrite is
z 4Au q Fe OH. q Cu
2
4.
2q
q 2S 0 q 8CNy
7.
4. Conclusions
For preg-robbing to occur from solution to a
pyrite or chalcopyrite mineral surface, it was found
the solution must be cyanide deficient. Preg-robbing
was found to occur if all the free cyanide was
consumed. When this consumption resulted in the
formation of metalcyanide complexes, such as
. 2y
. 4y
. xy1.y, it
AgCN.y
2 , Zn CN 4 , Fe CN 6 , Cu CN x
was found that these complexes would precipitate
before the aurocyanide complex. These complexes
therefore serve to stabilise the aurocyanide in solution.
The propensity of an ore to rapidly adsorb gold is
not only a function of the organic carbon concentration, but also related to how quickly the ore consumes cyanide. This is not necessarily just a function
of mineralogy, as the pyrite concentrate and gold-free
pyrite sample had similar mineralogy, though the
gold-free pyrite had faster cyanide consumption.
79
Acknowledgements
The authors wish to gratefully acknowledge
Newcrest Mining and the Australian Research Council for funding this research. Gratitude is expressed
to the staff of the Telfer gold mine, who provided the
ores for experimentation. Much appreciation goes
towards Dr. Ratan Chowdhury for his helpful discussions.
References
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cyanidation of carbonaceous gold ores from Carlin, NV, in:
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the Second International Congress on Applied Mineralogy in
the Minerals Industry, Metallurgical Society of AIME, Los
Angeles, CA,1984, pp. 833856.
w2x S.R.L. Brooy, H.G. Linge, G.S. Walker, Review of gold
extraction from ores, Minerals Engineering 7 10. 1994.
12131241.
w3x G. Beer, Processing options for the treatment of preg-robbing
ore at the Macreas gold mine, 6th AusIMM Extractive
80
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