You are on page 1of 17

Hydrometallurgy 50 1998.

205221

Effect of the composition of some sulphide minerals


on cyanidation and use of lead nitrate and oxygen to
alleviate their impact
a,)

Guy Deschenes , Marlaine Rousseau b, Jean Tardif c ,
P.J.H. Prudhomme a
a
Mining and Mineral Sciences Laboratories, CANMET, Natural Resources Canada, 555 Booth St., Ottawa,
Ontario, Canada, K1A 0G1
b
Chemical Engineering, Uniersity of Sherbrooke, Sherbrooke, Quebec, Canada, J4K 5G4
c
Mining and Metallurgical Engineering, Laal Uniersity, Ste-Foy, Quebec, Canada, G1K 7P4

Received 6 May 1997; revised 22 June 1998; accepted 6 August 1998

Abstract

An investigation was carried out on synthetic ores containing high purity pyrite, pyrrhotite and
chalcopyrite and on two gold ores currently processed to evaluate the impact of cyanicides on
cyanidation and to improve the leaching performance by using a pre-leaching, injecting oxygen
and adding lead nitrate. With regard to the synthetic ores, it was found that pyrrhotite did not
generate a high cyanide consumption while pyrite and chalcopyrite were detrimental. Pre-leaching
was deleterious for the ore containing chalcopyrite while pre-leaching with lead nitrate was very
efficient to decrease the reactivity of the ore containing pyrite. The two gold ores studied had very
different compositions. The low sulphide ore had a low sulphide content 1.36% S., present as
pyrrhotite while the second had a very high sulphide content 20.2% S., in the form of pyrite,
pyrrhotite and chalcopyrite. The efficiency of the process conditions was peculiar to the ores. The
high sulphide ore required a stronger, longer pre-leaching period 12 h. with greater amounts of
lime 7.0 kgrt. and lead nitrate 600 grt. than the low-sulphide ore. The ore with a low sulphide
content required a pre-leaching of only 1 h with a small quantity of PbNO 3 . 2 50 grt. and
leaching can be performed at 360 ppm NaCN to allow a recovery of 96.4% Au and a low cyanide
consumption at 0.18 kgrt. As for the high sulphide ore, cyanidation had to be conducted at 560
ppm NaCN to recover 88.4% Au with a cyanide consumption of 0.80 kgrt. An increase in the
amount of lime enhanced oxidation of soluble sulphides. Lead nitrate stabilized copper and iron

)
Corresponding author. Tel.: q1-613-992-0415; Fax: q1-613-996-9041; E-mail: gdeschen@nrcan.gc.ca

0304-386Xr98r$ - see front matter q 1998 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 9 8 . 0 0 0 5 5 - 3
206 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

dissolution by forming a passivation layer at the surface of sulphide minerals. Lead nitrate also
prevented the formation of a passive layer at the surface of gold. q 1998 Published by Elsevier
Science B.V. All rights reserved.

Keywords: Cyanidation; Gold; Lead nitrate; Oxygen; Recovery; Leaching; Pyrite; Pyrrhotite; Chalcopyrite

1. Introduction

Among reagents that improve cyanidation, oxygen and lead nitrate are known to
enhance gold recovery and lower cyanide consumption, especially in the presence of
sulphide minerals w13x. A survey of Canadian cyanidation plants indicated that the level
of lead nitrate addition varies from one location to another w4x. There is no obvious
relation between the composition of the ore and the addition rate.
It was found that lead nitrate is detrimental to the process when not added properly
w1,35x. It can inhibit the kinetics of dissolution of gold and increase the cyanide
consumption. Research on the electrochemical aspects of lead nitrate suggests that its
addition increases the dissolution kinetics of gold, even in the absence of sulphides w6,7x.
The benefits of using lead nitrate in the treatment of a gold ore containing no sulphide
were reported and studied briefly forty years ago w8x. It has also been reported that its
influence was especially noticeable at low cyanide levels and that there was no
advantage at high cyanide addition rates w9x. These conclusions are contradicted by other
publications w13,5x. The objective of the present study was to improve the understand-
ing of the effect of lead nitrate in presence of different sulphide minerals at various
addition levels. Work was carried out on synthetic ores containing high purity pyrite,
pyrrhotite and chalcopyrite and on two gold ores currently processed. The two gold
deposits selected had a low sulphide content with an average gold content and a high
sulphide with a low gold content, respectively.

2. Materials

Samples of chalcopyrite 60% grade., pyrite 97% grade. and pyrrhotite 72% grade.
minerals were used to make the synthetic ores. The mineral samples were split and
pulverized at 90% -212 mm, mixed with fine quartz, homogenized and cut in 200 g lots.
Pure gold foils 99.9% Au., 2.0 cm2 , were added to the pulp. Mineral identification and
modal analysis were carried out by means of an image analyser MP-SEM-IPS.. The
synthetic ores contained, respectively, 3.0% chalcopyrite, 9.7% pyrite and 7.2%
pyrrhotite. The mineralogical composition appears in Table 1.
The low sulphide gold ore was ground to 78% -74 mm, homogenized and divided
into 500 g batches. Fire assay indicated that the ore contained 6.56 grt gold, most of
which occurred as free gold according to the mineralogical study conducted in a
previous project w3x. As Table 1 shows, the main minerals in the ore, determined by
image analysis, were quartz SiO 2 . at 35%, muscovite-2M1 KAl 2 Si 3 Al.O10 OH, F. 2 .
at 28%, albite NaAlSi 3 O 8 . at 14%, dolomite CaMgCO 3 . 2 . at 14% and pyrrhotite
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 207

Table 1
Mineralogical analysis of the ores
Mineralogical analysis %.
Mixed pyrite Mixed pyrrhotite Mixed chalcopyrite High sulphide Low sulphide
Quartz 90 90 95 48 35
Muscovite 28
Pyrite 9.7 1.1 0.5 48
Albite 14
Dolomite 14
Clinochlore 2.6
Sphalerite 0.5 1.9
Pyrrhotite 7.2 0.4 1.3 3.7
Calcite 0.1 1.2
Chalcopyrite 0.1 3.0 0.3
Galena 0.1

Fe 7 S 8 . at 3.7%. The elements found in greatest quantity in the ore were oxygen at 46%
and silica at 26%. A low quantity of sulphur was detected 1.36%, Table 2..
The high sulphide gold ore was the flotation tailing of a copper flotation circuit. The
sample was 68% -74 mm. It was dried at room temperature, homogenized and divided
into batches of 500 g. The mineralogy of this material is given in Table 1. This ore
contained 2.88 grt gold Table 2. and a low quantity of copper 0.18%.. The gold
occurred mostly as free gold and electrum particles and in lesser amounts as grains
encapsulated in pyrite, pyrrhotite, chalcopyrite and galena w10x. The gold was also
present in solid solution in pyrite andror arsenopyrite. The major phases were siliceous
gangue at 48% and pyrite FeS 2 . at 48%. The minor phases were sphalerite Zn,Fe.S.

Table 2
Chemical analysis of the ores
Chemical analysis %.
High sulphide Low sulphide
Au grt. 2.88 6.56
Si 22.2 74.5
Fe 22.0 2.56
Ca 2.07 2.13
S 20.2 1.36
Al 5.33 0.91
Cu 0.18 - 0.05
Mg 0.66 0.86
Ti NrA 0.17
As - 0.1 - 0.1
Sb - 0.06 - 0.06
Pb 0.10 - 0.10
Te - 0.001 - 0.001
208 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

at 1.9%, pyrrhotite at 1.3% and chalcopyrite CuFeS 2 . at 0.3%. Galena PbS. and
arsenopyrite FeAsS. were present as traces.

3. Equipment and experimental procedure

The lime, sodium cyanide, lead nitrate and oxygen used in this study were all
certified reagent grade chemicals. The gold leaching cell was made of glass and had 1-l
capacity. The cover had four openings which allowed insertion of the electrodes, the
agitator and the oxygen injection tube. Mixing was provided by an agitator with 2.5 cm
teflon paddles powered by a variable-speed electric motor. The agitation speed was kept
constant at 400 rpm. The tests were performed on pulps with a solidrliquid ratio of 33%
or 50% by weight for a given treatment time. For each test, 500-g samples of ore and
500 ml of leaching solution were used for the commercial ores. For the synthetic ores,
200-g samples and 400 ml distilled water were used. The ore was introduced into the
reactor and pulped for a few minutes.
The pre-leaching pre-aeration. varied in duration, depending on the ore. Air or a
mixture of air and oxygen was injected to maintain the dissolved oxygen level constant
78 ppm.. A 10-ml sample of pulp was taken at intervals of 30 min, 1 h, 2 h, 4 h and at
the end of this treatment. Water was added to maintain a constant pulp density. Lime
was added to maintain pH. A Chemcadet pH monitor gave pH readings. Where lead
nitrate was added to the pre-leaching, it was introduced immediately after stabilization
of the pH in the first minutes of the treatment. At the end of the pre-leaching, there was
no filtration and the pulp was directly cyanided.
Cyanide was added during the test to maintain an average concentration of free
cyanide at "5%. The free cyanide was measured and adjusted at 0.5 h, 1.0 h, 2.0 h,
4.0 h, 6.0 h, 24.0 h and at the end. A 20-ml sample of pulp was taken with a pipette after
4.0 h, 6.0 h and 24.0 h and at the end for the determination of dissolved gold DO.. The
solids were returned to the reactor. The oxygen content was increased by bubbling a
mixture of oxygen and air for control purposes. The oxygen content was kept constant
by using a mass flow monitor and a dissolved oxygen electrode. At the end of the test,
the filter cake was washed with 1000 ml of distilled water. The cake was analysed for
gold by fire assay after it has been dried, homogenized and sampled. The gold extraction
calculations are based on the gold content values of the processed tailings, compared
with a single gold content value in the head sample. A material balance for gold was
performed for each experiment, comparing recoveries calculated from solids analysis
with those obtained from the assay of solutions. It indicated that the gold was uniformly
distributed in the samples, since gold recovery based on the liquids varies by 1.4% or
less from that of the solids for both ores examined. Accuracy of the fire assay on the
leach residue was "0.02 grt.
The pregnant solution and wash solutions were titrated for free cyanide with silver
nitrate using rhodamine as the indicator, and assayed for gold and base metals Fe, Cu.
by atomic absorption spectrophotometry. The values for gold content in the solutions
gave the extraction kinetics plot. The presence of copper cyanide caused interference
during titration with silver nitrate because CuCN.43y is an easily dissociable complex
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 209

and the loss of CNy from the copperrcyanide complex increases the value for free
cyanide. This also increases with the increase of copper concentration. However, we did
not quantify the error because the gold plants from which the samples came use the
same titration procedure. Analysis of sulphate, thiosulphate and trithionate was per-
formed with HPLC.

4. Results and discussion

4.1. Part 1: synthetic ores

Fig. 1 illustrates the gold dissolution rates of straight cyanidation experiments on


silica, pyrite, pyrrhotite and chalcopyrite synthetic ores. The presence of pyrite and
pyrrhotite increased the dissolution rate while chalcopyrite created a significant de-
crease. The results are different than previous work by Liu and Yen w11x who reported a
moderate decrease in the leaching rate for chalcopyrite and pyrite at 8 ppm oxygen and
0.25 grl NaCN initially added. The higher concentration of cyanide, controlled at 500
ppm NaCN, and the higher pH, 11.5 may account for this difference. The higher iron
dissolution resulting in the formation of ferricyanide explains the increase in the
leaching rate. Iron acts as oxidant for gold dissolution according to:
3y y 4y
Au q 2CNyq Fe CN . 6 Au CN . 2 q Fe CN . 6 1.
A recent investigation on the effect of ferricyanide demonstrated the positive effect of
this complex w12x. The dissolution of copper from chalcopyrite is the reason for the low

Fig. 1. Effect of sulphide minerals on gold leaching rate. Cyanidation: pH 11.5, 500 mgrl NaCN, 8 ppm O 2 .
210 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

leaching rate for the chalcopyrite mixture. Previous work on a coppergold ore indicated
that the concentration of free cyanide is the limiting factor w1x. Below a certain
concentration of free cyanide, there is a major decrease in the leaching kinetics. For the
copper gold ore that contained 1.1% chalcopyrite, this limit was 640 ppm NaCN at
15 ppm oxygen. In the actual situation, the chalcopyrite content was 3 times higher and
the experiment was conducted at 500 ppm NaCN and 8 ppm oxygen. Consequently,
there was a very low leaching rate.
An effort to enhance the gold leaching rate by adding lead nitrate addition was not
successful. Experiments with a fine gold powder mixed with the ore indicated a
relationship between the gold surface and the lead added. Below a certain value, lead
had no effect. Additional experiments are required to resolve this issue.
The effect of lead nitrate on cyanide consumption is shown in Fig. 2. For chalcopy-
rite, a pre-leaching without any lead nitrate made the chalcopyrite more reactive and
increased cyanide consumption from 1.81 kgrt to 1.92 kgrt. The addition of lead nitrate
to the pre-leaching was even more detrimental to cyanide consumption with a 28%
increase in cyanide 1.812.31 kgrt.. For pyrite, a pre-leaching without lead nitrate was
beneficial with a decrease of 83% in cyanide consumption from 1.23 kgrt to
0.21 kgrt.. The addition of lead nitrate to the pre-leaching had no significant benefit.
With pyrrhotite, a pre-leaching with or without lead nitrate had no significant effect on
cyanide consumed.
While the cyanide consumption for the sulphide-free mixture was almost nil at
0.03 kgrt, the consumption of cyanide was relatively low for the pyrrhotite mixture at

Fig. 2. Effect of the nature of the pre-leaching of sulphide minerals on cyanide consumption. Pre-leaching:
pH 11.5, 8 ppm O 2 , 2 h, 100 grt PbNO 3 . 2 when applied. Cyanidation: pH 11.5, 500 mgrl NaCN, 8 ppm O 2 ,
4 h.
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 211

Fig. 3. Effect of lead nitrate addition on leaching of a low sulphide-bearing gold ore. Pre-leaching: 1 h,
15 ppm O 2 . Cyanidation: pH 11.1, 810 mgrl NaCN, 15 ppm O 2 .

0.14 kgrt. This result is in agreement with the work of Dunn who found a low solubility
of pyrrhotite in cyanide solution w13x. The cyanide consumption by the pyrite mixture
9.7% pyrite. was 7 times higher than for the pyrrhotite 1.23 kgrt vs. 0.17 kgrt..
Chalcopyrite was the most soluble mineral with a cyanide consumption 10 times higher
than pyrrhotite 1.81 kgrt vs. 0.17 kgrt..

4.2. Part 2: low sulphide bearing gold ore

4.2.1. Pre-leaching
Fig. 3 shows the influence of pre-leaching on gold recovery with 810 ppm NaCN. A
pre-leaching improved significantly the leaching kinetics and reduced cyanide consump-
tion. In fact, recovery after 24 h was only 88.3% without pre-leaching test 1., while
pre-leaching without lead nitrate indicated 94.1% gold recovery. Addition of PbNO 3 . 2
to the pre-leaching produced better kinetics; 50200 grt lead nitrate test 3, 57.
increased gold recovery to 96.5% in 24 h.
At 0.35 kgrt NaCN, the cyanide consumption was not high for a straight cyanidation,
indicating a low solubility of pyrrhotite. Pre-leaching without lead had no significant
effect on reducing cyanide consumption which was 0.31 kgrt in a 24-h test. The
addition of lead nitrate reduced the dissolution of pyrrhotite and decreased the cyanide
consumption by 0.15 kgrt Table 3.. In the pre-leaching, pyrrhotite was oxidized and
precipitated as an insoluble product, ferric hydroxide, according to:
Fe 7 S 8 q 3.5O 2 q 7H 2 O 7Fe 2qq 8S q 14OHy 2.
2q 3q y
2Fe q 0.5O 2 q H 2 O 2Fe q 2OH 3.
Fe 3qq 3OHy Fe OH . 3 4.
212 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

Table 3
Compilation of tests for the low-sulphide bearing gold ore
Test Duration PbNO 3 . 2 wNaCNx O2 Au recovery Tailings NaCN
h. grt. ppm. ppm. %. grt Au. consumption
kgrt.
1a 48 None 810 15 95.9 0.27 0.35
2 24 None 810 15 94.1 0.37 0.31
3 24 50 810 15 96.5 0.23 0.20
4 24 50 360 7 96.4 0.24 0.18
5 48 100 810 15 97.1 0.19 0.29
6 24 100 810 15 95.6 0.29 0.21
7 24 200 810 15 96.5 0.23 0.32
8 48 None 550 15 95.3 0.31 0.26
9 48 None 550 7 95.7 0.28 0.20
10 24 200 810 7 96.2 0.25 0.22
11 24 200 550 7 96.3 0.24 0.12
12 24 200 360 7 93.9 0.40 0.08
13 24 200 230 7 93.6 0.42 0.05
a
No pre-leaching performed.

In the presence of cyanide, pyrrhotite reacts with cyanide to form thiocyanate:


Fe 7 S 8 q CNy 7FeS q CNSy 5.
and further dissolution produces FeII. cyanide:
4y
2FeS q 12CNyq 5O 2 q 2H 2 O 2Fe CN . 6 q 2SO42y q 4OHy 6.
Various aqueous sulphur species can also be formed w14x. The region of the predomi-
nance of FeCN. 64y complex is illustrated in Fig. 4 w15x. This figure indicates that
pyrrhotite is soluble in the pH range used in cyanidation. As shown by Eq. 4.,

Fig. 4. EhpH diagram for the FeSCNH 2 O system at 258C w15x.


et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 213

pyrrhotite reacts with cyanide to form thiocyanate. Consequently, the reduction of


pyrrhotite dissolution decreases the formation of thiocyanate. Indeed, the analysis of
thiocyanate contained in the leach solution indicated a 60 ppm drop in concentration
with the addition of lead nitrate. This drop is responsible for 50% of the reduction in
cyanide consumption. The formation of FeCN. 64y was rather limited and accounted
only for 3% to 10% of the cyanide consumed.
The presence of pyrrhotite warrants the use of lead nitrate. However, there is a
controversy on the solubility of pyrrhotite in cyanide solutions. Hedley and Tabachnick
w8x reported that pyrrhotite is known to be readily soluble in cyanide, retarding the
dissolution of gold. Dunn found a low solubility for pyrrhotite w13x. The slower leaching
could be attributed partly to the fact that solubilized sulphides are adsorbed on the
surface of gold and passivate the surface. Therefore, lead nitrate avoids the formation of
a passive layer. Surface analysis of the pyrrhotite with XPS indicated the presence of a
lead precipitate on the particles passivating them w16x.

4.2.2. Influence of oxygen


Let us first consider the general equation for gold leaching:
y
4Au q 8CNyq O 2 q 2H 2 O 4Au CN . 2 q 4OHy 7.
This equation shows that the addition of oxygen favours the reaction to the right and
thus the extraction of gold. Fig. 5 shows the effect of injecting oxygen to raise the DO
from 7 ppm to 15 ppm. It shows that oxygen injection did not enhance the leaching
kinetics. The final gold recovery was roughly the same 95.3% for 15 ppm oxygen and
95.7% for test at 7 ppm oxygen.. Oxygen is unnecessary and may even slow gold
dissolution by forming cyanate oxidation of free cyanide.. Indeed, cyanide consumption
was slightly higher with oxygen enrichment 0.26 kgrt vs. 0.20 kgrt.. The oxygen

Fig. 5. Effect of oxygen on gold leaching of a low sulphide-bearing gold ore. Cyanidation: pH 11.1,
550 mgrl NaCN, 48 h.
214 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

effect was the same in the presence of lead nitrate test 7 and test 10.. The gold recovery
was about the same while cyanide consumption increased by 0.10 kgrt.

4.2.3. Influence of cyanide concentration


The decrease in cyanide concentration usually causes a reduction in leaching kinetics
and cyanide consumption. Fig. 6 compares gold recovery kinetics for NaCN concentra-
tions from 230 ppm to 810 ppm. As expected, the leaching kinetics increased with the
free cyanide concentration. There was a significant decrease in gold extraction when the
sodium cyanide concentration was lower than 360 ppm. Indeed, gold extraction was
93.9% at 230 ppm NaCN test 13.. Cyanide consumption went from 0.22 kgrt at
810 ppm NaCN test 10. to 0.05 kgrt at 230 ppm NaCN test 13.. This ore had a low
cyanide consumption and required a free cyanide concentration a little higher because of
the presence of pyrrhotite. For an ore that has a low cyanicides content, the required free
cyanide concentration is usually around 60 to 150 ppm NaCN w4x.

4.3. Part 2: high sulphide-bearing gold ore

4.3.1. Effect of lime addition during pre-leaching


The high concentration of pyrite 48%., combined with the presence of pyrrhotite
1.3%. and chalcopyrite 0.3%. indicated that a more extensive pre-leaching is required
to improve the efficiency of cyanidation. In the pre-leaching, soluble sulphides were
dissolved and oxidized to thiosulphate S 2 O 32y ., sulphate SO42y ., trithionate S 3 O62y .
and tetrathionate S 4 O62y .. The effect of the lime addition on metallic sulphides
oxidation is illustrated in Fig. 7. There was a gradual increase in thiosulphate concentra-
tion, whereas the concentration of sulphate passed through a maximum and then
decreased. The shape of the plot for the sulphate concentration remains unexplained.

Fig. 6. Effect of cyanide concentration on leaching of a low sulphide-bearing gold ore. Pre-leaching: 1 h,
200 grt PbNO 3 . 2 . Cyanidation: pH 11.1, 7 ppm O 2 , 24 h.
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 215

Fig. 7. Kinetics of the oxidation of soluble sulphides to sulphate and polythionates in the pre-leaching of a
high sulphide-bearing gold ore.

Fig. 8 shows the total oxidized sulphur species concentration for a lime addition of
7.0 kgrt. The equilibrium for total sulphide oxidation was not reached within 12 h,
which is the limit of the treatment period for the plant that processed this ore. The
amount of metallic sulphides oxidized in this period was about 1% because of the mild

Fig. 8. Kinetics of the oxidation of soluble sulphides to sulphate and polythionates in the pre-leaching of a
high sulphide-bearing gold ore with 7 kgrt CaO.
216 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

oxidation conditions utilized. With this lime addition, the amount of trithionate and
tetrathionate increased significantly. However, previous work indicated that there was no
direct relation with the oxidation of sulphides and the efficiency of cyanidation w1x.
Pyrrhotite is much less stable than pyrite and most of it was probably oxidized in the
pre-leaching. As we saw for the low-bearing sulphide ore which had 3 times more
pyrrhotite, a 1-h pre-leaching with 0.5 kgrt time was long enough. For the high bearing
sulphide ore, the pre-leaching was then performed to ensure the oxidation of the reactive
pyrite and the chalcopyrite in order to have a significant effect on gold leaching. This is
why it advantageously and substantially influences the consumption of cyanide.
Fig. 9 illustrates the relationship between lime addition and the thiocyanate forma-
tion. The greater the lime addition, the greater the sulphides oxidation, and the lower the
formation of thiocyanate. Cyanidation thus becomes more efficient. However, the
incomplete oxidation of sulphide is a problem. Thiosulphate reacts with cyanide
according to w14x:
S 2 O 32y q CNy SO 32y q CNSy 8.
Copper dissolution passed through a maximum at about 7.8 kgrt CaO. Thus, the
relationship between cyanide consumption and chalcopyrite dissolution is a second
degree relationship.
The effect of lime addition on the leaching kinetics is shown in Fig. 10. The addition
of a large amount of lime 7 kgrt., with lead nitrate, during the pre-leaching proved to
be beneficial. Without any pre-leaching, gold recovery was only 79.2% Table 4, test
14.. Gold extraction passed through an optimum at 88.2% with 7.0 kgrt lime test 16..
A lime addition greater than 7.0 kgrt reduced gold recovery test 17.. On the other
hand, this increase in added lime during the pre-leaching had a positive effect on the

Fig. 9. Effect of lime addition in the pre-leaching on gold extraction and cyanide consumption of a high
sulphide-bearing gold ore. Pre-leaching: 12 h, 600 grt PbNO 3 . 2 . Cyanidation: pH 11.2, 640 mgrl NaCN,
8 ppm O 2 , 24 h.
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 217

Fig. 10. Effect of lime addition in the pre-leaching on leaching kinetic of a high sulphide-bearing gold ore.
Pre-leaching: 12 h, 600 grt PbNO.. Cyanidation pH 11.2, 640 mgrl NaCN, 8 ppm O 2 , 24 h.

consumption of cyanide Fig. 11.. Cyanide consumption was inversely proportional to


the amount of lime added. A cyanide reduction of 23% 0.3 kgrt. was observed
1.33 kgrt vs. 1.02 kgrt, tests 15 and 17..
Thiocyanate was the cause of 38% of cyanide consumption at 4.4 kgrt CaO. Its
effect dropped to 29% of the cyanide consumed with the addition of 7.0 kgrt CaO, and
to 25% when the added lime reached 9.0 kgrt. The proportion attributable to copper is
difficult to determine because of the presence of three possible complexes CuCN.y2,
CuCN. 32y and CuCN.43y ., but it is undoubtedly the main consumer of cyanide.

Table 4
Compilation of tests for the high-sulphide ore
Pre-leaching Cyanidation
Test CaO PbNO 3 . 2 wNaCNx Au recovery Tailings NaCN
kgrt. grt. ppm. %. grt Au. consumption
kgrt.
14 0 0 640 79.2 0.60 1.43
15 4.4 600 640 86.8 0.38 1.33
16 7.0 600 640 88.2 0.34 1.17
17 9.0 600 640 82.3 0.51 1.02
18 7.0 800 640 84.0 0.46 1.13
19 7.0 400 640 83.6 0.47 1.50
20 7.0 200 640 83.9 0.45 1.65
21 7.0 0 640 82.3 0.51 1.14
22 7.0 600 560 86.8 0.38 1.06
23 7.0 600 780 84.2 0.45 1.58
24 7.0 600 440 81.3 0.54 0.93
25 7.0 600 360 85.8 0.41 0.83
26 7.0 600 230 61.5 1.11 0.71
218 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

Fig. 11. Effect of lime addition on gold leaching kinetics of a high sulphide-bearing gold ore. Pre-leaching
12 h; 600 grt PbNO 3 . 2 . Cyanidation: pH 11.2, 640 mgrl NaCN, 8 ppm O 2 , 24 h.

4.3.2. Effect of lead nitrate concentration during pre-leaching


Lead nitrate has a different effect than lime addition. Fig. 12 shows that increasing
the lead nitrate concentration initially increased cyanide consumption from 0100 grt
lead nitrate. and than reduced it back to 1.13 kgrt at 800 grt lead nitrate. Cyanide
consumption caused by the formation of thiocyanates was thus about 30% and copper

Fig. 12. Effect of lead nitrate on gold extraction and cyanide consumption of a high sulphide-bearing gold ore.
Pre-leaching: 12 h, 7.0 kgrt CaO, 8 ppm O 2 . Cyanidation: pH 11.2, 640 mgrl NaCN, 8 ppm O 2 , 24 h.
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 219

was the main cyanide consumer. Since copper dissolution increased slightly with lead
nitrate 50 ppm., it means that lead nitrate attenuated cyanide consumption, but its
action was only related to iron sulphides passivation. It was found in Part 1 of this report
that lead nitrate was ineffective in decreasing copper dissolution and had no significant
effect on iron sulphide minerals. Fig. 12 shows that lead nitrate works on pyrite by
decreasing cyanide consumption. The difference in the nature of the results may be
related to the amount of pyrite, the length of the pre-leaching, and the amount of lead
nitrate added.
The gold content in the leach residue was higher by about 0.15 grt in absence of lead
nitrate. This value does not seem to be very high. However, it represents a substantial
amount of money on an annual basis. As an example, a plant processing 300 000 tryear
would have an additional revenue of CAN$675 000 by getting an extra recovery of
0.15 grt Au.

4.3.3. Effect of cyanide concentration


The effect of free cyanide concentration was studied from 230 ppm to 780 ppm
NaCN. Fig. 13 illustrates that there was a significant decrease in gold extraction when
the NaCN concentration was below 360 ppm. In fact, at 560 ppm NaCN, gold extraction
was 86.8% test 22. and decreased to 85.8% at 360 ppm NaCN test 25.. The extraction
was as low as 61.5% at 230 ppm NaCN test 26.. Because of the interference created by
copper cyanide during the nitration with silver nitrate, the real concentration of free
cyanide was lower than 230 ppm NaCN. This explains the significant decrease in gold
extraction at this concentration. Cyanide consumption gradually decreased with the
reduction of free cyanide concentration. The system considered to be optimum used 560
ppm NaCN and reached equilibrium in 18 h for a cyanide consumption of 0.80 kgrt.

Fig. 13. Effect of cyanide concentration on leaching of a high sulphide-bearing gold ore. Pre-leaching: 12 h,
7.0 kgrt CaO, 600 grt PbNO 3 . 2 , 8 ppm O 2 . Cyanidation: pH 11.2, 8 ppm O 2 , 24 h.
220 et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes

It is not unusual to notice no effect for free cyanide above a certain concentration.
Indeed, this was reported previously w1,2x. For a sulphide bearing gold ore w2x, there is a
range of concentration where there is almost no change in the leaching kinetics but
where increasing cyanide concentration only leads to increased reagent consumption.

5. Conclusions

Cyanidation of sulphide-bearing ores has to be adjusted as a function of the


mineralogical composition. A pre-leaching successfully hinders the effect of pyrite and
pyrrhotite on cyanide consumption and leaching kinetics. The pre-leaching has no
beneficial effect on chalcopyrite as far as cyanide consumption goes. Additional work
has to be conducted on sulphide minerals to characterize the processing parameters
required to alleviate their negative effect and to comprehend the mechanisms involved.
A gold ore containing a small amount of pyrrhotite 4%. can be easily processed with
a short pre-leaching period and with a small addition of lead nitrate. An ore containing a
large quantity of pyrite 48%. and a small quantity of chalcopyrite 0.3%. is more
difficult to treat. It requires a long pre-leaching 12 h. with a large quantity of lime
7 kgrt. and lead nitrate 600 grt.. The cyanidation has to be performed at a high
concentration of cyanide 560 ppm NaCN. to get an acceptable gold recovery. Lead
nitrate is beneficial in both cases to improve leaching kinetics and keep cyanide
consumption low. Oxygen injection is not required for pyrrhotite at low level. The
action of lead nitrate seems to be 2-fold: 1. prevent passivation of the gold surface and
2. stabilize metallic sulphide dissolution by passivation of the surface of the particles.

Acknowledgements

The authors wish to thank the Analytical Services Group of Mining and Mineral
Sciences Laboratories, especially Jean Cloutier for the fire assay, Gilles Laflamme, Dr.
Rolando Lastra and Dr. John Wilson for the mineralogical analysis, Mike Fulton for his
assistance to finalize the work and to Dr. Henry Steger for his editorial comments.

References

w1x G. Deschenes,
P.J.H. Prudhomme, Cyanidation of a coppergold ore, Int. Journal Min. Proc. 50 1997.
127141.
w2x G. Deschenes,
G. Wallingford, Effect of oxygen and lead nitrate on the cyanidation of a sulphide-bearing
gold ore, Minerals Engineering 8 8. 1995. 923931.
w3x C. Dufresne, G. Deschenes,
D. Cimon, J. Corrigan, Control of cyanidation at the Yvan Vezina plant,
Minerals Engineering 7 11. 1994. 14271434.
w4x G. Deschenes,
A. Putz Eds.., The second survey of gold cyanidation plants, MSL Report 95-14 CR.,
April 1995.
w5x G. Deschenes,
M. Fulton, Improving cyanidation of a sulphide ore by using an efficient pre-leaching,
Proceedings of the Int. Symp. on the Recovery of Gold, Montreal, 47 May 1998.
et al.r Hydrometallurgy 50 (1998) 205221
G. Deschenes 221

w6x M. Jeffrey, I.M. Ritchie, S.R. La Brooy, The effect of lead on the electrochemistry of gold: myth or
magic, Electrochemical Soc. Meeting, LA, USA, 510 May 1996.
w7x S. Jin, E. Ghali, G. Deschenes,
Electrochemical study of the mechanism of the accelerating effect of lead
nitrate on gold dissolution, Proceedings of the Int. Symp. In the Recovery of Gold, CIM, Montreal, 47
May 1998.
w8x N. Hedley, H. Tabachnick, Chemistry of Cyanidation, Mineral Dressing Notes 23, American Cyanamid,
1958.
w9x J. Weicheselbaum, J.A. Tumilty, C.G. Schmidt, Improved gold recovery by cyanidationa kinetics
problem, Proc. Extraction Metallurgy 89, IMM, London, 1013 July 1989, pp. 679690.
w10x J.H.G. Laflamme, W. Petruk, R. Lastra, Mineralogical study of cyanidation tails for Agnico-Eagle
Limited, MMSL report 95-28 CR..
w11x G.Q. Liu, W.T. Yen, Effect of sulphide minerals and dissolved oxygen on the gold and silver dissolution
in cyanide solution, Minerals Engineering 8 12. 1995. 111123.
w12x M. Aghamirian, PhD Thesis, Mining Engineering, Queens University, Kingston, Ontario, 1997.
w13x J.G. Dunn, The dissolution of pyrrhotite in cyanide solution, Proc. Randol Gold ForumPerth95, Perth,
Australia, 1417 March 1995, pp. 145148.
w14x J. Marsden, I. House Eds.., The Chemistry of Gold Cyanidation, Ellis Horwood, 1992.
w15x K. Osseo-Asare, T. Xue, S.T. Ciminelli, Solution chemistry of cyanide leaching systems, in: V. Kudryk,
D.A. Corrigan, W. Liang Eds.., Precious Metals: Min. Extr. and Proc., Metall. Soc. AIME, 1984, pp.
173197.
w16x R. Lastra, J. Brown, G. Deschenes,
Fundamental mechanisms of the effect of lead nitrate on the surface
of gold and metallic sulphides, Internal report, June 1998.