Mincrak Engineering. Vol. 8, No. 8, pp.

923-931, 1995
Elsevier Science Ltd
Perpmcan Printedin Great Britain
08924875(%)00054-2 0892-6875/QS $9.5OtO.oO

TECHNICAL NOTE
EFFECT OF OXYGEN AND LEAD NITRATE ON THE CYANIDATION
OF A SULPHIDE BEARING GOLD ORE

G. DESCI-&NES and G. WALLINGFORD

Resource Utilization Laboratory, CANMET, Mineral Sciences Laboratories

555 Booth St., Ottawa KIA OGl, Canada
(Received 3 August 1994; accepted 5 April 199.5)

ABSTRACT

Various leaching parameters such as particle size, cyanide concentration, pH and the application of oxygen
and lead nitrate have been investigated for the recovery of gold from an ore containing pyrite and small
amounts of pyrrhotite and chulcopyrite.

The application of lead nitrate in combination with oxygen generated the best results. Gold extraction of
96% can be obtained with cyanide consumption of 0.51 kg/t and lime consumption of 0.60 kg/.. in 24 hours.
A four hour pre-leuch followed by cyanidation is required (free cyanide concentration 480 ppm, pH 10.5,
lead nitrate 200 g/t and 16 ppm 0,). Compared to the plant performance that uses direrent leaching
conditions, these results show three fold reduction in cyanide consumption and a 20% enhancement of gold
leaching kinetics.

Keywords
Gold, cyanide, oxy,gen, lead nitrate, extraction, leaching.

INTRODUCTION

Cyanidation is the most common process for the recovery of gold from ores. An assessment of the
parameters involved in the leaching mechanism has been done by Habashi [ 11.Haque [2] published a review
oriented specifically on the effect of oxygen. Weichselbaum et al. [3] worked on the kinetics of cyanidation
of Witwaterstand ores and found that oxygen and lead nitrate are beneficial for the treatment of sulphide
ores. Studies by Stoychevski and Williams [4] on the effect of various oxidants on the treatment of a pyritic
gold ore showed that oxidants enhance the leaching kinetics. Lorenzen and Van Deventer [5] demonstrated
that the passivation due to film formation illustrated the detrimental effect of minerals such as pyrrhotite
and pyrite on leaching kinetics and recovery. The benefit8 related to the addition of lead nitrate and oxygen,
with a simultaneously tight control of cyanide, were demonstrated in a plant study by Dufresne, Deschenes
et al. [6].

A deposit located in Northwest Quebec, Canada, showed some refractoriness during cyanidation with slow
kinetics and high cyanide consumption. An investigation was initiated to optimize leaching conditions in
order to improve the gold extraction rate and to minimize the cyanide consumption.

Q 1995 Minister of Supply and Services, Canada

923
924 Technical Note

EXPERIMENTATION

OlK?

The mineralogical analysis of the ore is illustrated in Table 1. The sample grinded at 80% -74 pm was
examined with an optic microscope and an electron microscope. Most of the gold is free (-90%) as native
gold; the rest is associated or included in pyrite according to Wilhelmy [7]. Fire assay indicates that the
sulphide bearing gold ore contains 6.75 g/t Au (variance 0.10). Quartz, muscovite, chlinochlore and pyrite
are the major phases. Cyanocides are pyrite, pyrrhotite and chalcopyrite.

TABLE 1 Chemical and mineralogical analyses of the sulphide bearing gold ore

Chemical analysis (%) Mineralogical analysis

Au 6.75 ppm Major: Quartz (43.0%),

Ag 10.75 ppm muscovite (19.8%),
Si 29.0 clinochlore (ferroan) (15.6%),
Fe 9.0 pyrite (12.3%);
S 6.9
Al 4.66 Minor: dolomite (4.7%),
Ca 2.89 calcite (3.0%),
Mg 1.62 pyrrhotite ( 1.4%);
cu 0.14
Zn 0.13 Traces: chalcopyrite and sphalerite.
Pb co.01
C <0.03
Cd <O.OOl
Sb <O.Ol
As ~0.006

Equipment and Experimental Procedure

A wet screen analysis of the plant sample indicated that the granulometry was 70% -74 pm. The sample
was thoroughly mixed and riffled into three lots. Two lots were grinded to 80% and 90% -74 pm. These
lots were also thoroughly mixed. The three lots were riflled into 500 g lots for testing.

Sodium cyanide, lime and lead nitrate were all reagent grade and distilled water was used. The gold
leaching was conducted in a one litre capacity glass reactor at room temperature, agitated by a variable-
speed stainless steel impeller. A Chemcadet instrument (Cole Palmer) was utilized for the measurement of
pH which was controlled by manual addition of solid lime during the experiment. In some experiments,
aeration (pre-leach) was performed for four hours at pH 10.5, with no air injection, 50% pulp and liquid
samples were taken at intervals of 30 minutes, one hour, two hours and four hours to evaluate soluble
sulphides and sulphate. Water was added at the end to compensate losses from sampling and then the
cyanidation was performed directly on the pulp without filtering.

The leach tests were conducted on pulps containing 50% solids over a period of 48 hours. The ore was
introduced into the reactor and stirred for a few minutes to stabilize the pH at the desired level and followed
by sodium cyanide addition in portions. The rest of cyanide was added gradually during the test in order
to maintain constant free cyanide level (*lo%). Lead nitrate was added a few minutes after the beginning
of the test. The stirring speed was kept constant at 400 rpm. A 25 ml pulp sample was removed at 2.0, 7.0,
24.0 h, and at the end of the test. The solids portion was returned to the reactor after filtering. The average
level of dissolved oxygen (DO) was 7.5 ppm. A higher oxygen level was established by sparging a mixture
of oxygen and air gas for control purposes. The dissolved oxygen was regulated by using a mass flow
 Technical Note 925

controller and an ‘oxygen electrode. At the end of the test, the filter cake was washed with 500 ml of
distilled water and analyzed for gold by fire assay. The solid samples were prepared for analysis by the
“cone and pie” method. The pregnant and wash solutions were analyzed for free cyanide by silver nitrate
titration, and quantitatively analyzed for gold and, where necessary, for base metals Fe, Cu by atomic
absorption spectroscopy.

The testwork program was initiated with leaching conditions close to plant conditions. The leaching practice
in the plant was: grinding 80% -74 um, 6 h aeration, 30 h leaching at pH 12.0, 1.5 kg/t NaCN and 450 g/t
lead nitrate; leached residue: 0.28 g/t Au.

RESULTS AND DISCUSSION

Effect of Size Distribution

Three size fractions were studied: 70, 80 and 90% of -74 pm. Leaching kinetics are illustrated in Figure
1. The best result was obtained at 80% -74 pm with a gold extraction of 96.1% and a cyanide consumption
of 1.04 kg/t with Z!4h treatment. Leaching kinetics are slower with 70% -74 l.un fraction and are related
to the coarser size of gold particles (87.7% Au recovery). Finer grinding (90%
-74 pm) did not generate a better gold extraction and was detrimental because of high cyanide consumption
(1.18 kg/t) (Table 2). The increase of the cyanide consumption is related to the higher surface area of
cyanide-consuming minerals. The presence of foreign ions such as ferrous ions and cupric ions and soluble
sulphides are known to generate a retarding effect on the leaching rate [ 11. Copper and iron have respective
concentrations of :80-120 ppm and 15-28 ppm which account for about 0.2 kg/t NaCN consumed. We
observed that it is possible to counteract the poisonous effect of sulphide by adding lead in solution. The
finer grinding does not increase the gold recovery probably because the residual gold is present as very fine
occlusions or as solid solution in mineral matrix.

24

Time (h)
Fig.1 IEffect of particle size on leaching of gold from a sulphide bearing gold ore;
CN- 480 ppm; pH 11.5.
926 Technical Note

TABLE 2 Cyanidation of a sulphide bearing gold ore; pH 11.5,480 ppm CN-

NaCN
particle size time Au recovery
consumption
(% 74 Pm) (h) (%)
(kg/t)

70 48 87.7 0.63

80 24 96.1 1.04

90 24 95.6 1.18

Effect of Pre-leach/Oxidation

The pre-leach was performed during 4 hours at pH 10.5 on a 50% pulp. This was long enough to oxidize
98% of soluble sulphides according to the analysis of soluble sulphide. No air was injected during the
experiment because the air infiltration was efficient enough. Cyanidation was conducted directly on the pre-
leached pulp. Figure 2 shows the effect of using a pre-leach ahead of cyan&&ion and addition of oxygen
and lead nitrate during gold leaching. The pre-leach dissolves and oxidizes soluble sulphides from pyrite,
pyrrhotite and chalcopyrite dissolution to sulphate according to:

(1)

_____---------___ -_
90 .
1 . ??
??

?? ’
. ??
. ??
. ??

. ??

. .*’
. 8’ ’
. ??

. ??

m Leach

?? Pre-leach

+ Leach + O2 + Pb(NO,)*

24
Time (h)
Fig.2 Effect of pre-leaching and oxidants on leaching of gold from a sulphide bearing gold ore;
CN- 480 ppm; pH 11.5; 80% -74 urn

As it is evident in Figure 2, the pre-leach tended to slow down gold dissolution and lowered the gold
recovery from 96.1 to 88.8%, probably because of an insufficient amount of oxidizing agents during the
cyanidation but there is no data to support this hypothesis. The additions of oxygen (16 ppm) and lead
nitrate (200 g/t) also decrease gold recovery to 91.6%. This combination however reduced the cyanide
 Technical Note 921

consumption considerably by almost 50% (horn 1.04 to 0.52 kg/t). The injection of oxygen maintained a
higher DO (dissolved oxygen level) to generate better leaching kinetics. The important role of oxygen, in
efficient dissolution of gold, is evident in Elsner’s reaction [2].

4Au+8CN-+02+2H20 + ~Au(CN)~-+~OH- (2)

Oxygen also oxidizes soluble sulphides according to equation 1. Lead nitrate is known to increase the rate
of dissolution of gold at low concentrations but retards the leaching rate at higher concentrations [8]. Thus
the combination of lead nitrate and oxygen are useful in reducing cyanide consumption but the reduction
of gold recovery is attributed to the fact that the gold leaching rate is function of the ratio of cyanide and
lead nitrate and the pH and the actual ratio is not optimized. The amount of lead nitrate required for an
effective leaching depends on the nature of the ore. Consequently, the leaching conditions are specific to
each ore. The requirements of reagents (lime and cyanide) are related to the behaviour of minerals that
compose the ore.

The rate of gold dissolution is related to the cyanide concentration and the dissolved oxygen level in the
pulp. At low cyanide concentration, the rate depends on the cyanide concentration according to Habashi’s
equation:

rate = 0.5 ADcN_ 6-l [CN- ] (3)

where A: gold surface, D: diffusion coefficient and 6: thickness of the boundary layer.

At high cyanide concentration, the rate of dissolution depends only on the oxygen concentration according
to:

rate = 2 AD, 6-r [02 I (4)

Figure 3 illustrates the effect of oxygen and lead nitrate separately. The addition of 100 g/t lead nitrate
yielded the best gold recovery (95.9%) and the lowest cyanide consumption (0.59 kg/t). The increase of lead
nitrate addition to 200 g/t and 400 g/t reduced gold recovery to 90.5% and 8 1.2% respectively.

m 100 ppm Pb(NOs),

+ mo Pm Pb(NOd,
?? ~0 pm Pb(NOd,

24

Time (h)
Fig.3 Effect of oxygen and lead nitrate on leaching of gold from a sulphide bearing gold ore;
CN- 730 ppm; pH 11.5; 80% -74 pm
928 Technical Note

The addition of oxygen (16 ppm) was less effective than lead nitrate at 100 g/t, because gold recovery was
94.2% with a higher cyanide consumption (0.93 kg/t). A higher level of oxygen did not appear to be of
interest and was not evaluated in this study.

Effect of pH (with oxygen and lead nitrate additions

The effect of pH was examined at 2 levels: 10.5 and 11.5 in presence of 200 g/t Pb(NO,), and 16 ppm 0,.
The pH was studied at these experimental conditions because it was found that the system requires a lower
concentration of free cyanide to reach the same gold recovery (480 ppm vs 730 ppm free cyanide). The
highest gold recovery was 96.0% at pH 10.5 with a cyanide consumption of 0.70 kg/t (Table 3). The gold
recovery was reduced to 91.2% and the cyanide consumption to 0.52 kg/t at pH 11.5. pH 10.5 demonstrated
to be more interesting in spite of the higher cyanide consumption. There is clearly a relation with the gold
leaching rate and the pH of this system.

TABLE 3 Effect of pH on cyanide leaching; 480 ppm CN-, 200 g/t Pb(NO&, 16 ppm O,, 24 h

Au NaCN
PH recovery consumption
(%) (kg/t)

10.5 96.0 0.70

11.5 91.2 0.52

Effect of Cyanide Concentration

The effect of cyanide concentration (230, 380, 480 and 760 ppm) was determined in the following
conditions: pH 10.5, 16 ppm 02, 200 g/t Pb(NO&. The results are illustrated in Figure 4. We mentioned
previously, presence of copper cyanide in the leach liqueur. This complex interferes with titration of free
cyanide using silver nitrate. However, the interference is not significant. Indeed, it represents l&3.5% error;
which is smaller than the accuracy related to cyanide control at 10%.

0 12 24 36 48

Time (h)
Fig.4 Effect of cyanide concentration on leaching of gold from a sulphide bearing gold ore;
0, 16 ppm; Pb(NO,), 200 g/t; pH 10.5; 80% -74 pm
 Technical Note 929

The gold extraction rate is very sensitive to the free cyanide concentration when lower than 380 ppm. Gold
extraction was best at a free cyanide concentration of 480 ppm with a recovery of 96.0% and a cyanide
consumption of 0.70 kg/t. At a free cyanide concentration of 380 ppm, gold recovery was slightly lower
at 95.3% and the cyanide consumption was almost similar at 0.65 kg/t. At the free cyanide concentration
of 230 ppm, there was a decrease of gold recovery to 76%. At the highest cyanide concentration, 760 ppm,
cyanide consumption increased to 1.35 kg/t and generated about the same gold recovery (95.6%) as the
experiment where free cyanide was 380 ppm. Using an excess of cyanide (above the optimum level) usually
results in unnecessary cyanide consumption and has no beneficial effect on gold recovery.

In this case, a high concentration of free cyanide is required to obtain an effective leaching of gold. The
reason is attributed to be the nature of the ore that contains soluble sulphides. The dissolved sulphide ion
reacts with free cyanide to form thiocyanate according to:

S2-+CN-+ l/202+H20 + CNS-+20H- (5)

There is also formation of a passivation film which inhibits gold dissolution [5].
Usual concentrations of free cyanide are between 150 ppm to 280 ppm to process normal gold ores [9].
Optimum Conditions

Table 4 displays the best leaching results using different leaching conditions. The gold recovery is about
the same for all of these experimental conditions. The gold recovery average 96.0%, considering the
accuracy of fire assay analysis. The experimental error related to the reproducibility of the tests is evaluated
at + 0.5%. The average lime consumption is evaluated at 0.60 kg/t. There is a steady decrease of cyanide
consumption by conducting a pre-leach and by adding 0, and Pb(NO,), during cyanidation. While the
addition of 16 ppm 02 and 200 g/t

TABLE 4 Cyanidation of a sulphide bearing gold ore; 480 ppm CN-, pH 10.5,24 h

Au NaCN
WNO,), 02 Au in tail
recovery consumption
(g/t) (ppm) (g/t)
(%) (kg/t)

o* 8 0.26 96.1 1.04

100 8 0.25 96.3 0.96

100 16 0.25 96.3 0.95

200 16 0.27 96.0 0.70

200@ 16 0.28 95.8 0.51

450p 8 0.28 95.8 1.50

* : conducted at pH 11.5
@ : 4 hours pre-leach
IP : plant practice, 6 hours pre-leach, 30 hours cyanidation, pH 12.0

Pb(N03)2 creates a decrease of cyanide consumption from 1.04 kg/t to 0.70 kg/t, using a pre-leach ahead
of cyanidation generated a larger reduction of cyanide consumed at 0.51 kg/t.

There is also a sign:ificant increase in leaching kinetics as it is evident in Figure 5. Indeed, with no additive,
it takes 24 hours toI reach the equilibrium while the equilibrium is reached within almost 12 hours with a
leach using addition of 0, and Pb(NO,),. Compared to the plant results observed on actual leaching
conditions (1.50 kg/t cyanide consumption and 95.8% gold recovery in 36 hours), these results show three
fold reduction in cyanide consumption and a 20% enhancement of gold leaching kinetics.
930 Technical Note

12 18 24

Time (h)
Fig.5 Best leaching conditions from a sulphide bearing gold ore

CONCLUSIONS

The leaching of gold from a free milling ore containing sulphide minerals indicates that pre-leaching ahead
of cyanidation is beneficial in reducing the cyanide consumption. The additions of lead nitrate and oxygen
during gold dissolution are also advantageous. A high concentration of free cyanide is required for an
efficient recovery.

An improved leaching practice in the plant would be pre-leaching with air for four hours followed by
cyanidation. The gold leaching conditions are 480 ppm CN-, 200 g/t Pb(NO,),, 16 ppm O,, pH of 10.5 and
a duration of 24 hours. The gold recovery is 95.8% and the associated cyanide consumption is 0.51 kg/t.
Adding only lead nitrate (100 g/t) generated almost the same gold recovery but the cyanide and pH had to
be maintained at a higher level (730 ppm, pH 11.5) and a slightly higher cyanide consumption was noticed
(0.59 kg/t). Compared to the actual plant performance that uses different leaching conditions, these results
show three fold reduction in cyanide consumption and a 20% enhancement of leaching kinetics.

ACKNOWLEDGEMENTS

The author wishes to thank the chemical laboratory for the analyses and J.T. Szymanski for the
mineralogical analysis.

REFERENCES

1. Habashi, F., Kinetics and mechanism of gold and silver dissolution in cyanide solutions;
Bulletin 59; Bureau of Mines; (April 1967).
2. Haque, K.E., The role of oxygen in cyanide leaching of gold ore; CIM Bull., 85, 363, 31-38
(1992).
 TechnicalNote 931

3. Weichselbaum, J., Tumilty, J.A. & Schmidt, C.G., Improved gold recovery by cyanidation -
a kinetic problem; Proc. Extraction Metallurgy ‘89; IMM; London; 679-690 (10-13 July 1989).
4. Stoychevski, M. & Williams, L.R., Influence of oxygen, hydrogen peroxide and oxone on
dissolution of gold from pyrite ore; Trans. Znstn Min. Metall. C; 93-98 (1993).
5. Lorenzen, L. & Van Deventer, J.S.J., The mechanism of leaching of gold from refractory ores;
Minerals Eng.; 5; 1-12; 1377-1387 (1992).
6. Dufresne, C., Desch&nes, G., Cimon, D. & Corrigan, J., Control of cyanidation at Yvan VBzina
plant; L)iv. report MSL 94-8 (OP&J); (1994).
7. Wilhelmy, J.F., Caract&isation de l’or dans un concentrb de pyrite; Rapport du CRM; (Mars
1992).
8. Lorenzen, L. & van Deventer, J.S.J., Electrochemical interactions between gold and its
associated minerals during cyanidation; HydromefufZurgy; 30, 177-194 (1992).
9. Kondoa, P., Bourassa, M. & Deschikes, G. et al., A survey of current operating practice in gold
cyanidation; Division Report MSL 93-24 (CR}; (March 1993).