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CANMET Mining and Mineral Sciences Laboratories

Laboratoires des mines et des sciences minérales de CANMET
DIVISION REPORT / RAPPORT DIVISION

USE OF LEAD NITRATE AND OXYGEN TO IMPROVE

GOLD RECOVERY OF A COPPER SULPHIDE ORE

G. Deschênes and P.J.H. Prud’homme

MPSL

April 1997

For presentation at the Randol Gold Forum ’97, Monterey, California, May 18-21, 1997
and for publication in the proceedings of the conference.

Project: MMSL No. 1184

Processing and Effluent Treatment of Gold Ores

DIVISION REPORT MMSL 97-011 (OP&J) DRAFT

Crown Copyrights Reserved

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USE OF LEAD NITRATE AND OXYGEN TO IMPROVE

GOLD RECOVERY OF A COPPER SULPHIDE ORE

by

G. Deschênes 1 and P.J.H. Prud'homme 2

ABSTRACT

A laboratory study was carried out to evaluate the effect of oxygen and lead nitrate on the recovery of
gold by cyanidation of a free milling go ld ore , which contains 0.4 % copper as chalcopyrite. Efficient gold
extraction is achieved only under specific conditions. The recovery of gold was increased from less than 90% to up
to 98% by addition of lead nitrate. In the pre-leaching, the kinetics of oxidation of soluble sulphides are not an
accurate indication for the length of the treatment. Even though the consumption of cyanide was reduced due to the
inhibition of the dissolution of chalcopyrite by increasing additions of lead nitrate, cyanide consumption had to the
held above 1.85 kg/t to maintain good recovery of gold. The continued addition of lead nitrate above 300 g/t had no
impact on the recovery of gold. It was also found that the addition of lead nitrate at the start of cyanidation gave the
same performance as when added during pre-leaching. The addition of oxygen increased the recovery of gold by
1.5%. The concentration of NaCN had to be maintained in the range of 700 mg/L because of the high concentration
of copper in solution. The recovery of gold dropped significantly when the average NaCN concentration fell below
640 mg/L. App lication of the findings of the laboratory study at the industrial scale led to improved plant
performance.

Keyw ords: Gold, cyanide, extraction, leaching, lead nitrate, oxygen, chalcopyrite.

1
Hyd rometallurgist, T o who m the correspondence should be ad dressed. 2 Technician, Mining and Mineral Sciences
Laborato ries, CA NM ET , Natural Resourc es Canada, 555 B ooth Street, O ttawa, O ntario, C anad a, K1 A 0G 1.
Tel: (613) 992-0415 Fax: (613) 996-9041; E-mail: gdeschen@nrcan.gc.ca
1. INTRODUCTION
The Yvan Vézina plant is a custom milling operation owned by Cambior. The mill processes two
very different types of ores which m ake cyanidation control mor e complex than a typical milling operation. One
ore contains no copper and 3.7% pyrrhotite while the second feed contains 0.4% Cu as chalcopyrite and 2.7%
pyrrhotite. Cyanidation tests showed that each ore differs in its response during gold leaching; the feed containing
copper being more difficult to process. The presence of copper increases the cyanide consumption by fifteen times
and also increases the lead nitrate req uirement and the oxygen requirement.

Despite the selectivity of cyanide for go ld, coppe r minerals rep resent a real problem because of their
solubility in cyanide solution s, and their abunda nce relative to gold. T he ad dition o f oxygen and lead nitrate is
known to enhance the kinetics of gold dissolution and/or cyanide consumption during processing ores containing
sulphide minerals (Deschênes and Wallingford, 1995 and Dufresne, Deschênes et al., 1995). It has also been
demonstrated that the addition of other oxidizing agents increases the kinetics of gold dissolution (Stoychevski and
Williams, 1993). The addition of lead nitrate and oxygen is a common practice during the cyanidation of sulphide
bearing gold ore s (De schênes and Putz, 199 5). An exhau stive bib liograp hical review ind icated that lead nitrate acts
as a catalyst at the surface of the gold, preventing passivation (Morrison, 1994). It also inhibits the dissolution of
metallic sulphides, thereby reducing cyanide consumption. From the lack of specific information in the literature
and diversity of practices in gold plants, it also became apparent that a systematic assessment of the addition of lead
nitrate and oxygen is required.

The goal of the current work is to characterize cyanidation conditions for this copper sulphide ore and
to quantify the influence o f lead nitra te and oxygen on the leaching kinetics and reagents consump tion to o btain
efficient extraction of gold and acceptable consump tion of cyanide, and to compare with the actual leaching
conditions used in the plant.

2. EXPERIMENTATION
2.1 Material
A sample was crushed, pulverized, grounded to 89% -74 :m and homo genized. Lots of 500 g were
used for leaching. The mineralogical analysis by X-ray diffraction (Table 1) indicated the presence of quartz,
chlorite and albite as major phases and pyrrhotite, chalcopyrite, ilmenite and magnetite as minor phases. The content
of chalcopyrite and pyrrhotite was respectively 1.2% and 2.7%. Most of the gold is free and is in the form of
electrum or pure gold. Som e of the gold o ccurs as small grains encapsulaled in pyrrhotite or in silicates.
Cyanidation of a sample ground to 100% -37 :m yielded a gold recovery of 99.0% (dup licated test). Water from the
plant was used in the cyanidation tests. The chemical analysis of the water indicates a small amount of free cyanide
(15 mg/L) and some co pper (39 mg/L). It also has a relatively high thiocyanate content (347 mg/L).

2.2Equipment and experimental procedure

The tests were performed on pulps at 50% weight. Agitation speed was kept constant at 400 rpm. To
quantify the kinetics of oxidation of metallic sulphides to sulphates and thiosulp hates, a p re-leaching test was do ne.
Lime was added to maintain pH at 10.5. Where lead nitrate was added during preprocessing, it was introduced
immediately after the adjustment of the pH. T he cyanide salt (NaCN ) was added at the end of the pre-leach with no
pulp filtration and leaching was performed for 48 h. Cyanide was added during the test to maintain a constant
concentration of free cyanide (±5%). A 25 mL sample of pulp was taken by pipette after 4.0 h, 6.0 h, 24.0 h and at
the end. After filtration of the samples, the solids were returned to the reactor. The oxygen content was kept
constant by using a mass flow meter and an electrode which measured the dissolved oxygen content (DO). At the
end of the test, the slurry was filtered and the filter cake was washed with 1000 mL of distilled water. This cake was
analyzed for precious metals by fire assay. The gold extraction was calculated on the basis of the gold content
values of the processed tailings, compared to the gold content value of the mill head sample.

The leach solution and wash solution were titrated for free cyanide with silver nitrate using rhodamine
as indicator and both were assayed for gold and copp er by atomic absorption spectroscopy. The results were
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reported as NaCN. The presence of copper cyanide caused interference during titration. Titration results indicated a
higher free cyanide concentration than was really present in the solution because of the com plexa tion of copp er with
cyanide. The results were not corrected because the plant that processes this ore uses the same titration method.

3. RESULTS
3.1 Pre-leaching
Figure 1 illustrates the oxidation of soluble sulphides to sulphate, thiosulphate and tetrathionate. For
this test, distilled water was used (room temperature). The pH was controlled at 10.5 and oxidation occurred in the
prese nce o f air only. T he resu lts indicate that 75% o f the solub le sulphides were oxidized to sulphate after 30 min.
This period of 30 min represented the time during which the ore was agitated with air in the mill circuit. Oxidation
of soluble me tallic sulphides to form thiosulphate and sulphate occurs ac cording to the following reactions:
2S 2- + 2O 2 + H 2O 6 S 2O 32- + 2OH- (1)
S 2O 32- + 2OH - + 2O 2 6 2SO 42- + H 2O (2)

Thiosulphate (S 2O 32-) can also be oxidized to tetrathionate (Latimer, 193 8):

2 S 2O 32- 6 S 4O 62- + 2e (3)

Tetrathionate is not stable in alkaline so lutions, being co nverted to thio sulpha te and trithionate acco rding to
(Goldhaber, 198 3): 4 S 4O 62- + 5 OH- 6 5 S 2O 32- + 2 S 3O 62- + 3 H 2O (4)

Figure 1 shows a very small concentration of thiosulphate (10 mg/L) and trithionate (58 mg/L) after 30 minutes; the
corresponding sulphate concentration is 626 mg/L. Soluble sulphides that are dissolved are pyrrhotite, marcosite and
chalcopyrite, pyrrhotite being the least stable.

3.2 Effect of pre-leaching and oxygen

Figure 2 illustrates the effects of pre-leaching with air and lead nitrate and the effect of injecting
oxyge n during cyanidation . Treatment withou t pre-leaching and without the injection of ox ygen results in a go ld
recovery of 89.6% and a cyanide consumption of 1.46 kg/t (test 1). Pre-leaching for 30 min with air (test 2) had
almost no effect, even if oxygen is added during cyanidation. The gold recovery and cyanide consump tion were
practically similar. The addition of 200 g/t Pb(NO 3) 2 during pre-leaching, without the injection of oxygen during
cyanidation, resulted in an obvious increase in gold recovery to 95.3%. There is an increase of 0.10 kg/t in cyanide
consumption, to 1.64 kg/t (test 3).

Elsner's equation shows the role of oxygen in the oxidation-reduction reaction:

4 Au + 8 CN- + O 2 + 2H 2O 6 4 Au(CN)2- + 4 OH- (5)

The combined use of lead nitrate during pre-leaching (200 g/t) and O 2 (15 ppm) during cyanidation
increased the gold recovery to 96.8%. However, cyanide consumption also increased to 1.85 kg/t. The use of lead
nitrate and oxygen provid ed the most rapid dissolution of the gold (test 4) and the highest gold re covery.

3.3 Effect of Pb(NO 3) 2 concentration during pre-leaching

An examination of Figure 3 indicates that gold recovery increased proportionally to lead nitrate added
during pre-leaching. In fact, it rose from 96.5% Au with 100 g/t Pb(NO 3) 2 to 97.8% with 300 g/t Pb(NO 3) 2 (tests 5
and 6). The gold recovery remained the same for Pb(NO 3) 2 concentrations greater than 3 00 g/t (test 7).
The literature (Morrison, 1995) indicates that lead nitrate can act in different ways. Indeed, it can activate the
surface of a passivated particle of gold, prevent the formation of a passivation film on the surface of gold, acts as an
oxidizing agent, pre cipitate the soluble sulp hides or promo te the oxidatio n of soluble sulphides to sulp hates. In this
case, lead nitrate favored the dissolution of gold, so it probably acted at the surface of the gold particles to prevent
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passivation. Although the system using 400 g/t Pb(NO 3) 2 showed the fastest dissolution kinetics during the first 16 h,
the gold recovery was about the same at 300 g/t and 400 g/t Pb(NO 3) 2 with 97 .8% and 9 7.3% , respectively.

The addition of Pb(NO 3) 2 increased cyanide consumption noticeably. In fact, consumption was
1.86 kg/t with 100 g/t Pb(NO 3) 2 and rose to 2.16 kg/t with 400 g/t Pb(NO 3) 2 . Previous work on a sulphide-bearing
gold ore ind icated a 50% d ecrea se in cyan ide co nsumption using lead nitrate while keeping the sam e gold recovery,
but increasing leaching kinetics by 30% (D eschênes and W allingford, 1995). T he difference in the response of the
ore to the ad dition of lead nitrate is attributed to the duration of the pre-leaching. In the previous wo rk, there was a
four-hour pre -leaching for an ore c ontaining 12% p yrite, 1.4% pyrrhotite and 0.14 % chalcopyrite. In the present test
work, the pre-leaching is only 0.5 h and the material has a copper content 3 times higher than the previous oreand
2.7% pyrrhotite and no pyrite.

Figure 4 shows the copper dissolution curve and thiocyanate formation as a function of the amount of
lead nitrate added . Between 0 to 10 0 g/t lead nitrate, there is selective leaching of copper and sulp hur.
Consequently, the concentration for copper and thiocyanate in solution increase. Accordingly, this causes an
increase in cyanide consumption. Wo rk on a different material, with surface analyses by TOF-LIM S (Time of Flight
Laser Ionisation Mass Spectrometry) (Martin and Cabri, 1994) indicates that chalcopyrite shows more pronounced
dissolution when treated with lead nitrate. According to this figure, the copper content reaches a maximum around
120 g/t of Pb(NO 3) 2, then decreases as more lead nitrate is added. At this level, lead nitrate passivates the surface of
the chalcopyrite. It seem s that there is a direct relationship between disso lved copp er, cyanide co nsumption and gold
recovery. The relationship among these three factors ceases to apply when the concentration of lead nitrate exceeds
200 g/t. Moreover, the CNS- content fluctuates without indicating any specific tendency. The copper and CNS-
contents thus canno t be used as ind icators to guid e the ad dition o f lead nitra te in defining the o ptimum system .

The optimized system uses between 100-300 g/t Pb(NO 3) 2. There is a small variation in profit (about
$1.00/t) in the range of content values between 100 and 400 g/t of Pb(NO 3) 2. As the optimum system is defined by
econo mic criteria, it can be seen that the be nefit generated by the increase in gold recovery is diminished by the cost
of adding m ore lead nitrate and consuming more cyanide.

3.4 Effect of cyanide concentration

The effect of the concentration of free cyanide (expressed as NaCN for practical reasons) was assessed
with the system using pre-lea ching with lead nitrate and injection of ox ygen during the 48-hour cyanida tion pe riod.
The results are given in Figure 5. An increase in cyanide content pro motes the dissolution of gold during the first
24 hours of leaching, but the optimum leaching kinetics are at an intermediate cyanide concentration, in this case,
710 mg/L. The gold extraction is not influenced by cyanide concentrations between 640 and 840 mg/L NaCN
(~96.6%). The extraction is very sensitive to the free cyanide concentration when the sodium cyanide concentration
falls below 640 mg/L; the yield drop s rapidly, to less than 90% with 500 m g/L NaC N, and this corresponds to a loss
of 6.7% (tests 10 and 12). There is also a significant increase in the cyanide consumption when the concentration of
NaCN is greater than 710 m g/L (from 1.8 5 kg/t to 2.78 kg/t).

The add itional free cyanide does not promote gold dissolution. Rather, the additional cyanide favors
the dissolution of copper, the concentration of which increases to 770 ppm . The increase of free cyanide
concentration should increase the concentration of Cu(CN) 43- and decrease the concentration of Cu(CN)2- (Hsu and
Tran, 1995). In fact, this increase is responsible for only about 0.24 kg/t of additional cyanide consumed. Note that
iron from pyrrhotite or chalcopyrite is only very slightly dissolved. The copper dissolution would be responsible for
90% of the cyanide consumed if it is assumed that the copper cyanide complex exists mostly as Cu(CN) 32- com plex.

Work indicated that the gold dissolution rate is accelerated in oxygen-enriched slurries in presence of
chalcopyrite and pyrrhotite (Liu and Yen, 1995). It is suggested that the Cu(CN)32- leaches gold according to the
following equation:
Au + 2 Cu(CN)32- 6 Au(CN)2- + 2 Cu(CN)2- + é (6)
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It was found that Cu(CN)43- is more effective for leaching than CN - (LaBrooy et al., 1991). It is believed that the
copper(I)cyanide solutions do not show limiting rate because of the high affinity of oxygen for copper(I) which
facilitates the oxygen transfer in solution.

The dissociation of the Cu(CN)43- complex causes a higher concentration of free cyanide. Since the plant uses the
same titration method, the values in this report are comparable with the production data, as the error induced is of the
same nature.

4. DISCUSSION
The high copp er content of this ore (0 .4% ) creates a kinetics pro blem for gold extraction. T his partly
explains why the add ition of lea d nitrate and o xygen enhan ces go ld disso lution and significantly improves gold
recovery. Lead nitrate has no effect on the overall gold extraction when ad ded in amo unts higher than 300 g/t.
However, lead nitrate does not appear to reduce cyanide consumption. This result is probably related to the very
short pre-leaching period used in the current work. A longer pre-leaching would have a positive impact on the
cyanid e con sump tion. Ind eed, the results indicate that lead nitrate can be adde d during pre-leaching or d irectly
during the cyanidation without any observable difference in final performance because the gain created by the
increasing gold extraction is attenuated by the increasing cyanide consumption. It also appears that the kinetics of
oxidation of soluble sulphides is not a good indication of the required pre-leaching time to have a positive effect on
cyanide consumption.

The conce ntration of thiocyanate and copper cannot be used as reliable indicators to adjust the
addition rate of lead nitrate. An excess of lead nitrate is detrimental because it increases cyanide consumption,
probably by oxidizing cyanide to cyanate. This hypothesis is difficult to confirm because this excess had no effect
on go ld recovery. The high copp er content of this ore justifies the high requirement of free c yanide for leaching.
The high concentration of free cyanide also leads to a high consumption of this reagent. Any concentration of
cyanide below a critical level, however, means a significant drop in gold extraction. The actual plant practice uses
leaching conditions that are close to the ones identified in this study. This ore is only a percentage of the feed
material of the plant. Consequently, lead nitrate addition and free cyanide concentration in the plant were lowered
while maintaining the sam e gold recovery. T his has reduced reagent costs.

5. CONCLUSIONS
Efficient gold leaching of a free milling ore, with a high copper content, is achieved under specific
conditions using oxygen, lead nitrate and cyanide. The kinetics of oxidation of soluble sulphides cannot be used as a
direct indication of the length of the pre-leaching required. Even though the consumption of cyanide was reduced
due to the inhibition of the dissolution of chalcopyrite by increasing additions of lead nitrate, cyanide consumption
had to be held above 1.85 kg/t to maintain good recovery of gold. The continued addition of lead nitrate above
300 g/t had no impact on the recovery of gold. It was also found that the addition of lead nitrate at the start of
cyanid ation gave the same performance as when ad ded during pre-lea ching. T he high conc entration of co ppe r in
solution requires a concentration of 70 0 mg/L NaCN for leaching. T he plant has co ntrolled the levels of lead nitrate
and cyanide additions in relation with the nature of the feed. Consequently, the reagents consumption has been
lowered.

ACKN OW LEDGM ENTS

The autho rs wish to thank D enis Couture, Clau de D ufresne and J ean C hâteauneuf of Cambio r for their
participation and collabora tion, the financing provide d under the project and the information conveyed . Thanks also
to our assay laboratory of Mining and Mineral Sciences, to Jean Cloutier for the fire assay, to Gilles Laflamme and
J.T. Szymanski for the mineralogical analysis and to M artin Fo rtier, a student trainee from Laval University, for his
assistance in the laborato ry tests.
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REFERENCES

1. Deschênes, G. and W allingford, G., Effect of Oxygen and Lead Nitrate on the Cyanidation of a
Sulphide-Bearing Gold Ore; Minerals Engineering; 8:8; 1995.
2. Dufresne, C ., Desc hênes, G., Cimon, D. et al, C ontro l of Cyanidation at the Y van V ézina Plant;
Minerals Engineering; 7:11; 1994; 1427-1434.
3. Goldhaber, M.B., Experimental Study of Metastable Sulfur Oxyanion Formation
during Pyrite Oxidation at pH 6 - 9 and 30 /C; Am. J. Of Science; 283; 1983; 193-217.
4. LaBroo y, S.R., Kom osa, T. and M uir, D.M., Selective Leaching of Gold from Co pper-Gold O res using
Ammonia-Cyanide Mixture;Proc.5th Extractive Metallurgy Conference, Perth,Australia;1991;
127-132.
5. Latimer, W .M., The Oxid ation S tates of the Elements and their Potential in Aqu eous Solutions,
Prentice-Hall Inc., N.Y., 1938.
6. Liu, G.Q. and Yen, W.T., Effect of Sulphide Minerals and Dissolved Oxygen on
Gold and Silver Dissolution in Cyanide Solutions; Minerals Engineering; 8:1/2; 1995; 111-123. 7.
Martin, C.J. and Cabri, L.J., An Investigation by TOF-LIMS of the Surface Composition of Sulphide
Minerals from Leaching and Electrochemical Experiments, AMTEL Report 94/39; Aug. 1994.
8. Mo rrison, R.M., Factors Impacting on Lead Nitrate Additions to Cyanidation Circuits, MSL R eport
94-42 (CR); Nov. 1994.
9. Morriso n, R.M ., Investigation of Lead Nitrate Effects in Go ld Cya nidatio n Circuits, MSL R epo rt 95-5
(CR); Feb. 1995.
10. Stoychevski, M. and Williams, L.R., Influence of Oxygen, Hydrogen Peroxide and Oxone on
Dissolution of Gold from Pyrite Ore; Trans. Instn. Min. Metall. C; 1993; 93-98.
11. Zheng, J., Ritchie, I.M., LaBrooy, S.R. and Singh, P., Study of Gold Leaching in Oxygenated
Solutions co ntaining C yanide -Cop per-A mmonia using a R otating Q uartz C rystal M icrob alance;
Hydrometallurgy; 39; 1995; 277-292.
12. The Sec ond Surve y of Gold C yanida tion Plants; Deschênes, G . and P utz, A., E ditors,
MSL Report 95-14 (CR); April 1995.
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Figure 1. Kine tics of the o xidatio n of soluble sulphides in the p re-leaching of a cop per-gold
ore with air. pH 10.5.

Figure 2. Effect o f pre-leaching and oxygen on go ld leaching of a cop per-gold o re.

Pre-leaching: Pb(NO 3) 2 200 g/t, 30 m in; cyanid ation: pH 1 0.5, N aCN 700 mg/L, O 2 15 ppm , 48 h.
 7

Figure 3. Effect o f lead nitra te on gold leaching of a co pper-gold ore. P re-leaching: 30 min; cyanidatio n:
pH 1 0.5, N aCN 710 mg/L, O 2 15 ppm , 48 h.

Figure 4. Copp er dissolution and formation of thiocyanate during cyanidation as a function of the concentration
of lead nitrate. Pre-leaching: 30 min; cyanidation: pH 10.5 , NaC N 7 10 m g/L, O 2 15 ppm , 48 h.
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Figure 5. Effect of cyanide concentration on gold leaching of a copper-gold ore.

Pre-leaching: Pb(NO 3) 2 200 g/t, 30 m in; cyanid ation: pH 1 0.5, O 2 15 ppm , 48 h.

Table 1 - Chemical and mineralogical analyses of the copper-gold ore

Chemical Analysis (%) Mineralo gical Analysis

Au 9 .55 g/t Major pha ses:

Si 22 .4 chlorite, quartz and albite.

Fe 10.9 Minor phases:

Al 6.9 chalcopyrite, pyrrhotite,

Ca 4 .8 ilmenite and magnetite.

Mg 3.4 Trac es:

S tot 1.58 sphalerite and marcasite.

Cu 0.40

Zn 0.3

As < 0.2

Pb 0.1

Sb < 0.1