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XXVIII Convencin Minera Internacional, AIMMGM AC, Veracruz, Ver.

, 28 al 31 de octubre de 2009

A NEW TECHNIQUE FOR RECOVERY GOLD AND


SILVER FROM BACIS ARGENTOPYRITE
CONCENTRATE
JOSE R. PARGA1*, JESUS. L. VALENZUELA2 y GUILLERMO T. MUNIVE2
1
Instituto Tecnolgico de Saltillo, Departamento de Metalurgia y Materiales, Saltillo, Coahuila, Mxico,
2
Universidad de Sonora, Departamento de Ingeniera Qumica y Metalurgia, Hermosillo, Sonora 83000, Mxico.
(*jrparga@its.mx)

RESUMEN
Por ms de un siglo el mtodo comercialmente empleado para la disolucin de los metales preciosos,
es la lixiviacin alcalina utilizando cianuro de sodio con inyeccin de oxigeno, sin embargo, cuando las
partculas de oro y de plata se encuentran finamente diseminadas o ocluidas en minerales de
arsenopitita, pirita o cuarzo las recuperaciones de estos metales preciosos no son muy eficientes. Por
consiguiente, en este estudio se describe un nuevo proceso para la recuperacin de oro y plata de un
o
concentrado argentopirita de la mina de Bacis el cual utiliza temperatura de 50 C y presin de oxigeno
2
de 50 Lb/In para que con estas condiciones el cianuro y el oxigeno disuelva simultneamente el oro y
la plata en un 96%, empleando un tiempo no mayor a los 90 minutos en un autoclave de acero
inoxidable. Posteriormente a la solucin rica de cianuro de oro y plata , los metales preciosos se
recuperan utilizando un proceso nuevo de Electrocoagulacin con electrodos de hierro con una
eficiencia del proceso del 99%.

ABSTRACT
For more than a century the used method for the dissolution of precious metals is the leaching with
alkaline sodium cyanide solution with air oxidation, however, where gold and silver are present in a
finely disseminated form within arsenopyrite and pyrite particles the recovery of precious metals did not
give recovered in high yield. Therefore, this study describes a new process for the recovery of precious
metals from argentopyrite concentrate from Bacis mine by using mild operating conditions of
temperature 50 C and 50 psi oxygen pressure, the oxidation and dissolution of gold and silver in
alkaline cyanide solution can be conducted simultaneously in the same autoclave in less than 90
minutes with a recovery that exceeds 96%. Then, for recovery gold and silver from cyanide solutions an
Electrocoagulation process was used with an efficiency of more than 99 %.

INTRODUCTION
At the present time, cyanidation has superseded all previous leaching processes, particularly
3
chlorination , because of its ability to effectively and economically treat ores containing as little as 1-3
g/ton gold. After the precious metals are dissolved in a dilute solution of sodium cyanide which is
recycled after precipitation of the precious metals values with zinc dust. A bleed of this barren solution
is often required to control the accumulation of deleterious impurities. Refractory gold-silver ores
contain precious metals locked up in a matrix of pyrite and/or arsenopyrite. Such ores are not
amenable to cyanidation. To liberate the gold-silver from the sulfide matrix and render it accessible to
1,2,3
cyanidation . It is a common practice to subject them to a preoxidation in order to enhance the
4,5 4,5,6,7,8,9
recovery of the precious metals . After review of the literature , it is clear that of the refractory
gold treatment plants installed during the past 25 years, pressure oxidation has been the most popular
(see Table I). This process, which is used in many commercial plants around the world, involves the
recovery of the precious metals by oxidation pretreatment followed by traditional cyanidation method.
By consequence the save in time for the gold and silver recovery from ore or concentrates is limited for
the conventional leaching step, a process which requires 72 hours. It should be remembered that the
pressure oxidation technology is not used to leach the gold and silver but only to make it accessible to
the cyanide in the host mineral.

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Table I. Existing commercial plants using pressure oxidation [4,5,6,7,8].

Plant Capacity Operation Data


Feed Medium
Location T/d T (C) P (psi) t (min)
McLaughlin, California
Ore Acid 2700 180 401 90
USA
So Bento
Concentrate Acid 240 190 230 90
Brazil
Barrick Mercur
Ore Alkaline 790 225 473 70
Utah, USA
Getchell
ore Acid 3000 210 420 130
USA
Goldstrike
ore Acid 1360 225 439 75
Nevada, USA
Goldstrike
ore Acid 5450 225 400 75
Nevada, USA
Porgera, Papua
concentrate Acid 1350 190 258 180
New Guinea
Campbell 120
concentrate Acid 70 195 305
Canada
Barrik
ore Acid 2000 220 450 100
USA
Goldstrike
ore Acid 11580 200 200 140
Nevada, USA
Santa Fe Pacific Gold
ore acid 4000 225 460 50
Nevada, USA
Sunshine Mining & Co
ore acid 1000 120 90 60
Idaho, USA
Porgera, Papua
concentrate acid 2700 190 250 150
New Guinea

EXPERIMENTAL
Mineralogical analysis indicates that the sulfide minerals for the Bacs concentrate include: silver iron
sulfide, silver sulfide or argentite, pyrite, pyrrhotite, arsenopyrite, chalcopyrite, covellite, hematite and
magnetite. The non-opaque minerals were quartz, calcite, apatite, gypsum, fluorite and barite. Also,
several photomicrographs indicate occlusion and/or dissemination of micron-size gold, silver, electrum
particles in the sulfide minerals such as pyrite, sphalerite, arsenopyrite and quartz (Figure 1). The
compositions are listed in Table II.

Table II. Analytical data for the composite samples


Composition g/ton %
Metal Au Ag Pb Zn Cu Fe As S
Concentrate 87.09 12320 2.6 3.8 0.5 29.2 0.15 32
Ore 4.12 289 0.5 0.4 0.04 3.67 0.1 3.7

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PYRITE





Figure 1. Photomicrograph, Argentite (ARG) occluded in pyrite, size 60 m.

Oxidation and Cyanidation Experiments


All experiments were conducted in a four-liter Parr autoclave assembled with impeller, thermowell,
pressure gauge, gas inlet and outlet pipes were used for simultaneous oxidation and cyanidation.
Samples were ground to 95% minus 20 m or finer, pulped with fresh tap water. Depending on test
requirements, variables such as NaCN, lixiviation time, temperature, particle diameter, pH and pulp
density were set and the leaching experiments were undertaken.

Table III. Optimum Parameters for the Autoclave


Solid % = 20 Cyanidation time = 60 min.
Temperature = 80C NaCN = 1%
2
Pressure = 5.6 kg./cm (80 psi) pH = 11.0
rpm = 600 PbO = 100g/ton

Process Chemistry
Pyrite along with arsenopyrite, sphalerite and covellite are the most common host minerals of gold,
silver and electrum. It is important from a process optimization standpoint to understand the behavior
of each of these minerals during alkaline pressure oxidation which leads to dissolution/destruction and
subsequent liberation of gold and silver which would then be available for cyanidation. Pressure
oxidation of pyrite involves reactions yielding ferrous ion, sulfate ion, and elemental sulfur as products
10,11
. The primary reactions are:
2+ 2- +
2FeS2 + 7O2 + 2H2O 2Fe + 4SO4 + 4H (1)
+ 2+ 0
FeS2 + 2H Fe + H2S + S (2)
Ferrous ions produced by reaction (1) and (2) are subsequently oxidized to ferric ions
2+ + 3+
2Fe + 1/2O2 + 2H 2Fe + H2O (3)
And contribute to the leaching of sulfides only as a source of ferric ions. The ferric ions can also
contribute to the oxidation of silver iron sulfide, argentite, pyrite, pyrrhotite, sphalerite and chalcopyrite:
3+ + 2+ 2- 0
AgFe2S3 + Fe Ag + 3 Fe + 2S + S (4)
3+ + 2+ 0
Ag2S + 2Fe 2Ag + 2Fe + S (5)

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3+ 2+ + 0 2-
FeS2 + 8Fe + 4H2O 9Fe + 8H + S + SO4 (6)
3+ 2+ + 2-
Fe7S8 + 32H2O + 62Fe 69Fe + 64H + 8SO4 (7)
3+ 2+ 2+ 0
ZnS + 2Fe Zn + 2Fe + S (8)
3+ 2+ 2+ 0
CuFeS2 + 4Fe Cu + 5Fe + 2S (9)
Then, elemental sulfur may also be further oxidized to sulfate by oxygen or by ferric sulfate:
0 + 2-
2S + 3O2 + 2H2O 4H + 2SO4 (10)
0 3+ 2+ + 2-
S + 6Fe + 4H2O 6Fe + 8H + SO4 (11)
This results in the formation of a porous, but nonprotective, elemental sulfur layer, thus allowing
cyanide and dissolved oxygen to access to the previously locked gold, silver and electrum. It was
-
thought that by maintaining high concentrations of CN ions in the pressure leach reactor it would be
possible to complex gold and silver (Eq. 12) as they became liberated and thus achieve both
objectives, i.e. decomposition of refractory minerals and Au/Ag recovery, in a single stage. Both gold
and silver extractions achieved were in fact greater than 96%. Since silver in Mexican ores occurs as
argentite the cyanidation and sulfide oxidation reaction are as follows:
- - 2-
Ag2S + 4CN 2Ag(CN) 2 + S (12)
2- - -
S + CN + 1/2O2 + H2O SCN + 2OH (13)
2- 2- -
2S + 2O2 + H2O S 2O 3 + 2OH (14)
2- - 2-
S 2O 3 + 2OH + 2O2 2SO4 + H 2O (15)
Sulfide ions are oxidized to thiosulphate and can contribute with the dissolution of gold. Also Graham
12
et al. . showed that an alkaline or near neutral solution of thiosulphate dissolved gold metal slowly in
the presence of a mild oxidant. The dissolution of the gold can be written as in Equation 16, where
oxygen is the oxidant and thiosulphate is the ligand.
2- 3- -
4 Au + 8S2O3 + O2 + 2H2O 4[Au(S2O3)2] + 4OH (16)
Better extractions of gold with thiosulphate are achieved when elevated temperatures (e.g. 65 C) are
13
used and also, cupric ion has been found to have a strong catalytic effect on the rate of oxidation.
The proposed physiochemical aspects of the leaching reaction mechanism for gold and silver
dissolution in relatively mild operating conditions of 80 C and 80 psi oxygen pressure are illustrated in
Figure 2, where the ore particle displaying different diffusing ions.

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2 CN
3+ Zn

Fe +

Ag(CN)2


ARGENTITE
SPHALERITE

PYRITE
ARGENTITE
PARTICLE
CN CN

O2
GALENA
GOLD

ARGENTITE
Au(CN)2
Ag(CN)2
Fe2(SO4)3

15O2+ 2Fe(SO4)2+
2H2O 2H2SO4

Figure 2. Schematic mechanism of gold and silver leaching.

RESULTS AND DISCUSSION

Ambient Condition
Preliminary batch testing had indicated that at ambient conditions (25C, 1atm.) direct cyanide leaching
of the concentrate with air gave poor silver and gold recoveries. The results obtained are shown in
Figures 3 and 4.

Temp.= 80 oC
100 P= 80 psi

Temp.= 25 oC
EXTRACTION, %

P= 1 atm
80

60
CONDITIONS
%Solids = 20
40 pH= 11.0
rpm = 300

20

0
0 50 100 150 200 250 300 350

TIME (min)

Figure 3. Comparison of silver extraction at ambient conditions and high pressure.

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100
P= 80 psi

EXTRACTION, %
T= 80 oC
80
P= 1 atm
Temp.= 25 C
60
CONDITIONS
%Solids= 20
pH= 11.0
40 rpm= 300

20

0
0 30 60 90 120 150 180 210 240 270 300

TIME (min)

Figure 4. Comparison of gold extraction at ambient conditions and high pressure.

Effect of the Autoclave Retention Time


There is an optimum leach time to achieve both maximum gold and silver extractions. The optimum
leach time appears to lie close to 60 minutes at 80C.

Increase in time beyond this value leads to chemical degradation of the complex cyanide, due to the
hydrogen ions produced by the sulfide oxidation. Also for prolonged leaching time there is significant
loss in cyanide, since the oxygen present oxidizes the cyanide to cyanate and ultimately to ammonia
and carbon dioxide.

Effect of Cyanide Concentration


Sodium cyanide addition appears to be the critical variable for good recovery. Concentrations of 0.6 -
1.1 wt. % sodium cyanide were used to leach the concentrate in the autoclave. When the concentration
of sodium cyanide was less than 0.6%, gold and silver extraction could not be completed optimally in a
single stage of autoclave leaching. Increasing the cyanide concentration resulted in an increase in the
gold and silver extraction.

Effect of Temperature
The concentrate was leached as 20-wt.% solids slurry with 1 wt.% of NaCN for 60 minutes.
Temperature was varied from 60 to 200C. As the temperature was increased, the gold and silver
extractions decreased, since at temperatures higher than 80C, the oxidation of cyanide ions is too
rapid resulting in the formation of CO2 gas and ammonium ion.Cyanide ion is then not available for
complexetion.
- + +
CNO + H2O + 2H CO2 + NH4 (17)

Table IV. Analysis of the pregnant solution


SOLUTION
CN g/ton Ag mg/L Au mg/L
0.26 91 0.9
Effect of pH
A pH range of 10.5-13, was examinated for the extraction of gold and silver. This behavior is because
in alkaline-oxidizing medium the pyrite and pyrrhotite in the concentrate competes with gold and silver
for consumption of oxygen, and this mechanism may be responsible for the decrease in extraction.

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2+ + 2-
2FeS2 + 7O2 + 2H2O 2Fe + 4H + 4SO4 (18)
2+ 2-
FeS + 2O2 Fe + SO4 (19)
Eventually the ferrous sulfate formed is converted to the stable, insoluble ferric hydroxide.

FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4 (20)


2Fe(OH)2 + 1/2O2 + H2O 2Fe(OH)3 (21)
The decrease in the extraction of gold and silver with increasing pH may also be due to a decrease in
the formation of ferric sulfate which is the reagent that contribute to the oxidation of sulfide minerals
which occlude gold and silver. Also Deitz [14] found that at high pH values between 12 to 13, the silver
surface got coated with a whitish film of CaO2 and thus the leaching process was retarded.

Recovery Gold and Silver by Electrocoagulation Process


Electrocoagulation has been known as an electrochemical phenomenon for the last century. It has
(16)
been employed previously for treating many types of wastewater with varying degrees of success .
The EC process operates on the principle that the cations produced electrolytically from iron and/or
aluminum anodes enhance the coagulation of contaminants from an aqueous medium. Electrophoretic
motion tends to concentrate negatively charged particles in the region of the anode and positively
charged ions in the region of the cathode. The consumable, or sacrificial, metal anodes are used to
continuously produce polyvalent metal cations in the vicinity of the anode. These cations neutralize the
negative charge of the particles carried toward the anodes by electrophoretic motion, thereby
facilitating coagulation. In the flowing EC techniques, the production of polyvalent cations from the
oxidation of the sacrificial anodes (Fe and Al) and the electrolysis gases (H2 and O2) works in
combination to flocculate the coagulant materials. Even inert electrodes, such as titanium and the
passage of an alternating current have also been observed to remove metal ions from solutions and to
initiate the coagulation of suspended solids. Figure 5 illustrates the schematic diagram of the process.
As mentioned above, gas bubbles produced by the electrolysis carry the pollutant to the top of the
solution where it is concentrated, collected and removed. The removal mechanisms in EC may involve
oxidation, reduction, decomposition, deposition, coagulation, absorption, adsorption, precipitation and
flotation.

Figure 5. An illustration of the electrocoagulation mechanism

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However, it is the reactions of the metal ions that enhance the formation of the coagulant. The metal
- - -
anions of Au(CN) 2 and Ag(CN) 2 react with the OH ions produced at the cathode during the evolution
of hydrogen to yield both soluble and insoluble hydroxides that will react with or adsorb pollutants,
respectively, from the solution and also contribute to coagulation by neutralizing the negatively charged
colloidal particles that may be present at neutral or alkaline pH. This enables the particles to approach
closely and agglomerate under the influence of van der Waals attractive forces.

The chemical reactions that have been proposed to describe EC mechanisms for the production of
- +
H2(g) and OH (aq) (cathode) and H (aq) (anode) [17] are:

When M(s) = Fe metal electrode


(22)

(23)

Anode:
(24)

(25)

Cathode:

(26)

(27)

Overall:

(28)

whereconstantaisastoichiometriccoefficient,andnisnumberofelectrons.
The pH of the medium rises as a result of this electrochemical process and the Fe(OH)n(s) formed
-
remains in the aqueous stream as gelatinous suspension, which can remove the Au(CN) 2 and
-
Ag(CN) 2 from cyanide solutions, either by complexation or by electrostatic attraction followed by
coagulation and flotation.

Experimental EC process
The electrocoagulation with air injection apparatus consisted of a flow-through reactor with parallel
vertical electrodes, a peristaltic feed pump, an air pump and a power supply. This EC system uses a
modified EC process where the arsenic contaminated water is passed through a porous tube medium
where air is injected before passing through the vertical electrodes in the EC cell. Seven vertical
carbon steel electrodes were used as anode and cathode. The vertical geometry of the plates allowed
the use of the gaseous O2 and H2 generated in the electrolysis of water to facilitate removal of the
ferric and ferrous species associated with arsenic contaminants. The neighboring vertical electrodes
(10.0 cm by 15.4 cm) were 6mm apart and the internal volume of the reactor was 1200 ml. A variable
transformer was used to control the current and potential. The electrolyte cyanide solutions were
prepared with the pregnant solutions from the autoclave, and the conductivity was controlled by adding
one gram of NaCl per liter of water (Fisher, 99.8% A.C.S. Certified, lot #995007). The gold and silver
cyanide solutions were collected from the pregnant solutions from the autoclave. The pH was adjusted
(as needed) using ~0.13 M NaOH solution prepared with NaOH pellets (EM, 97%, lot #36349739).
Prior to each trial, the pH and conductivity of each solution were recorded. The aerated solution was
pumped through the cell at a flow rate of about 600 ml/min and after 2.0 to 4.0 liters of well water
solution were treated, the runs were stopped and the slurry pH and conductivity were recorded. The

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solutions and solids were then separated by filtration through cellulose filter paper. The sludge from the
EC was dried either in an oven or under vacuum at room temperature. The samples were analyzed by
atomic absorption spectroscopy (AAS, model Varian A 220).

RESULTS AND DISCUSSION

Gold and Silver Removal by Electrocoagulation with Air Injection


The H2 (g) and O2 (g) produced as a result of the redox reactions and the air injection may remove any
suspended particles of iron coagulant impregnated with gold and silver by electroflotation. Exact
electrochemical reaction mechanisms involved are not yet completely understood. However, the EC of
gold and silver cyanide solutions produces an insoluble complex sludge, containing iron and gold and
silver and hydroxides while leaving negligible or zero concentrations of gold and silver from the
pregnant cyanide solutions. Table 5 shows a comparison of the results by using electrode of iron and
aluminium.

Table V. Comparison of EC Results By Using Fe and Al Electrodes

Cyanide Solution
Type of Residencie
electrode Time Au Ag
pH initial pH final
(ppm) (ppm)
0 10.7 29.4 2439 10.7
Iron 1 minute 10.0 17.5 468.0 11.2
Aluminum 1 minute 10.0 9.75 54.25 11.1
Iron 3 minutes 9.0 4.5 8.0 10.9
Aluminum 3 minutes 9.0 6.0 40.5 10.5
Iron 5 minutes 8.0 0.9 1.6 10.6
Aluminum 5 minutes 8.0 4.85 35.15 10.7

CONCLUSIONS
As seen, Direct Pressure leaching Cyanidation is advantageous over numerous pressure oxidation
plants for the pretreatment of gold/silver ores and concentrates in that it is faster, uses lower
temperatures, uses lower pressures and uses stainless steel autoclave and with these conditions
15
cheaper autoclaves can be used. Thomas shows that a 1400 T/d acid pressure oxidation circuit
might cost C$30 million while the corresponding non-acid circuit might cost only C$15 million.

The recovery of precious metals by EC is an excellent process for recovery gold and silver from
cyanide solutions.

The electrocoagulation results shows that the iron electrode had recoveries higher than 99 %.

ACKNOWLEDGMENTS
The author thanks the management of Group Bacs Mining S. A., SEP, DGIT and CONACYT for the
support and permission to publish this paper.

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