Beruflich Dokumente
Kultur Dokumente
a,*
Department of Metallurgical Engineering, University of Utah, 135 S. 1460 E. Room 412, Salt Lake City, UT 84112-0114, United States
b
Newmont Mining Co., 10101 E. Dry Creek Road, Englewood, CO 80112, United States
c
Metallurgy Consultant, 9634 Kalamere Court, Highlands Ranch, CO 80126, United States
Received 11 April 2005; accepted 18 September 2005
Available online 17 November 2005
Abstract
The inuence of pyrite pre-oxidation in alkaline solutions on gold recovery by cyanidation from Twin Creek refractory gold ore in
which pyrite was identied as the major sulde mineral has been investigated with the aid of electrochemical measurements, leaching
experiments, and direct analysis of reaction products for selected residues. It was found that gold recovery by cyanidation in bottle roll
experiments mainly depended on the extent of pyrite pre-oxidation. The rate of pyrite oxidation in alkaline solutions measured by electrochemical measurements, including chronoamperometry and linear sweep voltammetry, increased with an increase in pH, potential,
and temperature. All alkaline reagents used for the electrochemical measurements, NaOH, NH4OH, Na2CO3 and Ca(OH)2, showed
a similar eect on pyrite oxidation kinetics. However, the results of alkaline pre-oxidation for pyrite of the Twin Creek refractory gold
ore suggested that NaOH and Na2CO3/Ca(OH)2 were superior to Ca(OH)2. Without pre-oxidation, cyanide leachable gold was found to
be only 20% which could be increased to 70% under appropriate pre-oxidation conditions. At the same time, cyanide consumption
decreased from 2.5 kg/t ore to 1.5 kg/t ore.
Selected residues after pre-oxidation and cyanidation were examined by X-ray diraction. Backscattered electron images of pyrite
particles in these residues were taken. The reaction products at the surface of pyrite particles were found to be iron-, silicon-, and calcium-bearing compounds with variable amounts of sulfur as determined by X-ray energy dispersion analysis. Additionally, some mineral
nes, such as aluminum and/or potassium-bearing minerals, were found to be present at the partially oxidized pyrite surface.
2005 Elsevier Ltd. All rights reserved.
Keywords: Sulde ores; Gold ores; Hydrometallurgy; Oxidation; Cyanidation
1. Introduction
With depletion of the oxidized free-milling gold reserves
close to the earths surface, most of the important new
deposits being mined today do not respond to direct cyanidation. It is found that the gold is very nely disseminated
and encapsulated in host matrices that are inert and/or
impermeable to the cyanide solution. In this case, it is necessary to rst break down the host matrices and then it is
possible to leach the liberated gold. In many cases, the host
matrices are sulde minerals, which exhibit a strong association with nely disseminated gold particles in many ore
*
Corresponding author. Tel.: +1 801 581 5160; fax: +1 801 581 4937.
E-mail addresses: jli@mines.utah.edu (J. Li), jdmiller@mines.utah.edu
(J.D. Miller).
0892-6875/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.09.052
884
during pre-oxidation processes for exposure of gold particles from suldes matrices.
For pressure oxidation in alkaline solutions, the rate of
pyrite oxidation was found to be surface-reaction controlled (Lowson, 1982; Brown and Jurinak, 1989; Ciminelli
and Osseo-Asare, 1995a,b). Some authors observed that
the oxidation rate increases with an increase of pH, reagent
concentration, and temperature (Brown and Jurinak, 1989;
Nicholson et al., 1988, 1990; Ciminelli and Osseo-Asare,
1995a,b; Envangelou et al., 1998). With more extensive
alkaline oxidation of pyrite, higher gold recovery is generally observed (Souza and Ciminelli, 1992).
The kinetics of pyrite oxidation in alkaline solutions
have been found to be aected by the nature of the reagents
used to control the pH of the systems. Among the reagents,
sodium carbonate/bicarbonate was claimed to be particularly eective in enhancing pyrite decomposition in aerated
solutions (Wheelock, 1981; Guay, 1981a,b; Souza and
Ciminelli, 1992). However, there still is some controversy
regarding this position. For instance, Warren (1956) found
that the addition of small amount of calcium carbonate for
pH adjustment caused a drastic reduction in the pyrite
decomposition rate. Warren (1956) explained the reduction
in rate as a consequence of the formation of a growing
iron-oxide lm on pyrite particles, the oxidation rate then
becoming controlled by diusion in the product layer. In
contrast, Guay (1981a,b) suggested that sodium carbonate
enhanced the rate of pyrite oxidation by favoring the
removal of the iron-oxide coating, thus increasing the
exposure of fresh surfaces to oxidation.
Caldeira et al. (2003) recently reported the product layer
constituents and morphology from pyrite oxidation by
molecular oxygen in alkaline solutions. In sodium hydroxide solutions, hematite was the main phase identied in the
product layer. In carbonate solutions, the main constituent
was ferrihydrite. In calcium hydroxide solutions, only calcium carbonate was detected on the surface of oxidized
pyrite in an amount that increased when the system was
opened to the atmosphere. The morphology of the product
layers demonstrated that in NaOH solutions the pyrite particles were initially covered by a thin oxide layer and then
the oxide layer fractured after longer reaction times. Pyrite
oxidation in Na2CO3/NaHCO3 solutions resulted in particles that were initially covered by a discontinuous oxide
coating that grew with reaction time, thus increasing the
overall pyrite surface coverage.
Upon review of the literature, the kinetics and products
of pyrite decomposition in alkaline solutions under oxidative conditions are dependent on many variables, such as
oxidation potential, temperature, solution composition,
whether the system is open to the atmosphere, etc. (Buckley
and Woods, 1987; Buckley et al., 1988; Ahlberg et al., 1990;
Kathe et al., 1993; Caldeira et al., 2003). Generally, it is
accepted that the oxidation of pyrite is described by the following overall reactions, in which the ferric ion precipitates
on the pyrite surface or reports to the solution in suspension as ferric hydroxide
1
2
FeS2 11H2 O FeOH3 2SO2
4 19H 15e
or
FeS2 19OH FeOH3 2SO2
4 8H2 O 15e
885
Fig. 1. Eect of applied potential (EAP) on the rate of pyrite oxidation by chronoamperometry at pH 11 and ambient temperature with a stationary pyrite
electrode, magnetically stirred solution (0.2 M Na2SO4, 500 rpm), and dierent alkaline reagents: NaOH, NH4OH, Na2CO3, and Ca(OH)2.
886
Ia
60 s= min
A=cm2
96 490 C=mol na
1000
where R is the rate of pyrite oxidation (mol/min cm2), Ia is
the anodic current density of pyrite oxidation (mA/cm2)
and na is the number of electrons transferred for pyrite
oxidation.
However, it is expected that the products from anodic
pyrite oxidation vary, for example, ferrous ion or ferric
ion and elemental sulfur or sulfate etc., depending on
experimental conditions. Because of the dierent reactions
that can occur, the na value cannot be dened unambiguously. For this case, the anodic current densities for pyrite
decomposition will be used as an indication of the rate for
pyrite oxidation in order to compare the inuence of some
important variables on pyrite oxidation rate.
R
887
888
reaction at the dierent potentials may have the same ratelimiting step and/or produce the same products under these
circumstances.
2.3.4. Alkaline reagents
It can be noted from review of the literature that the
kinetics of pyrite oxidation in alkaline solutions are dependent not only upon pH, potential and whether the system is
open to the atmosphere, but also upon the solution composition or reagents used to adjust the solution pH (Lowson,
1982; Brown and Jurinak, 1989; Nicholson et al., 1990;
Ciminelli and Osseo-Asare, 1995a,b; Caldeira et al., 2003).
In the current research, the inuence of dierent alkaline
reagents on pyrite oxidation kinetics, including sodium
hydroxide, ammonium hydroxide, sodium carbonate, and
calcium hydroxide, was examined by chronoamperometry
Fig. 10. Eect of pH on the rate of pyrite oxidation by chronoamperometry at elevated temperature (45 C and 65 C), and applied potential
0.258 V (SCE) with a stationary pyrite electrode and magnetically stirred
solution (0.2 M Na2SO4, 500 rpm).
S-total
(%)
S-sulfate
(%)
S-sulde
(%)
C-total
(%)
C-org.
(%)
Fe
(%)
As
(%)
2.49
3.45
0.39
3.06
0.60
0.61
4.52
0.20
889
Table 2
Summary of baseline cyanide/CIL test results
Test
Sulde
oxidation
(%)
Au in
residue
(g/t ore)
Au
recovery
(%)
NaCN
consumption
(kg/t ore)
1
2
6.2
14.4
2.0
1.68
19.9
32.4
2.5
2.7
Table 3
Alkaline pre-oxidation tests at 60 C for 6 h followed by cyanide/CIL
Test
Reagent
pH
Sulde
oxidation
(%)
Au
extraction
(%)
3
4
5
6
7
NaOH
Ca(OH)2
Na2CO3
Ca(OH)2
10
11
10
11
10
26.1
67.6
17.3
28.4
23.8
38.4
63.1
32.9
37.0
41.1
14.6
62.7
18.2
41.1
48
1.6
1.2
1.2
1.3
1.3
11
67.9
54.4
147.5
0.7
Alkaline
reagent
(kg/t)
NaCN
(kg/t)
Fig. 12. Eect of the pre-oxidation slurry pH on gold extraction from the
oxidized residues by cyanide/CIL (Test 2 as a reference: gold extraction
32% for the pre-oxidation without addition of alkaline reagent).
Table 5
XRD analysis of Twin Creek refractory gold ore and pre-oxidation
residues (%)a
Table 4
Eect of lime addition in grinding circuit
Test
Lime in
grinding
(g/kg)
pH
Sulde
oxidation
(%)
CIL Au
Extraction (%)
9
10
11
12
13a
14a
5
5
10
10
5
5
10
11
10
11
10
11
49.6
79.6
37.1
71.8
48.4
88.0
62.9
71.4
47.6
63.3
62.8
69.8
Mineral
Formula
Anatase
Calcite
Muscovite/
Illite
Pyrite
Quartz
TiO2
CaCO3
KAl2(AlSi3O10)(OH)2/
K0.7Al2(Si,Al) O10(OH)2
FeS2
SiO2
Total
a
Head
Test
4
Test
10
Test
12
1
12
22
25
26
1
13
23
6
67
2
71
2
62
2
63
100
100
100
100
890
Fig. 13. BSE images of pyrite (py) in the Test 4 residue sample. Cyan arrows show EDS analysis points in rimming material, conrming S removal with Ca
and Si addition. Upper image includes an arsenopyrite (asp) grain. Right-hand pyrite in lower image has attached muscovite/illite (labeled) that shows no
eect from chemical treatment. (For interpretation of the references in colour in this gure legend, the reader is referred to the web version of this article.)
891
Fig. 14. BSE images of pyrite (py) in the Test 10 (lime 5 g/kg ore) residue sample. Cyan arrows show EDS analysis points in the surrounding material,
conrming S removal with Ca and Si addition. The upper-most EDS spectrum shows evidence for a small amount of Cl. (For interpretation of the
references in colour in this gure legend, the reader is referred to the web version of this article.)
892
Fig. 15. BSE image of pyrite (py) in the Test 10 (lime 5 g/kg ore) residue sample surrounded in this case by mineral nes. The pyrite appears to be
disintegrating. Cyan arrows show EDS analysis points. The upper-most spectrum indicates mostly quartz with a trace amount of muscovite/illite. The
other spectra show higher quantities of Ca and Fe. The S contents at the analysis points are less than the limit of detection (0.4%). (For interpretation of
the references in colour in this gure legend, the reader is referred to the web version of this article.)
dation pretreatment, the maximum achievable gold recovery would only be about 80% due to the preg-robbing
activity of the ore sample.
3.2. Alkaline cyanide/CIL tests for gold leaching
An alkaline cyanide/CIL test was performed directly on
the ne-ground samples without pre-oxidation at ambient
temperature with 20 g/L carbon for 24 h and an initial
sodium cyanide concentration of 1 g/L. The alkaline cyanide/CIL test result (Test 1) is given in Table 2.
Table 2 also includes a pre-oxidation test followed by
cyanide/CIL (Test 2). The pre-oxidation was carried out
with oxygen at 60 C for 6 h without the addition of alkaline chemical reagent. Alkaline cyanide/CIL testing
resulted in gold recovery of 20%. After aerated with oxygen
for 6 h at the elevated temperature, the subsequent gold
extraction by alkaline cyanide/CIL increased to 32%.
3.3. Comparison of alkaline pre-oxidation at pH 10
and pH 11
Results of alkaline pre-oxidation with selected alkaline
reagents and gold leaching by cyanidation/CIL are listed
893
Fig. 16. BSE image and EDS spectra from two pyrite (py) grains in the Test 12 (lime 10 g/kg ore) residue sample. Cyan arrows show analysis points. The
upper-right pyrite grain contains arsenic (lower-right EDS spectrum). The darker gray along the right side of this grain may be quartz, with the iron and
sulfur of the EDS spectrum from the nearby pyrite. The upper-most and lower-most EDS spectra are typical of most of the pyrite coatings observed during
this study, showing increased iron and lower sulfur in comparison to pyrite, with the addition of calcium and silicon. (For interpretation of the references
in colour in this gure legend, the reader is referred to the web version of this article.)
894
Fig. 17. BSE image showing two pyrite grains (light gray, upper-left and lower-right) in the Test 12 (lime 10 g/kg ore) residue sample. Cyan arrows show
EDS analysis points in coatings around pyrite. All of the coatings contain calcium and silicon, and higher Fe:S ratios than pyrite. Aluminum and
potassium of the lower-right EDS spectrum indicates muscovite/illite. (For interpretation of the references in colour in this gure legend, the reader is
referred to the web version of this article.)
shows that the residues from tests where Ca(OH)2 was used
contain 1213% calcite in addition to the quartz, muscovite/illite, pyrite, and anatase.
The pyrite particles and the reaction products at the surface of pyrite particles after the alkaline pre-oxidation and
cyanidation were examined in these three residue samples
by BSE images and EDS spectroscopy. Fig. 13 shows the
BSE micrographs of pyrite particles and the EDS spectra
of the reaction products at the surface of pyrite in the residue sample from Test 4. Figs. 14 and 15 show the results in
the residue sample from Test 10, and Figs. 16 and 17 show
the results in the residue sample from Test 12. These BSE
images and EDS spectra clearly show that iron-, silicon-,
and calcium-bearing compounds, with variable amounts
of sulfur, commonly surround the pyrite particles. Some
mineral nes were found in the product layer, such as
arsenic, aluminum, and/or potassium-bearing minerals.
Additionally, it can be noted that the EDS spectrum intensity for elemental calcium at the surface of pyrite particles
is signicantly greater for lime addition 10 g/kg ore (Figs.
16 and 17) than the calcium intensity for a lime addition
is 5 g/kg ore (Figs. 14 and 15). This result supports the
hypothesis that when lime is added in excess (10 g/kg) the
895