Hydrometallurgy 82 (2006) 126 132 www.elsevier.

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Ammoniacal thiosulphate leaching of gold in the presence of pyrite

D. Feng , J.S.J. van Deventer
Department of Chemical Engineering, University of Melbourne, Victoria, 3010, Australia Available online 27 April 2006

Abstract The effect of pyrite on gold dissolution was investigated in the ammoniacal thiosulphate leaching system using pure gold foils. Special emphasis was placed on gold leaching in association with pyrite dissolution, thiosulphate decomposition and gold leaching passivation. The presence of pyrite retarded gold dissolution and this detrimental effect became more pronounced at higher pyrite contents. Pyrite catalysed the decomposition of thiosulphate to trithionate. The addition of sulphate enhanced gold leaching by retarding the dissolution of pyrite in ammoniacal thiosulphate solutions. XPS analysis indicated the presence of iron hydroxide species at the gold surfaces in the presence of pyrite, which was likely responsible for the reduced gold dissolution. SEM analysis indicated a lesser extent of gold dissolution occurring in the presence of pyrite. 2006 Elsevier B.V. All rights reserved.
Keywords: Gold leaching; Thiosulphate; Pyrite; Passivation

1. Introduction Thiosulphate as an alternative lixiviant for gold has received much attention in recent years due to the growing environmental concerns over the use of cyanide. Acceptable gold leaching rates using thiosulphate were achieved in the presence of ammonia with the cupric ion acting as the oxidant (Abbruzzese et al., 1995; Langhans et al., 1992; Tozawa et al., 1981; Kerley, 1981, 1983; Block-Bolten and Torma, 1986; Hemmati et al., 1989; Groudev et al., 1996; Marchbank et al., 1996; Wan, 1997; Wan et al., 1994; Wan and Brierley, 1997; Thomas et al., 1998; Zipperian et al., 1988). The leaching of gold in thiosulphate solutions is an electrochemical reaction, with the constituent half reactions being the oxidation of gold to gold thiosul-

phate, and the reduction of Cu(II) ammine to Cu(I) thiosulphate, as shown in Eqs. (1) and (2), respectively. Au 2S2 O2 AuS2 O3 3 e 3 CuNH3 2 3S2 O2 e CuS2 O3 5 3 4 3 4NH3 1 2

The thiosulphate leaching system is complicated by the homogeneous reduction of Cu(II) by thiosulphate according to the simplified overall reaction, Eq. (3). 2CuNH3 2 8S2 O2 2CuS2 O3 5 8NH3 3 4 3 S4 O2 6 3

Corresponding author. Fax: 61 3 8344 4153. E-mail address: dfeng@unimelb.edu.au (D. Feng). 0304-386X/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2006.03.006

Gong et al. (1993) suggested that the kinetics of leaching gold from an auriferous pyrite concentrate could be controlled by a corrosion reaction of the ammonia-thiosulphatecopper system on pyrite. From Xray powder diffraction studies, Qian et al. (1993) observed less chalcopyrite present in thiosulphate leached residues than in the original ore. They concluded

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that an ammonia-thiosulphate solution containing copper, leached chalcopyrite by a corrosive process. Scanning electron microscope showed clear scarring on leached chalcopyrite grains. These authors also observed some dissolution of pyrite in the residues. Copper sulphide minerals, other than chalcopyrite, also dissolved readily in an aerated thiosulphate leach solution, particularly when ammonia was present. Other sulphide minerals also showed varied extents of dissolution in thiosulphate leach solutions (Feng and Van Deventer, 2002). However, the relationship between gold dissolution and the dissolution of sulphides has not yet been investigated in detail in the ammoniacal thiosulphate system. It is the objective of this investigation to conduct a systematic study of the gold dissolution in the presence of pyrite in ammoniacal thiosulphate systems. 2. Experimental 2.1. Minerals and reagents Pyrite (Py) and quartz (Qz) samples were obtained from Geological Specimen Supplies, Australia. The minerals were crushed, dry milled in a ring mill, sieved into the size fraction of 4575 m and stored in air-tight plastic bags in a refrigerator to avoid any further oxidation. Quantitative XRD results indicated that the mineral samples are of over 98% purity. Gold foils (99.99% Au, thickness 0.2 mm) were used in the experiments with a surface area of about 0.20 cm2. Laboratory grade ammonium thiosulphate, ammonium sulphate and ammonia solution (25%) were provided by Westlab Chem Supply Pty Ltd, Australia. Analytically pure cupric sulphate, hydrogen peroxide (30% w/v), and hydrochloric acid were obtained from Merck. Distilled water was used in the experiments. 2.2. Analytical techniques Elemental concentrations in solutions were determined by ICP-OES, involving the oxidation of sulphur species as very stable sulphates prior to the analysis. After oxidation by hydrogen peroxide, HCl was added to the solution, which was boiled to ensure complete conversion of the metal species to the chloride form. The thiosulphate concentration was determined by iodometric methods. In order to eliminate the effect of the cupricammonia complex on iodine titration, a certain amount of acetic acid (10% solution) was added prior to the titration with the indicator Vitex. Polythionates were determined by ion-chromatography on Dionex DX-500 (Sunnyvale, CA, USA) using ion-

interaction chromatography with conductivity and UV detection, as described by O'Reilly et al. (2002). Polythionates were eluted within 18 min using an eluant comprising an acetonitrile step gradient at 0 min from 15% to 28% v/v, 3 mM TBAOH and 2.5 mM sodium carbonate, operated using a Dionex NS1 column with guard. A platinum electrode (M21Pt, Radiometer) was used to measure the mixed solution potential with a doublejunction reference electrode (Ag/AgCl, saturated KCl, Orion) to avoid the interference of thiosulphate with the reference electrode. All potentials are given with respect to SHE. X-ray photon spectroscopy (XPS) was used to identify the surface species of the leached gold foil and pyrite samples. XPS was performed on a nanoprobe (Fisons Instruments) at about 10 8 Torr (using monochromatic the Al K X-ray at 1486.6 eV). The pyrite samples were filtered and rinsed with distilled water for three times and dried under vacuum overnight for XPS analysis. Similarly, the leached gold foils were rinsed with distilled water and dried under vacuum overnight for XPS and SEM (Phillips XL30)/EDAX (Oxford) analysis. 2.3. Experimental method Experiments were performed in a 400 mL open-top reactor using a magnetic stirrer at a rotating speed of 400 min 1. 250 mL of solution was added to desired amounts of the quartz and pyrite samples. The gold plate surfaces were polished by 2000 grid sand papers, washed with acetone twice and rinsed with de-ionised water before each test. The gold plates were suspended in the upper part of the leaching reactor with a nylon thread, ensuring no contact with the reactor wall during leaching. All experiments were performed at room temperature (20 1 C). Samples were taken continuously at certain intervals during a total retention time of 24 h. The samples were centrifuged and filtered for the subsequent iodine titration, polythionate determination and oxidation for ICP analysis. The gold dissolution rate was calculated based on the dissolved gold mass per m2 of the gold plate surface. All the experiments were conducted with the reagent dosages of 0.5 M (NH4)2S2O3, 0.012 M CuSO45H2O and 2.0 M NH4OH at pH 10.5. 3. Results and discussion 3.1. Dissolution of gold in the presence of pyrite Fig. 1 shows gold dissolution in the presence of varied amounts of pyrite. In comparison, the effect of varied

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350
Qz (0.4) Py (0.4)

D. Feng, J.S.J. van Deventer / Hydrometallurgy 82 (2006) 126132

Trithionate can also further decompose to give thiosulphate and sulphite, as shown in Eq. (5): 2S3 O2 6OH S2 O2 4SO2 3H2 O 6 3 3 5

Gold dissolution, g/m2

280

Py (2.0) Py (8.0) Py (16)

210

140

70

0 0 5 10 15 20 25

Time, h
Fig. 1. Effect of pyrite on gold dissolution in ammoniacal thiosulphate. Pyrite content: 0.4, 2.0, 8.0 and 16 g/L.

amounts of inert quartz on the rate of gold dissolution was also evaluated. The gold dissolution rates in the quartz slurries were used as standards to compare the rates in the presence of pyrite. The gold dissolution exhibited an approximately linear relationship with time in the presence of quartz. Quartz had only a marginal effect on reducing gold dissolution at a higher content. The rate reduction is attributed to quartz slime in the solutions partially blocking the gold plate surfaces. In the quartz slurry, the gold surface showed light brown after leaching regardless of the quartz content in the slurries. In contrast, the gold plates appeared dark-brown in the pyrite systems and the leached gold surfaces became darker with an increase in the pyrite content. This indicates that leaching passivation occurred in the presence of pyrite and became more pronounced at higher pyrite contents. This is in line with the leaching result where the gold dissolution and leaching kinetics were significantly reduced with the addition of pyrite and this detrimental effect became more remarkable at higher pyrite contents (Fig. 1). 3.2. Effect of pyrite on thiosulphate oxidation Thiosulphate is a metastable anion that tends to readily undergo chemical decomposition in aqueous solutions, particularly in acidic solutions. In the presence of cupric ions, thiosulphate can be oxidised to tetrathionate following the route in Eq. (3). Tetrathionate can further decompose to higher or lower polythionates through the formation of trithionate (Byerley et al., 1973a,b, 1975). The reaction is catalysed by the presence of thiosulphate with the overall reaction shown in Eq. (4): 2S4 O2 6 3OH
5

The decomposition of tetrathionate to form trithionate is much faster in alkaline solutions following Eq. (4), in comparison with the decomposition of trithionate as shown in Eq. (6) (Zhang and Dreisinger, 2002). Under the reagent conditions of this work, only trithionate was determined, as shown in Fig. 2. Clearly, the trithionate concentration increased almost linearly with time. In terms of the changes of trithionate concentrations, the presence of 0.4 to 16 g/L pyrite significantly increased the decomposition of thiosulphate and this effect became more remarkable with an increase in the pyrite content (Fig. 2). In contrast, the trithionate concentration was only slightly increased when the quartz content was increased from 0.4 to 16 g/L. Polythionates were found to reduce copper(II) ions and hence decrease the leaching kinetics of gold (Chu et al., 2003). This could be one of the reasons causing lower gold dissolution in the presence of pyrite. In addition, the decomposition of thiosulphate has been reported to form passivation layers of elemental sulphur and copper sulphide, which prevent thiosulphate solutions from diffusing to gold surfaces (Bagdasaryan et al., 1983; Pedraza et al., 1988). Therefore, the higher decomposition of thiosulphate could cause a larger extent of passivation in the presence of pyrite. The slurry pH remained constant at 10.5 during + leaching, due to the buffering effect of NH3 and NH4 . The mixed potential was in the range of 155 to 175 mV

28
Qz (0.4) Qz (16) Py (0.4) Py (2.0) Py (8.0) Py (16)

21

[S3O62-], mM

14

0 0 5 10 15 20 25

Time, h
Fig. 2. Variation of trithionate concentration during gold dissolution in the presence of pyrite and quartz. Quartz content: 0.4 and 16 g/L. Pyrite content: 0.4, 2.0, 8.0 and 16 g/L.

=2 S2 O2 3

S3 O2 6

=2 H2 O
3

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in the presence of quartz. The mixed potentials were slightly lower in the presence of pyrite and this trend became more obvious at higher pyrite contents. In theory, the oxidative decomposition of thiosulphate should be lower at a lower mixed potential. As a consequence, the excessive consumption of thiosulphate was likely due to the catalytic effect of pyrite on the decomposition of thiosulphate. Xu and Schoonen (1995) proposed that the pyrite-surface-catalysed oxidation of thiosulphate to tetrathionate by dissolved oxygen was the dominant thiosulphate decomposition mechanism in aqueous solution of pH 2.98.6 at 20 C, and that the rate of tetrathionate formation was first order with respect to the pyrite surface concentration. The catalysis of pyrite in this reaction originated from its strong affinity for aqueous sulphur species and its semi-conducting properties. Pyrite was believed to form an interfacial intermediate complex with thiosulphate, the aqueous electron donor, on anodic sites, and oxygen, the terminal electron acceptor, on cathodic sites. The electrons could transfer from the anodic site to the cathodic site via the conduction band of pyrite. This mechanism could also contribute to the catalytic effect of pyrite on the oxidative decomposition of thiosulphate in alkaline aqueous solutions. In the presence of the copper(II)-ammine complex, the electron acceptor would be preferentially the copper(II)-ammine complex. 3.3. Effect of sulphate on gold dissolution Fig. 3 shows the effect of sulphate on gold dissolution in the mineral slurry systems. With the addition of 0.5 M 2 SO4 , the gold dissolution rate slightly increased in the quartz slurry, while it was significantly increased in the pyrite slurry. This observation was in accordance with
350

those of Hu and Qian (1991) and Hu and Gong (1989). The decomposition of thiosulphate was slightly reduced 2 with the addition of 0.5 M SO4 in both quartz and pyrite systems. It was shown that sulphate competed with thiosulphate in complexing to Cu(II) at the axial sites, thus reducing the rate of thiosulphate oxidation by Cu(II) (Breuer and Jeffrey, 2003). The decrease in the decomposition of thiosulphate with the addition of sulphate could reduce the formation of passivation layers of elemental sulphur and copper sulphide and hence, increase the dissolution of gold. Oxidative dissolution of pyrite in the ammoniacal thiosulphate leach is expected to form the final product of sulphate. The addition of sulphate depressed the dissolution of pyrite in terms of the variation of the sulphur concentrations in solutions. The released sulphur concentration from pyrite was reduced from 21.3 to 12.5 mg/L in the presence of 2 g/L pyrite. Perez and Garaviz (1987) reported that at pH levels lower than 8.0, metallic iron (from grinding media) and iron salts dissolve in solution resulting in a decrease in gold dissolution. The formation of colloidal iron oxide or hydroxide particles at gold surfaces could retard gold dissolution. This could be one of the reasons why pyrite retarded the gold dissolution. Therefore, the reduced dissolution of pyrite with the addition of sulphate may reduce the tendency to form the passivation layers of iron species at gold surfaces and enhance the dissolution of gold as a result. 4. XPS studies The XPS analysis of sulphur and iron speciation at the pyrite and gold surfaces after contact with ammoniacal thiosulphate solutions by using XPS allows a better understanding of the mechanism for pyrite reducing gold dissolution. The XPS spectra were recorded for Fe 2p and S 2p for these samples. Fig. 4 shows the S 2p spectra for the sulphide samples before and after contact with solution. The S 2p spectrum for the original sulphide was composed of three peaks at around 163.2, 164.2 and 169.3 eV, while the S 2p spectrum for the sulphide after contact in the ammoniacal solution had two clear peaks at around 163.2 and 169.3 eV and a broad peak in the range of 163.9 and 166.4 eV, which was de-convoluted to two peaks at around 164.2 and 164.9 eV, respectively. The peak at around 164.2 eV was assigned to elemental sulphur S8 (Wagner, 1990), the 2 peak at around 163.2 eV was originated from the S2 in pyrite (Descostes et al., 2001), and the peak at around 2 169.3 eV resulted from SO4 (Wagner, 1990). The peak at around 164.9 eV was attributed to intermediate

Gold dissolution, g/m2

280

Qz Qz (SO4) Py Py (SO4)

210

140

70

0 0 5 10 15 20 25

Time, h
Fig. 3. Effect of sulphate on gold dissolution in the presence of pyrite and quartz. Mineral content: 2 g/L; 0.5 M SO2. 4

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28 25

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70
Before After

kCPS (X1000)

19 16 13 10 7 172

kCPS (X1000)

22

60

50

40

170

168

166

164

162

160

30 724

718

712

706

700

Binding energy, eV
Fig. 4. S 2p spectra for pyrite before and after 24 h contact with thiosulphate leach solution.

Binding energy, eV
Fig. 6. Fe 2p spectra for gold leached in the presence of 16 g/L pyrite.

sulphur species between elemental sulphur and sulphite such as thiosulphate (Descostes et al., 2001). The presence of the thiosulphate-like intermediate sulphur species at the pyrite surface was possibly the result of the interaction between the adsorbed thiosulphate and the pyrite surface. Clearly, the elemental sulphur concentration became higher after leaching, indicating that the decomposition of pyrite partially formed some elemental sulphur (Fig. 4). Both sulphur and copper species were detected at the surfaces of the gold foils leached in the presence of quartz and pyrite. The dominant sulphur species were found to be thiosulphate and the dominant copper species were in copper(I) form. The Fe 2p spectra for pyrite in Fig. 5 indicated that the pyrite surface after leaching in ammoniacal thiosulphate solutions was oxidised to form FeOOH showing a peak at 711.8 eV (Harvey and Linton, 1981). In comparison, the original pyrite only showed an iron peak at 708 eV,
105

which was Fe2+ in FeS2. The Fe 2p spectra for the gold leached in the presence of pyrite showed a clear peak at 711.8 eV, which was the characteristic peak for FeOOH (Fig. 6). This could be caused by the

Before

CPS (X1000)

80
After

55

30 716 713 710 707 704

Binding energy, eV
Fig. 5. Fe 2p spectra for pyrite before and after 24 h contact with thiosulphate leach solution. Fig. 7. Typical SEM images of the leached gold surfaces in the presence of (a) quartz and (b) pyrite. Mineral content: 2 g/L; leaching time: 24 h.

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precipitation of pyrite fines at the gold surfaces and the subsequent oxidation of pyrite. The formation of iron hydroxide at the gold surfaces could be the main reason causing the decrease of gold dissolution in the presence of pyrite. 5. Topological studies on the leached gold foils In order to study the surface morphology of the gold foils after leaching, the gold foils were subjected to SEM analysis coupled with EDAX. Fig. 7a and b shows the SEM images of the leached gold surfaces in the presence of quartz and pyrite, respectively. Clearly, the leached gold foil surfaces show varied degrees of erosion, and different morphological structures. In the absence of sulphides, the leached gold foil surface showed a regular net-work structure as depicted in Fig. 7a. The leached gold surface in the presence of pyrite appeared to be relatively smooth, and a very thin waterprint-like film was spotted unevenly at the surfaces. The composition of the film could not be identified by the EDAX due to its low sensitivity. The film is possibly an iron oxide formed in the dissolution of pyrite, which retarded the further gold dissolution. 6. Conclusions The presence of pyrite significantly reduced gold dissolution in ammoniacal thiosulphate solutions and this detrimental effect became more prominent at higher pyrite contents. Pyrite had a catalytic effect on the decomposition of thiosulphate. The decomposition of thiosulphate mainly formed trithionate under the experimental conditions. The addition of sulphate in the pyrite system increased the gold dissolution rate because of the depression of pyrite dissolution in the leaching system. XPS results indicated the formation of iron hydroxide species at the gold surfaces in the presence of pyrite, which likely contributed to the reduced gold dissolution. Topological studies by SEM demonstrated that gold dissolved to a lesser extent in the presence of pyrite. Acknowledgements The financial support from Newcrest Mining Limited, Placer Dome Technical Services Limited, and the Australian Research Council is gratefully acknowledged. Appreciation is also expressed to Hui Tan for assistance with the experimental work.

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