Minerals Engineering 23 (2010) 143150

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Thiosulphate leaching of gold in the presence of ethylenediaminetetraacetic acid (EDTA)

D. Feng *, J.S.J. van Deventer
Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010, Australia

a r t i c l e

i n f o

a b s t r a c t
The addition of low levels of ethylenediaminetetraacetic acid (EDTA) in the ammoniacal thiosulphate gold leach system lowered the catalytic cupric/cuprous redox equilibrium potential, hence the mixed solution potential and reduced the consumption of thiosulphate. In the leaching of pure gold, gold dissolution was enhanced in the presence of EDTA at a relatively low concentration, but excessive EDTA decreased gold dissolution. Raman analysis of the leached gold foil indicated that the stabilisation of thiosulphate by EDTA decreased the formation of the passivation layers of elemental sulphur and copper sulphide at the gold surface. In the leaching of a sulphide ore, the leaching kinetics and overall extractions of gold and silver were enhanced substantially, while the consumption of ammonium thiosulphate was reduced from 9.63 kg/t to 3.85 kg/t in the presence of 2.0 mM EDTA after 24 h leaching. This benecial effect became more pronounced at a higher EDTA concentration. The enhanced gold and silver extractions by EDTA were attributed to the increase in the dissolution of gold and silver bearing sulphides, the stabilisation of copper and thiosulphate in leach solutions, the prevention of leaching passivation and the decrease in the interference of foreign heavy metal ions. The use of EDTA in the ammoniacal thiosulphate leaching system makes it practical to achieve satisfactory gold extraction over extended periods of leaching under low reagent concentrations, where the consumption of thiosulphate is low. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 30 August 2009 Accepted 22 November 2009

Keywords: Gold ores Sulphide ores Grinding Leaching Surface modication

1. Introduction Thiosulphate gold leaching has received much attention as an alternative technology to the cyanidation of gold ores in recent years due to the growing environmental concerns over the use of cyanide. Thiosulphate leaching is effective for the treatment of complex and carbonaceous-type ores through the degradation of sulphide matrices and the prevention of preg-robbing (Abbruzzese et al., 1995; Alymore and Muir, 2001; Muir and Aylmore, 2004; Senanayake, 2004, 2005; Zipperian et al., 1988). Generally the thiosulphate leaching conditions reported in the literature are severe with high reagent consumption. In order to achieve satisfactory gold extraction from high sulphide containing ores, high reagent concentrations were applied (Alymore and Muir, 2001; Muir and Aylmore, 2004). From an economic point of view, it is required that the leaching should be carried out under low reagent concentrations over extended periods where reagent consumption is low. Efforts were made to minimise thiosulphate consumption by reducing the concentration of thiosulphate in solution (Cao et al., 1992). Nevertheless, dilute solutions of thiosulphate (<0.01 M) were found to
* Corresponding author. Tel.: +61 3 83449570; fax: +61 3 83444153. E-mail address: dfeng@unimelb.edu.au (D. Feng). 0892-6875/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2009.11.009

decompose more rapidly than concentrated solutions (>0.1 M) (Dhawale, 1993). Alternatively, sulphite was added to the leaching solution to stabilise thiosulphate (Kerley, 1981, 1983). However, sulphite signicantly retarded the thiosulphate leaching of gold by reducing Cu2+ in solution and hence lowering the potential of the solution. The major role of the cupric ion in the thiosulphate leaching system is to catalyse the dissolution of gold. It was reported that copper ions in solution could speed up the dissolution of gold by 1820 times (Ter-Arakelyan et al., 1984). Acceptable gold leaching rates using thiosulphate can be achieved in the presence of ammonia with cupric ion acting as the oxidant. However, thiosulphate degradation to tetrathionate is promoted by the Cu2+ ion as well (Alymore and Muir, 2001; Muir and Aylmore, 2004; Senanayake, 2004). A relatively low concentration of the cupric ion is preferred owing to its catalytic effect on thiosulphate degradation. However, this may result in slow leaching kinetics of gold. Ammonia is used for stabilising copper in solution in the ammoniacal thiosulphate system. At a low ammonia concentration, it is problematic to maintain copper at low concentrations in solution in the leaching of sulphide containing ores due to the adsorption of copper species on the mineral substrates especially sulphide minerals in gold ores. As a result, it is necessary to introduce additives to stabilise copper in solution at low reagent concentrations of ammonia, copper and thiosulphate. Brown et al. (2003) reported

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that various ligand classes, e.g. pyridyls, polyamines, aminocarboxylates and picolinates could stabilise thiosulphate. Ethylenediaminetetraacetic acid (EDTA) can form stable complexes with most multivalent heavy metal ions in solution. It has been recognised by numerous workers (e.g. Grano et al., 1988; Rumball and Richmond, 1996; Greet and Smart, 2002) that EDTA has the ability to solubilise the oxidation products of sulphide minerals in the otation of sulphide ores. Excessive EDTA leached bulk sulphide minerals besides the oxidative products at the sulphide surfaces (Wang and Forssberg, 1990; Pang and Chander, 1992). It is reasonable to assume that EDTA could form cupric EDTA complexes to stabilise cupric ions in solution. This will lower the catalytic cupric/cuprous redox equilibrium potentials, and hence reduce the thiosulphate consumption. EDTA was previously observed to stabilise thiosulphate (Xia et al., 2003). It is the purpose of this paper to evaluate the effect of EDTA on thiosulphate leaching of pure gold and a sulphide ore at low reagent concentrations. 2. Experimental work 2.1. Materials Gold foils (99.99% Au, thickness 0.2 mm) were used in the experiments with a surface area of about 20 mm2. The gold foils were polished with 0.1 lm monocrystalline diamond paste (Electron Microscopy Sciences), washed with acetone twice and rinsed with distilled water and swept with lint-free paper. A new gold foil was used for each leaching experiment. EDTA (analytically pure from Merck) was used to prepare 0.1 M stock solution with the addition of distilled water. All other chemicals are analytical or reagent grade. Pyrite samples with 99% purity and a trace of silica, which were obtained from Geological Specimen Supplies, Australia, were crushed, milled to 100% 45 lm and stored in air-tight plastic bags in a refrigerator. A sulphide gold ore was obtained from a Newcrest gold mine with a particle size of 80% passing 75 lm. A rotary splitter was used to obtain representative samples of the ore for experimental use. Quantitative X-ray Diffraction (XRD) was used to determine the mineralogy of the sulphide ore. An elemental analysis was performed by digestion of the ore. The mineralogical and elemental analysis results are shown in Table 1, which lists only the elements considered most important in the study. 2.2. Analytical techniques Elemental concentrations in solutions were determined by Inductively coupled plasma-optical emission spectrometry (ICP OES), involving the oxidation of sulphur species as stable sulphates prior to the analysis. After oxidation by hydrogen peroxide, solutions were acidied by HCl and HNO3 and boiled to ensure complete conversion of the metal species to the chloride form. For silver analysis, the oxidised solutions were only acidied by

HNO3. The thiosulphate concentration was determined by an iodometric method with the addition of acetic acid (10% solution) for eliminating the interference of the cupric tetra-amine complex with the titration. A platinum electrode (M21Pt, Radiometer) was used to measure the mixed solution potential with a double-junction reference electrode (Ag/AgCl, saturated KCl, Orion) to avoid the interference of thiosulphate with the reference electrode. All potentials were given with respect to the standard hydrogen electrode (SHE). Raman spectroscopy was used to identify the surface species of the leached gold foils. The Raman scans were run on a Renishaw 100 Raman Analyser. 100 scans were accumulated, using 633 nm radiation from a HeNe laser of 10 mW at the sample surfaces. 2.3. Leaching tests Leaching of pure gold was performed in a 250 ml reactor with a sampling port using a magnetic stirrer. A leach solution of 200 ml was used with desired concentrations of EDTA. The gold foils were suspended in the upper part of the leaching reactor with a nylon thread, ensuring no contact with the reactor wall during leaching. The stirring speed was maintained constantly at 400 min1. The gold dissolution rate was calculated based on the dissolved gold mass per m2 of the gold foil surface. After leaching, the gold foils were taken out of the leach solutions, rinsed with a substantial amount of warm distilled water and dried under vacuum. The leached gold foils were subjected to Raman spectroscopic analysis for surface speciation. Copper adsorption tests were conducted in a similar system, with the addition of 10 g pyrite samples in 200 ml solutions. Leaching of the sulphide ore was performed in a 1.5 L bafed PVC reactor using an overhead at-bladed impeller. The reactors were open to the air through the sampling ports. A leach solution of 1 L was added to the sulphide ore of 400 g. A natural pH of about 10.3 was used in the experiments, due to the buffering effect of NH /NH3. Leaching tests were performed at a rotation speed of 4 250 min1, and a temperature of 25 C in a water bath. Samples were taken continuously at certain intervals during a total retention time of 48 h. The samples were immediately subjected to iodine titration and oxidation for ICPOES analysis. The extraction of gold and silver was calculated on the basis of dissolved gold and silver in solution and compared with re-assay values of the starting ore and selected residues. Duplicate experiments were conducted with only average results reported, due to the standard deviations of all the tests being within 3%. 3. Results and discussion 3.1. Adsorption of copper on pyrite It is common practice to activate sulphides such as pyrite and pyrrhotite with the addition of Cu2+ in the otation of sulphides (Finkelstein, 1997). The Cu2+ ion may readily adsorb on pyrite surfaces and enhance collector adsorption thus rendering the pyrite hydrophobic. Early investigations into the mechanism for copper activation of pyrite proposed an ion exchange mechanism where Fe2+ was replaced by Cu2+ resulting in the production of covellite and elemental sulphur on the pyrite surface (Finkelstein, 1997). Voigt et al. (1994) showed that Cu2+ ions adsorbed on pyrite surfaces regardless of pH and were subsequently reduced to Cu+ via sulphur oxidation and that the mechanisms of copper uptake varied with solution pH. In addition Cu2+ ions were deposited on pyrite at pH > 6 via a hydrolysis mechanism forming complex hydrated species (Voigt et al., 1994). Weisener and Gerson (2000) showed a Cu+ layer covered by a Cu2+ rich layer on pyrite surfaces,

Table 1 Chemical and metallurgical analysis of the sulphide ore. Quantitative XRD analysis Mineral Albite Arsenopyrite Calcite Chalcopyrite Dolomite Gypsum Pyrite Quartz Content (mass%) 23.5 0.1 1.1 0.1 21.2 0 5.4 41.3 Elemental analysis Element Cu (%) Fe (%) S (%) As (mg/kg) Au (mg/kg) Ag (mg/kg) Ni (mg/kg) Zn (mg/kg) Content 0.07 5.27 2.9 383 4.3 2.0 65 23

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indicating the presence of adsorbed Cu+ covered by precipitated Cu(OH)2 at pH 8.5. Based on TOF-SIMS and XPS analysis, it was concluded that oxidised sulphur species formed on the pyrite surface with the reduction of Cu2+Cu+. In the ammoniacal thiosulphate leaching system, the Cu2+ ion is used to catalyse the dissolution of gold. Hence, a high Cu2+ ion concentration will result in fast leaching kinetics of gold. However, high cupric ion concentrations will accelerate the degradation of thiosulphate, due to the catalytic effect of Cu2+ ions on thiosulphate oxidation. As a result, low cupric ion concentrations are preferred for thiosulphate leaching of gold over extended leaching periods. The stability of Cu2+ ions in ammoniacal solutions in the presence of pyrite has never been reported in the literature. This is of great signicance in thiosulphate leaching of sulphide gold ores with low Cu2+ ion concentrations. Fig. 1 shows the adsorption of the Cu2+ ion on pyrite in the presence of ammonia. In the absence of ammonia, the Cu2+ ion was not stable at pH 8, likely due to the chemical adsorption of Cu2+ ions on pyrite surfaces together with the precipitation of Cu2+ ions as Cu(OH)2. Clearly, ammonia stabilised the Cu2+ ion in solution, and this benecial effect became more prominent at a higher ammonia concentration (Fig. 1). However, a substantial amount of Cu2+ ions still adsorbed on pyrite at an ammonia concentration of up to 0.6 M (Fig. 1). As mentioned above, high reagent concentrations are undesirable in terms of economic application of thiosulphate leaching in practice. As a consequence, the adsorption of Cu2+ ions on sulphides is not avoidable at low reagent concentrations. In the presence of 0.5 mM EDTA, the Cu2+ ion was stabilised in solution with almost no adsorption on pyrite, as shown in Fig. 1. Therefore, the introduction of a small amount of EDTA would allow a minimised usage of ammonia to stabilise the Cu2+ ion in the ammoniacal thiosulphate leaching system. About 60 mg/L iron was present in solution with the addition of 5 mM EDTA, while no iron was observed in the solutions without EDTA. Pyrite dissolved in ammoniacal solutions and formed iron oxide and hydroxide species at the pyrite surface, hindering further dissolution of pyrite. Pyrite dissolved to a larger extent in the presence of EDTA due to iron being stabilised by EDTA in solutions. This is benecial for the leaching of sulphide gold ores, as some gold can be partially exposed to leach solutions for effective dissolution via the degradation of the sulphide matrices.

3.2. Effect of EDTA on gold dissolution Fig. 2 illustrates gold dissolution in ammoniacal thiosulphate solution in the presence of EDTA at varied concentrations. After leaching, the gold foils showed brown surfaces in the absence of EDTA, while the surface colour became lighter for the gold foils with the addition of EDTA. This effect became more noticeable in the presence of EDTA at a higher concentration. At an excessive dosage of EDTA the surface colour of the gold foils remained unchanged during the leaching. As noted from Fig. 2, under the standard condition without EDTA the gold dissolution rate slowed after 7 h. This indicates that a passivation layer possibly formed with time. Bagdasaryan et al. (1983) and Pedraza et al. (1988) observed a sulphur layer as well as copper sulphide forming at the gold surface in a thiosulphate leaching system. Both elemental and sulphide sulphur can result from the decomposition of thiosulphate in alkaline solutions. The formation of the passivation layer at the gold surface could prevent thiosulphate from diffusing to the gold surface, hence inhibiting the gold dissolution. In contrast, in the presence of 0.125 mM EDTA the dissolution rate for gold remained almost constant in the leaching (Fig. 2), indicating EDTA stabilised the leaching system. After 24 h leaching, the overall gold dissolution was much higher in the presence of 0.125 mM EDTA than under the standard condition without EDTA. The dissolution rates for gold decreased with an increase in the EDTA concentration over 0.125 mM. The leach trends for gold appeared substantially linear with time in the presence of EDTA over 0.125 mM (Fig. 2). The mixed solution potentials decreased in the presence of EDTA, and this effect became more pronounced at a higher EDTA concentration. EDTA has stronger abilities than ammonia to complex the cupric ion, as indicated in Table 2 (Smith et al., 1998). In the ammoniacal thiosulphate leaching system, the mixed solution potential is determined by the redox equilibrium potential of the cupric/cuprous couple. A higher concentration of the cupric tetraamine complex will result in a higher equilibrium potential of the cupric/cuprous couple, hence a higher mixed solution potential. When a certain amount of EDTA is present in ammoniacal thiosulphate solutions, a part of the cupric tetra-amine complex will be converted to the cupric EDTA complex, and the cupric/cuprous complex equilibrium potential will decrease as a result. When sufcient EDTA is present in the leaching system, the cupric tetra-amine complex will be completely converted to the cupric

50
30

40

pH8 25

O 0.125 mM 0.25 mM 1.0 mM

[Cu], mg/L

30

Gold dissolution, g/m

0.2 M NH3 0.4 M NH3

20 15 10 5 0

20

0.6 M NH3 0.4 M NH3 (EDTA)

10

10 15 Time, h

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10

15 Time, h

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Fig. 1. Adsorption of Cu2+ ions on pyrite in the presence of ammonia. Pyrite < 45 lm; pyrite 10 g; solution 200 ml; initial Cu2+ concentration 45 mg/L; EDTA 5 mM.

Fig. 2. Thiosulphate leaching of pure gold in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.125, 0.25 and 1.0 mM. O standard condition without EDTA.

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Table 2 Stability constants of metal complexes at 25 C (source: Smith et al., 1998). Metal ions Ligand (L) Ammonia Species Cu+ Cu2+ Fe2+ Fe3+ Ni2+ Cr3+ Cr2+ Pb2+ Zn2+ Ag+ CuL2 CuL4 NiL6 ZnL4 AgL Stability 10.58 13.00 9.08 9.65 3.3 Thiosulphate Species CuL3 FeL NiL PbL4 Zn2L2 AgL3 Stability 13.71 1.98 0.78 6.2 5.84 13.1 EDTA Species CuL FeL FeL NiL CrL CrL PbL ZnL AgL Stability 18.7 14.27 25.0 18.52 23.4 13.6 17.88 16.44 7.32

but decreases the dissolution rate for gold, as observed in Fig. 2. It is reasonable to assume that EDTA at a relatively low concentration was able to stabilise the thiosulphate leaching system without much sacrice of the leaching rate for gold.

3.3. Surface speciation by Raman spectroscopy Fig. 4 shows the Raman spectra for the gold foils after leaching with and without EDTA. To obtain Raman spectra for thiosulphate, S8 sulphur and cupric sulphide, solid sodium thiosulphate, S8 sulphur and copper sulphide (CuS) standards were recorded separately under the same conditions. Solid sodium thiosulphate displayed bands at 434 cm1 and 1017 cm1, which were assigned to m(SS) and m(SO), respectively (Gabelica, 1980; Haigh et al., 1993; Jeffrey et al., 2008). The spectrum for S8 sulphur showed a m(SS) band at 471 cm1 and corresponding d(SSS) bands at 216 cm1 and 152 cm1 (Eckert and Steudel, 2003). Copper sulphide displayed the main m(SS) band at $473 cm1 and a lattice mode at $266 cm1. Thiosulphate can decompose to various sulphur species such as polythionates, sulphate, sulphite and elemental sulphur. As presented in Fig. 4, all spectra show a shoulder at $434 cm1, which was likely attributed to thiosulphate. Thus, the gold foils which were leached with or without EDTA contained a certain amount of thiosulphate species. Clearly, the spectrum for the gold foil after leaching under the standard condition without EDTA showed a wide peak at $471473 cm1, which possibly originated from the overlap of the peaks for sulphur and copper sulphide. A peak at $266 cm1 also appeared on the spectrum for gold after leaching without EDTA. Therefore, copper sulphide likely formed at the gold surface after leaching in the ammoniacal thiosulphate solution without EDTA. No clear peaks at $216 cm1 and $152 cm1 were observed on the spectrum for gold leaching without EDTA. However, this could not exclude the possibility of formation of sulphur at the gold surface. Polymeric sulphur chains likely formed at the gold surface instead of S8 rings (Parker et al., 2008). In contrast, the gold foil in the presence of 0.125 mM EDTA did not show clear characteristic peaks for sulphur and copper sulphide in its spectrum (Fig. 4). This indicates that the presence of EDTA decreased the formation of elemental sulphur and copper sulphide at the gold surface during the thiosulphate leaching process. EDTA could prevent cupric ions from precipitating out of solution as copper sulphide by complexing cupric ions. This is in good agreement

EDTA complex. Therefore, the mixed solution potential was lower with the addition of EDTA and the corresponding dissolution rate for gold was initially lower, as observed in Fig. 2. At high EDTA concentrations, the catalytic dissolution of gold by cupric ions was inhibited where almost all cupric ions were complexed by EDTA. As a consequence, the gold dissolution was low in such cases. The introduction of EDTA decreased the concentration of the oxidative cupric tetra-amine complex, and hence lowered the catalytic cupric/cuprous redox equilibrium potentials. It was indicated that the cupric tetra-amine complex promoted the oxidative degradation of thiosulphate to tetrathionate (Hemmati et al., 1989; Byerley et al., 1973a,b, 1975). Therefore, the oxidative decomposition of thiosulphate by the cupric tetra-amine complex was relatively lower in the presence of EDTA, as reected in Fig. 3. This benecial effect became more pronounced with an increase in the EDTA concentration. The minimisation of the thiosulphate decomposition likely decreased the formation of passivation layers at the gold surface during the thiosulphate leaching. Due to the stabilisation of thiosulphate by EDTA, the overall gold dissolution was higher in the presence of EDTA at 0.125 mM than under standard condition without EDTA after 24 h leaching. However, at high EDTA concentrations the oxidative cupric tetra-amine concentrations were low for gold oxidation, although the decomposition of thiosulphate was extremely low in such cases. Thus, the presence of EDTA at a higher concentration stabilised thiosulphate,

0.101 0.099 0.097 [S2O3 ], M

55000
434

45000 Intensity 35000

473 471

266 216 152

0.095 0.093 0.091 0.089 0.087 0

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Raman shift, cm

Fig. 3. Thiosulphate decomposition in the leaching of pure gold in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.125, 0.25 and 1.0 mM. O standard condition without EDTA.

Fig. 4. Raman spectra for gold after leaching with and without EDTA. Leaching: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.125 mM. O standard condition without EDTA.

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with the leach data, where the consumption of thiosulphate was low and less leaching passivation appeared in the presence of EDTA. 3.4. Thiosulphate leaching of the sulphide ore in the presence of EDTA Fig. 5 shows the leaching of the sulphide ore in ammoniacal thiosulphate solution in the presence of EDTA at varied concentrations. The leaching rates for gold at the initial stage were remarkably higher under all the conditions, and afterwards became lower. This was possibly because the exposed gold, being readily accessible by the ammoniacal thiosulphate solutions, was easily leached out at the start. In the absence of EDTA, the rate of gold leaching gradually levelled off after an extended period (Fig. 5). Gold leaching passivation likely occurred after a certain time of leaching in the absence of EDTA. It is expected that near 100% extraction of gold was unachievable with a further increase in the leaching time. In contrast, with EDTA present, the gold extraction still gradually increased with time after the initial fast leaching stage and near 100% extraction of gold was achievable after an extended period of leaching (Fig. 5). Therefore, it is reasonable to assume that the leaching passivation was reduced or eliminated with the addition of EDTA. In the leaching of pure gold, the gold dissolution increased only in the presence of EDTA at a low concentration, while the gold dissolution became lower with the increase in EDTA concentration over this certain level (Fig. 2). However, the kinetics increased in the leaching of the sulphide ore and near 100% gold extraction was reached within a shorter time with an increase in the EDTA concentration (Fig. 5). The difference in the effect of the EDTA concentration on the leaching of pure gold and the sulphide ore was possibly attributed to the dissolution of sulphide minerals in the ore and the release of heavy metal ions from the sulphide minerals. Clearly, the dissolution of sulphides increased signicantly in the presence of EDTA in the thiosulphate leaching of the sulphide ore, as indicated by a sharp increase in the sulphur concentration in Fig. 6. In terms of the sulphur concentration in solution, the sulphide minerals dissolved to a greater extent at a higher EDTA concentration. A larger extent of the breakdown of the sulphide matrices increased the gold leaching and the benecial effect became more pronounced at a higher EDTA concentration (Fig. 5). The dissolution of sulphide minerals likely formed secondary oxide and hydroxide phases on the sulphide mineral surfaces and hence hindered further dissolu-

17000 15000 13000

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Fig. 6. Sulphide dissolution in the thiosulphate leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

tion. EDTA continuously removed the oxidative layers from the sulphide mineral surfaces, enhancing the dissolution of the sulphide minerals (Wang and Forssberg, 1990; Pang and Chander, 1992). The dissolution of the sulphide minerals reached a plateau within 10 h in the absence of EDTA (Fig. 6), due to the occurrence of the passivation layers of oxidative products at the sulphide mineral surfaces. The dissolution of the sulphide minerals reached a dynamic equilibrium after an extended period in the presence of EDTA. A higher EDTA concentration allowed further dissolution of the sulphide minerals over the extended period, due to the availability of EDTA for more metal complexation. This also explains the fact that the gold extraction still gradually increased in the presence of EDTA, while it remained unchanged without EDTA after extended leaching periods. EDTA stabilised cupric ions in solutions in the presence of pyrite, as discussed above. In such a system, pyrite only dissolved to a small extent and other foreign cations were very limited for EDTA to complex. In addition, EDTA has a stronger ability to stabilise the cupric ion than the iron ions (Table 2). Therefore, a small amount of

100

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80 Gold extraction, %

61 [Cu], mg/L

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O 0.15 0.25 0.5 1.0 2.0

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Fig. 5. Thiosulphate leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

Fig. 7. Variation of copper concentration with time in the thiosulphate leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

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EDTA could stabilise the cupric ions in solutions. In the thiosulphate leaching of the sulphide ore, signicant amounts of foreign ions such as Pb ($4 mg/L), Zn ($0.5 mg/L), Ni ($12 mg/L), Ca ($200 mg/L) and Mg (30 mg/L) in solutions competed with the cupric ion for EDTA complexition. Fig. 7 shows the variation of the copper ion concentration with time in the leaching of the sulphide ore. In the absence of EDTA, the copper concentration decreased sharply at the initial stage of leaching, followed by a quick increase and a gradual increase till the end of the leaching period (Fig. 7). The initial sharp decrease of the copper concentration was likely due to the adsorption of copper on the sulphide mineral surfaces. During the initial stage, the copper minerals in the ore dissolved fast and released copper ions into the solution. As a consequence, a quick increase in the copper concentration was observed after the initial leaching stage despite some of the released copper ions adsorbing back to the sulphide mineral surfaces again. The dissolution of the sulphide minerals reached a dynamic equilibrium after about 7 h, as observed in Fig. 6. The following gradual increase in the copper concentration was likely attributed to the adsorption of tetrathionate on the sulphide mineral surfaces, which could replace the cupric ions originally adsorbing on them (Fig. 7). Tetrathionate as the oxidative product of thiosulphate was found to have strong afnity to ion exchange resins (Zhang and Dreisinger, 2002). It is also expected that tetrathionate can adsorb strongly on the sulphide mineral surfaces. The concentration of tetrathionate increased with time, due to the decomposition of thiosulphate in the leaching. Clearly, the copper concentration in solution increased with the addition of EDTA, and in general the copper concentration became higher at a higher EDTA concentration (Fig. 7). In the presence of EDTA, the copper concentration increased during the initial 5 h due to the fast dissolution of the copper minerals in the ore, but dropped afterwards due to the adsorption of copper on the sulphide mineral surfaces. With the proceeding of the leaching process, the copper concentration gradually increased likely due to the replacement of copper ions by tetrathionate. Fig. 8 shows the variation of mixed solution potential with time in the leaching of the sulphide ore. Clearly, the mixed potential decreased in the presence of EDTA and this effect became more noticeable at a higher EDTA concentration. Under all the conditions, the mixed potentials followed a similar trend, i.e. the mixed potentials sharply decreased within the rst 3 h, and gradually increased afterwards (Fig. 8). The mixed potential in the ammoniacal

thiosulphate leaching system is substantially determined by the Cu2+/Cu+ redox equilibrium potential under the specic conditions. Within the rst several hours of leaching, the sulphide minerals in the ore dissolved rapidly (Fig. 6). The oxidation of the sulphides was accompanied by the reduction of the cupric tetra-amine complex and the consumption of dissolved oxygen (Feng and Van Deventer, 2002a). In addition, the cupric tetra-amine complex also decreased during the oxidation of gold. The formed cuprous ions could not be converted to the cupric tetra-amine complex immediately, owing to the lack of dissolved oxygen in solutions. Consequently, the mixed potentials decreased sharply within the rst 3 h. After the initial stage, more dissolved oxygen would be present in solutions as the dissolution of the sulphide minerals nearly reached a dynamic equilibrium. In addition, more copper ions were available due to the dissolution of the copper minerals and the gradual release of the adsorbed copper ions from the sulphide mineral surfaces in the presence of tetrathionate. As a result, the concentrations of the cupric tetra-amine complex gradually increased and hence the mixed potentials increased accordingly after 3 h. The presence of EDTA reduced the decomposition of thiosulphate in the leaching of the sulphide ore (Fig. 9). Thiosulphate decomposed to a lesser extent at a higher EDTA concentration (Fig. 9). The consumption of ammonium thiosulphate reduced from 9.63 kg/t to 3.85 kg/t at 2.0 mM EDTA after 48 h leaching. In comparison with the leaching of pure gold, the leaching of the sulphide ore consumed more thiosulphate due to the presence of the semi-conductive minerals such as sulphide and iron minerals (Xu and Schoonen, 1995; Benedetti and Boulegue, 1991). The catalysis of sulphide minerals in the thiosulphate decomposition was believed to originate from its strong afnity for aqueous sulphur species and their semi-conducting properties. Sulphides were thought to form interfacial intermediate complexes with the electron donor, thiosulphate, on anodic sites, and the terminal electron acceptor, oxygen, on cathodic sites. The electrons would transfer from the anodic site to the cathodic site via the conduction band of the sulphide minerals. Apart from semi-conducting minerals, some heavy metal ions were also found to catalyse the decomposition of thiosulphate (Feng and Van Deventer, 2002b). EDTA could form stable species with heavy metal ions (Table 2). This was likely the reason for lower thiosulphate consumption in the presence of EDTA, as observed in Fig. 9. The minimisation of the thiosulphate decomposition could decrease the formation of passivation layers of elemental sulphur and copper sulphide at the gold surfaces.

280 275
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[S2O3 ], M

265

O 0.15 0.25 0.5 1.0 2.0

10

20 Time, h

30

40

50

Fig. 8. Variation of mixed potential with time in the thiosulphate leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

Fig. 9. Thiosulphate consumption in the leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

D. Feng, J.S.J. van Deventer / Minerals Engineering 23 (2010) 143150

149

90 75 Silver extraction, % 60 45 30 15 0

O 0.15 0.25 0.5 1.0 2.0

10

20

30 Time, h

40

50

Fig. 10. Silver extraction in the leaching of the sulphide ore in the presence of EDTA. Solution: 0.1 M (NH4)2S2O3, 0.5 M NH3 and 50 mg/L Cu2+. EDTA 0.15, 0.25, 0.5, 1.0 and 2.0 mM. O standard condition without EDTA.

ing period because of the stabilisation of thiosulphate by EDTA. An excessive EDTA dosage caused a decrease in gold dissolution. Surface speciation by Raman spectroscopy on the leached gold surfaces indicated that the presence of EDTA decreased the formation of the passivation layers of elemental sulphur and copper sulphide at the gold surface. In the leaching of the sulphide ore, the addition of EDTA decreased the mixed solution potentials and the consumption of ammonia thiosulphate from 9.63 kg/t to 3.85 kg/t at 2.0 M after 48 h. The consumption of thiosulphate was relatively higher in the leaching of the sulphide ore than pure gold. The leaching kinetics and overall gold extraction substantially increased in the presence of EDTA especially at a higher concentration. Similarly, the addition of EDTA also signicantly enhanced the silver extraction. The enhanced gold and silver extractions by EDTA were attributed to the increased dissolution of the gold and silver bearing sulphide minerals, the stabilisation of copper and thiosulphate in leach solutions, the prevention of leaching passivation and the decrease in the interference of foreign heavy metal ions. Under the low reagent concentrations, near 100% gold recovery from the sulphide ore was achievable over extended periods of leaching in the presence of EDTA. Acknowledgements The nancial support from Newcrest Mining Limited, Placer Dome Limited, and the Australian Research Council is gratefully acknowledged. References
Abbruzzese, C., Fornari, P., Massidda, R., Veglio, F., Ubaldini, S., 1995. Thiosulphate leaching for gold hydrometallurgy. Hydrometallurgy 39, 265276. Alymore, M.G., Muir, D.M., 2001. Thiosulphate leaching of gold a review. Minerals Engineering 14 (2), 135174. Bagdasaryan, K.A., Episkoposyan, M.L., Ter-Arakelyan, K.A., Babayan, G.G., 1983. The kinetics of the dissolution of gold and silver in sodium thiosulphate solutions. Soviet Journal of Non-Ferrous Metals 376, 6468. Benedetti, M., Boulegue, J., 1991. Mechanism of gold transfer and deposition in a supergene environment. Geochimica et Cosmochimica Acta 55 (6), 15391547. Brown, T., Fischmann, A., Spiccia, L., McPhail, D.C., 2003. Alternative copper(II) catalysts for gold leaching: use of multidentate ligands to control thiosulphate oxidation. In: Young, C.A., Alfantazi, A.M., Anderson, C.G., Dreisinger, D.B., Harris, B., James, A. (Eds.), Hydrometallurgy 2003Fifth International Conference in Honour of Professor Ian Ritchie, vol. 1: Leaching and Solution Purication, Vancouver BC Canada, August 2427, TMS. The Minerals, Metals & Materials Society, Warrendale, USA, pp. 213226. Byerley, J.J., Fouda, S., Rempel, G.L., 1973a. Kinetics and mechanism of the oxidation of thiosulphate ions by copper(II) ions in aqueous ammonia solution. Journal of Chemical Society: Dalton Transactions 889, 893. Byerley, J.J., Fouda, S., Rempel, G.L., 1973b. The oxidation of thiosulphate in aqueous ammonia by copper(II) oxygen complexes. Inorganic Nuclear Chemistry Letters 9, 879883. Byerley, J.J., Fouda, S., Rempel, G.L., 1975. Activation of copper(II) ammine complexes by molecular oxygen for the oxidation of thiosulphate ions. Journal of Chemical Society: Dalton Transactions 1329, 1338. Cao, C., Hu, J., Gong, Q., 1992. Leaching of gold by low concentration thiosulphate solution. Randol Gold Forum, Vancouver92. Randol International, Colorado, USA. pp. 293298. Dhawale, S.W., 1993. Thiosulphate. Journal of Chemical Education 70 (1), 1214. Eckert, B., Steudel, R., 2003. Molecular spectra of sulphur molecules and solid sulphur allotropes. In: Steudel, R. (Ed.), Topics in Current Chemistry: Elemental Sulphur and Sulphur-Rich Compounds II. Springer Verlag, Berlin, pp. 3198. Feng, D., Van Deventer, J.S.J., 2002a. Leaching behaviour of sulphides in the ammoniacal thiosulphate systems. Hydrometallurgy 63, 189200. Feng, D., Van Deventer, J.S.J., 2002b. The inuence of heavy metal ions on the gold dissolution in thiosulphate solutions. Hydrometallurgy 64, 231246. Finkelstein, N.P., 1997. The activation of sulphide minerals for otation: a review. International Journal of Mineral Processing 52, 81120. Gabelica, Z., 1980. Structural study of solid inorganic thiosulphates by infrared and Raman spectroscopy. Journal of Molecular Structure 60, 131138. Grano, S.R., Ralston, J., Johnson, N.W., 1988. Characterisation and treatment of heavy media slimes in the Mont Isa Mines leadzinc concentrator. Minerals Engineering 1 (2), 447459. Greet, C., Smart, R.St.C., 2002. Diagnostic leaching of galena and its oxidation products with EDTA. Minerals Engineering 15, 515522.

Heavy metal ions such as Ni, Zn and Cr were found to retard gold leaching especially at relatively higher concentrations due to the formation of passivation layers at gold surfaces (Feng and Van Deventer, 2002b). This was possibly one of the reasons for limited increase in the gold extraction after extended periods of the leaching of the sulphide ore without the addition of EDTA (Fig. 5). The decreased interference of foreign metal ions with the addition of EDTA partly ensured the achievement of near 100% gold extraction after extended periods of gold leaching. Fig. 10 shows silver extraction in the leaching of the sulphide ore with the addition of EDTA at varied concentrations. Similar to the gold extraction, the silver extraction from the sulphide ore also increased in the presence of EDTA, and the benecial effect became more pronounced with an increase in the EDTA concentration (Fig. 10). The silver extraction no longer increased with a further increase in the EDTA concentration over 2.0 mM, despite slightly higher leaching kinetics. The leaching mechanism for silver by ammoniacal thiosulphate solutions with copper is similar to that of gold where an oxidant is necessary (Zipperian et al., 1988). Silver leaching was found to increase with increasing copper and thiosulphate concentrations, and to decrease with increase in ammonia concentration (Zipperian et al., 1988). As discussed above, the introduction of a small amount of EDTA would allow the use of a low concentration of ammonia for the stabilisation of copper in solutions. Likewise, EDTA could stabilise thiosulphate and eliminate the formation of passivation layers. Therefore, silver leaching under low reagent concentrations was achievable with low additions of EDTA.

4. Conclusions The effect of EDTA on leaching of pure gold and a sulphide ore was investigated in ammoniacal thiosulphate solutions. EDTA stabilised the cupric ion in solutions at a lower ammonia concentration, due to the formation of a more stable complex with the cupric ion than ammonia. The introduction of a small amount of EDTA in the ammoniacal thiosulphate system lowered the catalytic cupric/cuprous redox equilibrium potential, hence the mixed solution potential and reduced the consumption of thiosulphate, since the interaction between thiosulphate and the cupric complexes was reduced. In the leaching of pure gold, EDTA at a low concentration increased the overall gold dissolution over a prolonged leach-

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