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d and Oxygen
P L Breuer1, D M Hewitt2, M I Jeffrey3 and J A Rumball4
ABSTRACT
Ion chromatography utilising an anion exchange column and UV detection has facilitated an improved understanding of sulfide mineral leaching in cyanide solutions. By analysing for sulfide, sulfite, thiocyanate, thiosulfate and metal cyanides it is possible to show that chalcocite dissolution is a non-oxidative process in which copper cyanide and sulfide ions are formed in solution. Further, the homogeneous oxidation of the sulfide ions by dissolved oxygen is slow, but catalysed by a surface of lead sulfide or pyrite. Polysulfides may also be formed as an intermediate oxidation product and these undergo further reaction to produce thiocyanate, thiosulfate and sulfite. The leaching of copper from a pyrite concentrate sample is shown to be rapid, and accompanied by significant iron dissolution; however, the iron is not believed to be from pyrite, pyrrhotite or chalcopyrite. The rate of iron leaching and cyanide consumption is reduced by maintaining low cyanide and high oxygen concentrations. Preoxidation or the addition of lead(II) ions does not reduce the iron dissolution from this pyrite concentrate.
INTRODUCTION
The recovery of gold from sulfide ores and concentrates is becoming more widespread as the supply of oxide orebodies diminishes. Many sulfide minerals are problematic in the cyanidation of these ores and concentrates, as they are known to consume oxygen and cyanide (Hedley and Tabachnick, 1968; Nicol, Fleming and Paul, 1987; Deschnes, 2005; Dai and Jeffrey, 2006; May et al, 2005). Most metal sulfides decompose in aerated, alkaline cyanide solution to form metal ions, metal oxides or metal cyanide complexes and various sulfur-containing species including thiocyanate, sulfide and thiosulfate ions, with polythionates and polysulfides having also been detected (Marsden and House, 1992). The negative impact that reactive sulfide minerals have on gold dissolution and cyanide and oxygen consumption has been widely studied, along with the addition of lead(II) ions to counteract their effect. A detailed description of this work can be obtained from the more recent publications and references cited above (Dai and Jeffrey, 2006; Deschnes, 2005; May et al, 2005). However, there is little fundamental understanding of the reactions and mechanisms involved. Chalcocite is one of the most reactive sulfide minerals, where the copper is leached to form copper cyanide and sulfide ions, leading to passivation of the gold (Liu and Yen, 1995). The sulfide ions are oxidised to form thiocyanate, consuming oxygen and more cyanide. Therefore, treatment of orebodies containing
1. 2. 3. Project Leader Gold Program, Parker Centre (CSIRO Minerals), PO Box 7229, Karawara WA 6152. Email: paul.breuer@csiro.au Project Scientist Gold Program, Parker Centre (CSIRO Minerals), PO Box 7229, Karawara WA 6152. Email: danielle.hewitt@csiro.au Principal Technologist Gold Program, Parker Centre (CSIRO Minerals), PO Box 7229, Karawara WA 6152. Email: matthew.jeffrey@csiro.au MAusIMM, Gold Program Manager, Parker Centre (CSIRO Minerals), PO Box 7229, Karawara WA 6152. Email: john.rumball@csiro.au
chalcocite by cyanidation is often not economic, unless some form of cyanide recovery is utilised. For example, the SART process at Telfer, which follows the cyanidation of a pyrite concentrate produced from the copper sulfide flotation tail (Barter et al, 2001). Pyrrhotite is believed to be the most reactive iron sulfide mineral in cyanide solutions, although it is not as reactive as chalcocite (Hedley and Tabachnick, 1968). When orebodies contain pyrrhotite, partial preoxidation (Ellis and Senanayake, 2004; Li et al, 2006) and/or the addition of lead(II) ions (Deschnes et al, 1998) may be used to improve the gold recovery and/or reduce reagent consumption. Partial preoxidation is considered to oxidise the surface of reactive iron sulfide minerals to reduce their dissolution in cyanide solution (Marsden and House, 1992). The addition of lead(II) ions is considered to act in a number of ways: it activates the gold surface for leaching and enhances oxygen reduction (Jeffrey and Ritchie, 2000); precipitates sulfide ions which promotes the oxidation of sulfide (Hedley and Tabachnick, 1968; Paul, 1984); and reduces the dissolution of reactive sulfide minerals (Deschnes et al, 1998). However, the effect of preoxidation and lead addition on the reaction pathways and products of sulfide mineral dissolution/ oxidation are poorly understood. This paper describes the development of an ion chromatography method to analyse for the various sulfide mineral dissolution/oxidation products generated during cyanidation. This method was used to study the cyanidation of both individual metal sulfides, and a pyrite concentrate. The effect of pyrite and lead(II) ions on the dissolution products is discussed and the reaction mechanisms involved are described.
EXPERIMENTAL PROCEDURES
Experiments were carried out in an enclosed 500 ml reactor fitted with baffles and an overhead stirrer rotating at 600 rpm. Experiments were conducted with a solution volume of 300 ml at room temperature (20C) and atmospheric pressure, with the gas sparge rate into the reactor maintained at 100 ml/min. This approach was adopted to provide a constant rate of oxygen addition to the reactor. Unless stated otherwise, 150 g (dry basis) of mineral sample ground to 100 per cent passing 106 m was used. In experiments with lead(II) present, the lead was added as a concentrated lead chloride solution to the slurry before cyanide was added to start the experiment. Lead nitrate could equally have been used, though nitrate interfered in the HPLC analysis for sulfite; the lead in both cases is precipitated as lead hydroxide on addition to the alkaline solution due to the low solubility. Unless stated otherwise, lead(II) was added at 100 mg/L. The pH and DO were both monitored, with the pH adjusted initially to 10.5 using lime, and controlled to above 11 in all experiments. Analytical grade cyanide was added directly or dissolved in 30 ml of DI water and added slowly via a dosing pump over five hours. Samples were taken at regular intervals and filtered before analysis by potentiometric silver nitrate titration for free cyanide, and ion chromatography for sulfur and metal cyanide species.
4.
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Copper (mM)
40 30 20 10 0 0 0.5 1 1.5 2 2.5 3 Nitrogen Oxygen Oxygen + Pb Oxygen + Pyrite Preoxidation - Oxygen + Pb
Time (h)
FIG 2 - Copper dissolution from chalcocite in a cyanide solution (5 g/L chalcocite, 10 g/L NaCN, pH >11).
Fe Cu S
2-
Absorbance
SCN SO32-
2-
S2O3
10
12
14
16
Time (min)
FIG 1 - Ion chromatograph at 214 nm showing identification of the various sulfur containing species and metal cyanides (10 L injection of 3 mM S2-, 4.7 mM SO32-, 4.9 mM SCN, 5.1 mM 2S2O3 , 100 ppm Cu, 50 ppm Fe).
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25
16 14
Thiocyanate (mM)
20
12 10 8 6 4 2 0
0.5
1.5
2.5
Time (h)
Time (h)
Thiosulfate (mM)
Sulfite (m M)
0.5
1.5
2.5
Time (h)
Time (h)
FIG 3 - Dissolved sulfur species formed from the dissolution of chalcocite in a cyanide solution (5 g/L chalcocite, 10 g/L NaCN, pH >11).
similar manner to the experiment with lead(II) ions added. No polythionates were found in solution, despite their presence being reported in the literature (Marsden and House, 1992). It is well known that the pathway for polythionate formation is the oxidation of thiosulfate by oxygen, and although pyrite catalyses this reaction, the overall rate is still relatively low (Xu and Schoonen, 1995). Hence it is likely that the absence of polythionates in the current study was due to the shorter time frame of the experiments. It is worth noting that during the initial stages of the experiments with lead(II) ions or pyrite added, the total sulfur expected in solution (based on the quantity of copper dissolved), was not accounted for by the formation of sulfide, thiocyanate, thiosulfate and sulfite. This difference, the unaccounted for sulfur, is shown in Figure 4. The profiles shown indicate that an intermediate species is formed during the oxidation of sulfide, and once the intermediate undergoes further reaction, all of the sulfur can be accounted for from the observed thiocyanate, sulfite and thiosulfate. Such a result implies that sulfate is not formed during the lead sulfide or pyrite catalysed oxidation of sulfide ions in cyanide solutions. A similar disparity in the sulfur balance observed during the oxidation of sulfide ions in the presence of lead(II) ions was attributed to the formation of polysulfides (Sx2-) as an intermediate (Breuer, Jeffrey and Hewitt, 2007). Polysulfides were also detected by ion chromatography, and the peak area from the HPLC chromatographs is shown overlaying the unaccounted for sulfur in Figure 4. Although the quantity of sulfur present as polysulfides cannot be quantified using ion chromatography (Steudel, Holdt and Gbel, 1989), it can be seen from Figure 4 that the polysulfide peak area closely correlates with the unaccounted for sulfur.
0.07 Pb Pyrite
Pb Pyrite
0.02 0.01
0.00
Time (h)
FIG 4 - Unaccounted for S (solid line and closed symbols) and polysulfide peak area (dashed line and open symbols) for chalcocite dissolution in the presence of lead(II) or pyrite (5 g/L chalcocite, 10 g/L NaCN, pH >11, oxygen).
It is interesting to note from Figure 4 that a lower polysulfide concentration was obtained in the presence of pyrite, in comparison to when lead(II) ions were added, even though the overall reaction rate was observed to be the same. In addition, significantly more thiosulfate was generated in the first 40 min in the presence of pyrite, suggesting that either the direct oxidation of some sulfide to thiosulfate, or the oxidation of polysulfide to thiosulfate, is also catalysed by the pyrite surface. This, and the combined effect of lead(II) ions with pyrite, is currently being investigated in detail.
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Effect of preoxidation
5
Thiocyanate (mM)
Oxygen was sparged into a chalcocite containing slurry at pH 10.5 in the presence of lead(II) ions for one hour to investigate what, if any, effect preoxidation has on the subsequent leaching of chalcocite in a cyanide solution. Figure 2 clearly shows that the copper dissolution was unaffected by the preoxidation, and analysis of the solution after one hour of preoxidation found no soluble sulfur containing species. Thus, it can be concluded that preoxidation (or the presence of lead(II) ions) has no effect on the dissolution of chalcocite in cyanide solutions.
Time (h)
FIG 6 - Thiocyanate formation from the dissolution of iron sulfide minerals in cyanide solutions (20 g/L iron sulfide mineral, 3 g/L NaCN, pH >11, air).
the chalcopyrite sample may be due to covellite (CuS) contamination of the mineral, since the dissolution of chalcopyrite (CuFeS2) would produce dissolved copper and sulfur in a mole ratio of 1:2.
0.6
6 Pyrite
Copper (mM)
Iron (mM)
0.4
0.2
0 2.5
2 2 Sx + 1 + S
Time (h)
FIG 5 - Iron dissolution from iron sulfide minerals in cyanide solutions (20 g/L iron sulfide mineral, 3 g/L NaCN, pH >11, air). Also shown is the copper dissolution from the chalcopyrite mineral sample.
The chemistry of this system is quiet complex as there also exists an equilibrium between sulfide ions and polysulfides:
2 2 S2 S2 x + S x 1 + S2
(4)
The measured thiocyanate formation (Figure 6) confirmed that the pyrite is not readily oxidised in cyanide solutions. However, for pyrrhotite, the quantity of thiocyanate formed is much greater than the quantity of iron dissolution (based on the mineral stoichiometry). This indicates that either:
The subsequent polysulfide reactions have been studied previously (Breuer, Jeffrey and Hewitt, 2007), with polysulfides homogeneously reacting to form thiocyanate, thiosulfate and sulfite (Equations 5 - 7). Thiosulfate may also be formed from the reaction of sulfite with polysulfides (Equation 8):
2 S2 x + CN SCN + S x 1 2 2 S2 x + O 2 + 2OH S 2O 3 + S x 2 + H 2O (x 3) 2 2 S2 x + O 2 + 2OH SO 3 + S x 1 + H 2O 2 2 2 S2 x + SO 3 S 2O 3 + S x 1
These equations are consistent with the results shown in Figures 3 and 4.
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Dissolution products
The dissolution products from leaching the pyrite concentrate in an aerated cyanide solution were investigated using ion chromatography. The main minerals identified in the concentrate by XRD were pyrite and quartz, with minor kaolinite, muscovite, albite and calcite. Figure 7 shows that the dissolution of copper and iron both occur rapidly, and that thiocyanate was the major sulfur containing species formed, along with some thiosulfate. The high quantity of copper and iron dissolved from the pyrite concentrate consumes a significant quantity of cyanide and attempts to reduce this are discussed in the following sections. It is worth noting that the rate of iron dissolution from the concentrate sample was much more rapid than that measured for the pyrite, pyrrhotite or chalcopyrite samples in cyanide solutions, and hence it is unlikely that these minerals are the dominant cause of the iron dissolution from the pyrite concentrate. After 30 minutes of leaching, the quantity of copper leached into solution was 29.7 mM, yet the dissolved sulfur calculated from thiocyanate, sulfite, sulfide and thiosulfate was only 5.9 mM. This is consistent with the initial formation of
40 35
polysulfides as an intermediate in the oxidation of sulfide ions, followed by the reaction of polysulfides to form mainly thiocyanate, as evidenced by the sharp increase in thiocyanate concentration between the 30 and 60 minute samples. Notably, the ratio of copper to total sulfur in solution after one hour was consistent with the stoichiometry of chalcocite.
Concentration (mM)
30 25 20 15 10 5 0 0 1 2 3
Time (h)
FIG 7 - Dissolved sulfur, copper and iron species formed during cyanidation of pyrite concentrate (33 wt per cent solids, 15 g/L NaCN, pH >11, air).
35 30
Concentration (mM)
FIG 8 - Non-oxidative dissolution from pyrite concentrate (33 wt per cent solids, 15 g/L NaCN, pH >11, nitrogen).
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continually increased with the slow cyanide addition and due to the lower iron dissolution in the presence of oxygen, it was over 4 g/L NaCN at four hours. After four hours, Figure 10 shows that the iron dissolution rate increases in the presence of oxygen, and this could be explained by the increasing free cyanide concentration; after five hours, the free cyanide concentration was 6.1 g/L NaCN. This is consistent with the results from an additional test conducted with slow cyanide addition, but where the cyanide concentration was controlled at 2 g/L from three to six hours, which showed less iron dissolution in the later part of the experiment. This indicates that the iron dissolution rate may be reduced by utilising both high oxygen and low free cyanide concentrations.
Cyanide added upfront Slow cyanide addition Slow cyanide addition with oxygen
Iron (mM)
12 10 8 6 4 2 0 0 1 2 3
Time (h)
FIG 9 - Effect of cyanide addition and oxygen concentration on iron dissolution from pyrite concentrate (33 wt per cent solids, 15 g/L NaCN, pH >11, air).
Iron (mM)
15
10
0 0 1 2 3 4 5 6 7
Time (h)
FIG 10 - Effect of preoxidation or lead addition on the iron dissolution from pyrite concentrate (33 wt per cent solids, 15 g/L NaCN, air).
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mineral. The effect of lead(II) ions on the copper and iron dissolution from the pyrite concentrate was also investigated and found to have no effect on either the copper dissolution (as observed for chalcocite) or iron dissolution (Figure 10). However, in the presence of lead, more thiocyanate and less thiosulfate were formed from the oxidation of the sulfide ions resulting from copper sulfide leaching.
Summary
Results showed that the leaching of copper from the pyrite concentrate sample behaved in a very similar manner to the pure chalcocite mineral. For all the tests conducted, the ratio of copper to the accounted for sulfur in solution were consistent. Whereas there appeared to be no relationship between the iron concentration and total dissolved sulfur, suggesting the iron dissolution was not from a sulfide mineral. This is also supported by the low iron dissolution observed from the more common iron sulfides leached under similar conditions. XRD analysis was unable to confirm the source of the cyanide soluble iron in the pyrite concentrate since the dissolved iron only equated to around 0.3 wt per cent of the concentrate. However, XRD of a magnetic fraction produced from the concentrate was found to contain both tramp iron and siderite (FeCO3); both are potential sources for the high iron leaching observed with the concentrate.
precipitated as an iron hydroxide during reaction of the sulfides, indicating that the source of the highly soluble iron was not likely to be a sulfide mineral. Further studies are required to establish whether the source of the soluble iron in the pyrite concentrate sample is siderite or tramp iron, since both have been identified in a magnetic fraction taken from the concentrate. Work is also required to identify a means of reducing the iron dissolution rate, since the cyanide consumed by iron cyanide formation is not recovered in a SART or AVR type process.
REFERENCES
Barter, J, Lane, G, Mitchell, D, Kelson, R, Dunne, R, Trang, C and Dreisinger, D, 2001. Cyanide management by SART, in Cyanide: social, industrial and economic aspects, in Proceedings 2001 TMS Annual Meeting (eds: C A Young, L G Tidwell and C G Anderson), pp 549-562 (Minerals, Metals and Materials Society/AIME: Warrendale). Breuer, P L, Jeffrey, M I and Hewitt, D M, 2007. Mechanisms of sulfide ion oxidation during cyanidation. Part I: The effect of lead(II) ions, submitted to Minerals Engineering. Dai, X and Jeffrey, M I, 2006. The effect of sulfide minerals on the leaching of gold in aerated cyanide solutions, Hydrometallurgy, 82:118-125. Deschnes, G, 2005. Advances in the cyanidation of gold, in Advances in Gold Ore Processing (ed: M D Adams), pp 479-499 (Elsevier: Amsterdam). Deschnes, G, Rousseau, M, Tardif, J and Prudhomme, P J H, 1998. Effect of the composition of some sulphide minerals on cyanidation and use of lead nitrate and oxygen to alleviate their impact, Hydrometallurgy, 50(3):207-223. Ellis, S and Senanayake, G, 2004. The effects of dissolved oxygen and cyanide dosage on gold extraction from a pyrrhotite-rich ore, Hydrometallurgy, 72(1-2):39-50. Hedley, N and Tabachnick, H, 1968. Mineral dressing notes No 23, in Chemistry of Cyanidation (American Cyanamid Company: New Jersey). Jeffrey, M I and Ritchie, I M, 2000. The leaching of gold in cyanide solutions in the presence of impurities I. The effect of lead, Journal of the Electrochemical Society, 147(9):3257-3262. Li, J, Dabrowski, B, Miller, J D, Acar, S, Dietrich, M, LeVier, K M and Wan, R Y, 2006. The influence of pyrite pre-oxidation on gold recovery by cyanidation, Minerals Engineering, 19:883-895. Liu, G Q and Yen, W T, 1995. Dissolution kinetics and carbon absorption for the cyanidation of gold ores in oxygen-enriched slurry, Canadian Institute of Mining and Metallurgy Bulletin, 88(986):42-48. Marsden, J O and House, I, 1992. The Chemistry of Gold Extraction (Ellis Horwood Limited: Chichester, England). May, O, Jin, S, Ghali, E and Deschnes, G, 2005. Effects of sulfide and lead nitrate addition to a gold cyanidation circuit using potentiodynamic measurements, Journal of Applied Electrochemistry, 35(2):131-137. Nicol, M J, Fleming, C A and Paul, R L, 1987. The chemistry of the extraction of gold, in The Extractive Metallurgy of Gold in South Africa (ed: G G Stanley), pp 831-905 (The Southern African Institute of Mining and Metallurgy: Johannesburg). Paul, R L, 1984. The role of electrochemistry in the extraction of gold, Journal of Electroanalytical Chemistry, 168:147-162. Steudel, R, Holdt, G and Gbel, T, 1989. Ion-pair chromatographic separation of inorganic sulphur anions including polysulphide, Journal of Chromatography, 475:442-446. Xu, Y and Schoonen, M A A, 1995. The stability of thiosulfate in the presence of pyrite in low temperature aqueous systems, Geochimica et Cosmochimica Acta, 59:4605-4622.
CONCLUSIONS
Ion chromatography has been used to measure the speciation of dissolved sulfur leached during the cyanidation of ores and concentrates containing reactive sulfide minerals. The dissolution of chalcocite in cyanide solutions was shown to be a nonoxidative process in which copper cyanide and free sulfide ions are formed in solution. Preoxidation, or the addition of lead(II) ions, was found to have no effect on the chalcocite dissolution. The homogeneous oxidation of sulfide ions by oxygen is slow, but the presence of pyrite or lead sulfide (formed when lead(II) ions are added) catalyses the oxidation of dissolved sulfide ions. This occurs via electron transfer from the sulfide ion to dissolved oxygen on the pyrite or precipitated lead sulfide surface, with polysulfides being formed as an intermediate oxidation product. Thiocyanate was mainly formed from the reaction of polysulfides and cyanide, along with some thiosulfate and sulfite from the oxidation of polysulfides. The dissolution of finely ground pyrite was found to be very slow under typical cyanidation conditions. Pyrrhotite was found to dissolve in cyanide solutions, although the iron may have precipitated as an iron hydroxide, rather than forming iron cyanide in solution, since the dissolved sulfur was significantly higher than the dissolved iron. The leaching behaviour of copper from a pyrite concentrate during cyanidation was consistent with the presence of chalcocite as the main copper mineral. Significant non-oxidative iron dissolution from the concentrate also occurred. The quantity of iron leached was found to decrease with increased oxygen concentration and decreasing free cyanide concentration in the leach. Preoxidation appeared to potentially increase the iron leaching, whilst the addition of lead(II) ions had no effect. The common iron sulfide minerals studied showed slow oxidation and produced little iron in solution, most likely because it was
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