Hydrometallurgy 78 (2005) 226 235 www.elsevier.

com/locate/hydromet

The behaviour of carbonaceous matter in cyanide leaching of gold

H. Tan, D. Feng, G.C. Lukey, J.S.J. van Deventer*
Department of Chemical and Biomolecular Engineering, University of Melbourne, Victoria 3010, Australia Received 22 July 2004; received in revised form 8 March 2005; accepted 21 March 2005

Abstract Carbonaceous matter was extracted from ore obtained from Stawell Gold Mine and characterised by microscopic methods and XRD. The carbonaceous matter was predominantly hexagonal crystalline graphite mixed with some minor semi-crystalline graphite or amorphous carbon. It was found that the natural carbonaceous matter had a low gold adsorption capability, dependent on cyanide concentration. No adsorption occurred with N 250 mg/L KCN. Auger studies demonstrated that during grinding, the carbonaceous matter preferentially smeared on iron sulphide rather than alumino-silicate surfaces present in the gold ore. The carbonaceous matter coated unevenly, preferentially at the edges and the defect sites. XPS analysis indicated that when gold foil was ground with the ore, the carbonaceous matter coated on gold surfaces mainly in the form of elemental carbon or graphite. Very limited amounts of organic carbon compounds smeared on the gold foils during grinding. Sulphur species were also present on the gold surfaces after grinding with sulphide ores. The current work shows that the carbonaceous coating had a significant detrimental effect on gold dissolution when gold was pre-ground with the carbonaceous ore. Sulphide coating on gold surfaces appeared to hinder gold dissolution to a lesser extent. The dissolution of gold foils artificially coated with the natural carbonaceous matter extracted from Stawell ore was also substantially retarded. In comparison, graphite had a much lower coating ability on gold. The addition of free carbonaceous matter to pre-ground non-carbonaceous sulphide gold ores did not have much effect on gold cyanidation. However, the carbonaceous matter ground with the non-carbonaceous sulphide ores significantly reduced gold leaching kinetics and recoveries. D 2005 Elsevier B.V. All rights reserved.
Keywords: Carbonaceous matter; Surface characterisation; Carbon coating; Gold cyanidation

1. Introduction With the depletion of oxide ores throughout the world, refractory gold ores are becoming of increas-

* Corresponding author. Fax: +61 3 8344 4153. E-mail address: jannie@unimelb.edu.au (J.S.J. van Deventer). 0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2005.03.001

ing importance to the mining industry. Refractory gold ores occur in several gold mining regions, including the Prestea, Tarkwa and Ashanti gold fields of Ghana, the Carlin Gold Mine of Nevada, U.S.A., the California mother lode in the U.S.A., the Kerr Addison Mines in Canada and the Bakyrchik and Natalkinsk mines in Russia (Leaver and Woolf, 1930; Barko, 1972; Afenya, 1976; Wells and Mul-

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

227

lens, 1973; Gasparrini, 1983). The poor leaching behaviour of these ores is attributed to the presence of sulphide minerals and carbonaceous matter. Carbonaceous material in sulphide ores has been shown to act like activated carbon and to adsorb solubilised gold cyanide as a bulk phenomenon (Abotsi and Osseo-Asare, 1986, 1987; Hausen and Bucknam, 1984; Jha, 1984; Quach et al., 1993). Hence, much research has been concentrated on the characterisation of carbonaceous matter. Apart from carbonates, carbonaceous material in refractory gold bearing ores consists of i) a native carbon component acting like activated charcoal and able to adsorb gold cyanide from solution (Hausen and Bucknam, 1984; OsseoAsare et al., 1984; Radtke and Scheiner, 1970; Zaitseva et al., 1973), ii) a high molecular weight hydrocarbon mixture which appears not to interact directly with gold (Radtke and Scheiner, 1970), and iii) a bhumic acidQ like component containing functional groups capable of complexing with soluble gold (Guay, 1981; Osseo-Asare et al., 1984; Radtke and Scheiner, 1970; Scheiner et al., 1971; Ehrlich and Brierley, 1990; Nice, 1971). Various methods have been used to deactivate this carbonaceous matter, e.g. chlorination (Hausen and Bucknam, 1984) and roasting (Nagy et al., 1976). Carbon-in-leach (CIL) is a common process alternative in which activated carbon is used to compete with carbonaceous matter for gold cyanide adsorption (Rees and van Deventer, 2000). However, the CIL process has much less effect on highly preg-robbing ores containing high concentrations of very fine carbon. Carbonaceous preg-robbing may be inhibited by the addition of blinding chemicals such as diesel, kerosene and heavy machine oils to the leaching circuit of a plant. At the Stawell Gold Mine in Australia, kerosene is used to reduce preg-robbing (Beer, 1994). In some cases, blinding chemicals are used in the CIL process. This action does not fully eliminate preg-robbing. Despite the volume of research on the characterisation of carbonaceous matter in gold ores, little is understood concerning the exact role of carbonaceous matter in the cyanidation of gold ores. Adams et al. (1996) showed that the preg-robbing effect of several preg-robbing minerals was greatly enhanced in the presence of an active carbonaceous material. In addition, Quach et al. (1993) reported

that pyrite was not preg-robbing unless there was a carbonaceous component in the pyrite. These studies indirectly show that the presence of carbonaceous matter enhances the preg-robbing effect of various minerals. It can be expected that gold and sulphide particles will be smeared with carbonaceous matter, such as carbon or graphite, during the grinding stage. If so, the carbon coating may affect physical, chemical and electrochemical properties of the gold and sulphide particles and have an impact on gold dissolution and adsorption. Overall, little improvements in gold recoveries have been achieved in the cyanidation of carbonaceous ores and much indirect evidence has shown that carbon coating may play an important role. However, this aspect has been overlooked in the literature. Too much emphasis has been placed instead on the blinding and characterisation of free carbon or graphite particles. It has been shown previously that carbonaceous coatings could significantly enhance the preg-robbing of sulphides (Tan et al., 2003), but its effect on gold dissolution has never been studied. Stawell gold ore is known to be highly preg-robbing, with graphite being considered responsible for this. But gold recovery has a poor relationship with the graphite content (Fander, 1999). Previous emphasis has been placed on the separation or blinding of graphite, but with little success (Doherty, 1994). This indicates that the carbonaceous matter itself may not only preg-rob gold, but may also affect gold dissolution. It is the purpose of this study to investigate whether carbonaceous coating occurs during fine grinding and whether such coating has a significant affect on subsequent gold dissolution. The characterisation of carbonaceous matter in the ore is conducted by microscopic methods; whilst the selective coating of carbonaceous matter on gold and mineral particles after fine grinding is monitored by Auger spectroscopy and X-ray photon spectroscopy (XPS). The carbonaceous matter is readily separated from the ore by flotation due to its natural hydrophobicity. Thus the effect of carbonaceous matter on gold dissolution is investigated using the natural carbonaceous matter and pure gold. Carbonaceous matter is also subjected to grinding with non-carbonaceous sulphide ores, in an attempt to understand the generic role of carbonaceous coatings in cyanidation.

228

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

2. Experimental 2.1. Materials Gold foil (99.99% Au) was used in gold dissolution tests, with each piece of foil having a surface area of 20 mm2 and a thickness of 0.2 mm. The gold foils were rubbed on 1200 silicon carbide paper. A fresh, run-of-mine, carbonaceous gold ore sample was provided by Stawell Gold Mine, Australia. The lump sample was jaw and roll crushed to 2 mm, split into 850 g batches and stored in zip locked plastic bags in a fridge until use. Two noncarbonaceous sulphide gold ores, designated B and M, were also studied. Table 1 shows the major mineralogical and chemical analyses in the ores. The total carbon was determined by using a Leco combustion unit. The carbonate carbon was analysed by a back titration with sodium hydroxide after digestion in hydrochloric acid. The native carbon was determined by removal of carbonate carbon by HCl dissolution, and organic acids by NaOH. The gold sulphide ore B contained 0.32% pyrite and 3.20 mg/kg Au with a negligible amount of elemental carbon whilst the gold sulphide ore M contained 3.4% pyrrhotite and 7.05 mg/kg Au with only 0.02% elemental carbon.

2.2. Gold cyanide leaching tests Experiments for pure gold dissolution were performed in reactors containing 500 mL solution at desired concentrations of KCN. The gold foils were suspended at a constant height in the reactors with a nylon thread, ensuring no contact with the reactor wall during leaching. Experiments were carried out at 20 8C. The dissolved oxygen concentration of each reactor was 6 mg/L. After each leaching test, the leached gold samples were rinsed with distilled water and dried with non-lint paper for the subsequent surface analysis. Ore leaching tests were conducted in PVC reactors with overhead stirrers kept at 200 rpm in a water bath at 20 8C, where 1 L leach solution was added into 400 g solids. The pH was maintained at 11.0 by adding Ca(OH)2. Duplicate tests were carried out with average results reported. The standard deviation was within 3%. The 2 mm Stawell gold ore was dry and wet ground in a ceramic ball mill to 90% passing 75 Am for Auger analysis. The sample was further wet ground in a mortar and pestle, and the resultant slurry was dropped on a 200 mesh copper grid for TEM analysis. In order to characterise the interaction of carbonaceous matter with gold surfaces, pure gold foils were dry and wet ground with Stawell ore, respectively. After grinding, the gold foils were rinsed and freeze dried for Auger and XPS analysis.

Table 1 Mineralogical and chemical analyses of Stawell ore, and sulphide ores Mineralogical analysis Mineral Quartz Chlorite Muscovite Dolomite Calcite Anorthite Magnesite Almandine Biotite Grunerite Pyrite Pyrrhotite Arsenopyrite Chalcopyrite Stawell 65 6 15 4 2 1.2 4.3 0.43 1.2 0.22 Ore B 27 7 22 5 37 0.32 Ore M 27.8 3.5 17.2 15.1 14.9 3.4 Chemical analysis Element Au (mg/kg) Ag (mg/kg) Fe (%) Cu (mg/kg) Pb (mg/kg) Zn (mg/kg) S (%) Ca (%) Si (%) Al (%) CO3 C (%) Native C (%) Stawell 3.65 0.8 10.04 184 30 189 3.47 1.76 30.1 3.12 1.06 0.25 Ore B 3.2 2.0 4.39 68.6 516 481 0.3 4.4 20.5 1.7 5.42 Ore M 7.05 1.0 22.3 851 20 80 1.91 2.13 23.5 4.22 0.13 0.02

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

229

2.3. Gold adsorption tests Gold adsorption experiments were conducted with 0.2 g carbonaceous matter in a 1L solution containing 2.00 mg/L Au as KAu(CN)2 at pH 11.0 at various cyanide levels for 24 h. The equilibrium gold concentration was determined by ICP-OES. In addition, the gold loaded carbonaceous matter after adsorption was filtered, rinsed with distilled water once, dried and ashed in a furnace at 950 8C for 9 h. The residues were digested with aqua regia and gold determined by a Perkin-Elmer ICP-OES. 2.4. Analytical methods The dissolved oxygen concentration was measured by a DO meter (Hanna HI 9143). A platinum electrode (M21Pt, Radiometer) was used to measure the mixed potential with a double-junction reference electrode (Ag/AgCl, saturated KCl) to avoid the interference of cyanide with the reference electrode. Cyanide concentration was determined by performing a silver nitrate titration, using rhodanine as an indicator. XRD (Phillips, PW1800 X-ray diffractometer) was employed to determine the structural state of the natural carbon in the Stawell gold ore. A Phillips XL30 SEM coupled with an Oxford Energy Dispersive Spectrometer was used for topological studies of the carbonaceous matter. Transmission electron micrographs (TEM) were obtained using a Philips CM-10 microscope at an accelerating voltage of 100 kV. Auger spectra were recorded by a scanning Auger electron spectrometer (Fisons Instrument) fitted with an electron gun that gave a spot size diameter of approximately 5 Am. Depth profiles were measured by progressively etching away the surface layer by argon-ion sputtering. The etching rate of the argon-ion gun was determined by sputtering a section of the leached surface of gold. The argon gun was operated at argon pressure of 2 10 7 Torr and the etching time was set at 60 s. XPS, used for the speciation of the gold and mineral surfaces, was performed on an ion probe (Fisons Instruments). The instrument was operated at about 10 9 Torr using the Al Ka radiation with a sample angle of 608. Specimens were prepared by mounting gold foil or mineral samples on a stainless steel holder.

3. Results and discussion 3.1. Characterisation of carbonaceous matter Preg-robbing tests were conducted on the Stawell gold ore sample by using the Barrick Gold Mines Incorporated preg-robbing test method (Schmitz et al., 2001). In this method, 10 mL of a 2.0 g/L NaCN solution spiked with 3 mg/L Au was equilibrated with 5.0 g of the fine ore sample for 15 min. The preg-robbing value (%) was determined to be 17.5, which confirms the value for Stawell gold ore as reported previously (Fander, 1999). This indicates that the ore sample was representative and preg-robbing. The carbonaceous matter was separated from 2 mm Stawell ore by flotation. The carbonaceous matter was light and hydrophobic, thus no surfactants were required during flotation. This also ensured that the chemical and physical properties of the carbonaceous matter remained unchanged after separation. The float froth was filtered, rinsed with distilled water repeatedly, and dried in a freeze drier for the subsequent SEM and XRD analyses. Fig. 1 shows typical SEM images of a carbon particle in Stawell gold ore. The carbon particles were irregularly shaped, with no characteristic hexagonal shape of graphite in this size range. The XRD diffractogram of the extracted carbonaceous matter showed a hump at 26.88 2h as well as some amorphous phases in this region, which is a characteristic peak of graphite (Stenebraten et al., 2000). This indicates that the natural carbonaceous matter ranged from predominantly crystalline graphite (hexagonal crystalline graphitic structural units) to some minor semi-crystallised graphite or amorphous carbon. This could be marked by increasing size of crystalline graphite, in accordance with the previous observation (Stenebraten et al., 2000). The presence of a mixture of different graphite particles in the extracted carbonaceous matter also indirectly indicates that a representative sample of all the carbonaceous matter in the ore was obtained, despite the fact that only liberated carbonaceous matter particles were extracted during the separation process. Fig. 1 shows that the surfaces of the carbon particles were porous. However, macro-pores were dominant, as the total pore volume for the extracted

230

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

(a)

(b)

Pores

cyanide free system, the gold loading on the natural carbonaceous matter was low (Table 2), in comparison with activated carbon. This was expected because the surface area was only 31.4 m2/g for the carbonaceous matter, compared to around 800 m2/g for activated carbon. Nevertheless, the amount of carbon present in the ore (2.5 g/kg) is sufficient to adsorb significant gold. Surprisingly, gold recoveries still remained low at high cyanide levels up to 1000 mg/L NaCN, despite the evidence in Table 2 showing that the carbonaceous matter does not adsorb gold at such a cyanide level. This directly demonstrates that the carbonaceous matter must also affect the leaching behaviour of gold possibly by coating both the mineral and gold surfaces during grinding and mixing processes which would affect the physical, chemical and electrochemical properties of the mineral and gold surfaces. In theory, natural carbonaceous matter should behave like activated carbon and graphite in terms of coatings of nanoscale thickness on gold surfaces, but may behave differently. 3.2. Carbon coating during grinding Mineral particle surfaces were subjected to microscopic and spectroscopic analysis after fine grinding. Free grains of gold in Stawell gold ore were around 30 Am in size, but the occurrence was very rare. Inclusions of gold were found in a number of pyrite grains, ranging from b 1 to 6 Am. Since the gold content in the ore was only 3.65 mg/kg it was difficult to observe the free gold particles in the ground samples. Thus, the carbon coating on the free gold surfaces could not be characterised.
Table 2 Gold adsorption on extracted carbonaceous matter at different cyanide levels [KCN], mg/L 0 100 200 250 400 600 Equilibrium [Au], mg/L 1.89 1.94 1.98 2.00 2.00 2.00 Au loading on carbon, mg/g 0.55 0.30 0.10 0 0 0 Au on solids, mg/g 0.63 0.34 0.08 0 0 0

Fig. 1. SEM images of carbonaceous matter in Stawell gold ore. (a) Carbon particle. (b) Surface of carbon particle.

carbonaceous matter was only 76 mm3/g, as determined by the hysteresis loop in N2 adsorptiondesorption. The BET surface area was 31.4 m2/g for the carbonaceous matter extracted from the 2 mm size fraction, compared to a slightly higher specific surface area of 37.8 m2/g from a finer ore size fraction (90% passing 75 Am). These BET surface area values were in the range for natural graphite obtained from other gold ores as reported previously (Stenebraten et al., 2000). Table 2 shows gold adsorption on the extracted carbonaceous matter. Clearly, the adsorption of gold on the carbonaceous matter was significantly dependent on the cyanide level. No gold adsorption was observed with N 250 mg/L KCN. Ashing analysis also confirmed that no gold adsorbed on the carbonaceous matter at high cyanide levels. This is in agreement with the previous observation (Fander, 1999). For the

Condition: carbonaceous matter 0.2 g, initial [Au] 2.00 mg/L, pH 11.0, rotation speed 200 min 1 ; contact time 48 h.

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

530000 Si Al S Fe Level 8
dN(E)/dE

231

3.2.1. Carbon coating on mineral particles Fig. 2 shows the depth profiles for the Auger spectra on a typical sulphide surface after wet grinding. The Auger depth profiles were recorded after each etching of 60 s with argon. Each measurement of Auger spectra was called a level, which was around 100 nm in this case. The etching thickness was inferred from the empirical model for the Auger machine (Fisons Instrument Handbook). Due to the different hardness and roughness of the sample surfaces, this etching thickness was only an indication rather than an absolute value. It should be noted that CO2 and O2 in the analysing chamber could adsorb on the sample surface even at a vacuum as high as 10 9 Torr. However, based on the depth profile of pure gold standard, the adsorption of CO2 and O2 was limited to a monolayer of molecules within the range of 10 nm. Therefore, the adsorption effects of O2 and CO2 are negligible in the determination of the oxide layer thickness and carbon coating thickness. The profiles show that the iron sulphide surface was covered with carbonaceous matter and oxide minerals. The oxide layer on the sulphide surface disappeared at level 2, giving an indicative thickness of b 100 nm. Given the evidence of no sulphur present at level 1, the oxide layer could be due to the oxidation of the sulphide surface. Carbon disappeared at level 7 with argon etching indicating an average thickness of the carbonaceous coating of ~ 600 nm. However, this thickness was only indicative, as the
Si S O Fe
dN(E)/dE

O 330000 C Level 7

Level 3 Level 2 Level 1 130000 0 500 1000 Energy, eV 1500 2000

Fig. 3. Auger spectrum of typical sulphide particle in Stawell ore after dry grinding.

mineral surface was rough and irregular. The carbonaceous matter coated on the iron sulphide surfaces after dry grinding (Fig. 3) was comparable to that after wet grinding. Likewise, the carbonaceous matter coated on the alumino-silicate gangue mineral particles, as indicated in Fig. 4, but the coating was much thinner than that on the iron sulphide surfaces. The carbon layer disappeared at level 3 in the depth profiles. This indicates that the carbonaceous matter preferentially coats hydrophobic iron sulphide surfaces rather than hydrophilic aluminosilicate surfaces. As it is known that the gold predominantly occurs in the iron sulphide grains of Stawell gold ore (Fander, 1999), it is expected that
Al 650000 S O Si
Level 4

750000

Al Level 8
dN(E)/dE

550000 C Level 7 Level 4 350000 Level 3 Level 1

C 450000

Level 3

Level 2

Level 1

150000 0 500 1000 Energy, eV 1500 2000

250000 0 500 1000 Energy, eV 1500 2000

Fig. 2. Auger spectrum of typical sulphide particle in Stawell ore after wet grinding.

Fig. 4. Auger spectrum of alumino-silicate particle in Stawell ore after wet grinding.

232

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

175 Dry grinding

the carbonaceous matter would also coat the surface of gold. TEM images show discontinuous deposition of varying size carbon particles, with preferential coating at the edges and defect sites of the mineral particles (Fig. 5). It should be noted that Auger spectra are recording average values of the electrons whilst scanning very rough mineral particle surfaces. However TEM measurements were conducted with ultra fine particles, which were subjected to further fine grinding. Therefore, the carbonaceous coating thickness observed from the TEM image was not comparable with that obtained from Auger depth profiling. 3.2.2. Carbonaceous coating on gold surface Since it was difficult to isolate the fine gold particles and prove the carbonaceous coating, gold foils were ground for 30 min with Stawell gold ore (90% 75 Am) in a ceramic ball mill, loaded with 5% ceramic balls, in an attempt to coat the gold surface with the carbonaceous matter. Fig. 6 shows the XPS C1s spectra for the gold foils after dry and wet grinding. The binding energy centre for C1s was mainly at about 285 eV indicating that the carbon was mainly in the form of graphitic carbon on the surface of the gold foils. After spectra de-convolution, there were also small peaks at around 288.7 eV which could be attributed to the presence of organic carbon compounds. The organic carbon content was

165

155
kCPS

145

135

Wet grinding

125 280 283 286 Binding energy, eV 289 292

Fig. 6. XPS C1s spectrum for gold foil surface after grinding with the Stawell ore.

very limited and was higher after dry grinding than wet grinding. Unfortunately, the speciation of the organic carbon was difficult to identify, but is attributed to high-molecular weight long-chain alkanes and humic acids. Depth profiles of the Auger spectra across the surface of the gold foil ground with Stawell gold ore are shown in Fig. 7. Carbon was present at the top layer, with an average thickness of around 300 nm. Sulphur was observed at all levels, but its concentration remained constant after level 2 indicating some sulphide particles could remain at the defect sites on the gold surface. Some oxygen species also appeared at the first three levels, likely due to the
500000
Au S Au

400000
dN(E)/dE

Level 19

Level 17 O Level 3 Au

300000
Level 2 Level 1

200000 0 500 1000 Energy, eV 1500 2000

Fig. 5. TEM image of carbonaceous coating on mineral particles in Stawell ore. Dark particlescarbonaceous matter; Scale bar50 nm.

Fig. 7. Auger spectrum of gold foil dry ground with the carbonaceous Stawell ore. Argon etching: 3 min.

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

5.0 Quartz
2

233

Gold dissolution, mg Au/m

4.0

Stawell B

3.0

2.0

1.0

0.0 0 10 20 30 40 Time, h 50 60 70

Fig. 8. Effect of carbonaceous coating on rate of gold foil leaching. [KCN]250 mg/L; pH11.

presence of oxide minerals, such as alumino-silicates on the gold surface. 3.3. Effect of carbonaceous coating on gold dissolution In order to understand the role of the carbonaceous coating in gold leaching, the gold foils ground with Stawell gold ore were subjected to cyanidation with 250 mg/L KCN. For comparative purposes, gold foils were ground with quartz and two non-carbonaceous gold ores, designated B and M, and leached under the same conditions. All the ores were ground to 90% passing 75 Am, then further ground for 30 min with the gold foils. Fig. 8 shows the leach curves for the dissolution of gold foils ground with the different ores. Typically, a linear increase of gold dissolution was observed between 3 and 32 h for all the gold foils. The dissolution rate of gold foil ground with quartz only was considered as the reference rate. Clearly, the gold dissolution rates were lower for the gold foils ground with different sulphide ores. The dissolution rate was the lowest for the gold foil ground with Stawell gold ore, followed by the gold foil ground with the sulphide ores M and B. Since Auger analysis had indicated that the sulphide minerals coated on the gold surfaces during grinding, it can be expected that this would affect gold dissolution, albeit to a lesser extent in comparison with a carbonaceous coating.

In order to investigate further the role of carbonaceous coating in gold leaching, the extracted carbonaceous matter from Stawell gold ore was manually smeared on the gold foils for the subsequent cyanide leaching. A clean gold foil was mixed with the extracted carbonaceous matter in a plastic bag, and rubbed for 10 min. The gold foil was taken out of the carbonaceous matter and rinsed with distilled water to remove loose carbonaceous matter from the gold surface prior to cyanidation. For comparison, graphite powder (b 10 Am) was similarly smeared on the gold foils. Fig. 9 shows the leach curves for the dissolution of gold with and without carbonaceous coatings. Again, a linear increase of gold dissolution between 3 and 32 h was observed under all conditions and clearly the natural carbonaceous matter from the Stawell ore hindered the gold dissolution to a larger extent in comparison with graphite. This could be because the natural carbonaceous matter had a larger surface area and more readily coated on the gold surface. With 250 mg/L KCN, the carbon coating does not adsorb gold during the leaching. Therefore the reduced gold dissolution in the presence of carbon coating is attributed to (i) physical blocking of the gold surface and/or (ii) electrochemical passivation of the gold surface. As it is expected from the above studies that the carbonaceous coating on the gold surface is not continuous, the partial carbon coating
4.0 3.5
Gold dissolution, mg Au/m
2

G Graphite

3.0 Carbon (Stawell) 2.5 2.0 1.5 1.0 0.5 0.0 0 10 20 30 Time, h 40 50

Fig. 9. Effect of graphite and extracted carbonaceous coating on gold foil dissolution. [KCN]250 mg/L; pH11. Ggold foil without coating.

234

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

should only slow the leaching kinetics and would have little impact on overall gold dissolution over an extended period of 48 h. The fact that the overall gold recovery remained low suggests that gold embedded in sulphide minerals and partially exposed may be completely covered by the carbonaceous material or affected electrochemically. 3.4. Effect of carbonaceous matter on gold ore leaching To understand whether free carbon affects gold leaching like gold coated with carbon, carbonaceous matter (0.2 g) extracted from Stawell ore was ground with 400 g of gold ore, B and M. For comparison, the same amount of carbonaceous matter was simply mixed with 400 g of gold ores B and M which had been pre-ground to the same extent (90% 75 Am). The resultant samples and the untreated ores were then leached with 400 mg/L KCN at pH 11.0. Fig. 10 shows that the leaching rates and overall gold recoveries were reduced for both sulphide ores M and B when 0.2 g carbonaceous matter was ground together with the ores, compared to simple addition of carbonaceous matter to pre-ground ores. Indeed, carbon itself had little effect on the leaching of either sulphide ores M and B as the leach curves without the addition of the carbonaceous matter proved to be the same (not shown). Gold adsorption was inhibited by a
96

relatively high concentration of cyanide. This indirectly supports the view that the smearing of carbonaceous material over gold particles reduces the kinetics and recovery of gold. Further experiments have been undertaken with Stawell ore with the separation of the carbonaceous matter at different grinding stages. The cyanidation results have shown that early separation of the carbonaceous matter during grinding will significantly improve the gold leaching. Other factors such as particle size were also investigated, showing that the finer grinding would intensify such a carbonaceous coating on particle surfaces.

4. Conclusions Natural carbonaceous matter extracted from Stawell gold ore is mainly crystalline graphite which has a BET surface area of only 31.4 m2/g. It showed a very low gold loading ability at a cyanide concentration of N 250 mg/L KCN. Auger spectra on typical mineral particles in ground Stawell gold ore demonstrated that the carbonaceous matter preferentially smeared on iron sulphide rather than alumino-silicate surfaces with discontinuous deposition of varying size carbon particles. TEM showed preferential coating at the edges and the defect sites of the mineral particles. XPS analysis of gold foil after grinding with Stawell ore indicated that the carbonaceous matter coated on gold surfaces mainly in the form of graphitic carbon. Whilst depth profiles of the Auger spectra showed both carbon and sulphur were present on the gold surface. This carbonaceous coating had a greater detrimental effect on gold dissolution than sulphide coating. Artificial coating of gold foil surfaces with the natural carbonaceous matter extracted from Stawell ore also retarded gold dissolution substantially. In comparison, graphite had a much lower coating ability on gold surfaces. The addition of free carbonaceous matter to pre-ground non-carbonaceous sulphide gold ores had little effect on gold cyanidation. In contrast, the carbonaceous matter ground with the same ores significantly reduced gold leaching kinetics and recoveries. This better understanding of the exact nature and effect of carbonaceous matter in gold leaching should lead to better strategies for the improvement of gold

Gold concentration, Au mg/L

76

56 M + 0.2g C M@0.2g C B + 0.2g C B@0.2 C 16 0 10 20 Time, h 30 40 50

36

Fig. 10. Effect of extracted carbonaceous matter on cyanidation of gold ores M and B. [KCN]400 mg/L; pH 11; 400g ore. C = carbonaceous matter extracted from Stawell ore; + indicates addition to pre-ground ore; @ indicates addition before grinding.

H. Tan et al. / Hydrometallurgy 78 (2005) 226235

235

recoveries from carbonaceous gold ores. More aggressive measures must be taken to reduce or eliminate carbonaceous coating of mineral particle surfaces such as oxidation or the use of surfactants or electrolytes. These surfactants or electrolytes should differ from conventional blinding chemicals, which reduce carbon activity by blocking its surface, but also block the surface of gold to leaching.

Acknowledgements The support from the Particulate Fluids Processing Centre, a Special Research Centre of the Australian Research Council, is gratefully acknowledged. Gratitude is also expressed to the staff of Stawell Gold Mine for supplying the ore samples.

References
Abotsi, G.M.K., Osseo-Asare, K., 1986. Surface chemistry of carbonaceous gold ores: I. Characterization of the carbonaceous matter and adsorption behaviour in aurocyanide solution. Int. J. Miner. Process. 18, 217 236. Abotsi, G.M.K., Osseo-Asare, K., 1987. Surface chemistry of carbonaceous gold ores: II. Effects of organic additives on gold adsorption from cyanide solution. Int. J. Miner. Process. 21, 225 239. Adams, M.D., Swaney, S.J., Friedl, J., Wagner, F.E., 1996. Pregrobbing minerals in gold ores and residues. Hidden Wealth. S. African. Inst. Min. and Metall., Johannesburg, pp. 163 172. Afenya, P.M., 1976. Studies in the processing of carbonaceous gold ores. PhD Thesis, University of London, London. Barko, A.B., 1972. Mining geology of the Prestea goldfields. PhD Thesis, University of Cagliari, Italy. Beer, G., 1994. Processing options for the treatment of preg-robbing ore at the macreas gold mine. Proc. 6th Aus.I.M.M. Extractive Metallurgy Conference, July 36, Australas. Inst. Min. and Metall., Melbourne, pp. 203 208. Doherty, R.J., 1994. Review of testwork associated with central ore campaign 12. Optimet Report 94054, Stawell Gold Mines Pty Ltd., 23 pp. Ehrlich, H.L., Brierley, C.L., 1990. Microbial Mineral Recovery. McGraw Hill Inc., New York. Fander, H.W., 1999. Mineralogy of ore samples B54, 55, 56, 58. Report CMS 99/1/2, Stawell Gold Mines Pty. Ltd., 21 pp. Gasparrini, C., 1983. The mineralogy of gold and its significance in metal extraction. CIM Bull. 76 (851), 144 153. Guay, W.J., 1981. The treatment of refractory gold ores containing carbonaceous material and sulphides. Proc.110th AIME Meet-

ing: Gold and Silver, Leaching, Recovery and Economics, Chicago. A.I.M.E, Warrendale, pp. 17 32. Hausen, D.M., Bucknam, C.H., 1984. Study of preg robbing in the cyanidation of carbonaceous gold ores from Carlin, NV. In: Park, W.C., Hausen, D.M., Hagni, R.D. (Eds.), Proc. Second Int. Congress on Applied Mineralogy in the Minerals Industry. Metallurgical Society of AIME, Warrendale, PA, pp. 833 856. Jha, M.C., 1984. Refractoriness of certain gold ores to cyanidation: Probable causes and possible solutions. Miner. Process. Extr. Metall. Rev. 2, 31 352. Leaver, E.S., Woolf, J.A., 1930. Re-treatment of Mother Lode (California) Carbonaceous slime tailings, U.S. Bureau of Mines, Tech. Paper. 481, pp. 120. Nagy, I., Mrkusic, P., McCulloch, H., 1976. Chemical treatment of refractory gold oresliterature survey. National Institute of Metallurgy, Johannesburg. Report No. 38. Nice, R.W., 1971. Recovery of gold from active carbonaceous ores at McIntyre. Can. Min. J. 65 (1), 41 49. Osseo-Asare, K., Afenya, P.M., Abotsi, G.M.K., 1984. Carbonaceous matter in gold ores: isolation, characterization and adsorption behaviour in aurocyanide solutions. In: Kudryk, V., Corrigan, D.A., Liang, W.W. (Eds.), Precious Metals: Mining, Extraction and Processing. Metallurgical Society of AIME, Warrendale, PA, pp. 125 144. Quach, T., Koch, D.F.A., Lawson, F., 1993. Adsorption of gold cyanide on gangue minerals. Proc. A.P.C.ChE. and Chemeca, vol. 93. Inst.Chem.Eng., Melbourne, pp. 101 106. Radtke, A.S., Scheiner, B.J., 1970. Studies on hydrothermal gold deposition, (I). Carlin gold deposit, Nevada: the role of carbonaceous materials in gold deposition. Econ. Geol. 65, 87 102. Rees, K.L, van Deventer, J.S.J., 2000. Preg-robbing phenomena in the cyanidation of sulphide gold ores. Hydrometallurgy 58, 61 80. Scheiner, B.J., Lindstrom, R.E., Henrie, T.A., 1971. Processing carbonaceous ores for gold recovery. J. Met. 23 (3), 37 40. Schmitz, P.A., Duyvesteyn, S., Johnson, W.P., Enloe, L., McMullen, J., 2001. Ammoniacal thiosulphate and sodium cyanide leaching of preg-robbing Goldstrike ore carbonaceous matter. Hydrometallurgy 60, 25 40. Stenebraten, J.F., Johnson, W.P., McMullen, J., 2000. Characterisa tion of Goldstrike ore carbonaceous material: Part 2. Physical characteristics. Miner. Metall. Process. 17 (1), 7 15. Tan, H., Feng, D., van Deventer, J.S.J., 2003. Effect of carbonaceous coatings on preg-robbing of chalcopyrite. In: Young, C.A., Alfantanzi, A.M., Anderson, C.G., James, A., Dreisinger, D.B., Harris, B. (Eds.), Hydrometallurgy 2003, Leaching and Solution Purification, vol. 1. TMS (The Minerals, Metals and Materials Society), Warrendale, PA, pp. 35 48. Wells, J.D., Mullens, T.E., 1973. Gold-bearing Arsenian pyrite determined by microprobe analysis, Cortez and Carlin Gold Mines, Nevada. Econ. Geol. 68, 187 201. Zaitseva, M.L., Ivanovski, M.D., Larina, N.K., 1973. An examination of the sorption properties of carbonaceous substance during the cyanidation of gold ores. Sov. J. Non-Ferr. Met. 14 (1), 78 80.