Assesment of Ammoniacal Ammonium Sulphate Leaching as a Pretreatment Process for Copper Bearing Gold Ores

Bas, A. D., Kucuk, A., Yazici, E. Y. and Deveci, H.* Div. of Mineral & Coal Processing, Dept. of Mining Engineering. Karadeniz Technical University, 61080, Trabzon, Turkey. ABSTRACT: In the current study, ammoniacal ammonium sulphate leaching (AASL) and pre-aeration as a pretreatment step before the cyanidation of a copper-bearing gold ore was studied. Direct cyanide leaching of the ore resulted in only a ~10% extraction of gold indicating the refractory character of the ore. The ammonia/ammonium sulphate leaching as a pretreatment process was shown to substantially improve the gold extraction (>90%) in subsequent cyanide leaching with a significant reduction in the consumption of cyanide. This could be linked with the ready dissolution/removal of copper in the pretreatment stage by ammonia/ammonium sulphate leaching. The pre-aeration of the ore ahead of cyanidation was also observed to enhance the extraction of gold, albeit, to a limited extent (i.e. from ~10% to ~30%). These findings have demonstrated that ammonia/ammonium sulphate leaching prior to the cyanide leaching can be used suitably for the pretreatment of refractory copper-bearing gold ores. INTRODUCTION Cyanide with its peculiarity to form strong complexes with gold is the most effective leaching agent for the extraction of gold from ores. However, cyanide leaching is not particularly selective in that many mineral phases present in the ore may also dissolve under the leaching conditions. To illustrate, most copper minerals are readily soluble in cyanide leaching (Table 1). Dissolution of copper minerals may adversely affect cyanide leaching leading to high consumption of cyanide and poor extraction of gold (Dawson et al, 1997, Alymore and Muir, 2001; Breuer et al, 2005; Muir, 2011; Bas et al., 2012, Kucuk, 2012). Dissolved copper also presents difficulties in downstream processes (Dawson et al, 1997). Copper-bearing gold ores can consume 30 kg/ton NaCN for every 1% reactive copper present, which may render cyanidation process uneconomic (Muir, 2011). Cyanide consumption can be even higher (e.g. up to 51.5 kg/ton per cent of copper contained) due to the formation of thiocyanate and cyanate in addition to copper cyanide when copper sulphides such as covellite are present (Sceresini, 2005). A copper content of 0.5% Cu is often considered as threshold for cyanide leaching of gold ores (Muir et al., 1991). Development of alternative processes to cyanide leaching is, therefore, required for the treatment of copper-rich gold ores. In this regard, flotation (Bulatovic, 1998; Forrest et al, 2001), thiosulphate leaching (Bas et al. 2011), leaching of copper ahead of cyanidation (Muir et al, 1991; Dawson et al., 1997; Sceresini, 2005) and cyanide recovery from effluents (e.g. SART process) (Dai et al., 2012) have been proposed for such ores.

Table 1. Solubility of copper minerals (in 0.1% NaCN solutions) (Marsden and House, 2006 after Hedley and Tabachnick (1958)) Mineral Formula %Cu dissolved 23oC 45oC Azurite 2Cu(CO)3.Cu(OH)2 94.5 100.0 Malachite 2CuCO3(OH)2 90.2 100.0 Chalcocite Cu2S 90.2 100.0 Covellite CuS Native copper Cu 90 100.0 Cuprite Cu2O 85.5 100.0 Bornite FeS.2Cu2S.CuS 70 100.0 Chalcopyrite CuFeS2 5.6 8.2 Tetrahedrite (Cu,Fe,Ag,Zn)12Sb4S13 21.9 43.7 Addition of ammonia as a modifying agent into cyanide solutions has been extensively tested to mitigate copper interferences (Dawson et al., 1997; Sceresini, 2005; Muir, 2011). The role of ammonia is to stabilize Cu2+ (1). Otherwise, copper forms strong complexes with cyanide, thus, leading to high consumption of cyanide (2) (Hayes and Corrans, 1992; Breuer et al, 2005; Muir, 2011; Dai et al, 2012). The addition of ammonia allows the selective extraction of gold over copper at a considerably reduced consumption of cyanide (Dawson et al., 1997; Hayes and Corrans, 1992). Muir et al. (1991) showed that the ammoniacal cyanide leaching was an effective system for the treatment of copper containing gold tailings (1.2% Cu, 5 g/ton Au) with a significant decrease in cyanide consumption from 30 kg/ton (in the absence of ammonia) to only 1.6 kg/ton NaCN (and 1.1 kg/ton NH3 in the presence of 0.3 kg/ton Cu2+). They also demonstrated the removal of copper (up to 95%) via ammonia leaching, which also substantially reduced the reagent consumption (down to 6 kg/ton NaCN) in the subsequent cyanide leaching.
Cu2 4NH3 Cu (NH3 ) 4 2

(1)

Cu

3CN Cu (CN) 2 0.5(CN) 2

(2)

Sulphide ion (S2-) that is released from sulphide phases including copper sulphides present in the ore can also lead to the passivation of gold surface in addition to its consumption of cyanide and oxygen (Marsden and House, 2006). Pre-aeration of the ore prior to the cyanidation can be beneficial to mitigate problems associated with sulphide minerals during cyanidation of gold (Kondos et al., 1995; Rajala and Deschenes, 2009). A successful pre-aeration process eliminates a significant proportion of cyanide and oxygen consumers (Rajala and Deschenes, 2009). In this preliminary study, ammoniacal ammonium sulphate leaching (AASL) as a pretreatment process ahead of cyanidation for the treatment of a copper-rich refractory gold ore was tested. Pre-aeration of the ore prior to cyanidation was also examined. Direct cyanide leaching of gold was tested for comparison. MATERIAL AND METHOD Ore Sample The ore sample was obtained from sulphide-rich zones of Mastra Gold Mine, located in Gmhane, Turkey. The crushed ore sample (down to -4 mm using laboratory jaw and then roll crushers) was ground to 80% passing -75 m (d80) in a rod mil (Figure 1).The ground ore was riffled and packed as 120 g portions for use in the leaching tests.

Cumulative Under size (%)

100 80 60 40 20 0 0 1 100 Particle Size (m) S 10000

Figur 1. Particl size distri re le ibution of th ore. he

2 () Fi igure 2. XR profile of the gold ore RD o o The chemi compos ical sition of the sample wa determin to be 85 SiO2, 1. 1% Cu, 3.1 S, 56 g/ e as ned 5% 1% /ton u /ton Ag (Ba et al, 20 as 012). The X XRD analys of the ore sample i sis indicated th presence of he e Au and 10 g/ qu uartz and co opper sulphi ides such as chalcopyr and cov a rite velline (Fig gure 2). Pyr rite, galena and sphaler rite we also repo ere orted to be d detected in the ore (Ser rbest, 2010; Ozdemir, 2011). ; 2 eaching Tes sts Le Le eaching test were carr ts ried out in 1000-ml be 1 eakers, whic received 480 ml of leach solut ch tion and 120 g 0 ore sample ( e (i.e. at 25% wt/vol pulp density (Kucuk, 2012). Leach solutio were prepared using % y) ons p deionised-dist tilled water Cyanide leaching tes were per r. l sts rformed at 1.5 g/L Na aCN while AASL prior to A r hing was car rried out at 0.5 M NH3 /0.5 M (NH4)2SO4. Overhead stir H rrers were used to agit u tate cyanide leach the leach pulp at 600 rp The bea e ps pm. akers were a aerated at a flowrate of 2 L per mi The top of the beak f in. kers we kept cov ere vered during the tests. In the leach g I hing tests, pH was contr H rolled at 10 0.5-11 by the addition o 1 e of M NaOH. At predetermin intervals, samples (10 ml) we removed and then c ned ere d centrifuged to obtain cl lear sup pernatants f analysis of free cya for s anide, gold and copper Free cyan was det r. nide termined by titration w y with silver nitrate u using p-dim methylamino o-benzal-rho odanine (0.0 02% w/w in acetone) a the indica n as ator. Following a leaching period of 24 h, leach 2 hing residue were separated by f es filtration. Th were th hey hen dri in an ov (at 105 ied ven 5C) and di igested in h aqua-reg for the analysis of metals (go silver a hot gia f old, and copper) using a Perkin E g Elmer AAn nalyst 400 a atomic abso orption spec ctrophotome eter. Metal extractions in s the leaching tests were de e etermined based on the results of residue analysis. b e r

RESULTS Fig. 3 demonstrates that direct cyanidation of the ore results in poor extraction of gold (i.e. only 4% over 24 h), confirming the earlier findings (Bas et al., 2011; Bas et al., 2012; Ozdemir, 2011). This indicates that the ore is refractory in character. Although the rationale behind the refractoriness of the ore is currently unclear, it is presumed to be associated with the presence of sulphide minerals (copper sulphides in particular) in the ore (Bas et al., 2012). The adverse effect of sulphides on gold extraction could be attributed mainly to the excessive consumption cyanide/oxygen (3), passivating effect of sulphide ion on gold and their pregrobbing characteristics (Sceresini, 2005, Bas et al., 2012; Bas et al., 2012a). Therefore, pre-aeration and ammoniacal ammonium sulphate leaching (AASL) of the ore were tested to improve the extraction of gold. (3) 2CuS 8CN 1 O2 H2O 2Cu (CN)32 2OH 2CNS 2 Pre-aeration of the ore shows an enhancement in the extraction of gold from 4% to 30% (Fig. 3). This improvement could be attributed to the amelioration of the passivation effect of sulphide ion. Previous studies (Lia et al., 2006; Li et al., 2009) have confirmed the benefits of pre-oxidation/aeration on subsequent cyanide leaching of gold ores. Sceresini (2005) also reported that the addition of lead nitrate improved the extraction of gold from a copper bearing sulphide ore presumably due to the alleviation of sulphide effect. However, no enhancement in the gold extraction from the ore sample used in the current study was observed in the presence of 100-1000 g/ton Pb(NO3)2 (Bas et al., 2012). The AASL of the ore was also examined to solubilize copper minerals prior to cyanidation. A significant improvement in the extraction of gold from 4 to 91 % was achieved (Fig. 3). This improvement appeared to be consistent with the ready dissolution of copper (54% Cu) in the ammoniacal ammonia leaching stage (Fig. 4). In the ammonia system, the dissolution of copper from oxides/sulphides (5-7) occurs slowly with relatively low copper extractions at low temperatures (Muir et al., 1991). Free ammonia and pH are important parameters controlling the dissolution process and solubility of copper-ammine complexes (Fig. 5) in that high concentrations of free ammonia (>0.45 M) in solution at relatively high pH (i.e. >pH 9.3) should be maintained. In this regard, the test conditions used in the current study was suitable for the dissolution of copper from the ore. Notwithstanding this, further tests are required to optimise dissolution/removal of copper from the ore before cyanide leaching.
Cu2O 2NH4 2NH3 1 O2 2Cu ( NH3 ) 4 2 H 2O 2

(5)
1 2

Cu2 S

2NH4

2NH3 1 O2 2

CuS Cu ( NH3 ) 4
2

H 2O H 2O
1 2

CuS 2NH4

2NH3 1 O2 2

Cu (NH3 ) 4

1 2

2 S 2O3

(6) (7)

100 Extraction of Au (%) 80 60 40 20 0 0

AASL Direct cyanidation Pre-aeration

12 16 20 Time in hours

24

Figure 3. Effect of pre-aeration (2 L/min) and ammoniacal ammonium sulphate leaching (AASL) (0.5 M NH3+0.5 M (NH4)2SO4) on the extraction of gold (1.5 g/L NaCN)

80 Dissolved Cu (%) 60 40 20 0 0

AASL Direct Cyanidation Pre-aeration

8 12 16 Time in hours

20

24

Figure 4. Dissolution of copper from the ore in preaeration (2 L/min), ammoniacal ammonium sulphate leaching (AASL) (0.5 M NH3+0.5 M (NH4)2SO4) and direct cyanide leaching (1.5 g/L NaCN)
0.0

L o g [N H 3 ] T O T

-0.1
Cu(N H 3 ) 4 2+

-0.2

-0.3

-0.4 7 8 9

CuO(cr)

10 pH

11

12

Figure 5. pH-dependent stability of copper species in ammonia solution (Medusa, 2004). Fig. 6 illustrates the effect of pre-aeration and AASL on the consumption of cyanide. A 16% reduction in the consumption of cyanide after the AASL was recorded (Fig. 6). This was consistent with the earlier studies where more extensive reduction in cyanide consumption (from 30 kg/ton to 2 kg/ton) was reported to occur (Bas et al., 2012; Muir et al., 1991). In contrast, pre-aeration was observed to lead to an increase in cyanide consumption (Fig. 6). This could be attributed to the partial oxidation of sulphides rendering copper readily soluble in cyanide solutions. It should be noted that the solubility of copper (Ksp = [Cu2+] [OH-]2 = 4.8x10-20) is limited under the aeration conditions in the absence of cyanide (Fig. 5).
12
NaCN consumption (kg/ton) Direct cyanidation Pre-aeration AASL

10 8 6 4 2 0

Figure 6. Effect of ammoniacal ammonium sulphate (0.5 M NH3+0.5 M (NH4)2SO4) leaching pretreatment (AASL) and pre-aeration on the consumption of NaCN (NaCN: 1.5 g/L)

CONCLUSIONS In this preliminary study, effect of ammoniacal ammonium sulphate leaching (AASL) and pre-aeration on the extraction of gold from a copper-rich ore in subsequent cyanide leaching was demonstrated. Direct cyanide leaching, which yielded poor extraction of gold (4% Au), confirmed the refractory nature of the ore. AASL ahead of cyanidation was found to substantially improve the extraction of gold (from 3.6% to 91.4%) with a concomitant reduction in cyanide consumption, apparently linked with removal of copper present in the ore. Pre-aeration prior to cyanidation was also observed to enhance the extraction of gold though, to a limited extent (i.e. 30%). These findings suggest that AASL and/or pre-aeration ahead of cyanidation could be exploited for the treatment of copper-rich refractory gold ores. Notwithstanding this, further detailed tests are required to develop and evaluate these pretreatment processes. ACKNOWLEDGEMENT The authors would like to express their sincere thanks to Assoc. Prof. Dr. I. Alp and Assist. Prof. Dr. O. Celep for their help during the testwork, and Mastra Gold Mine-Koza Gold Operations for kindly providing ore samples. REFERENCES Alymore, M. G. and Muir, D., 2001. Thiosulphate leaching of gold- A review, Minerals Engineering, Vol. 14, pp. 135-174 Bas, A. D., Ozdemir, E., Yazici, E. Y., Celep, O. and Deveci, H., 2011. Ammoniacal thiosulphate leaching of a copper-rich gold ore, Proceedings of Int. Conference on Environmental and Mineral Processing EaMP 2011, Ostrava, Czech Republic, pp. 83-90. Bas, A.D., Yazici E.Y. and Deveci, H., 2012. Treatment of A Copper-Rich Gold Ore by Ammonia Assisted Cyanide Leaching, XXVI International Mineral Processing Congress (IMPC 2012), September 24-28, New Delhi, India. Bas, A.D., Altnkaya P., Yazici E.Y. and Deveci, H., 2012a. Preg-robbing potential of sulphide-bearing gold ores, XIIIth International Mineral Processing Symposium IMPS 2012, October 10-12, Bodrum, Turkey. Breuer, P. L., Dai, X. and Jeffrey, M. I., 2005. Leaching of gold and copper minerals in cyanide deficient coper solutions, Hydrometallurgy, Vol. 78, pp. 156-165. Bulatovic, S. M. 1998. Flotation behaviour of gold during processing of porphyry copper-gold ores and refractory gold-bearing sulphides, Minerals Engineering, Vol. 10, pp. 895908. Dai, X., Simons, A. and Breuer, P., 2012. A review of copper cyanide recovery technologies for the cyanidation of copper containing gold ores, Minerals Engineering, Vol. 25, pp.1-13. Dawson, J N, La Brooy, S. R. and Ritchie, I. M., 1997. Copper-Gold Ore Leaching: A Kinetic Study on the Ammoniacal Cyanidation of Copper, Chalcociteand Chalcopyrite, The AusIMM Annual Conference, Ballarat, March 12-15, pp. 291-297. Forrest, K., Yan, D. and Dunne, R., 2001. Optimisation of gold recovery by selective gold flotation for copper-gold-pyrite ores, Minerals Engineering, Vol. 4, pp. 227-241. Hayes, G. A. and Corrans, I. J., 1992. Leaching of gold-copper ores using ammoniacal cyanide, Extractive Metallurgy of Gold and Base Metals, Kalgoorlie, October 23-25, pp. 349-354. Kondos, P.D., Deschnes, G. and Morrison, R.M. 1995. Process optimization studies in gold cyanidation, Hydrometallurgy, Vol. 39, pp. 235-250. Kucuk, A., 2012. Effect of pre-aeration and ammoniacal ammonium sulphate leaching pretreatment on the extraction of gold from Mastra gold ore, BSc. Tehss, Karadeniz Technical University, Dept. of Mining Engineering, Trabzon, Turkey (In Turkish).

Li, Q., Li, D. and Qian, F., 2009. Pre-oxidation of high-sulfur and high-arsenic refractory gold concentrate by ozone and ferric ions in acidic media, Hydrometallurgy, Vol. 97, pp. 61-66. Lia, 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, Vol. 19, pp. 883-895. Marsden, J.O. and House, C.I. 2006. Chemistry of Gold Extraction (2nd Edition). Society for Mining, Metallurgy, and Exploration (SME). MEDUSA, 2004. Software for chemical equilibrium diagrams, version 18. Royal Institute of Technology, Sweeden. Muir, D. M., 2011. A review of the selective leaching of gold from oxidised coppergold ores with ammoniacyanide and new insights for plant control and operation, Minerals Engineering, 24, pp. 576582. Muir, D. M., La Brooy, S. R. and Fenton, K., 1991. Processing copper-gold ores with ammonia or ammonia-cyanide solutions, Proceedings of World Gold 91, Cairns, April 21-25, pp.145-150. Ozdemir, E., 2011. Thiosulphate leaching of gold from copper-rich Mastra gold ore, BSc. Thesis, Karadeniz Technical University, Dept. of Mining Engineering, Trabzon, Turkey. (In Turkish). Rajala, J. and Deschnes, G. 2009. Extraction of gold and silver at the Kupol Mill using CELP, Proceedings of World Gold Conference 2009, pp. 35-42. Sceresini, B. 2005.Gold-copper ores (Chapter 32), Advances in Gold Ore Processing, Adams A.D. (ed.), Developments in Mineral Processing, Vol 15, Elsevier, Amsterdam, The Netherlands, pp.789-824. Serbest, V. 2010.Effect of secondary copper minerals on cyanide leaching of gold ores, BSc. Thesis, Karadeniz Technical University, Dept. of Mining Engineering, Trabzon, Turkey. (In Turkish)