Hydrometallurgy 104 (2010) 119122

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Kinetics and deposit morphology of gold cemented on magnesium, aluminum, zinc, iron and copper from ammonium thiosulfateammonia solutions
M. Karavasteva
Faculty of Chemistry, Soa University, 1 James Bourchier Avenue, Soa 1164, Bulgaria

a r t i c l e

i n f o

a b s t r a c t
The kinetics of gold cementation by magnesium aluminum, zinc, iron and copper at equal conditions as well as the morphology of cementation products and the dissolution of cementing agents were investigated. Both the effect of cementing agents on gold cementation rate and the dissolution of metals decrease in order Cu N Zn N Mg N Fe N Al. High dissolution of magnesium, zinc, iron and copper per mol deposited gold was found. Zinc is the most efcient cementing agent. Magnesium and iron can be used in gold cementation practice but the extremely slow cementation rate prevents the practical application of aluminum. Signicant differences in the morphology of gold deposits on magnesium, aluminum, zinc, iron and copper were found: thick deposit layers with small or large cracks were observed on magnesium or zinc; porous layers of fern leaf-shaped dendrites on copper; compact smooth deposit of ne crystallites on iron and small very rare formations of ne dendrites on aluminum. 2010 Elsevier B.V. All rights reserved.

Article history: Received 20 January 2010 Received in revised form 14 April 2010 Accepted 16 April 2010 Available online 29 April 2010 Keywords: Gold cementation Magnesium Zinc Iron Copper

1. Introduction Thiosulfate leaching of gold containing ores and materials is investigated as a non-toxic alternative to cyanide leaching process (Aylmore and Muir, 2001; Navarro et al., 2002; Molleman and Dreisinger, 2002; Ficeriova et al., 2002; Grosse et al., 2003; Chandra and Jeffrey, 2004). On the other hand, gold recovery by cementation from cyanide and thiosulfate solutions is performed using different cementing agents as magnesium (Kuntyi et al., 2007), aluminum (Arima et al., 2002; Fujita et al., 2003; Yen and Liu, 2008), zinc (Arima et al., 2002; Navarro et al., 2004; Yen and Liu, 2008), iron (Wang et al., 2007) and copper (Guerra and Dreisinger, 1999; Hiskey and Lee, 2003; Arima et al., 2002; Choo and Jeffrey, 2004; Yen and Liu, 2008). The investigations are performed in order to reveal the mechanism of gold cementation as well as to obtain the optimal conditions concerning the effect of the following parameters: pH, temperature, thiosulfate and ammonia concentration, metal/gold ratio. Gold, present in ammonium thiosulfate solutions with pH 910.5, forms two complexes, goldthiosulfate Au(S2O3)3 and gold ammonia Au (NH3)+. The thiosulfate species are more stable gold 2 (I) species at pH values around 10 (Grosse et al., 2003). As Yen and Liu (2008) have indicated, during the cementation of gold cementing agents form the following types of complex: Zn(S2O3)2, Zn(NH3)2+, 2 4 Cu(S2O3)3, Cu(NH3)2+, [Al(S2O3)2], and (NH4) [Al(OH)4]. The 2 4 formation of Cu(NH3)2+ and its reaction with deposited gold 4 contributes re-dissolution of gold (Navarro et al., 2004). Cementa-

tion deposits are AuMe alloys instead of pure gold (Hiskey and Lee, 2003; Lee and Hiskey, 2008). The aim of the present paper is to study the kinetics of gold cementation by magnesium aluminum, zinc, iron and copper at equal conditions from ammonium thiosulfate solutions. The morphology of cementation products is examined using scanning electron microscopy. The cementing agent dissolution and stoichiometric molar ratio of metal dissolved per deposited gold, is also determined.

2. Experimental Gold cementation on magnesium, aluminum, zinc, iron and copper from ammonium thiosulfateammonia solution containing 0.4 mol L 1 (NH4)2S2O3, 1 mol L 1 NH4OH, and 24 mg L 1Au was carried out at 30 C, pH 9.59.7, constant stirring rate (300 min 1) and 5.10 3 mol of cementing agent in a 250 mL thermostatic cell. The stirring was performed by glass propeller with high surface. An oxygen free environment was provided by passing puried nitrogen through the solution 30 min before and during the experiments. The cementing agents were magnesium, aluminum, zinc, iron and copper powders, fraction with a particle size (100 + 50 m). They were treated with dilute sulfuric acid to remove any surface oxide layer and washed with twice-distilled water. Water remaining in the treated material was absorbed by pressing with lter paper. The samples were weighed after the mentioned treating. During the kinetic investigations aliquots of 5 mL were taken and analyzed from ammonium thiosulfateammonia solution for gold and corresponding cementing agent using inductively coupled plasma spectrometry (ICPS). Cementation products were ltered, washed with twice-

E-mail address: mkaravasteva@chem.uni-soa.bg. 0304-386X/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2010.04.007

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M. Karavasteva / Hydrometallurgy 104 (2010) 119122 Table 1 Values of KMe, metal dissolution and RMe. Metal 103rate constant, s 1 2.19 0.10 2.92 1.03 3.30 Metal dissolution, % 18.6 0.3 22.4 10.2 30.3 RMe, mol metal/mol Au 31.7 3.8 36.6 22.2 50.0

distilled water, dried at room temperature and prepared for SEM examination.

3. Results and discussion 3.1. Cementation kinetics Gold cementation on magnesium, aluminum, zinc, iron and copper from ammonium thiosulfateammonia solution was investigated at 30 C. As previously described by Navarro et al. (2004) the overall reaction of gold cementation on zinc can be presented by the following equation: Zn 2AuS2 O3 2
0 3

Mg Al Zn Fe Cu

2Au 4S2 O3 Zn

where Zn2+ immediately complexes with ammonia to form the corresponding zincammonia complex: Zn
2

4NH3 ZnNH3 4

Also, cupric ions in ammonia solution predominantly exist as cupric tetramine, [Cu(NH3)4]2+ (Guerra and Dreisinger, 1999). The formation [Zn(NH3)4]2+ and [Cu(NH3)4]2+ complexes increases dissolution of cementing agents and provokes the reactions with a negative effect on gold precipitation (Guerra and Dreisinger, 1999; Navarro et al., 2004): CuNH3 4
2

Cu 6S2 O3 2CuS2 O3 3

4NH3

ZnNH3 4

2OH ZnO H2 O 2NH3

The obtained results indicate substantially different effect of magnesium, aluminum, zinc, iron and copper on gold cementation kinetics as well as very high losses of dissolved cementing agents per mol deposited gold. High dissolution of cementing agents was probably due to side reactions such as 3 and the formation of Me (Mg,Zn, Fe, Cu)ammonia complexes. The effect of cementation agents on gold cementation rate, the dissolution of metals and the values of RMe decrease in the order Cu N Zn N Mg N Fe NAl. Therefore, the highest cementation rate and the highest dissolution of cementing agent are found during the gold deposition on copper. Cementation rate during the gold deposition on copper is 3.2, 1.51 and 1.13 fold higher compared to iron, magnesium and zinc. On the other hand, the molar consumption of copper is 1.58, 1.36 and 2.27 fold higher than that of magnesium, zinc and iron. Comparing the values of KCu and RCu with those for magnesium, zinc and iron (Table 2) suggests that zinc is the most efcient cementing agent during gold cementation from ammonium thiosulfate solutions. On the other hand, magnesium and iron can be used in the practice for the cementation of gold. Their lower effect on gold cementation rate is recompensed by their lower molar consumption. Comparing the results, obtained on gold cementation in ammonium thiosulfateammonia medium with our previous data on silver cementation by zinc, iron, copper and aluminum in acid medium (Karavasteva, 2009) suggests that: a) Aluminum shows the lowest effect as cementation agent in both conditions; b) The consumption of cementation agents per mol deposited gold in ammonium thiosulfateammonia medium is substantially higher compared to the consumption of cementation agents per mol deposited silver in acid medium (Table 3). 3.2. Morphology Scanning electron micrographs of the gold deposits on magnesium, aluminum, zinc, iron and copper shown in Fig. 2 indicate signicant differences in the morphology of cementation products. Gold deposition causes complete layers on all metals expect

ZnNH3 4

2OH ZnOH2 2NH3

The concentration of gold at time t (Ct) and initial gold concentration (C0) were used to characterize the cementation kinetics. Fig. 1 shows the variation of log (Ct / C0) with time. It is evident that gold cementation follows rst order kinetics in all experiments. The gold cementation rate on aluminum was strikingly lower than on the other metals and a slight excess of aluminum consumption was found over its stoichiometry. Rate constants (KMe), fractions of metal dissolved during the cementation (in %) and stoichiometric molar ratio of cementing agent per deposited gold (RMe) are shown in Table 1.

Table 2 Values of KCu / KMe and RCu / RMe. Me Mg Zn Fe KCu / KMe 1.51 1.13 3.2 RCu / RMe 1.58 1.37 2.25

Table 3 Values of (RMe)Au / (RMe)Ag. Me Al Zn Fe Cu (RMe)Au / (RMe)Ag 9 3.8 3.7 12.8

Fig. 1. Variation of log(Ct / C0) with time for gold cementation on magnesium, aluminum, zinc, iron and copper from ammonium thiosulfateammonia solution at 30 C.

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Fig. 2. Scanning electron micrographs of gold deposits on magnesium (A), aluminum (B), zinc (C), iron (D) and copper (E).

aluminum where rare formations of ne dendrites were found (Fig. 2B). Thick deposit layers with large or small cracks were observed on zinc (Fig. 2C) and magnesium (Fig. 2A), respectively. The formation of cracks improves the contact between the solution and zinc or magnesium surface truth the thick gold layers. Cementation of gold on copper leads to the formation of fern leaf-shaped dendrites (Fig. 2E). The porous gold layer on copper probably causes both intensive hydrogen evolution and high copper dissolution obtained during the experiments. The compact smooth deposit of ne crystallites was noted on iron (Fig. 2D). The signicant decrease of reaction surface because of low deposit porosity substantially inhibits gold cementation on iron. The morphology of deposits perfectly corresponds to the obtained effect of different cementing agents on the gold cementation kinetics. 4. Conclusions Gold cementation rate strikingly depends on cementing agent. On the other hand, a large difference appears in the amount of metals

dissolved per mol gold deposited. Both the highest cementation rate and the highest dissolution of cementing agent occur during gold deposition on copper. Zinc is the most efcient cementing agent. Both magnesium and iron can be used in gold cementation practice but the extremely slow cementation rate prevents the practical application of aluminum. Signicant differences in the morphology of gold deposits on magnesium, aluminum, zinc, iron and copper are found: thick deposit layers with large or small cracks were observed on zinc and magnesium, formation of porous layer of fern leaf-shaped dendrites on copper, compact smooth deposit of ne crystallites on iron and small very rare formations of ne dendrites on aluminum. References
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