Hydrometallurgy 113114 (2012) 3138

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Thiocyanate hydrometallurgy for the recovery of gold. Part V: Process alternatives for solution concentration and purication
Jinshan Li a, M. Sadegh Safarzadeh a, Michael S. Moats a, Jan D. Miller a,, K. Marc LeVier b, Meg Dietrich b, Rong Yu Wan c
a Department of Metallurgical Engineering, College of Mines and Earth Sciences, University of Utah, 135 South 1460 East, Room 412 William C. Browning Building, Salt Lake City, UT 84112-0114, United States b Plato Malozemoff Technical Facility, Newmont Mining Corporation, 10101 East Dry Creek Road, Englewood, CO 80112-1556, United States c Deceased, formerly Metallurgy Consultant, 9634 South Kalamere Court, Highlands Ranch, CO 80126-4904, United States

a r t i c l e

i n f o

a b s t r a c t
The goldthiocyanate system is of interest as it could offer a number of advantages over the gold-cyanide system such as acidic leaching and less toxicity. In the goldthiocyanate system, the rate of leaching can be accelerated by employing ferric ion as an oxidant. Ultimately, this would lead to a contaminated gold-bearing leach solution that would need to be treated. In this regard, process alternatives for solution concentration and purication are considered including solvent extraction, cementation, and carbon adsorption. The effect of ferric ion on the extraction and stripping of gold was studied. It was demonstrated that ferric ion has an adverse effect on the rate of gold stripping with thiourea. This situation was overcome by controlling the system chemistry-relatively low SCN concentration (0.02 M) in aqueous phase and low amine concentration (0.010.02 M) in the organic phase. Strategies other than solvent extraction including cementation with iron and zinc as well as activated carbon adsorption were considered and results reported. Finally, based on this study a conceptual owsheet is given for the recovery of gold through thiocyanate hydrometallurgy. 2011 Elsevier B.V. All rights reserved.

Article history: Received 9 June 2011 Received in revised form 15 November 2011 Accepted 16 November 2011 Available online 27 November 2011 Keywords: Thiocyanate Alamine 336 Gold Ferric iron Stripping Solvent extraction Cementation Carbon adsorption

1. Introduction Solvent extraction, cementation, and activated carbon adsorption are the most common process strategies for the recovery of gold from pregnant solutions. Therefore, these three process options were considered and examined for the recovery of gold from thiocyanate solutions. From our previous experimental results on solvent extraction (part (IV)) it was demonstrated that tertiary amines (Alamine 336 used in the study) are effective extractants for the recovery of gold from thiocyanate solutions with fast kinetics of extraction and high loading capacity (maximum loading capacity corresponds to a mole ratio of amine to gold 1 in the organic phase). Based on preliminary experiments, it was found that ferric ion is simultaneously extracted into the organic phase with gold. Experimental results, fortunately, demonstrated that the presence of ferric ion in the system, or extraction of ferric, does not affect the gold extraction.
This paper is an extension of the work presented and published in Hydrometallurgy 2008, 6th International Symposium, Phoenix, AZ, United States (Li et al., 2008). Corresponding author. Tel.: + 1 801 5815160; fax: + 1 801 5814937. E-mail address: jan.miller@utah.edu (J.D. Miller). 0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2011.11.008

Some experiments indicated that the extracted ferric-thiocyanate species in the organic phase was replaced by the gold (I)-thiocyanate species. This phenomenon was based on the fact that if the organic phase (amine-hexane-decanol) was saturated with ferric ion prior to gold extraction, gold recovery was found to be equivalent to that with a fresh organic phase without ferric ion in the system. Alamine 336 is of moderate alkalinity and extracts the dissolved goldthiocyante complex in the form of the auro-dithiocyanate anion. Thiourea was used to strip the gold from the organic phase. Thiourea has been proven to be an efcient reagent for the stripping of gold from the loaded amine with fast kinetics and high efciency (~100%) in the absence of ferric ion (Li et al., 2008). Also thiourea has been used to strip precious metals from hydroxyquinoline (Gefvert, 1994). One important aspect of solvent extraction of gold is the effect of ferric iron on gold stripping, and the alternatives for solution concentration and purication. Ferric ion extracted into the organic phase by Alamine 336 is expected to be in the form of ferric-tetrathiocyanate anionic complex, which would hinder gold stripping. This was further proven through some preliminary experiments. It was found that stripping becomes very difcult, that is, stripping requires more than 2 h if the initial ferric ion exceeds 1 g/L in the aqueous phase. This situation may be overcome or the stripping rate improved if

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J. Li et al. / Hydrometallurgy 113114 (2012) 3138

+ 3 Au(SC(NH2)2)2 , only the Au(S203)2 species was different with respect to the adsorption by carbon. The ability of activated carbon to adsorb gold complexes has the following order (Marsden and Iain House, 2006; McDougall and Hancock, 1981):

the ferric ion could be selectively reduced to ferrous ion with an appropriate reductant during the stripping stage and, at the same time, the auro-dithiourea complex stabilized in the system in the presence of the reductant. In this case, ferrous ion produced from the selective reduction would form a weak and positively charged complex with thiocyanate, i.e. ferrous-monothiocyanate (FeSCN +) with complexing constant of 6.5. FeSCN + is not extractable in the current system (Li et al., 2008). It was found from some investigations that formic acid (Prabhananda, 1978) or oxalic acid (Feather et al., 1997; Yunus et al., 1996) shows significant improvement of gold stripping kinetics by selective reduction of ferric to ferrous ion while the gold (I)-dithiourea complex is stable in aqueous solution. Nevertheless, it is expected that this method will lead to high operating costs and that the addition of these reductants with the subsequent redox reaction between ferric ions and oxalic/formic acid will make the system more complicated (Li, 2004). In this regard, another approach was examined to improve the slow stripping kinetics by control of the system chemistry. Ferric extraction into the organic phase may be controlled by SCN concentration in the aqueous solution during leaching and by amine concentration in the organic phase during extraction for gold recovery. This principle is based on the fact that the kinetics of gold leaching in thiocyanate-ferric sulfate solutions is not signicantly sensitive to variation of SCN and ferric concentrations (Li et al., 2008). In addition to solvent extraction, the possibility of gold recovery from acidic thiocyanate solutions by cementation with metals has been investigated by Wang et al. (2007a, 2007b). It was found that the gold cementation from thiocyanate solutions by iron powder is a feasible process (Wang et al., 2007a). The gold cementation reaction was greatly affected by the solution pH, stirring speed, initial gold concentration, iron/gold mass ratio, dissolved oxygen and presence of iron (III), while the reaction temperature and thiocyanate concentration only slightly affected the cementation reaction. The authors concluded that the gold cementation reaction obeyed rst-order kinetics with an activation energy of 9.3 kJ/mol, conforming to a diffusion controlled process. While the de-aeration of the solution enhanced the gold recovery, the presence of ferric ions resulted in the low efciency of gold precipitation as well as the low grade of the cements. In yet another study, the same authors (Wang et al., 2007b) studied the cementation of gold from acidic thiocyanate solutions with aluminum. The experimental results showed the feasibility of gold cementation by aluminum powder. Temperature, pH, deoxygenation and presence of ferric ions in solution, affected the cementation process. However, the cementation reaction was less dependent on thiocyanate concentration and stirring speed. The gold cementation reaction obeyed rst-order kinetics, with an activation energy of 41.9 kJ/mol in the absence of ferric ions and the presence of uoride ions in solution, conforming to a chemically controlled reaction. It was found that the presence of ferric ions signicantly inhibited the cementation reaction. However, the addition of uoride into the leach solution could overcome the inhibitory effect of ferric ions and considerably enhanced the gold cementation rate. Reductionprecipitation of gold with sodium borohydride (SBH) from thiocyanate solutions has also been reported to be quite effective (Awadalla and Ritcey, 1990). Finally, the adsorption of gold by activated carbon, well-known for over seventy years (McDougall and Hancock, 1980), has been considered. The adsorption of gold on activated carbon from different solutions has been studied by several researchers. However, less wellknown is the activated carbon adsorption of gold from thiocyanate solutions. Gallagher (1987) and Gallagher et al. (1990) studied the activated carbon adsorption of gold complex ions with different ligands including thiosulfate, thiocyanate, chloride and thiourea. Among the 3 studied gold complexes Au(S203)2 , Au(SCN)2 , AuCl4 , and

AuCl4

> AuCN2

> AuSCN2

3 > Au SCNH2 2 2 > AuS2 03 2

The mechanism of gold adsorption from chloride and thiocyanate solutions is reported to involve the reduction of gold to the metallic state (Marsden and Iain House, 2006). In view of the important role of ferric ion in solvent extraction and stripping, it is noted that a major part of this paper is devoted to the evaluation of the effect of ferric ion in the solvent extraction of gold from thiocyanate solutions. Cementation and activated carbon adsorption of gold from acidic thiocyanate solutions were considered to a lesser extent. 2. Solvent extraction 2.1. Materials and methods The tertiary amine, Alamine 336 (trialkyl (C8-C10) amine), was obtained from Cognis Company and used as received. Decanol (Cognis Company) was added to improve the solubility of gold and ferric species in the organic phase and to mitigate viscosity of the organic phase when loaded with ferric ion in some experiments. Hexane (SigmaAldrich Company) was employed as received and used as the diluent. Sulfuric acid and sodium hydroxide (both AR, Mallinckrodt) were used to adjust pH. Ammonium hydroxide and thiourea (both AR, Mallinckrodt) were used for gold stripping. NaSCN, 98.2%, was purchased from Fisher Scientic. In all experiments DI water was used to prepare the aqueous solution. For the purpose of mixing a shaker (MAX Q 2000, Barnstead/Lab-Line) was used. Chemical analyses were performed using ICP-OES for gold and standard titration with KSCN for ferric iron. 2.2. Extraction of ferric iron Ferric ion forms a series of complexes with thiocyanate, as outlined and discussed in part (I). It is expected that the anionic complexes of thiocyanate and ferric ion could be extracted into the organic phase during gold extraction. Thus, the extraction of ferric ion was examined. Based on results from part (IV), it was determined that solvent extraction of gold from thiocyanate solutions with Alamine 336 is promising. The selective extraction of gold from free thiocyanate ion can be achieved by pH control. Strong extraction of ferric ion at high acidity (pH 1.0) occurs with Alamine 336. When the pH of the aqueous solution is above 1.5, ferric ion undergoes hydrolysis. Therefore, it is evident that the selectivity of gold over ferric ion during extraction and stripping is one of the issues that should be resolved for the purpose of gold solvent extraction from thiocyanate solutions. A summary of ferric extraction at different pH values is given in Table 1. 2.3. Isotherms for iron extraction The isotherms for iron extraction were determined and the effect of decanol in the organic phase was evaluated (Fig. 1). It was observed that the extracted iron/amine species have low solubility in the organic phase and precipitated during the experiments, which limits the iron loading capacity of the organic phase. By adding decanol (20 vol.%) the loading capacity increased. However, the organic phase loaded with iron became signicantly viscous.

J. Li et al. / Hydrometallurgy 113114 (2012) 3138 Table 1 Summary of ferric ion extraction by Alamine 336 (~ 23 C, O/A of 1:1, Alamine 336 0.1 M, Fe3 + 1 g/L, and SCN 0.1 M, stirring speed 500 rpm). pHinitial Fe extraction/observations

33

100 90 80

Fe extraction (%)

1.0 1.5 2.0 2.5 3.0

~ 100% Partial extraction (black organic phase), partial hydrolysis in organic phase, and third phase formation. Limited extraction, hydrolysis in aqueous phase, and third phase formation. No extraction, complete hydrolysis in aqueous phase, and third phase formation. No extraction, complete hydrolysis in aqueous phase, and third phase formation.

70 60 50 40 30 20 10

2.4. The effect of thiocyanate concentration on the extraction of ferric iron The molar ratio of SCN/Fe was varied with an amine concentration of 0.2 M, decanol 20 vol.% and with an aqueous phase of Fe (III) 0.05 M, and pH 1.8 at 23 C, O/A of 2 and a mixing time of 20 min. Fig. 2 clearly shows that the effect of thiocyanate concentration or molar ratio of SCN/Fe on iron extraction is signicant. When the ratio is above 3, anionic iron thiocyanate complexes are stabilized and extraction is evident (see discussion in part (III)). When the ratio is below 3, iron extraction is obviously limited. In this way iron extraction may be depressed by starvation with thiocyanate in actual leaching practice. 2.5. The effect of iron loaded organic phase on gold extraction Based on the extraction data for ferric ion, it is expected that ferric ion may load onto the extractant during gold extraction under actual leaching conditions. Therefore, the effect of ferric ion preloaded in the organic phase on gold extraction was examined. Table 2 shows the results of gold extraction experiments under different conditions. In experiment 1, gold was extracted using a fresh organic phase, which serves as a reference point for subsequent experiments. Experiment 2 examined gold extraction with an organic phase equilibrated with ferric sulfate solution (initial ferric ion concentration 0.01 M, pH 1.8) prior to gold extraction. In experiment 3, the organic phase from experiment 2 was used to extract more gold from a new

0 0 1 2 3 4 5 6 7 8 9 10

SCN/Fe molar ratio

Fig. 2. The effect of SCN concentration on iron extraction by Alamine 336. O/A of 1:2, pH 1.8, Fe (III) 0.05 M, 23 C. Organic phase: Alamine 336 0.2 M and hexane. Mixing time 20 min.

aqueous solution. Likewise, experiment 4 used the organic phase from experiment 3 to recover gold from another new aqueous solution. The results show that the presence of ferric ion in the organic phase did not affect gold extraction under the conditions studied. 2.6. The effect of decanol on gold extraction As previously discussed, the organic phase loaded with ferric ion became viscous and the solubility of ferric thiocyanate-amine extracted species was limited. In order to reduce the viscosity of the organic phase, it was necessary and/or benecial to add a modier (e.g. decanol) to the organic phase. Since it appears that a modier may be used in practice, the effect of decanol addition on gold extraction was examined. The results indicated that decanol did not affect gold extraction up to 15 vol.% under the experimental conditions studied (O/A of 1:2, Au 10 mg/L, SCN 0.05 M, pH 1.8, and 23 C. Organic phase: Alamine 336 0.1 M and hexane, and mixing time 20 min). 2.7. Stripping kinetics

50 45 40 35
Alamine 336, 0.04 M Alamine 336, 0.04 M + 20 vol% decanol

[Fe]organic (mM)

30 25 20 15 10 5 0 0 10 20 30 40 50 60 70

As mentioned in the Introduction, stripping becomes very difcult in the presence of ferric ions exceeding 1 g/L in the aqueous phase. The possibility for improvement in the rate of gold stripping was considered by control of the system chemistry (SCN concentration in the aqueous solution and amine concentration in the organic phase). The effect of SCN concentration (0.01 to 0.05 M) at 0.1 M Alamine 336

Table 2 The effect of ferric loaded in the organic phase on gold extraction. Experiment Conditions no. 1 2 Fresh Alamine 336, 0.02 M, 23 C Organic phase loaded with Fe/Au, O/A of 1:2, pH 1.8, Au 10 mg/L, mixing time 20 min., 23 C Organic phase loaded with Fe/Au, O/A of 1:2, pH 1.8, Au 10 mg/L, mixing time 20 min., 23 C Organic phase loaded with Fe/Au, O/A of 1:2, pH 1.8, Au 10 mg/L, mixing time 20 min., 23 C Au extraction (%) 96.7 95.8 97.1 97.9

[Fe]aqueous (mM)
Fig. 1. Isotherms for iron extraction from aqueous solution by Alamine 336 (0.04 M). SCN 0.25 M, pH 1.8, and 23 C. O/A of 1:2 and mixing time 20 min.

3 4

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J. Li et al. / Hydrometallurgy 113114 (2012) 3138

concentration on gold stripping was studied and the results are shown in Fig. 3a. The effect of Alamine 336 concentration (0.02 to 0.1 M) at SCN 0.05 M on gold stripping is presented in Fig. 3b. It is evident that the kinetics of gold stripping in the presence of ferric iron can be improved signicantly by decreasing the thiocyanate and Alamine 336 concentrations. Further discussion is given in Section 2.8. 2.8. Discussion of solvent extraction and stripping 2.8.1. Structure of thiocyanate complexes Thiocyanate is an ambidentate ligand: S-thiocyanate (SCN ) and N-thiocyanate (NCS ). According to Lewis's acidbase theory, the nitrogen atom in SCN coordinates with ferric ion, forming Fe(III)(NCS)4 , for example. The sulfur atom in SCN coordinates with the aurous ion, forming Au(SCN)2 (see the Reactions (1) and (2)). Fe
3

2.8.2. Extraction Alamine 336, a tertiary amine, has a moderate alkalinity. When contacting with the acidic (pH 1.8) leaching solution, it is rst protonated, forming the cationic ion, R3NH+, in the organic phase or in the interfacial region between the aqueous and organic phases (where R3N represents the tertiary amine). Ferric ion and dissolved gold (I) in thiocyanate solution are extracted into the organic phase in the form of anions. The solvent extraction of ferric and aurous anions can be expressed according to Reactions (3) and (4). R3 N:H FeNCS4

R3 N:H:FeNCS4 R3 N:H:AuSCN2

3 4

R3 N:H AuSCN2

4NCS

FeNCS4

1 2

Au 2 SCN

AuSCN2

Similarly, the hydration or hydrophilicity of the gold complex, Au(SCN)2, is less than that of the iron complex, Fe(NCS)4.

where the over score indicates the organic phase. The aurodithiocyanate complex is preferentially extracted into the organic phase with respect to the ferric-tetrathiocyanate complex since the hydration or hydrophilicity of the former is less than that of the latter. If the ferric species is rst extracted or if the organic phase is saturated with the ferric species in the system, the gold species is able to exchange with the ferric species in the organic phase. In this way, the presence of ferric ion in the system does not signicantly affect the rate or extent of gold extraction. 2.8.3. Stripping If ferric ion is not present in the system, gold stripping with thiourea from the organic phase is easy and ~100% recovery is achieved within about 5 min. The principle of gold stripping with thiourea is based on the fact that the aurous ion forms a more stable cationic complex with thiourea (log 2 = 21.96) than an anionic complex with thiocyanate (log 2 = 19.16). Therefore ligand replacement occurs and the more stable cationic thiourea complex is released to the aqueous phase as indicated by Reaction (5).

100 90 80

Au stripping (%)

70 60 50
SCN 0.05 M

40 30 20 10 0 0 10 20 30

R3 NH:AuSCN2 2 Tu R3 N:HSCN AuTu

SCN

SCN 0.02 M SCN 0.01 M

40

50

Time (min.)

100 90 80

Au stripping (%)

70 60 50 40 30 20 10 0 0 10 20 30 40 50
Alamine 336, 0.1 M Alamine 336, 0.05 M Alamine 336, 0.02 M

However, when ferric ion is present in the system, it is simultaneously extracted into the organic phase with gold and makes the gold stripping difcult. For example, under similar experimental conditions, only ~ 80% gold stripping was achieved in 40 min, as opposed to the experiment in the absence of ferric ions, where ~ 100% gold was stripped. If ferric and gold (I) complexes with thiocyanate are simultaneously extracted into the organic phase at relatively high SCN and Alamine 336 concentrations, the polymerization between gold (I) and the ferric species may occur to a certain extent. For example, the nitrogen atom of the gold thiocyanate complex could coordinate and be shared with the ferric thiocyanate since SCN is an ambidentate ligand and ferric ion has a tendency to form complexes with 5 or 6 SCN ligands. This issue can be expressed with the following reaction in the organic phase (Reaction (6)).
R3 N:H:FeNCS4 R3 N:H:AuSCN 2 R3 N:H:NCS:Au:SCN:FeNCS4 HNR3

6 In such a way gold stripping with thiourea is expected to become slow or difcult. This hypothesis is consistent with improved stripping by selective reduction of ferric to ferrous ion using oxalic or formic acid and by depression of ferric extraction at low SCN and low amine concentrations. It is important to note that in the aqueous phase the complexation of ferric thiocyanate, Fe(SCN)4 , is strong with a complexation con6 stant of 2.5 10 and that the complexation between ferrous and SCN is very weak, forming a cationic complex, FeSCN +, with a

Time (min.)
Fig. 3. The effect of (a) SCN concentration and (b) Alamine 336 concentration on the kinetics of gold stripping from thiocyanate solutions. Extraction conditions: aqueous phase: Au 10 mg/L, SCN 0.05 M, Fe (III) 1 g/L, pH 1.8; organic phase: Alamine 336, decanol 5 vol.%, hexane as carrier. Stripping conditions: Loaded organic phase Au 9.7 mg/L; aqueous phase: thiourea 0.1 M, O/A of 1, 23 C, pH 1.8.

J. Li et al. / Hydrometallurgy 113114 (2012) 3138

35

complexation constant of 6.5. The weak and cationic ferrousthiocyanate complex is not extracted by Alamine 336. However for stripping, these properties suggest that if an appropriate reductant can selectively reduce ferric ion to ferrous ion and maintain the gold species in the system it would improve the rate of gold stripping, which was discussed in the Introduction. 2.9. Conditions for effective extraction and stripping The results presented in Fig. 4 reveal conditions for the effective extraction and thiourea stripping of gold from acid thiocyanate solution using Alamine 336. At Alamine 336 concentrations below 0.01 M, the gold extraction increases with increasing Alamine 336 concentration. As the ferric ion concentration is increased to 3 g/L, the extraction is inuenced to a modest extent at 0.05 M SCN. At Alamine 336 concentrations above 0.1 M, gold stripping with thiourea decreases with an increase in the amine concentration under the conditions studied. It can be concluded from these equilibrium results in Fig. 4 and the kinetic results shown in Fig. 3 that the relatively low amine concentration in the organic phase (0.01 0.1 M) and the low thiocyanate concentration (less than 0.05 M) in the aqueous phase signicantly improve the rate of gold stripping and ensure, at the same time, satisfactory gold extraction from thiocyanate leaching solutions. In summary, Fig. 4 shows that there is a window for extraction and stripping with Alamine 336 in the 0.020.1 M concentration range. Under these conditions excellent results are obtained for both extraction and stripping with thiourea. 3. Cementation Generally iron, zinc, aluminum and copper are the metals that have been used for the cementation of gold from thiocyanate solution. Iron is the rst choice for gold cementation, because ferric iron is used as an oxidant in thiocyanate gold leaching systems. In fact, the barren thiocyanate solutions left after gold cementation can be recycled back to the leaching step and reused (Wang et al., 2007a).

The cathodic reaction for gold cementation from acidic thiocyanate solutions can be written as: AuSCN4

3e

Au 4SCN

E o 0:636 V

The anodic reactions for iron and zinc are as follows: Fe

2

2e

Fe Zn

E o 0:410 V E o 0:763 V

8 9

Zn

2e

The overall cementation reactions for iron and zinc will be respectively: 2AuSCN4 3Fe 2Au 3Fe G o 623:0 kJ=mol
2

8SCN

E o 1:046 V

10

2AuSCN4 3Zn 2Au 3Zn G o 810:0 kJ=mol

8SCN

E 1:399 V

11

The G values for Reactions (10) and (11) indicate that both reactions are spontaneous, with Reaction (11) being more favorable. It should be noted that reactions 10 and 11 both have potentials greater than 0.36 V (difference between half cell reactions), and are likely to be diffusion-controlled (Power and Ritchie, 1976). 3.1. Materials and methods Sulfuric acid and sodium hydroxide (both AR, Mallinckrodt) were used to adjust pH. In all experiments, DI water was used to prepare the aqueous solution. An overhead mixer was used for mixing. Chemical analyses were performed using ICP-OES. The kinetics of gold cementation with iron and zinc powders were determined with variation of solution volume (mL)/amount of metal (g) ratio and reaction time. Cementation experiments were performed at room temperature. 3.2. Results and discussion The results for gold cementation from acidic thiocyanate solutions with iron and zinc powders are shown in Figs. 5 and 6, respectively. In the cementation with iron, it was observed that ferric ion hydrolysis occurred. This phenomenon was also observed by Wang et al. (2007a). Several possibilities have been considered by these authors that contribute to side reactions that would decrease the efciency of gold cementation by iron. These possibilities include iron powder

100

100

90

90

Au extraction (%)

Extraction and stripping window

80

100 80

Au stripping (%)

90 80

Gold recovery (%)

70
Fe (III) 1 g/L, Extraction Fe (III) 3 g/L, Extraction Fe (III) 1 g/L, Stripping Fe (III) 3 g/L, Stripping

70

70 60 50 40 30 20
100 40 10

60

60

50

50

Solution/iron (mL/g)

Gold/iron (molar ratio) 2.85 10

-4 -4

40 0.002

0.005

0.01

0.02

0.05

0.1

0.2

40 0.5

10 0 0 2 4 6 8

1.13 10 -5 2.85 10
12 14 16 18 20 22 24

Alamine 336 concentration (M)

Fig. 4. The effect of Alamine 336 and ferric concentrations on solvent extraction and thiourea stripping of gold. Extraction conditions: aqueous phase: Au 10 mg/L, SCN 0.05 M, Fe (III) 1 and 3 g/L, pH 1.8; organic phase: Alamine 336, decanol 5 vol.%, hexane as carrier. Stripping conditions: Loaded organic phase Au 9.7 mg/L; aqueous phase: thiourea 0.1 M, O/A of 1, 23 C, pH 1.8.

10

Time (h)
Fig. 5. Kinetics of gold recovery from acidic thiocyanate solution by cementation with iron powder. Au 10 mg/L, SCN 0.1 M, Fe (III) 1.0 g/L, pH 2, and stirring speed 500 rpm (particle size 425850 m).

36

J. Li et al. / Hydrometallurgy 113114 (2012) 3138

100 90 80

100 90 80

Gold recovery (%)

60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16 18 20 22 24
100 40

Gold recovery (%

70

70 60 50 40 30 20 10 0 0 2 4 6 8

Solution (mL)/AC (g)

200 100 40

Solution/zinc (mL/g)

Gold/zinc (molar ratio) 3.32 10 -4 1.33 10

-4

Time (h)
Fig. 6. Kinetics of gold recovery from acidic thiocyanate solution by cementation with zinc powder. Au 10 mg/L, SCN 0.1 M, Fe (III) 1.0 g/L, pH 2, and stirring speed 500 rpm (particle size 75425 m).

10

12

14

16

18

20

22

24

Time (h)
Fig. 7. Kinetics of gold recovery from acidic thiocyanate solution by adsorption with activated carbon. Au 10 mg/L, SCN 0.1 M, Fe (III) 1.0 g/L, pH 2, 23 C and stirring speed 500 rpm (particle size 212425 m).

oxidation and dissolution in the acidic solution, iron (III)-thiocyanate complexes formation in thiocyanate solutions, and iron hydroxide formation due to hydrolysis. The pH increased from 2 to about 4 for the iron system and from pH 2 to about 6.6 for the zinc system. As expected, no consumption of thiocyanate was detected in either case. Fig. 5 demonstrates that the rate of gold cementation with iron is such that the reaction is completed in about 1 h. Gold recovery is satisfactory (~98%) with high ratios (100 and 40) of solution volume (mL)/ amount of iron (g). The recovery at the low ratio (10) of solution volume (mL)/amount of iron (g) reaches a maximum (~98%) at 1 h, decreases with an increase in reaction time and then increases again. It is expected that this behavior may be related to the abovementioned reasons. Fig. 6 shows that the zinc system is not as effective as the iron system, depending on the solution volume (mL)/amount of zinc (g) ratio. Gold recovery is less than 80% with a ratio of 40 and less than 60% with a ratio of 100. 4. Activated carbon adsorption 4.1. Materials and methods Activated carbon was obtained from Calgon. Sulfuric acid and sodium hydroxide (both AR, Mallinckrodt) were used to adjust pH. In all experiments, DI water was used to prepare the aqueous solution. An overhead mixer was used for mixing. Chemical analyses were performed using ICP-OES for gold analysis and standard titration with KSCN for ferric iron analysis. 4.2. Results and discussion

the consumption may result from adsorption and catalytic degradation of thiocyanate in the presence of ferric ion. See Fig. 8 and further discussion in Section 4.2.1. 4.2.1. Kinetics Further results for the rate of gold adsorption by activated carbon (10 g/L, 1.4 2.6 mm, Calgon) are presented in Fig. 8, which shows that adsorption reaches equilibrium in ~ 2 h and that gold recovery is ~98%. Meanwhile, these results suggest that ferric reduction is fast in the presence of activated carbon with 98% ferric reduction and that about 20% thiocyanate consumption is observed. As discussed in part (III), the redox reaction between thiocyanate and ferric ion is catalyzed by activated carbon, which is one of the important factors causing thiocyanate consumption. 4.2.2. The effect of pH According to the results presented in Fig. 9, gold adsorption by activated carbon is not sensitive to pH variation in the range 1.83. However, the effect of pH on ferric reduction and thiocyanate decomposition by ferric oxidation is signicant. Specically, while ferric reduction at pH 1.8 reaches almost 100% in 3 h (see Fig. 8); ferric

100 90 80 70
SCN consumption

Adsorption of gold from acid thiocyanate solution by activated carbon (AC) was measured and the rate was determined with variation of solution volume (mL)/amount of AC (g) ratio and reaction time. The particle size of the activated carbon particles fell within the range 212425 m. The results presented in Fig. 7 show that activated carbon is effective as revealed by the adsorption rate and gold recovery. Gold recovery of above 98% is achieved in 1 h. Both rate and recovery are not dependent on the ratio of solution volume (mL)/amount of AC (g), indicating that the system is suitable to a wide range of ratios under the experimental conditions studied. During the experiments, it was observed that the pH of the aqueous solution increased from pH 2 to about pH 2.4, and that no ferric hydroxide precipitation was detected. Thiocyanate was consumed from ~2% at a high ratio (200) of solution volume (mL)/amount of AC (g) to ~19% at a low ratio of solution volume (mL)/amount of AC (g). It is expected that

Percent

60 50 40 30 20 10 0 0 20 40 60 80 100

Fe (III) reduction Au adsorption

120

140

160

180

200

Time (min.)
Fig. 8. Examination of gold adsorption, ferric reduction, and SCN consumption during the adsorption of gold with activated carbon. Au 10 mg/L, Fe (III) 1 g/L, SCN 0.05 M, 23 C, activated carbon content 10 g/L, at pH 1.8.

J. Li et al. / Hydrometallurgy 113114 (2012) 3138

37

50 45 40
pH 1.8 pH 2.6 pH 3.0

Auriferous sources, oxides, pre-oxidized sulfides

SCN consumption (%)

35 30 25 20 15 10 5 0 0 20 40 60 80 100 120 140 160 180 200

Removal of Fe (III) if necessary, by precipitation

Leaching SCN 0.05 M, pH 2.5 - 3.0 Fe 3+ 0.1 g/L

S L

Tailings

Time (min.)
Fig. 9. The effect of pH on SCN consumption during the adsorption of gold with activated carbon. Au 10 mg/L, Fe (III) 1 g/L, SCN 0.05 M, 23 C, activated carbon content 10 g/L.

Raffinate

Solvent extraction of gold Alamine 336 0.05M, Decanol 2-5 vol%, O/A1:5,pH 3

Barren organic

reduction at pH 3 is only about 15%. Thiocyanate consumption, at the same time, decreases from 25% at pH 1.8 to 5% at pH 3 (Fig. 9). 4.2.3. The effect of temperature The effect of temperature (2385 C) on the rate of gold adsorption and on the loading capacity of activated carbon was investigated. The results suggest that the adsorption rate is fast with ~ 97% gold recovery within 2 h at 23 C. Temperature does not inuence the equilibrium gold loading, but does increase the initial adsorption rate. The loading capacity of the activated carbon for gold was determined using standard methods and the K value was found to be 10.4 mg (Au)/g (AC). It is worthwhile to note that this is signicantly less than the K value obtained for loading from cyanide solution which was determined experimentally to be 23 mg (Au)/g (AC). 5. Thiocyanate owsheet for gold recovery Based on the results for thiocyanate leaching and solvent extraction of gold presented in parts (I)(IV) as well as the results presented in part (V), the following owsheet (Fig. 10) was prepared for the extraction of gold from auriferous resources. 6. Toxicity and environmental issues Thiocyanate is an interesting alternative as it is an acid stable reagent; thereby it can be used for gold extraction in an acidic environment. The potential for use of thiocyanate requires consideration of thiocyanate toxicity (Li et al., 2008). Thiocyanate is a naturally occurring compound found in food products. Examples of foods containing thiocyanate are given in Table 3. The family of plants, Cruciferae, is a signicant source of thiocyanate in animal foods. Probable toxicity of thiocyanate for mammals is considered to be relatively low. A 150-pound individual would have to ingest 29 g of potassium thiocyanate as a potential single lethal dose (Menne, 2003). Thiocyanate is up to 1000 times less toxic than cyanide for test animals. Comparative material safety data sheet (MSDS) information indicates that potassium thiocyanate is less toxic and more easily handled when compared to sodium cyanide. In the gold leaching process, the stability of the thiocyanate species is strongly dependent on oxidation potential and leaching conditions. Thiocyanate is oxidized to sulfate and metastable cyanide or hydrocyanic acid, depending on solution pH. Cyanide and hydrocyanic acid are further oxidized in aqueous solution to cyanate (CNO), which is subsequently oxidized to carbonate and ammonia. Common microorganisms in soil and

Stripping of gold Tu 0.1-0.5 M, O/A 5, pH ~2

Thiourea

Electrowinning of gold from thiourea solution

Gold bullion
Fig. 10. Conceptual owsheet for thiocyanate leaching and recovery of gold.

aquatic environments degrade thiocyanate. Continued development of the thiocyanate process for gold recovery requires further investigation of thiocyanate degradation products in waste streams and detoxication processes to meet Environmental Protection Agency (EPA) discharge standards that may be developed. 7. Conclusions Process strategies for gold recovery from acid thiocyanate solutions have been considered including solvent extraction, cementation, and activated carbon adsorption. In the case of solvent extraction experimental results show that ferric ion was almost completely extracted when the initial pH of the aqueous solution was about pH 1. However, the presence of ferric ion does not affect gold extraction. Decanol was added due to viscosity changes caused by high iron loadings. Ferric iron was extracted in signicant quantities at a SCN/Fe molar ratio of above 3. The presence of decanol did not affect gold extraction. It was found that ferric ion has an adverse effect on the kinetics of gold stripping with thiourea from thiocyanate solutions. The strategy used to overcome this problem was the control of system chemistry (SCN concentration in aqueous solution and amine concentration in the organic phase for solvent extraction) instead of using reducing

Table 3 Thiocyanate content in common foods. Food Beets Cabbage Cauliower Milk Thiocyanate content (mg per 100 g food product) 10 8.55 8.8 8.615.7 mg/L

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J. Li et al. / Hydrometallurgy 113114 (2012) 3138

agents such as oxalic or formic acid, which would complicate the system and impose additional costs. The results clearly showed that this goal can be achieved by maintaining appropriate values of SCN concentration (0.02 M) in the aqueous phase and low amine concentration (0.010.02 M) in the organic phase. A window for optimum gold extraction and stripping in the presence of ferric ion was recognized and illustrated. Gold cementation with iron powder from thiocyanate solution was effective with respect to kinetics (reaction completed in 1 h) and gold recovery (~98%). However, cementation of gold with iron has some potential problems with side reactions of iron that would increase the consumption of iron and decrease the efciency of gold cementation. This makes the iron balance considerations necessary. This disadvantage should be weighed against the advantage of regeneration of thiocyanate leaching reagent from the barren solutions. Cementation with zinc powder was not as efcient as with iron powder, despite more favorable thermodynamics. Rapid kinetics (about 1 h) and high gold recovery ( 98%) were achieved with activated carbon adsorption. However, this process suffers from the high consumption of thiocyanate due to the enhancing effect of the activated carbon on the redox reaction between thiocyanate and ferric ion, which is generally used as an oxidant. Therefore, the potential use of activated carbon adsorption as a process strategy may be limited. A review of the literature indicates that thiocyanate toxicity is much less than that of cyanide. Further study of the thiocyanate system is warranted. Results suggest that thiocyanate hydrometallurgy may be an interesting process alternative for the recovery of gold.

Special thanks go to Ms. Dorrie Spurlock for proofreading the manuscript, and providing great suggestions. Any opinions, ndings and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reect the views of Newmont Mining Corporation. References
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Acknowledgements The authors would like to thank Newmont Mining Corporation for providing nancial support for this project and the permission to publish this paper. Also, the contributions of Dr. Rong Yu Wan, now deceased, are recognized for her enthusiastic support of hydrometallurgy research, in general, and this thiocyanate research, in particular.