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Article history:
Received 30 May 2011
Received in revised form 15 November 2011
Accepted 16 November 2011
Available online 27 November 2011
Keywords:
Solvent extraction
Gold
Amines
Thiocyanate
Alamine 336
Stripping
a b s t r a c t
Solvent extraction with amines has been evaluated as a possible method to purify and concentrate gold from
thiocyanate solutions. No signicant difference was observed in gold extraction with commercially available
tertiary amines (Alamine 336, Alamine 308, and Alamine 3041). The effects of Alamine 336 and thiocyanate
concentrations were examined for gold extraction. Gold extraction isotherms were established at different
thiocyanate concentrations. The extraction and stripping of gold showed satisfactory results at an organic/
aqueous (O/A) ratio of 1:5 for extraction (~100%) and 5:1 for stripping (~92%), in the presence of decanol.
Possible solvent extraction reactions and stripping reactions with thiourea are discussed in order to better
understand the system chemistry. Sodium hydroxide/thiocyanate, ammonium hydroxide, and acidic thiourea
were examined for the stripping of gold from the loaded organic phase. Acidic thiourea gave the best results
(with complete stripping of gold) under the conditions studied.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Much has been written over the past years on the recovery of
gold from thiourea (Li and Miller, 2006) and cyanide solutions
(Marsden and House, 2006; Senanayake, 2005). However, the investigation of thiocyanate leaching and recovery of gold is more limited
(Barbosa-Filho and Monhemius, 1989, 1994a, 1994b, 1994c; Broadhurst
and Du Preez, 1993; Li et al., 2008; Monhemius and Ball, 1995).
Recovery of gold from thiocyanate solutions by activated carbon adsorption (Kholmogorov et al., 2002; Kononova et al., 2005; Monhemius
and Ball, 1995), ion exchange (Fleming, 1986; Kholmogorov et al., 2002;
Monhemius and Ball, 1995), cementation (Ravaglia and Barbosa-Filho,
2000, 2005; Wang et al., 2007; Yen et al., 1998) and reductionprecipitation with sodium borohydride (Awadalla and Ritcey, 1991) has been
reported. According to these studies, activated carbon has strong adsorption properties for Au-SCN complexes for high gold recovery, and
rapid kinetics, but lacks selectivity, and needs stripping at high temperatures (about 150 C). Strong base ion exchange resin has similar properties to activated carbon. Medium base resin shows promising
potential high gold recovery and easy stripping conditions at room
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.2011.11.006
experiments. Hexane (Sigma-Aldrich Company) was employed as received for the dilution.
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. In all experiments, DI
water was used to prepare the aqueous solutions.
For the purpose of comparing three amine extractants, experiments were performed in separatory funnels at a volumetric
phase ratio of 1 (organic/aqueous: O/A) with a shaker (MAX Q 2000,
Barnstead/Lab-Line) for equilibration. However, this shaker was
found to be inadequate for solvent extraction of gold at a high
phase ratio and hence hand shaking was used for those experiments.
Gold thiocyanate solutions were prepared and extracted with amine.
Chemical analyses were performed using an ICP-OES.
10
9
8
7
6
pH final
26
5
Alamine 308
Alamine 336
Alamine 304-1
2
1
0
pH initial
3.1. Scoping experiments
For the initial scoping experiments, pH was not controlled and
thus the initial and nal pHs were not the same. Comparison of the
three tertiary amines was made with respect to their extraction of
gold and thiocyanate as shown in Fig. 1. Gold-thiocyanate anionic
complexes and free thiocyanate appear to be co-extracted into the organic phase. However, selectivity of the gold species over free thiocyanate appears to be possible by pH control.
Fig. 2 illustrates the relationship between the initial pH and nal
pH for these experiments. As tertiary amines have moderate alkalinity, it is expected that acid will be extracted from aqueous solutions
which appears to be the case. These results suggest that the tertiary
amines examined have similar properties under the conditions investigated. Alamine 336 was chosen for use in subsequent experiments
due to its slightly better gold extraction curve.
Fig. 2. Variation of pH before and after gold extraction by Alamine 336, Alamine 308,
and Alamine 304. Initial aqueous phase composition: SCN 0.1 M, Au 10 mg/L. Initial organic composition: Alamine 336, Alamine 308, or Alamine 3041 0.1 M, using hexane
as solvent/carrier at room temperature (~ 23 C). O/A of 1 and mixing time of 20 min.
As presented in Fig. 5, at a relatively high Alamine 336 concentration of 0.05 M, the variation of thiocyanate concentration from 0.01 to
0.2 M does not signicantly affect the extraction of gold under the
conditions employed.
However, at low Alamine 336 concentrations it can be seen that at
equal molar Alamine 336 and gold concentrations the effect becomes
100
100
95
90
Gold
90
70
Au extraction (%)
Extraction (%)
80
Thiocyanate
60
50
40
Alamine 308, Au
30
Alamine 336, Au
Alamine 304-1, Au
20
85
80
75
70
65
10
0
0
10
Final pH
Fig. 1. The effect of nal pH on the extraction of gold and thiocyante. Initial aqueous
phase composition: SCN 0.1 M, Au 10 mg/L. Initial organic composition: Alamine 336,
Alamine 308, or Alamine 3041 0.1 M, using hexane as solvent/carrier at room temperature (~ 23 C). O/A of 1 and mixing time of 20 min.
60
0
0.05
0.1
0.15
0.2
0.25
100
27
100
90
80
Au extraction (%)
90
80
70
60
70
60
50
SCN 0.02 M
40
SCN 0.05 M
30
SCN 0.1 M
20
50
10
0
40
0
10
11
10
20
30
signicant, i.e. increasing the thiocyanate concentration results in decreasing gold extraction, as illustrated in Fig. 6.
3.5. Determination of gold extraction isotherms
Extraction isotherms for gold were determined at various thiocyanate concentrations from 0.02 to 0.1 M at an Alamine 336 concentration of 4 10 4 M, pH 1.8, 23 C, O/A of 1:2, and mixing time of
20 min (Fig. 6). Gold loading in the organic phase was limited since
the Alamine 336 concentration was low (4 10 4 M). Under these
conditions, it appears that free SCN can limit gold extraction. Gold
loading in the organic phase increased with an increase in Alamine
336 concentration, which is shown in Table 1.
3.6. Stripping of gold
50
60
70
80
Fig. 6. Isotherms of gold extraction from SCN aqueous solution by Alamine 336
(4 10 4 M) at pH 1.8, 23 C, O/A of 1:2 with various SCN concentrations. Mixing
time 20 min.
Au 2 SCN
Stripping of gold from Alamine 336 was performed with sodium
hydroxide/thiocyanate, ammonium hydroxide, and acidic thiourea.
The selection of these reagents was based on the depression of gold
extraction seen previously in alkaline solution or the conversion of
100
AuSCN2
98
2;SCN
1:47 10
19
99
Au extraction (%)
40
R3 N AuSCN2
H2 O
Thiocyanate concentration in the aqueous phase was 0.2 M. Sodium hydroxide was used to adjust pH. The results presented in Fig. 7
show that gold stripping increases with an increase in pH until pH
10 and then reaches a maximum (~80%) in the pH range of 1011.
This is in complete agreement with Reaction (2).
97
96
95
94
93
Table 1
The effect of Alamine 336 concentration on gold extraction. Au 20 mg/L, SCN 0.05 M,
pH 1.8, 23 C. Mixing time 20 min, O/A of 1:2, and hexane as solvent/carrier.
92
91
90
0
0.04
0.08
0.12
0.16
0.2
0.24
Alamine 336
concentration (M)
[Au]Aqueous (mg/L)
[Au]Organic (mg/L)
1 10 2
5 10 3
2 10 3
1 10 3
1 10 4
0.3
0.4
0.6
0.7
4.4
39.8
39.6
39.0
38.9
31.3
28
100
90
Au stripping (%)
80
70
60
50
40
Au 2 SCNH2 2 Au SCNH2 2
30
20
0
7
10
11
12
AuSCN2
pH
Au 2 NH3 AuNH3 2
2;NH3 5:72 10
28
And, NH3 can replace SCN to form Au(NH3)2+, as shown in Reaction (4).
KSCN=NH3 3:90 10 4
The efciency of ammonium hydroxide for gold stripping is presented in Fig. 8. Gold stripping increases with an increase in pH up
to 10, above which complete stripping is achieved. Ammonium
hydroxide more completely strips gold than the sodium hydroxide/
thiocyanate solution. However, the consumption of ammonium
120
100
Au stripping
100
70
80
60
60
50
40
40
30
20
NH4OH consumption
(mL/L of organic phase)
Ammonium hydroxide
consumption
80
2;SCNH22 2:10 10
21
2SCNH2 2 Au SCNH2 2
2
Fig. 7. The effect of pH on gold stripping from organic phase of Au 8.16 mg/L, Alamine
336 0.1 M/hexane and aqueous phase of SCN 0.2 M/NaOH. O/A of 1:2 and 23 C. Mixing
time 20 min.
90
10
Au stripping (%)
20
10
0
0
6
10
11
12
pH
Fig. 8. Solid curve: stripping of gold from organic phase (Au 10 mg/L, Alamine 336
0.1 M, and SCN 0.04 M) with concentrated ammonium hydroxide. Dashed curve: ammonium hydroxide consumption. O/A of 1:2, 23 C, and mixing time of 20 min.
Table 2
Summary of gold stripping with acidic thiourea. pHequilibrium 1.8, O/A of 1:2, equilibrium time 20 min and 23 C.
Thiourea concentration (M)
Au stripping (%)
Thiourea extraction (%)
0.1
100
0
0.2
100
0
0.5
100
0
1.0
100
0
29
2.5
100
90
2
Au extraction (%)
80
70
1.5
60
50
Au extraction
40
1
Au concentration in
raffinate
30
20
0.5
Au concentration in raffinate
(mg/L)
10
0
0
0
10
20
30
40
50
Time (min.)
60
95
55
90
50
85
45
Au stripping
40
80
Au concentration in
stripping solution
75
35
70
30
65
25
60
20
0
Decanol (vol%)
Fig. 9. The effect of decanol on gold stripping. Extraction conditions: aqueous phase: Au
2 mg/L, SCN 0.020.05 M, Fe (III) 2 g/L, pH 1.8; organic phase: Alamine 336 0.01
0.02 M, decanol 5 vol.%, hexane as carrier, O/A of 1:5, pH 1.8, 23 C, 20 min. Stripping
conditions: aqueous phase: Tu 0.1 M, pH 1.8; organic phase: Au ~ 10 mg/L, Alamine
336 0.010.02 M, decanol 5 vol.%, hexane as carrier, O/A: 5:1, pH 1.8, 23 C.
60
100
90
50
80
70
40
60
50
30
Au stripping
40
20
Au concentration in
stripping solution
30
20
10
10
0
100
Au stripping (%)
The effects of SCN and Alamine 336 concentrations on gold extraction and thiourea concentration on gold stripping were examined.
Fig. 10. Kinetics of gold extraction at 0.02 M SCN and 0.01 M amine. Extraction conditions: aqueous phase: Au 2 mg/L, SCN 0.02 M, Fe (III) 2 g/L, pH 1.8; organic phase: Alamine 336 0.01 M, decanol 5 vol.%, hexane as carrier, O/A of 1:5, pH 1.8, 23 C.
Au stripping (%)
4.2. Kinetics of gold extraction from SCN 0.02 M, pH of 1.8, with Alamine
0.01M
0
0
10
20
30
40
50
Time (min.)
Fig. 11. Kinetics of gold stripping at 0.01 M amine and 0.1 M thiourea. Stripping conditions: aqueous phase: Tu 0.1 M, pH 1.8; organic phase: Au ~ 10 mg/L, Alamine 336
0.01 M, decanol 5 vol.%, hexane as carrier, O/A: 5:1, pH 1.8, 23 C.
30
Table 3
The effect of SCN, Alamine 336, and thiourea concentrations on gold extraction and stripping. Extraction conditions: aqueous phase: Au 2 mg/L, SCN 0.02 and 0.05 M, Fe (III) 2 g/L,
pH 1.8; organic phase: Alamine 336 0.01 or 0.02 M, decanol 5 vol.%, hexane as carrier, O/A of 1:5, pH 1.8, 23 C, 20 min. Stripping conditions: aqueous phase: Tu 0.1 or 0.2 M, pH 1.8;
organic phase: Au ~ 10 mg/L, Alamine 336 0.02 M, decanol 5 vol.%, hexane as carrier, O/A: 5:1, pH 1.8, 23 C, 20 min, thiourea concentration in the second stage stripping 0.5 M.
Experimental conditions
Amine
Amine
Amine
Amine
0.01 M
0.02 M
0.02 M
0.02 M
SCN
SCN
SCN
SCN
0.02 M
0.02 M
0.05 M
0.05 M
Tu 0.1 M
Tu 0.1 M
Tu 0.2 M
Tu 0.5 M
Extraction
Stripping
Au in rafnate
(mg/L)
Au recovery
(%)
Au in stripping
solution (mg/L)
Au in re-stripping
solution (mg/L)
Total Au
recovery (%)
0.14
0.10
0.43
0.40
93.0
95.0
78.5
80.0
48.3
47.0
45.5
41.0
0.51
0.83
0.60
0.56
97.6
95.7
92.2
83.1
5. Conclusions
Solvent extraction of gold was examined with selected tertiary
amine extractants (Alamine 336, Alamine 308, and Alamine 3041).
It was found that these amines have similar properties for extraction
of gold. Therefore, Alamine 336 was selected for the extraction of the
anionic gold complex (Au(SCN)2) from thiocyanate solution. It was
demonstrated that effective extraction of the gold thiocyanate anion
occurred below pH 5.5, whereas SCN extraction was observed below
pH 3.5.
The kinetics of gold extraction were found to be fast and the
phases were easily separated. The loading capacity for gold was
found to be high. Gold extraction of about 98% was achieved at a
molar ratio of Alamine 336/gold above 10, where extraction was independent of Alamine 336 concentration. At lower molar ratios, the
extraction was found to be dependent on Alamine 336 concentration.
When the Alamine 336 concentration was 0.05 M, the variation of
thiocyanate concentration from 0.01 to 0.2 M did not affect the extraction of gold, whereas at low Alamine 336 concentrations increasing the thiocyanate concentration resulted in a decrease in gold
extraction.
Ammonium hydroxide was found to be more efcient than sodium hydroxide for gold stripping in alkaline solution, but the reagent
consumption was high. It was shown that most effective stripping
was achieved with thiourea at high phase ratios (O/A of 1:5 in extraction and 5:1 in stripping). However, it is expected that high phase ratios would need more vigorous agitation and longer reaction times to
achieve satisfactory gold recoveries in extraction and stripping
operations.
Effective stripping of gold (about 100%) was achieved using an
acidic thiourea solution to stabilize gold as a cation and allow its release from the amine extractant.
Acknowledgments
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.
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.
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