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i n f o
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
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.
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
32
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
studied gold complexes Au(S203)23 , Au(SCN)2, AuCl4, and
Au(SC(NH2)2)2+, only the Au(S203)23 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):
AuCl4
> AuCN2
> AuSCN2
> Au SCNH2 2
> AuS2 03 2
100
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).
90
pHinitial Fe extraction/observations
80
1.0
1.5
70
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.
Fe extraction (%)
2.0
33
60
50
40
30
20
10
0
0
10
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.
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
50
45
40
[Fe]organic (mM)
35
30
25
20
Table 2
The effect of ferric loaded in the organic phase on gold extraction.
15
10
5
0
0
10
20
30
40
50
60
Experiment Conditions
no.
Au extraction
(%)
1
2
96.7
95.8
70
[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
97.1
97.9
34
Fe
Au 2 SCN
FeNCS4
AuSCN2
4NCS
100
Au stripping (%)
80
70
60
50
R3 N:H AuSCN2
R3 N:H:FeNCS4
R3 N:H:AuSCN2
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.
SCN 0.05 M
40
SCN 0.02 M
30
SCN 0.01 M
20
10
0
0
10
20
30
40
50
Time (min.)
100
90
80
Au stripping (%)
R3 N:H FeNCS4
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).
90
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).
70
60
SCN
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)).
50
Alamine 336, 0.1 M
Alamine 336, 0.05 M
Alamine 336, 0.02 M
40
30
20
10
0
10
20
30
40
50
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.
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.
Fe
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.
Zn
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).
3e
Fe
E o 0:410 V
Zn
E o 0:763 V
2e
2e
The overall cementation reactions for iron and zinc will be respectively:
8SCN
8SCN
E o 1:046 V
10
11
E 1:399 V
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
100
70
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
60
60
50
50
90
80
80
Au stripping (%)
80
70
60
50
40
Solution/iron (mL/g)
0.005
0.01
0.02
0.05
0.1
0.2
40
0.5
30
-4
2.85 10
100
40
10
20
40
0.002
E o 0:636 V
Au 4SCN
90
90
Au extraction (%)
100
100
AuSCN4
10
-4
1.13 10
-5
2.85 10
0
0
10
12
14
16
18
20
22
24
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).
100
100
90
90
80
80
70
70
Gold recovery (%
36
60
50
40
Solution/zinc (mL/g)
30
-4
100
20
3.32 10
-4
1.33 10
40
10
60
200
100
50
40
40
30
20
10
0
0
10
12
14
16
18
20
22
24
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).
100
90
80
Percent
60
Fe (III) reduction
Au adsorption
50
40
30
20
10
0
0
20
40
60
80
100
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.
50
pH 1.8
45
pH 2.6
pH 3.0
40
37
Removal of Fe (III) if
necessary, by precipitation
35
30
25
Leaching
SCN 0.05 M, pH 2.5 - 3.0
Fe 3+ 0.1 g/L
20
15
10
Tailings
0
0
20
40
60
80
100
120
140
160
180
200
Time (min.)
Raffinate
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.
Barren organic
Thiourea
Stripping of gold
Tu 0.1-0.5 M, O/A 5, pH ~2
Gold bullion
Fig. 10. Conceptual owsheet for thiocyanate leaching and recovery of gold.
Table 3
Thiocyanate content in common foods.
Food
Beets
Cabbage
Cauliower
Milk
10
8.55
8.8
8.615.7 mg/L
38
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.
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.
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
Awadalla, F.T., Ritcey, G.T., 1990. Recovery of gold from thiourea, thiocyanate or thiosulfate solutions by reduction - Precipitation with a stabilized form of sodium borohydride. Randol, Squaw Valley 90, 296305.
Feather, A., Sole, K.C., Bryson, L.J., 1997. Gold rening by solvent extraction- the Minataur
Process. J. S. Afr. Inst. Min. Metall. 169173 (July/August issue).
Gallagher, N.P., 1987. Interaction of gold cyanide, thiocyanate, thiosulfate and thiourea
complexes with carbon matrices. M.Sc. Thesis, University of Nevada, Reno.
Gallagher, N.P., Hendrix, J.L., Milosavljevic, E.B., Nelson, J.H., Solujic, L., 1990. Afnity of
activated carbon towards some gold (I) complexes. Hydrometallurgy 25, 305316.
Gefvert, D.L., 1994. Solvent extraction of precious metals with hydroxyquinoline and
stripping with acidied thiourea. U.S. Patent 5,284,633.
Li, J., 2004. Reaction kinetics of gold dissolution in acidic thiourea solution. PhD. dissertation,
University of Utah.
Li, J., Wan, R.Y., LeVier, K.M., Miller, J.D., 2008. Thiocyanate process chemistry for gold recovery. In: Young, C.A., Taylor, P.R., Anderson, C.G., Choi, Y. (Eds.), Hydrometallurgy 2008,
Proceedings of the Sixth International Symposium. Phoenix, AZ, USA, pp. 824836.
Marsden, J.O., Iain House, C., 2006. The chemistry of gold extraction. Second edition.
SME, Littleton, CO.
McDougall, G.J., Hancock, R.D., 1980. Activated carbons and golda literature survey.
Miner. Sci. Eng. 12 (2), 8589.
McDougall, G.J., Hancock, R.D., 1981. Gold complexes and activated carbon: a literature
review. Gold Bull. 14 (4), 138153.
Menne, D.M., 2003. Key environmental toxicologies of the main cyanidation detoxication
options. http://www.members.iinet.au/~menne/scncno.htm. Accessed April 29, 2003.
Power, G.P., Ritchie, I.M., 1976. A contribution to the theory of cementation (metal
displacement) reactions. Aust. J. Chem. 29 (4), 699709.
Prabhananda, B.S., 1978. Kinetics of ferric thiocyanate formation in the presence of aliphatic
acids A temperature jump study. J. Inorg. Nucl. Chem. 40, 525532.
Wang, Z., Chen, D., Chen, L., 2007a. Gold cementation from thiocyanate solutions by
iron powder. Miner. Eng. 20, 581590.
Wang, Z., Chen, D., Chen, L., 2007b. Application of uoride to enhance aluminum
cementation of gold from acidic thiocyanate solution. Hydrometallurgy 89,
196206.
Yunus, W.M.Z.W., Haron, J., Heong, T.L., 1996. Separation of gold from nickel, cobalt and
zinc by a poly (hydroxallic acid) ion-exchange resin. Pertanika J. Sci. Technol. 4,
149155.