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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

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

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

32

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

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

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

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

2.4. The effect of thiocyanate concentration on the extraction of ferric


iron

0
0

10

SCN/Fe molar ratio


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

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

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

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

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

Alamine 336, 0.04 M

45

Alamine 336, 0.04 M + 20 vol% decanol

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

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

97.1
97.9

34

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)).
3

Fe

Au 2 SCN

FeNCS4

AuSCN2

4NCS

Similarly, the hydration or hydrophilicity of the gold complex,


Au(SCN)2, is less than that of the iron complex, Fe(NCS)4.

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.

R3 NH:AuSCN2 2 Tu R3 N:HSCN AuTu

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

R3 N:H:FeNCS4 R3 N:H:AuSCN 2 R3 N:H:NCS:Au:SCN:FeNCS4 HNR3

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.

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 constant of 2.5 10 6 and that the complexation between ferrous and
SCN is very weak, forming a cationic complex, FeSCN +, with a

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.

The cathodic reaction for gold cementation from acidic thiocyanate


solutions can be written as:

2.9. Conditions for effective extraction and stripping

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

Extraction and stripping


window

The anodic reactions for iron and zinc are as follows:

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:

2AuSCN4 3Fe 2Au 3Fe


G o 623:0 kJ=mol

8SCN

2AuSCN4 3Zn 2Au 3Zn


G o 810:0 kJ=mol

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

Gold recovery (%)

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

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.

Gold/iron (molar ratio)

30
-4

2.85 10

100
40
10

20
40
0.002

E o 0:636 V

Au 4SCN

90

90

Au extraction (%)

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

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).

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

100

100

90

90

80

80

70

70

Gold recovery (%

Gold recovery (%)

36

60
50
40

Solution/zinc (mL/g)

Gold/zinc (molar ratio)

30
-4

100

20

3.32 10
-4
1.33 10

40

10

Solution (mL)/AC (g)

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).

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.

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).

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

4.2. Results and discussion


70
SCN consumption

Percent

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

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.

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

Auriferous sources, oxides,


pre-oxidized sulfides

50
pH 1.8

45

pH 2.6
pH 3.0

40

SCN consumption (%)

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

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

Thiourea

Solvent extraction of gold


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

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

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

Thiocyanate content (mg per 100 g food product)

Beets
Cabbage
Cauliower
Milk

10
8.55
8.8
8.615.7 mg/L

38

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.

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.
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