Minerals Engineering 20 (2007) 581590

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Gold cementation from thiocyanate solutions by iron powder

Zhike Wang
b

a,b,*

, Donghui Chen a, Liang Chen

a
School of Environmental Science and Engineering, Donghua University, Shanghai 201620, PR China
School of Chemistry and Environmental Science, Henan Normal University, Henan Key Laboratory for Environmental Pollution Control,
Xinxiang 453007, PR China

Received 13 August 2006; accepted 14 December 2006

Available online 12 February 2007

Abstract
Gold cementation with iron powder from thiocyanate solutions was conducted without de-aeration. The eects of various parameters
such as pH, thiocyanate concentration, gold concentration, iron/gold mass ratio, temperature, stirring speed and presence of iron(III) in
the solution were examined. These parameters were varied according to the ranges typically found in the literature. The eect of gas
atmosphere on cementation of gold was also examined by owing nitrogen gas through the solution during the runs and the recovery
of gold was enhanced. The presence of iron(III) results in the low eciency of gold precipitation as well as the low grade of the cements.
It was established that the rate of the reaction was rst-order with respect to the gold concentration. The activation energy was found to
be 9.3 kJ/mol and the cementation process was considered to be diusion-controlled. A general mechanism for gold cementation is
proposed.
2007 Elsevier Ltd. All rights reserved.
Keywords: Cementation; Gold ores; Hydrometallurgy

1. Introduction
There has been considerable interest in identifying and
developing alternative reagents for leaching gold from various ores over the past two decades. Alternative reagents
include thiourea, thiosulfate, chlorine, bromine, iodine
and thiocyanate. Among these non-cyanide lixiviants, thiocyanate gains much attention due to its non-toxicity and
other benets (Eisele, 1988; Undup et al., 1990; Sparrow
and Woodcock, 1995; Aylmore and Muir, 2001; Andrew
et al., 2003; Fleming et al., 2003; Kozin and Melekhin,
2004; Muir and Aylmore, 2004; Senanayake, 2004; Hilson
and Monhemius, 2005; Li and Miller, 2006). Thiocyanate
was widely investigated for gold leaching since White
(1905) reported its ability to dissolve gold in the presence
of a suitable oxidizing agent (Barbosa-Filho and Monhem*
Corresponding author. Address: School of Environmental Science and
Engineering, Donghua University, Shanghai 201620, PR China. Tel.: +86
21 67792534; fax: +86 21 67792535.
E-mail address: wangzhike@mail.dhu.edu.cn (Z. Wang).

0892-6875/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2006.12.009

ius, 1989; Broadhurst and Du Preez, 1993; Barbosa-Filho

and Monhemius, 1994a,b,c; Monhemius and Ball, 1995;
Munoz and Miller, 2000; Kholmogorov et al., 2002).
Wan et al. (2003) highlighted the continuing research interest in the use of thiocyanate for gold recovery in an acidic
environment from a bio-oxidized low grade sulphidic ore.
Kononova et al. (2005) also demonstrated the possibility
of ecient loading of gold and silver on carbon adsorbents
from thiocyanate solutions. However, the drawback associated with the use of thiocyanate as a leaching agent is that
it is known to form complexes with metal cations, which
would make the economies of the process even less
favorable.
With the development of non-cyanide lixiviants, nding
ecient methods for recovering gold from non-cyanide
solutions has been the target of various research eorts.
Several processes have been proposed for the recovery of
gold from leaching liquors: that is, cementation (Nicol
et al., 1979; Kenna et al., 1990; Miller et al., 1990; Oo
and Tran, 1991; Angelidis and Kydros, 1996; Hsu and
Tran, 1996; Zhang et al., 1996; Lee et al., 1997; Nguyen

582

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

et al., 1997; Ardiwilaga, 1999; Guerra and Dreisinger,

1999; Vilchis-Carbajal et al., 2000; Arima et al., 2002; Hiskey and Lee, 2003; Choo and Jerey, 2004; Navarro et al.,
2004), adsorption (Schmidt et al., 1988; Soto and Machuca,
1989; Lu and Bai, 1992; Juarez and Oliveira, 1993; Teirlinck and Petersen, 1996; Zhang et al., 2004), direct electrowinning (Juarez and Dutra, 2000; Steyn and Sandenbergh,
2004), solvent extraction (Zhao et al., 1997, 1998a,b;
Liu et al., 2004) and ion-exchange (Ciminelli, 2002;
Nicol and OMalley, 2002; Zhang and Dreisinger, 2002;
Arima et al., 2003; Zhang and Dreisinger, 2004). Among
these processes, cementation gained prominence due to
its extensive application in practice for gold recovery from
cyanide leach solutions until the advent of the activated
carbon absorption method for processing gold containing
cyanide solutions. In general, iron, zinc and copper are
the metals that have been studied for cementing agents.
The kinetics and electrochemistry of gold cementation by
base metals such as iron, zinc and copper have been widely
investigated (Nicol et al., 1979; Kenna et al., 1990; Miller
et al., 1990; Oo and Tran, 1991; Angelidis and Kydros,
1996; Hsu and Tran, 1996; Zhang et al., 1996; Lee et al.,
1997; Nguyen et al., 1997; Ardiwilaga, 1999; Guerra and
Dreisinger, 1999; Vilchis-Carbajal et al., 2000; Arima
et al., 2002; Hiskey and Lee, 2003; Choo and Jerey,
2004; Navarro et al., 2004). However, there is not much
research on the gold cementation from thiocyanate solutions. Among these cementation agents (iron, zinc, copper,
aluminium), iron may be the rst choice for gold cementation from thiocyanate solutions since the iron(III) is the
oxidant in thiocyanate gold leaching systems. The barren
thiocyanate solutions, originating from gold cementation
steps, could be recycled back to the leaching steps and
reused. The objective of this paper is to investigate the
eects of the experimental parameters related to gold
cementation from thiocyanate solutions by iron powder
and propose the mechanism.

The Gibbs free energy for Eq. (3), at room temperature

and for reactant concentrations of 1.0 mol/L, is 623 kJ/
mol, which indicates that gold cementation from thiocyanate complex is a spontaneous process. This is also made
clear by an inspection of Fig. 1 which is a superposition
of the relevant sections of EhpH diagrams for iron and
gold in thiocyanate solution at 25 C (Barbosa-Filho and
Monhemius, 1989, 1994a). As shown in Fig. 1, the equilibrium line of the Fe2+/Fe is well below that of the

AuSCN4 /Au couple with the two lines being separated
by a margin of 1.11 V. This indicates that there is no com
mon region of stability for AuSCN4 and Fe over the
entire pH range portrayed, and iron powder can reduce

the AuSCN4 to metallic gold. Hence, the cementation
of gold from thiocyanate solutions by iron powder is feasible according to the thermodynamic predictions.
According to Power and Ritchie (1976), cementation
reactions whose constituent half-reactions have redox
potentials which dier by greater than 0.36 V are likely to
be diusion-controlled. It is evident that the redox potentials dierence between gold reduction and iron oxidation
as shown in Eqs. (1) and (2) are greater than 0.36 V. Thus,
gold cementation from thiocyanate solutions may be under
diusion control. Diusion of the gold(III) thiocyanate
complex through the bulk solution may be eliminated in
a well-stirred solution. Diusion through a boundary layer
could be a rate-controlling step. That is, the rate of cementation of gold is expected to be proportional to the surface
area of iron powder and also proportional to the concentration gradient of gold between the solutions and iron
powder surface. Then, the well-known mass transport
equation may be used to describe the rate of cementation.
In a batch reactor, assuming that gold thiocyanate complex
concentration is negligibly low at the iron/solution interface, it can be shown that the gold cementation reaction
obeys the rst-order kinetics below:
V dC=dt kSC;

2. Theoretical background
1.0

The cathodic and anodic reactions of gold cementation

by iron powder from thiocyanate solutions may be
described as follows:
The cathodic reaction:


E 0:636 V

0.5

Eh (V)

AuSCN4 3e Au 4SCN

Au(SCN)4

0.0

The anodic reaction:

Fe2 2e Fe

E 0:44 V

From the above half-reaction equations, the overall equation of cementation of gold with iron powder would be
possibly represented as follows:
2AuSCN
4

3Fe 2Au 3Fe

8SCN

E 1:076 V
3

-0.5

Fe
-1.0

pH
Fig. 1. EhpH diagram of the AuFeSCNH2O system at 25 C.
[Au] = 104 M, [SCN] = 0.1 M, [Fe2+] = 0.1 M.

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

where C is the gold concentration in the bulk solution at

time t; k is the rst-order rate constant; S is the surface
area; V is the volume of reactant solution.
In gold cementation system, the gold concentration is
considered to be diminished continuously with time, if
the changes of the reaction surface area and the volume
of reactant solution may be considered to be negligible with
the progress of the cementation reaction, the following
integrated form is achieved (Choo et al., 2006).
C C 0 expktS=V ;

where C0 is the initial gold concentration.

Therefore, a plot of ln C versus t should yield a straight
line.
Since the leach liquors without de-aeration contain several ions, the following side reactions may also occur:
(1) Iron dissolution and oxidation in the acidic solution
without de-aeration.
Fe 2H Fe2 H2

2Fe 4H O2 2Fe

6
2

2H2 O

4Fe2 4H O2 4Fe3 2H2 O

The consumption of iron powder in the acidic solution as shown in Eqs. (6) and (7) results in a lower
eciency and negatively aects the gold recovery.
However, the oxidation of Fe2+ as shown in Eq. (8)
results in a decrease of Fe2+ concentration and causes
the gold precipitation reaction as shown in Eq. (3) to
shift to the right and positively aects the gold recovery. Thus, the inuence of these reactions seems to be
signicant in stirred acidic aqueous solution.
(2) Iron(III)-thiocyanate complexes formation in thiocyanate solutions.
Iron(III) ion, oxidation product of Fe2+ shown in Eq.
(8) forms a number of thiocyanato complexes in thio
cyanate solutions such as Fe(SCN)2+, FeSCN2 ,
Fe(SCN)3 and so on. The blood-red color, which
is characteristic of the iron(III)-thiocyanate complexes (Barbosa-Filho and Monhemius, 1994b), was
observed during the gold cementation from synthetic
thiocyanate solutions without the addition of
iron(III) ion. The formation of iron(III)-thiocyanate
complexes also results in a decrease of Fe2+ concentration and causes the gold precipitation reaction to
shift to the right.
(3) Iron hydroxide formation due to hydrolysis.
Iron(III) hydrolyses readily, beginning at a pH as low
as 1, precipitation of iron(III) hydroxide would still
occur in the presence of thiocyanate according to
the thermodynamic predictions (Broadhurst and Du
Preez, 1993).
(4) Iron(III) reduction by iron powder
2Fe3 Fe 3Fe2
This reaction shows that the presence of Fe
solution would consume the iron powder.

9
3+

in the

583

3. Experimental
Cementation experiments were carried out in a 750 ml
glass reaction vessel placed in a thermostatic water bath
and agitated with a stirring motor. An amount of 500 ml
of the pregnant solution was placed in the vessel maintaining the stirring speed constant and a predetermined
amount of iron powder was added to the solution. An
amount of 3 ml of each solution was taken for the determination of gold content at convenient time intervals. The
determination of gold in the solution was carried out by
atomic absorption spectrometry. The cements after ltering
and vacuum drying were stored in a desiccator for the morphological characterization. Laser diraction particle size
analyzer (LS 13 320) and scanning electron microscopy
(JSM-5600LV) were used to analyze size distribution and
morphological characterization, respectively.
On the other hand, the eect of gas atmosphere on
cementation of gold was also examined. High purity nitrogen was passed through 500 ml of solution, via a dispersion
tube, before and during the experiment to minimize the
interference of oxygen. Prior to the beginning of an experiment, the nitrogen gas was bubbled for at least 30 min.
The reproducibility of experiments was determined by
performing six cementation runs under the same conditions. Experiments of the rate control regime of the gold
cementation reaction were conducted as the above reproducibility experiments except the variation of temperature
at levels of 5 C, 15 C, 25 C, 35 C, 45 C and 50 C.
The solutions used in the cementation experiments were
prepared using high purity reagents in the concentration
ranges typical of leach studies found in the literature. Gold
stock solution was prepared by dissolving HAuCl4 in distilled water. The synthetic leach solutions were prepared
by dilution of the above and addition of the optimum
amount of the thiocyanate salt. Finally, the pH of the solution was adjusted with 1 M sulfuric acid. The iron powder
(from Sinopharm Chemical Reagent Co., Ltd.), purity > 98.0%, and the chemical analysis of the powder indicates negligible presence of copper in the material.
4. Results and discussion
4.1. Reproducibility of cementation experiments
The experimental conditions for testing reproducibility
are: 10 mg/L gold, 0.2 M thiocyanate, pH 2, 25 C, iron/
gold mass ratio 50 and 450 rpm. The results obtained are
presented in Fig. 2, which depicts the relationship between
gold concentration and time. The experimental error in all
data points for six parallel runs did not exceed 5%.
4.2. Eect of pH
The eect of initial pH of solution on gold cementation
was studied in the range of 13 as shown in Fig. 3. The gold
cementation rate increases as the pH decreases in 5 min of

584

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

gold is directly proportional to the thiocyanate concentration (Barbosa-Filho and Monhemius, 1994c; Munoz and
Miller, 2000; Wan et al., 2003). The eect of thiocyanate
concentration on the gold cementation was investigated
at dierent thiocyanate concentrations ranging from 0.01
to 0.2 M while other variables were kept constant. The
results were plotted in Fig. 4. It can be seen from the gure
that the eect of thiocyanate concentration on gold recovery is very slight. The increase of gold recovery at a high
thiocyanate concentration may be attributed to the formation of iron(III)thiocyanate complexes, which results in a
decrease in the concentration of iron(II) ion by the shift of
reaction (8) in the right direction and further causes the
gold precipitation reaction to shift to the right.

100
90

Gold Recovery (%)

80
70
60

Run 1
Run 2
Run 3
Run 4
Run 5
Run 6

50
40
30
20
10
0

10

Time (min)

4.4. Eect of initial gold concentration

Fig. 2. Testing the reproducibility of experiments. Aqueous phase

(500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio: 50,
stirring speed: 450 rpm, temperature: 25 C.

100
90

Gold Recovery (%)

80
70
60
50
40

pH=1
pH= 2
pH= 3

30
20

Theoretical analysis shows that the cementation of gold

onto iron powder is controlled by a diusion step, and the
rate of cementation of gold is expected to be proportional
to the concentration gradient of gold between the solutions
and iron powder surface at a constant iron/gold mass ratio.
Plots of gold recovery against time showing the eect of initial gold concentration in the range of 520 mg/L are presented in Fig. 5. The results show that the gold cementation
rate and recovery increase with the increase of gold concentration. The marked concentration eect may be attributed
to the increase in gold concentration gradient between the
solutions and iron powder surface. Thus, high initial gold
concentration favors the gold cementation.
4.5. Eect of iron/gold mass ratio
As can be seen from the Eq. (4), the rate of gold cementation is expected to be proportional to the surface area of

10
0
0

10

Time (min)
100

Fig. 3. Eect of pH on gold cementation. Aqueous phase (500 ml): 10 mg/

L gold, 0.2 M SCN, iron/gold mass ratio: 50, stirring speed: 450 rpm,
temperature: 25 C.

80

Gold Recovery (%)

reaction. However, the nal gold recovery at pH 2 is higher

than that at pH 1. It may be attributed to the dual eects of
pH. Decreasing the pH of solution would favor the
decrease of Fe2+ concentration, as shown in Eq. (8) and
further shift the gold precipitation reaction shown in Eq.
(3) to the right. However, decreasing the pH of solution
would decrease the eective surface area of the iron powder
and increase the concentration of Fe2+ due to the side reactions as shown in Eqs. (6) and (7), and then negatively
aect the gold precipitation.

90

70
60
50
-

0.01 M SCN
0.05 M SCN
0.1 M SCN
0.2 M SCN

40
30
20
10
0
0

4.3. Eect of initial thiocyanate concentration

In thiocyanate leaching systems, the thiocyanate is the
gold complexing ligand. Generally, the leaching rate of

10

Time (min)
Fig. 4. Eect of initial thiocyanate concentration on gold cementation.
Aqueous phase (500 ml): 10 mg/L gold, pH 2, iron/gold mass ratio: 50,
stirring speed: 450 rpm, temperature: 25 C.

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

4.6. Eect of stirring speed

100
90

The eect of stirring speed on the gold cementation was

presented in Fig. 7. As can be seen from the gure, the rate
of gold cementation increases with an increase in stirring
speed. The signicant eect of stirring speed may be attributed to the fact that the gold cementation from thiocyanate
solutions by iron powder is a diusion-controlled process.
Increasing the rate of stirring will decrease the diusion
layer thickness, so increasing the cementation rate. Therefore, agitation aects positively the kinetics of gold cementation process.

Gold Recovery (%)

80
70
60
50
40

5 mg/L
10 mg/L
15 mg/L
20 mg/L

30
20
10
0

4.7. Eect of temperature

0

10

Time (min)
Fig. 5. Eect of initial gold concentration on gold cementation. Aqueous
phase (500 ml): 0.2 M SCN at pH 2, iron/gold mass ratio: 50, stirring
speed: 450 rpm, temperature: 25 C.

The eect of temperature on gold cementation was

investigated in the range of 550 C. As shown in Fig. 8,
the experimental results show that the gold recovery
increases slightly as the temperature increases. The reasons
of increasing gold recovery by increasing the temperature
may be attributed to a decrease in solution viscosity which
allows the gold thiocyanate complex to move more freely
through the liquid phase (Guerra and Dreisinger, 1999).
4.8. Eect of initial iron concentration
The gold leaching systems consist of ligands and oxidants. In the thiocyanate gold leaching systems, the thiocyanate is ligand. Generally, the Fe3+ is selected as oxidant.
The presence of Fe3+ in leach solutions aects negatively
the gold recovery as shown in Fig. 9. The negative eect
of iron(III) on gold cementation may be attributed to several reasons as follows: (i) the decrease of eective reaction
surface area due to the oxidation of iron powder by
iron(III) ion as shown in Eq. (9), (ii) the re-dissolution of

100

100

90

90

80

80

Gold Recovery (%)

Gold Recovery (%)

iron powder at the constant concentration gradient of gold

between the solutions and iron powder surface. Hence, the
amount of iron powder added has a positive eect on the
precipitation of gold. The eect of iron/gold mass ratio
on the gold cementation was investigated at dierent
iron/gold mass ratios ranging from 25 to 100, while other
variables were kept constant. The rate of gold cementation
increases as the iron/gold mass ratio increases, as illustrated in Fig. 6. It may be attributed to an increase in the
eective reaction surface area of iron powder on which
gold cementation takes place.

70
60
50
40
30

10

70
60
50
40
30

25
50
75
100

20

585

10
0

150 rpm
300 rpm
450 rpm

20

10

Time (min)
Fig. 6. Eect of iron/gold mass ratio on gold cementation. Aqueous phase
(500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, stirring speed: 450 rpm,
temperature: 25 C.

10

15

20

25

30

Time (min)
Fig. 7. Eect of stirring speed on gold cementation. Aqueous phase
(500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio: 50,
temperature: 25 C.

586

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

100
90

Gold Recovery (%)

80
70
60
50

5 C
o
15 C
o
25 C
o
35 C
o
45 C
o
50 C

40
30
20
10
0
0

10

Time (min)
Fig. 8. Eect of temperature on gold cementation. Aqueous phase
(500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio: 50,
stirring speed: 450 rpm.

Fig. 10. Morphology of the cements after gold cementation. Aqueous

phase (500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio:
50, stirring speed: 450 rpm, temperature: 25 C.

100
90

Gold Recovery (%)

80
70
60
50
40
30
3+

0 M Fe
3+
0.01 M Fe

20
10
0

10 12 14 16 18 20 22 24 26 28 30 32

Time (min)
Fig. 9. Eect of initial iron concentration on gold recovery. Aqueous
phase (500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio:
50, stirring speed: 450 rpm, temperature: 25 C.

deposited gold in iron(III)thiocyanatesulfuric acid systems, (iii) the formation of solid iron(III) hydroxide which
adheres to the surface of iron powder and results in the
decrease of eective reaction surface area, (iv) the layer
of iron(III) hydroxide may hinder transport of the Fe2+
ions into the bulk of the solution to such an extent that
the rate of their removal becomes smaller than the rate of
their formation, thus decreasing the eciency of gold
precipitation.
The morphology of the cements after gold cementation
by iron powder in thiocyanate solution was shown in Figs.
10 and 11. Comparing these gures, it can be concluded
that the deposited layer in the presence of iron(III) is denser than the layer in the absence of iron(III). By the comparison of the morphology of the cements obtained under

Fig. 11. Morphology of the cements after gold cementation in the

presence of Fe3+. Aqueous phase (500 ml): 10 mg/L gold, 0.01 M Fe3+,
0.2 M SCN at pH 2, iron/gold mass ratio: 100, stirring speed: 450 rpm,
temperature: 25 C.

dierent cementation conditions, it is concluded that the

signicant passivation may be mainly attributed to the formation of iron(III) hydroxide, which adheres to the surface
of iron powder and decreases the eective area of gold
cementation reaction. The negative eect of iron(III) ions
is a potential drawback in subsequent operations, because
the barren thiocyanate solutions with a high gold grade
cannot be recycled to leaching. In order to decrease the
inhibitory eect of Fe3+, it is better to minimize the initial
Fe3+ ion concentration at both the leaching and cementation stages.
4.9. Eect of gas atmosphere
According to the theoretical analysis provided previously, in the cementation of gold from acid thiocyanate

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

587

solutions, an important parameter to be considered is the

dissolved oxygen. In the present work, the cementation of
gold was also carried out under nitrogen atmosphere
to avoid this oxygen eect and the results were listed in
Table 1. The reasons for increasing gold recovery by
employing the nitrogen atmosphere in the runs may be
attributed to the inhibition of iron oxidation reaction as
shown in Eq. (7). Therefore, the cementation of gold from
the acid thiocyanate solutions carried out under nitrogen
atmosphere will be more feasible than in the presence of
oxygen.
5. Kinetic model
According to the proposed kinetic model, the gold
cementation rate is proportional to the iron powder surface
area, and the surface area is mainly determined by the size
distribution of the powder, thus the size distribution is an
important parameter which aects the gold cementation
kinetics. The eect of particle size on gold cementation
was examined in some gold cementation systems previously. In general, the gold cementation yield as well as
the apparent rate constant, as expected, increases considerably as the size of the particles decreases, and the gold
cementation obeys the rst-order reaction kinetics (Miller
et al., 1990; Angelidis and Kydros, 1996; Hiskey and Lee,
2003). The phenomena that the gold cementation reaction
deviates from the rst order reaction kinetics were
observed and evaluated in other gold cementation systems
(Nguyen et al., 1997; Guerra and Dreisinger, 1999; Sedzimir, 2000; Hiskey and Lee, 2003; Navarro et al., 2004).
The size distribution and morphological characterization
of the iron powder before cementation were shown in Figs.
12 and 13, respectively. The mean diameter of the powder
is 28.34 lm, and a more size distribution for the iron powder is shown in Fig. 12. In order to conrm that the gold
cementation from acid thiocyanate solution obeys the
rst-order reaction kinetics and is a diusion-controlled
process, the gold cementation experiments were investigated at dierent temperatures ranging from 5 C to
50 C, while other variables were kept constant. The results
were presented in Fig. 14. As can be seen from the gure,
the plots of ln C versus time are straight. This is consistent
with the result of theoretical analysis. It may be concluded
that the gold cementation from the acid thiocyanate soluTable 1
Cementation conditions and corresponding results under nitrogen gas
atmosphere
Addition of iron(III)

N2 gas

Times (min)

Gold recovery (%)

None
None
0.01 M Fe3+
0.01 M Fe3+

None
De-aeration
None
De-aeration

10
10
30
30

97
98.5
55.3
80.9

Initial conditions. Aqueous phase (500 ml): 10 mg/L gold, 0.2 M SCN at
pH 2, iron/gold mass ratio: 50, stirring speed: 450 rpm, temperature:
25 C.

Fig. 12. Size distribution for the iron powder.

Fig. 13. SEM micrograph of iron powder before cementation.

tions onto iron powder obeys rst-order kinetics during

the course of the reaction. Similar results were concluded
previously in dierent gold cementation systems (Miller
et al., 1990; Angelidis and Kydros, 1996; Zhang et al.,
1996; Lee et al., 1997). By taking the logarithms of absolute
values of the initial slopes in Fig. 14 and plotting them
against the reciprocal of the absolute temperature at a constant stirring speed, Fig. 15 was obtained. The experimental points lie on a straight line over the temperature range
550 C, with a slope corresponding to an activation
energy of 9.3 kJ/mol. Thus, the cementation process is
deemed to be diusion-controlled. The result, at least over
the temperature range investigated, was consistent with the

588

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

Ln C

0
o

5 C
o
15 C
o
25 C
o
35 C
o
45 C
o
50 C

-1

-2
0

10

Time (min)
Fig. 14. Eect of temperature on gold cementation. Aqueous phase
(500 ml): 10 mg/L gold, 0.2 M SCN at pH 2, iron/gold mass ratio: 50,
stirring speed: 450 rpm.

-0.9

3m

Fe3 mSCN FeSCNm

-1.0

Fe

-1.1

Ln k

can be considered as a separate reaction involving both a

forward and reverse direction. Therefore, the amount
reacted and the rate of consumption of iron powder for this
ideal case must be related to the amount reacted and the
rate of production of metallic gold by the stoichiometry
of the reaction. It can be seen from the Eq. (2) that decreasing the concentration of Fe2+ in the solution shifts the corresponding reaction to the left, thus increasing the rate of
gold precipitation.
According to the predictions of Power and Ritchie
(1976) and previously presented results, the gold cementation is a diusion-controlled process. That is, the cementation reaction may be controlled by the rate of diusion of

AuSCN4 ions to the iron powder surface. The representation of mechanism of gold cementation on iron is similar
to gold precipitation from cyanide solution. The overall
reaction is presented as Eq. (3). AuSCN
4 ion is reduced
to elemental gold on iron powder and metallic iron is dissolved to Fe2+ ion. Fe2+, the oxidation product of gold
cementation reaction, is further oxidized to Fe3+ as shown
in Eq. (8). Fe3+ may undergo reduction, complexation and
hydrolysis reactions as shown in Eqs. (9)(11).

-1.2

-1.3

-1.4

-1.5

-1.6

3.1

3.2

3.3

3.4

3.5

3.6

1/T x 10-3, k
Fig. 15. Arrhenius plot for the cementation of gold with iron powder.

predictions of Power and Ritchie (1976) and was also

observed in other gold cementation systems (Miller et al.,
1990; Angelidis and Kydros, 1996; Zhang et al., 1996;
Guerra and Dreisinger, 1999; Lee et al., 1997; Navarro
et al., 2004).

3H2 O FeOH3 3H

10

11

The appearance and following gradual disappearance of

the blood-red color which is characteristic of the iron(III)
thiocyanate complexes during the gold cementation process
from synthetic thiocyanate solutions without the addition
of iron(III) ion may demonstrate that the iron(III)thiocyanate complexes are intermediate products of the reaction.
In addition, the solution pH increases gradually as the
cementation reaction proceeds. For the test conducted at
initial pH 2.0, the pH value increased to 2.37 due to consumption of hydrogen ions according to Eqs. (6)(8). As
a result, formation of iron hydroxide would occur more
easily in this pH range. The Fe(OH)3 may be one of the
nal products of the cementation reaction. Hence, the
overall reaction shown in Eq. (3) may be rewritten as Eq.
(12).

2AuSCN
4 4H 2O2 7Fe 2H2 O

2Au 5Fe2 8SCN 2FeOH3 H2

12

6. Cementation mechanism

7. Conclusions

According to theoretical analysis and previously presented results, a possible gold cementation mechanism
from thiocyanate solutions without de-aeration may be
established.
In the cementation solution, iron powder and gold(III)
thiocyanate complex are in contact with each other and
with the electrolyte, forming a short-circuited cell. The gold
cementation reaction from thiocyanate solutions consists
of two electrochemical half-cell reactions as shown in
Eqs. (1) and (2). The half-cell reaction, Eqs. (1) and (2)

The results obtained from this investigation show that

the gold cementation from thiocyanate solutions by iron
powder is feasible in technique. It is concluded that the
cementation of gold onto iron powder is dependent on various factors such as gold concentration, stirring speed and
solution pH. It is found that the gold cementation reaction
is greatly aected 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 aect the gold

Z. Wang et al. / Minerals Engineering 20 (2007) 581590

cementation reaction. The gold cementation reaction obeys

the rst-order kinetics and the activation energy is 9.3 kJ/
mol. The cementation process is determined to be under
diusion control. The de-aeration of solution would
enhance the gold recovery. However, the presence of
iron(III) in leach solution results in the low eciency of
gold precipitation as well as the low grade of the cements.
The role of iron(III) ions in the cementation process needs
further consideration.
Acknowledgement
The nancial support provided by Shanghai science and
technology development fund (No. 042312006) is gratefully
acknowledged.
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