Hydrometallurgy 69 (2003) 169 176

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Leaching of finely disseminated gold ore with cyanide and

thiourea solutions
N. Gonen *
Department of Metallurgical and Materials Engineering, Osmangazi University, Eskis
ehir, Turkey
Received 9 August 2002; received in revised form 16 December 2002; accepted 16 December 2002

Abstract
In this study, the aim was to investigate the gold recovery from finely disseminated ore by using thiourea as an alternative to
the cyanidation process. Experimental studies were carried out on the Gumus hane-Mastra (East Black Sea Region, Turkey)
epithermal ore samples, which contain finely disseminated gold. The effects of parameters such as grinding particle size, mixing
time, extractant and oxidant concentrations, and pH on agitation leaching were examined for both methods and the reagent
consumption values under satisfactory conditions were determined. The experimental results were compared with respect to
consumed reagent amounts and technological efficiencies, and it was revealed that cyanidation is more advantageous. Gold
recovery decreases and a higher reagent consumption is required for thiourea treatment. In leaching, using thiourea and
increasing oxidant content and mixing time improved the process up to a certain level. Elemental sulfur formation and
adsorption hindered diffusion. Thus, leaching extent higher than 78% could not be obtained.
D 2003 Elsevier Science B.V. All rights reserved.
Keywords: Gold; Gold recovery; Cyanidation; Thiourea

1. Introduction
Nowadays, low-grade and finely disseminated gold
ores are treated by the cyanidation technique. It has
been more than a hundred years since a chemical
metallurgical process for gold production from ores
was developed (Bayraktar, 1995; Zhang et al., 1997).
This method, based on the use of an alkaline cyanide
solution, has not changed since it was first patented.
Its long acceptance for gold processing is due to its
simplicity and its economy. There are several disadvantages. Leaching rates are low and cyanide solu-

* Tel.: +90-222-2393750/3272; fax: +90-222-2393613.

E-mail address: ngonen@ogu.edu.tr (N. Gonen).

tions are toxic and have disposal problems (Wadsworth et al., 2000; Tukel et al., 1996).
Although a number of gold extractants have been
considered as an alternative to cyanide, the most
promising results have been obtained from thiourea
leaching. However, it has not been used industrially up
to now. So extensive investigations continue about
thiourea leaching (Bruckard et al., 1993; Ubaldini et
al., 1998).
The gold recovery with thiourea leaching includes
stages similar to the cyanidation process such as
crushing, grinding, leaching, activated carbon adsorption, desorption, and electrowinning. The difference
between the two processes is based on a principle of
using thiourea or cyanide solution as an extracting
agent for gold recovery in leaching. A strong anionic

0304-386X/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0304-386X(03)00005-7

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N. Gonen / Hydrometallurgy 69 (2003) 169176

Table 1
Results of analysis of ore sample
Optical spectrographic analysis %
(semiquantitative analysis)

Chemical %
analysis

Cr
Fe
Ag
Ca
Ba
Cu
Ti
Mg
Si
Mn
Al

SiO2
Al2O3
Fe
Pb
S
Cu
Zn
Cd
As
Sb
Hg

0.02
2.0
0.001
0.015
0.2
0.02
0.04
0.04
>10
0.003
>1

91.80
2.85
1.92
0.36
0.40
0.02
0.005
< 0.001
140 mg/kg
50 mg/kg
1 mg/kg

complex formed with cyanide is seen in alkaline

solutions, while a strong cationic complex formation
takes place with thiourea in acidic solution. In cyanidation, air is enough as an oxidizing agent; on the
other hand, in thiourea leaching, the use of a strong
oxidizing agent such as Fe2(SO4)3 or H2O2 is required
(Marsden and House, 1991; Arriagada and Garcia,
1997; Urbanski et al., 2000).
Cyanidation

part of the thiourea coverts to formamidine disulphide

(FDS) with the effect of an oxidizing agent, and this
formamidine disulphide reacts with gold in excessive
thiourea medium in the second step (Urbanski et al.,
2000; Schulze, 1984):
2TU 2Fe3 ! H2NCNHSSCNHNH2
FDS
2Fe2 2H
FDS 2TU 2Au 2H ! 2AuTU
2:

3
4

As a result of the addition of two parallel reactions

(reactions (3) and (4)), the overall leaching reaction
(reaction (2)) is obtained. Depending on the emf value
of the matrix, FDS, which is formed due to the
reversible equilibrium reaction and provides gold
extraction, can also be irreversibly oxidized to
unwanted products:
FDS ! TU H2 NCN S:

When these conditions are applied, thiourea consumption increases and passivation occurs at the
reaction surface due to the formation of ultimate
sulfide. To prevent these, solution pH and potential
values (mV) must be controlled.

2. Materials and methods


4Au 8CN O2 2H2 O ! 4AuCN
2 4OH

Thiourea leach (TU: H2N CS NH2);

2
Au 2TU Fe3 ! AuTU
2 Fe

The formation mechanism of Au(TU)2+ cationic

complex is composed of two steps. In the first one,

The experimental studies were performed in the

laboratories of MTA (General Directorate of Mineral

Fig. 1. Cyanide consumption rate versus leaching time.

N. Gonen / Hydrometallurgy 69 (2003) 169176

171

Fig. 2. Cyanide consumption versus leaching time.

Research and Exploration of Turkey). The ore samples were taken from the Gumus hane-Mastra gold
deposit (situated in the East Blacksea Region of
Turkey) in an amount of about 25 30 tons for
pilot-scale gold recovery experiments carried out
by the cyanide leaching process. These samples
contain 12.5 g/ton Au and 15.2 g/ton Ag and a high
percentage of SiO2 (>90%). Semiquantitative optical
spectrographic and chemical (when required) analysis results are given in Table 1 for a representative
ore sample of high quartz content, taken from the
field formerly on which cyanidation experiments
were applied. Finely disseminated gold ( < 40 Am)
is found in the ore. Ore microscopy and polished
section examinations indicate that ore minerals are
composed of lesser amounts of fine-grained pyrite

and arsenopyrite as well as native gold in 5, 10, 20,

and 40 Am size and native silver and electrum
(Gonen et al., 1993, 1997).
The 40- to 50-kg samples were subjected to crushing, grinding, and sampling processes and about 230
240 g of sample was prepared for each experiment.
Leaching experiments were carried out in 600- to
2000-mL glass beakers by agitation at room temperature. The solid/liquid (S/L) weight ratio was held
constant at 1/1.5 in all experiments. A vacuum pump
was used for the solid/liquid separation and solid
phases were washed with water at S/L = 1/1.5. pH
and potential values were evaluated with glass calomel and Pt calomel electrodes, respectively.
The leaching recovery calculations were based on
residual gold assays. The analyses were performed

Fig. 3. Effect of leaching time on the gold recovery.

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N. Gonen / Hydrometallurgy 69 (2003) 169176

Table 2
Results of thiourea oxidation
Time (h)

0.5
2.0
4.0
6.0
8.0

Fe3 +/TU molar ratio 1/1

Fe3 +/TU molar ratio 2/1

pH

Emf (+ mV)

TUt concentration
(g/L)

STUt concentration
(%)

pH

Emf (+ mV)

TUt concentration
(g/L)

STUt concentration
(%)

1.77
1.81
1.82
1.78
1.78

285
290
293
291
286

2.48
1.74
1.25
1.03
0.94

38.0
56.5
68.7
74.2
76.5

1.49
1.57
1.61
1.61
1.60

306
327
345
344
350

2.34
1.20
0.51
0.23
0.09

41.5
70.0
87.2
94.2
97.8

TU0 (initial concentration), 4 g/L; STUt (cumulative consumption, %); (TU0  TUt)  100/TU0.

using the cupellation method. Liquid phase cyanide,

thiourea, and Fe3 + concentrations were determined by
titration with AgNO3, EDTA, and KIO3 solutions,
respectively.

3. Results and discussion

3.1. Cyanidation
In cyanidation, NaCN and calcined limestone
(Ca(OH)2) were used as extractant and pH regulator,
respectively. Air was fed by a compressor during
agitation leaching in order to supply sufficient oxygen.
3.1.1. Lime and cyanide consumption
The changes in lime and cyanide consumption with
respect to time were examined on the basis of

pH z 10.5 and 1.5 g/L NaCN as initial values for

0.212- and 0.104-mm grain sizes. The ambient pH
values did not change significantly after the initial
regulation and the lime consumption was 1.1 kg
Ca(OH)2/ton ore for both grain sizes. The cyanide
consumption rates (consumed cyanide value per unit
time, kg NaCN/ton ore h) were decreased with time
and became slower and slower after 33 h (Fig. 1). At
the end of 41st hour for 0.212- and 0.104-mm grain
sizes, 1.55 and 2.26 kg NaCN/ton ore were consumed,
and 82.4% and 97.4% gold recovery values were
obtained, respectively (Fig. 2).
3.1.2. Effect of particle size and leaching time
The samples of 0.150 and 0.104 mm were leached
for convenient times according to the initial experimental conditions of 2.5 kg NaCN/ton ore and 1.1 kg
Ca(OH)2/ton ore (pH z 10.5). Gold recovery versus

Fig. 4. Thiourea consumption rate versus oxidation time.

N. Gonen / Hydrometallurgy 69 (2003) 169176

Table 3
Fe3 +/TU molar ratio and reactant consumptions
Fe3 +/TU
(molar ratio)

Emf
(+ mV)

Consumption (kg/ton ore)

Fe2(SO4)3

TU

H2SO4

0
1.0/2.0
1.0/1.5
1.0/1.0
1.5/1.0
2.0/1.0
2.25/1.0
1.5/1.0 + 3 kg
H2O2/ton ore

74
115
127
144
160
195
224
382

0
4.61
8.31
15.44
27.22
40.25
47.36
22.50

0.56
0.75
0.98
2.82
5.76
8.97
11.51
5.76

5.84
5.65
5.93
4.77
2.85
1.04
0
2.30

TU0, 2 g/L; pH, 2; leaching time, 6 h.

time graphs are shown in Fig. 3. Higher leaching

extents are obtained for lower contact time for 0.104mm particle size. Gold dissolution reached completion
after about 40 h for 0.104 mm. By taking this fact into
account, a satisfactory agitation time was determined
as 41 h. Gold recovery increases rapidly in the first
stages, then it becomes constant and increases again
after 34 h. This can be explained by the dissolution of
gold particles that can be liberated or contacted with
cyanides at the interface, and later by the dissolution
of gold surrounded by quartz and other minerals by
way of diffusion.
3.2. Thiourea leaching
In all experiments, Fe2(SO4)3 was used as an
oxidizing agent and pH was adjusted with H2SO4.

173

The leaching of gold ore samples was carried out at

constant conditions of grinding fineness of  0.104
mm (satisfactory grain size for cyanidation) and S/L =
1/1.5. Satisfactory results were obtained for  0.038
mm.
3.2.1. Oxidation kinetics of thiourea
Before the leaching experiments on ore samples,
the oxidation kinetics of thiourea (TU) with Fe3 +
ions to give Fe2 + and FDS was investigated. The
initial concentration of thiourea solution was held
constant as 4 g/L TU for all experiments, and Fe3 +/
TU molar ratio was made 1/1 and 2/1 by changing
Fe3 + amounts.
As seen in Table 2 and Fig. 4, cumulative thiourea
consumption calculated as [(TU0  TUt)  100/TU0]
for various mixing durations reaches higher values in
shorter times for Fe3 +/TU = 2/1; and thiourea consumption rates (% thiourea consumption/h) decreases
significantly after 6 h for both ratios. The pH value
decreased to 1.5 although no acid was added to
adjust the pH. This may be due to the acidic
character of Fe2(SO4)3. In the case of Fe3 +/TU = 1/
1, a yellowish precipitate (elemental sulfur) was
obtained after 16 h.
3.2.2. Effect of oxidizing agent amount
In the first investigation on the ore samples, the
initial thiourea addition period of 90 min and the
mixing time of 6 h were fixed, and only the Fe3 +/TU
molar ratio was changed.

Fig. 5. Leaching extent versus oxidizing agent consumption.

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N. Gonen / Hydrometallurgy 69 (2003) 169176

Fig. 6. Leaching extent of gold versus pH.

In each additional period, pH and thiourea and

Fe3 + concentrations were measured and the reactants
were added to each sample in equal amounts to
consumption values. After 6 h, the total thiourea,
ferric sulfate, and H2SO4 consumption values were
determined. As can be seen in Table 3, iron(III) sulfate
and TU consumptions increased and H2SO4 consumptions, required to hold pH at 2, decreased while the
Fe3 +/TU molar ratio was increased (increase in Fe3 +
amount). No acid addition was required in the case of
Fe3 +/TU = 2.25/1.0. Although oxidant (Fe3 +) and TU
consumptions increased due to the increase in Fe3 +/
TU molar ratio, gold leaching efficiency values did
not increase significantly from a 40 kg Fe2(SO4)3/ton
ore consumption value corresponding to Fe3 +/TU = 2/
1 (Fig. 5). Thus, optimal gold leaching extent was
determined as 74.6% according to the consumption
amounts of 40.25 kg of Fe2(SO4)3, 8.97 kg of TU, and
1.0 kg H2SO4/ton ore at Fe3 +/TU = 2/1.

1.0
1.5
2.0
2.3 2.7

3.2.3. Effect of pH
For pH values of 1.0, 1.5, 2.0, and 2.5, experiments
were carried out with initial concentrations of 4 g/L TU
and 5 g/L Fe3+ (Fe3 +/TU = 1.5/1.0) for 6 h. The acidic
character of ferric sulfate was provided by holding the
pH at 2.5; therefore, acid addition was not required
throughout the experiment. The convenient pH interval was determined as 2.3 2.7 for the experiment.
The highest extraction extent (69.9%) was obtained
at natural pH interval (Fig. 6). An increase in thiourea
consumption at high pH values shows that thiourea is
more stable under the acidic conditions (Table 4).
Table 5
Time pH, emf values, and leaching extent

Table 4
pH reactant consumptions
pH

In order to increase the potential (emf) of the

medium, 3 kg H 2 O 2 /ton ore was added (Fe 3 + /
TU = 1.5/1.0); but the result is negative (47.5%). An
excessive increase in potential resulted in thiourea
decomposition and a decrease in gold leaching extent.

Emf
(+ mV)

Consumption (kg/ton ore)

TU
(Thiourea)

Fe2(SO4)3

H2SO4

163
158
155
153

4.3
5.2
5.4
5.6

24.4
25.5
25.9
26.4

24.4
17.4
3.2
0

TU0, 4 g/L; Fe3 +/TU, 1.5/1.0; mixing time, 6 h.

Time (h)

pH

Emf (+ mV)

Leaching
extent (%)

0.5
2
4
5
6
8
10

1.91
1.80
2.09
2.20
2.27
2.33
2.40

360
310
265
232
215
208
204

61.96
73.09
75.52
74.69
70.77
62.77

TU, 8.97 kg/ton ore; Fe2(SO4)3, 40.25 kg/ton ore.

N. Gonen / Hydrometallurgy 69 (2003) 169176

175

Fig. 7. Effect of leaching time on gold recovery.

However, this stability negatively affected the gold

extraction and the extent of extraction decreased at
low pH values. Also, the acid consumption increased
markedly at this condition.
3.2.4. Effect of leaching time
The effect of mixing time was investigated at 8.97
kg TU 40.25 kg Fe2(SO4)3/ton ore consumption
values and at natural pH conditions (Table 5).
The extraction extent increased with time at the
beginning of the experiment. After 5 h, it reached the
highest value (75.5%) and then decreased (Fig. 7).
This shows that there was no dissolution by diffusion.
After 5 6 h, the negative factors such as thiourea
decomposition, sulfur passivation, or adsorption of
Au(TU) 2+ complex became important and this
decreased the gold extraction extent.
3.2.5. Effect of grain size
Suitable values of Fe3 +/TU = 2/1, 8.97 kg TU/ton
ore, 40.25 kg Fe2(SO4)3/ton ore, 5 h mixing time, and
the natural pH conditions determined for a grain size

Table 6
Grain size pH, emf values, and leaching extent
Grain size
(mm)

0.104
0.038

pH and emf values at the end of

the experiment
pH

emf (mV)

2.20
2.27

232
235

Leaching
extent (%)

75.5
78.0

TU, 8.97 kg/ton ore; Fe2(SO4)3, 40.25 kg/ton ore; mixing time, 5 h.

of  0.104 mm (93.3% < 0.104 mm) were applied for

the experiments on the samples, 95.2% of which had a
grain size of  0.038 mm.
During the experiment, pH changed between 1.85
and 2.27, and emf was measured as + 235 mV at the
end of the experiment. The extraction extent reached
only 78.0% with a 2.5% increase (Table 6).
Although the ore grain size was decreased to 0.038
mm, the expected extent of extraction could not be
obtained. When the cost is considered, 0.104 mm is
more suitable for extraction.

4. Conclusion
Suitable leaching conditions for the processes of
cyanidation and thioureation are:

Leaching grain size

S/L weight ratio
Reactant consumption

pH
Leaching (mixing) time
Leaching extent

Cyanidation

Thioureation

0.104 mm
1.0/1.5
2.26 kg
NaCN/ton ore
1.1 kg
Ca(OH)2/ton ore
z 10.5
41 h
97.5%

0.104 mm
1.0/1.5
8.97 kg
TU/ton ore
40.25 kg
Fe2(SO4)3/ton ore
1.8 2.2
5h
75.5%

When suitable conditions of cyanidation and thiourea treatment for the same ore were compared,
thiourea was poorer, except that the mixing time of

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N. Gonen / Hydrometallurgy 69 (2003) 169176

thiourea treatment was about eight times shorter than

that of cyanidation. Using thiourea, higher reagent
consumption is required than for gold recovery. These
disadvantages are due to causes such as thiourea
decomposition during leaching and sulfur passivation
and readsorption of dissolved Au(TU)2 complex on
solid surfaces. These results are in agreement with
other results found in the literature (Tukel et al., 1996;
Ubaldini et al., 1998; Li and Miller, 2002).
However, this situation, which originates from the
structural properties of the ore, may show some differences for other gold ores. Therefore, studies on this
method should be continued in order to improve the
technique by taking environmental aspects into consideration.

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