Hydrometallurgy 69 (2003) 169 – 176

www.elsevier.com/locate/hydromet

Leaching of finely disseminated gold ore with cyanide and

thiourea solutions
N. Gönen *
Department of Metallurgical and Materials Engineering, Osmangazi University, Eskis
ßehir, 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 Gümüsß 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 tions are toxic and have disposal problems (Wad-

sworth et al., 2000; Tükel et al., 1996).
Nowadays, low-grade and finely disseminated gold Although a number of gold extractants have been
ores are treated by the cyanidation technique. It has considered as an alternative to cyanide, the most
been more than a hundred years since a chemical promising results have been obtained from thiourea
metallurgical process for gold production from ores leaching. However, it has not been used industrially up
was developed (Bayraktar, 1995; Zhang et al., 1997). to now. So extensive investigations continue about
This method, based on the use of an alkaline cyanide thiourea leaching (Bruckard et al., 1993; Ubaldini et
solution, has not changed since it was first patented. al., 1998).
Its long acceptance for gold processing is due to its The gold recovery with thiourea leaching includes
simplicity and its economy. There are several disad- stages similar to the cyanidation process such as
vantages. Leaching rates are low and cyanide solu- crushing, grinding, leaching, activated carbon adsorp-
tion, desorption, and electrowinning. The difference
between the two processes is based on a principle of
* Tel.: +90-222-2393750/3272; fax: +90-222-2393613. using thiourea or cyanide solution as an extracting
E-mail address: ngonen@ogu.edu.tr (N. Gönen). 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
170 N. Gönen / Hydrometallurgy 69 (2003) 169–176

Table 1 part of the thiourea coverts to formamidine disulphide

Results of analysis of ore sample (FDS) with the effect of an oxidizing agent, and this
Optical spectrographic analysis % Chemical % formamidine disulphide reacts with gold in excessive
(semiquantitative analysis) analysis
thiourea medium in the second step (Urbanski et al.,
Cr 0.02 SiO2 91.80 2000; Schulze, 1984):
Fe 2.0 Al2O3 2.85
Ag 0.001 Fe 1.92 2ðTUÞ þ 2Fe3þ ! H2NCNHSSCNHNH2
Ca 0.015 Pb 0.36
Ba 0.2 S 0.40
ðFDSÞ
Cu 0.02 Cu 0.02 þ 2Fe2þ þ 2Hþ ð3Þ
Ti 0.04 Zn 0.005
Mg 0.04 Cd < 0.001 FDS þ 2ðTUÞ þ 2Au þ 2Hþ ! 2AuðTUÞþ
2: ð4Þ
Si >10 As 140 mg/kg
Mn 0.003 Sb 50 mg/kg As a result of the addition of two parallel reactions
Al >1 Hg 1 mg/kg
(reactions (3) and (4)), the overall leaching reaction
(reaction (2)) is obtained. Depending on the emf value
complex formed with cyanide is seen in alkaline of the matrix, FDS, which is formed due to the
solutions, while a strong cationic complex formation reversible equilibrium reaction and provides gold
takes place with thiourea in acidic solution. In cyani- extraction, can also be irreversibly oxidized to
dation, air is enough as an oxidizing agent; on the unwanted products:
other hand, in thiourea leaching, the use of a strong
oxidizing agent such as Fe2(SO4)3 or H2O2 is required FDS ! TU þ H2 NCN þ S: ð5Þ
(Marsden and House, 1991; Arriagada and Garcia,
1997; Urbanski et al., 2000). When these conditions are applied, thiourea con-
Cyanidation sumption increases and passivation occurs at the
reaction surface due to the formation of ultimate
4Au þ 8CN þ O2 þ 2H2 O ! 4AuðCNÞ
2 þ 4OH

sulfide. To prevent these, solution pH and potential
ð1Þ values (mV) must be controlled.

Thiourea leach (TU: H2N – CS – NH2);

Au þ 2ðTUÞ þ Fe3þ ! AuðTUÞþ 2þ 2. Materials and methods
2 þ Fe ð2Þ
The formation mechanism of Au(TU)2+ cationic The experimental studies were performed in the
complex is composed of two steps. In the first one, laboratories of MTA (General Directorate of Mineral

Fig. 1. Cyanide consumption rate versus leaching time.

 N. Gönen / Hydrometallurgy 69 (2003) 169–176 171

Fig. 2. Cyanide consumption versus leaching time.

Research and Exploration of Turkey). The ore sam- and arsenopyrite as well as native gold in 5, 10, 20,
ples were taken from the Gümüsß hane-Mastra gold and 40 Am size and native silver and electrum
deposit (situated in the East Blacksea Region of (Gönen et al., 1993, 1997).
Turkey) in an amount of about 25 – 30 tons for The 40- to 50-kg samples were subjected to crush-
pilot-scale gold recovery experiments carried out ing, grinding, and sampling processes and about 230 –
by the cyanide leaching process. These samples 240 g of sample was prepared for each experiment.
contain 12.5 g/ton Au and 15.2 g/ton Ag and a high Leaching experiments were carried out in 600- to
percentage of SiO2 (>90%). Semiquantitative optical 2000-mL glass beakers by agitation at room temper-
spectrographic and chemical (when required) analy- ature. The solid/liquid (S/L) weight ratio was held
sis results are given in Table 1 for a representative constant at 1/1.5 in all experiments. A vacuum pump
ore sample of high quartz content, taken from the was used for the solid/liquid separation and solid
field formerly on which cyanidation experiments phases were washed with water at S/L = 1/1.5. pH
were applied. Finely disseminated gold ( < 40 Am) and potential values were evaluated with glass – calo-
is found in the ore. Ore microscopy and polished mel and Pt –calomel electrodes, respectively.
section examinations indicate that ore minerals are The leaching recovery calculations were based on
composed of lesser amounts of fine-grained pyrite residual gold assays. The analyses were performed

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

172 N. Gönen / Hydrometallurgy 69 (2003) 169–176

Table 2
Results of thiourea oxidation
Time (h) Fe3 +/TU molar ratio 1/1 Fe3 +/TU molar ratio 2/1
pH Emf (+ mV) TUt concentration STUt concentration pH Emf (+ mV) TUt concentration STUt concentration
(g/L) (%) (g/L) (%)
0.5 1.77 285 2.48 38.0 1.49 306 2.34 41.5
2.0 1.81 290 1.74 56.5 1.57 327 1.20 70.0
4.0 1.82 293 1.25 68.7 1.61 345 0.51 87.2
6.0 1.78 291 1.03 74.2 1.61 344 0.23 94.2
8.0 1.78 286 0.94 76.5 1.60 350 0.09 97.8
TU0 (initial concentration), 4 g/L; STUt (cumulative consumption, %); (TU0  TUt)  100/TU0.

using the cupellation method. Liquid phase cyanide, pH z 10.5 and 1.5 g/L NaCN as initial values for
thiourea, and Fe3 + concentrations were determined by 0.212- and 0.104-mm grain sizes. The ambient pH
titration with AgNO3, EDTA, and KIO3 solutions, values did not change significantly after the initial
respectively. 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
3. Results and discussion time, kg NaCN/ton ore h) were decreased with time
and became slower and slower after 33 h (Fig. 1). At
3.1. Cyanidation 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,
In cyanidation, NaCN and calcined limestone and 82.4% and 97.4% gold recovery values were
(Ca(OH)2) were used as extractant and pH regulator, obtained, respectively (Fig. 2).
respectively. Air was fed by a compressor during
agitation leaching in order to supply sufficient oxygen. 3.1.2. Effect of particle size and leaching time
The samples of 0.150 and 0.104 mm were leached
3.1.1. Lime and cyanide consumption for convenient times according to the initial exper-
The changes in lime and cyanide consumption with imental conditions of 2.5 kg NaCN/ton ore and 1.1 kg
respect to time were examined on the basis of Ca(OH)2/ton ore (pH z 10.5). Gold recovery versus

Fig. 4. Thiourea consumption rate versus oxidation time.

 N. Gönen / Hydrometallurgy 69 (2003) 169–176 173

Table 3 The leaching of gold ore samples was carried out at

Fe3 +/TU molar ratio and reactant consumptions constant conditions of grinding fineness of  0.104
Fe3 +/TU Emf Consumption (kg/ton ore) mm (satisfactory grain size for cyanidation) and S/L =
(molar ratio) (+ mV) Fe2(SO4)3 TU H2SO4 1/1.5. Satisfactory results were obtained for  0.038
0 74 0 0.56 5.84 mm.
1.0/2.0 115 4.61 0.75 5.65
1.0/1.5 127 8.31 0.98 5.93 3.2.1. Oxidation kinetics of thiourea
1.0/1.0 144 15.44 2.82 4.77
Before the leaching experiments on ore samples,
1.5/1.0 160 27.22 5.76 2.85
2.0/1.0 195 40.25 8.97 1.04 the oxidation kinetics of thiourea (TU) with Fe3 +
2.25/1.0 224 47.36 11.51 0 ions to give Fe2 + and FDS was investigated. The
1.5/1.0 + 3 kg 382 22.50 5.76 2.30 initial concentration of thiourea solution was held
H2O2/ton ore constant as 4 g/L TU for all experiments, and Fe3 +/
TU0, 2 g/L; pH, 2; leaching time, 6 h. TU molar ratio was made 1/1 and 2/1 by changing
Fe3 + amounts.
time graphs are shown in Fig. 3. Higher leaching As seen in Table 2 and Fig. 4, cumulative thiourea
extents are obtained for lower contact time for 0.104- consumption calculated as [(TU0  TUt)  100/TU0]
mm particle size. Gold dissolution reached completion for various mixing durations reaches higher values in
after about 40 h for 0.104 mm. By taking this fact into shorter times for Fe3 +/TU = 2/1; and thiourea con-
account, a satisfactory agitation time was determined sumption rates (% thiourea consumption/h) decreases
as 41 h. Gold recovery increases rapidly in the first significantly after 6 h for both ratios. The pH value
stages, then it becomes constant and increases again decreased to 1.5 although no acid was added to
after 34 h. This can be explained by the dissolution of adjust the pH. This may be due to the acidic
gold particles that can be liberated or contacted with character of Fe2(SO4)3. In the case of Fe3 +/TU = 1/
cyanides at the interface, and later by the dissolution 1, a yellowish precipitate (elemental sulfur) was
of gold surrounded by quartz and other minerals by obtained after 16 h.
way of diffusion.
3.2.2. Effect of oxidizing agent amount
3.2. Thiourea leaching In the first investigation on the ore samples, the
initial thiourea addition period of 90 min and the
In all experiments, Fe2(SO4)3 was used as an mixing time of 6 h were fixed, and only the Fe3 +/TU
oxidizing agent and pH was adjusted with H2SO4. molar ratio was changed.

Fig. 5. Leaching extent versus oxidizing agent consumption.

174 N. Gönen / Hydrometallurgy 69 (2003) 169–176

Fig. 6. Leaching extent of gold versus pH.

In each additional period, pH and thiourea and In order to increase the potential (emf) of the
Fe3 + concentrations were measured and the reactants medium, 3 kg H 2 O 2 /ton ore was added (Fe 3 + /
were added to each sample in equal amounts to TU = 1.5/1.0); but the result is negative (47.5%). An
consumption values. After 6 h, the total thiourea, excessive increase in potential resulted in thiourea
ferric sulfate, and H2SO4 consumption values were decomposition and a decrease in gold leaching extent.
determined. As can be seen in Table 3, iron(III) sulfate
and TU consumptions increased and H2SO4 consump- 3.2.3. Effect of pH
tions, required to hold pH at 2, decreased while the For pH values of 1.0, 1.5, 2.0, and 2.5, experiments
Fe3 +/TU molar ratio was increased (increase in Fe3 + were carried out with initial concentrations of 4 g/L TU
amount). No acid addition was required in the case of and 5 g/L Fe3+ (Fe3 +/TU = 1.5/1.0) for 6 h. The acidic
Fe3 +/TU = 2.25/1.0. Although oxidant (Fe3 +) and TU character of ferric sulfate was provided by holding the
consumptions increased due to the increase in Fe3 +/ pH at 2.5; therefore, acid addition was not required
TU molar ratio, gold leaching efficiency values did throughout the experiment. The convenient pH inter-
not increase significantly from a 40 kg Fe2(SO4)3/ton val was determined as 2.3 – 2.7 for the experiment.
ore consumption value corresponding to Fe3 +/TU = 2/ The highest extraction extent (69.9%) was obtained
1 (Fig. 5). Thus, optimal gold leaching extent was at natural pH interval (Fig. 6). An increase in thiourea
determined as 74.6% according to the consumption consumption at high pH values shows that thiourea is
amounts of 40.25 kg of Fe2(SO4)3, 8.97 kg of TU, and more stable under the acidic conditions (Table 4).
1.0 kg H2SO4/ton ore at Fe3 +/TU = 2/1.
Table 5
Time – pH, emf values, and leaching extent
Table 4
pH – reactant consumptions Time (h) pH Emf (+ mV) Leaching
extent (%)
pH Emf Consumption (kg/ton ore)
(+ mV) 0.5 1.91 360 –
TU Fe2(SO4)3 H2SO4 2 1.80 310 61.96
(Thiourea) 4 2.09 265 73.09
1.0 163 4.3 24.4 24.4 5 2.20 232 75.52
1.5 158 5.2 25.5 17.4 6 2.27 215 74.69
2.0 155 5.4 25.9 3.2 8 2.33 208 70.77
2.3 – 2.7 153 5.6 26.4 0 10 2.40 204 62.77
TU0, 4 g/L; Fe3 +/TU, 1.5/1.0; mixing time, 6 h. TU, 8.97 kg/ton ore; Fe2(SO4)3, 40.25 kg/ton ore.
 N. Gönen / Hydrometallurgy 69 (2003) 169–176 175

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

However, this stability negatively affected the gold of  0.104 mm (93.3% < 0.104 mm) were applied for
extraction and the extent of extraction decreased at the experiments on the samples, 95.2% of which had a
low pH values. Also, the acid consumption increased grain size of  0.038 mm.
markedly at this condition. During the experiment, pH changed between 1.85
and 2.27, and emf was measured as + 235 mV at the
3.2.4. Effect of leaching time end of the experiment. The extraction extent reached
The effect of mixing time was investigated at 8.97 only 78.0% with a 2.5% increase (Table 6).
kg TU – 40.25 kg Fe2(SO4)3/ton ore consumption Although the ore grain size was decreased to 0.038
values and at natural pH conditions (Table 5). mm, the expected extent of extraction could not be
The extraction extent increased with time at the obtained. When the cost is considered, 0.104 mm is
beginning of the experiment. After 5 h, it reached the more suitable for extraction.
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 4. Conclusion
decomposition, sulfur passivation, or adsorption of
Au(TU) 2+ complex became important and this Suitable leaching conditions for the processes of
decreased the gold extraction extent. cyanidation and thioureation are:

3.2.5. Effect of grain size

Cyanidation Thioureation
Suitable values of Fe3 +/TU = 2/1, 8.97 kg TU/ton
Leaching grain size 0.104 mm 0.104 mm
ore, 40.25 kg Fe2(SO4)3/ton ore, 5 h mixing time, and
S/L weight ratio 1.0/1.5 1.0/1.5
the natural pH conditions determined for a grain size Reactant consumption 2.26 kg 8.97 kg
NaCN/ton ore TU/ton ore
1.1 kg 40.25 kg
Table 6 Ca(OH)2/ton ore Fe2(SO4)3/ton ore
Grain size – pH, emf values, and leaching extent pH z 10.5 1.8 – 2.2
Grain size pH and emf values at the end of Leaching Leaching (mixing) time 41 h 5h
(mm) the experiment extent (%) Leaching extent 97.5% 75.5%

pH emf (mV)
0.104 2.20 232 75.5 When suitable conditions of cyanidation and thio-
0.038 2.27 235 78.0 urea treatment for the same ore were compared,
TU, 8.97 kg/ton ore; Fe2(SO4)3, 40.25 kg/ton ore; mixing time, 5 h. thiourea was poorer, except that the mixing time of
176 N. Gönen / Hydrometallurgy 69 (2003) 169–176

thiourea treatment was about eight times shorter than Gönen, N., Bilgen, N., Gürel, U., Cßelik, Ö., Demir, E., Kücßük, A.,
that of cyanidation. Using thiourea, higher reagent 1993. Experimental studies of the Gümüsßhane-Mastra gold ore,
MTA (General Directorate of Mineral Research and Explora-
consumption is required than for gold recovery. These tion), Rep. No. 208, Ankara, July.
disadvantages are due to causes such as thiourea Gönen, N., Kızılkaya, B., Yıldırım, M., 1997. Gold recovery from
decomposition during leaching and sulfur passivation Gümüsßhane-Mastra ores with thiourea, MTA (General Director-
and readsorption of dissolved Au(TU)2 complex on ate of Mineral Research and Exploration), Rep. No. 1790, An-
kara, July.
solid surfaces. These results are in agreement with
Li, J., Miller, J.D., 2002. Reaction kinetics for gold dissolution in
other results found in the literature (Tükel et al., 1996; acid thiourea solution using formamidine disulfide as oxidant.
Ubaldini et al., 1998; Li and Miller, 2002). Hydrometallurgy 63, 215 – 223.
However, this situation, which originates from the Marsden, J., House, I., 1991. The Chemistry of Gold Extraction.
structural properties of the ore, may show some differ- Prentice-Hall, New Jersey. 400 pp.
ences for other gold ores. Therefore, studies on this Schulze, R.G., 1984. New aspects in thiourea leaching of precious
metals. Journal of Metals (June).
method should be continued in order to improve the Tükel, Cß., Cßelik, H., İpekoǧlu, Ü., Tanrıverdi, M., Mordoǧan, H.,
technique by taking environmental aspects into con- 1996. Leaching of Ovacık gold ore with cyanide and thiourea.
sideration. Changing Scopes in Mineral Processing, Proceedings of the 6th
International Mineral Processing Symposium, Kusßadası/Turkey,
September 24 – 26.
Ubaldini, S., Fornari, P., Massidda, R., Abbruzzese, C., 1998. An
References innovative thiourea gold leaching process. Hydrometallurgy 48,
113 – 124.
Arriagada, R., Garcia, R., 1997. Retention of aurocyanide and thi- Urbanski, T.S., Fornari, P., Abbruzzese, C., 2000. Gold electrowin-
ourea – gold complexes on activated carbons—obtained from ning from aqueous – alcoholic thiourea solution. Hydrometal-
lignocellulosic materials. Hydrometallurgy 46, 171 – 180. lurgy 55, 137 – 152.
Bayraktar, İ., 1995. Cevherlerden Altın Üretimi, Türkiye’de Altın Wadsworth, M.E., Zhu, X., Thompson, J.S., Pereira, C.J., 2000.
Madenciliǧi Potansiyel-Ekonomi-Tenoloji-Yapısal Boyut, Yurt Gold dissolution and activation in cyanide solution: kinetics
Madenciliǧi Vakfı Yayınları (Gold Production from Ores, Gold and mechanism. Hydrometallurgy 57, 1 – 11.
Mining in Turkey: Potential-Economy-Technology, Mining in Zhang, Y., Fang, Z., Muhammed, M., 1997. On the solution chem-
the Country Foundation Publications). Mining in the Country istry of cyanidation of gold and silver bearing sulphide ores. A
Foundation, Istanbul, pp. 59 – 74. critical evaluation of thermodynamic calculations. Hydrometal-
Bruckard, W.J., Sparrow, G.J., Woodcock, J.T., 1993. Gold and lurgy 46, 251 – 269.
silver extraction from Hellyer Lead – Zinc Flotation Middlings
using pressure, oxidation and thiourea leaching. Hydrometal-
lurgy 33, 17 – 41.