International Journal of Minerals, Metallurgy and Materials

V olume 20 , Number 4 , April 2013 , P age 323

DOI: 10.1007/s12613-013-0730-7

Study on gold concentrate leaching by iodine-iodide

Hai-xia Wang1) , Chun-bao Sun1) , Shao-ying Li1) , Ping-feng Fu1) , Yu-guo Song2) , Liang Li2) , and
Wen-qing Xie3)
1) Key Laboratory of the Ministry of Education of China for High-Efficient Mining and Safety of Metal Mines, University of Science
and Technology Beijing, Beijing 100083, China
2) China Gold Association, Beijing 100011, China
3) Shuangqishan Gold Mine, Fujian 362509, China
(Received: Received: 17 June 2012; revised: 27 September 2012; accepted: 28 September 2012)

Abstract: Gold extraction by iodine-iodide solution is an effective and environment-friendly method. In this study, the
method using iodine-iodide for gold leaching is proved feasible through thermodynamic calculation. At the same time,
experiments on flotation gold concentrates were carried out and encouraging results were obtained. Through optimizing
the technological conditions, the attained high gold leaching rate is more than 85%. The optimum process conditions at
25◦ C are shown as follows: the initial iodine concentration is 1.0%, the iodine-to-iodide mole ratio is 1:8, the solution
pH value is 7, the liquid-to-solid mass ratio is 4:1, the leaching time is 4 h, the stirring intensity is 200 r/mim, and the
hydrogen peroxide consumption is 1%.
Keywords: gold extraction; leaching; iodine; iodides

1. Introduction cyanicides such as copper, antimony, arsenic, iron, zinc,

Gold as a kind of unique precious metal that has and sulfur [8]; and lower leaching rate for refractory gold
played an important role since ancient times. The demand ore. Especially, the cyanide is an extremely toxic substance
for gold is increasing with the world’s economy develop- and it is seriously harmful to human beings and the sur-
ment. Meanwhile, gold extraction technologies have been rounding environment. According to the developments of
improved dramatically. There are many kinds of methods science and the increasing concern of environment, these
to leach gold from ores, such as cyanidation, amalgama- disadvantages are unbearable. New gold extraction tech-
tion, thiosulfate, thiourea, lime sulfur, rhodanate, poly- nology is needed urgently. Compared with the cyanide,
sulfide, bromine, and iodine-iodide methods [1-4]. The iodine is a nontoxic reagent, and it is popularly applied in
most widely used method is cyanidation. Cyanidation has medicine [7]. Gold leaching by iodine-iodide solution from
been invented for more than 100 years. The advantages the ore has been studied by some researchers worldwide
of cyanidation include perfect process flow, higher recover- [9-11], but the treatment of gold concentrate has not been
ies, strong adaptability of ore, and technological simplicity researched. In this article, through the mechanism analysis
[5]. The cyanidation method becomes more practiced af- and single-factor experiments, gold leaching using iodine-
ter the further study of gold extraction from pregnant so- iodide solution was discussed on flotation gold concentrate
lution, such as zinc dust precipitation, carbon adsorption, from Shuangqishan, Fujian Province, China.
ion exchange, and solvent extraction [6]. Approximately
70% of new plants are still adopting this process now [7].
2. Theoretical basis of gold leaching by
However, there are several disadvantages of the cyanida- iodine-iodide solution
tion method: longer leaching time (more than 24 h; the The stability study of gold anion complexes AuX2 (X
heap leaching is even longer); higher production cost be- is an anion) by the Moscow National Precious Metal Ex-
cause more cyanide will be consumed when ore contains ploration Institute showed that CN− >> I− > Br− > Cl−

Corresponding author: Chun-bao Sun E-mail: suncb@[Link]


c University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg 2013
324 Int. J. Miner. Metall. Mater., V ol. 20 , No. 4 , Apr. 2013

> NCS− > NCO− [12]. It meant that the strength of the ple, according to Eqs. (8) and (9), under the condition
gold-iodine complex is weaker than the gold-cyanide com- that α(AuI− −
2 ) = α(AuI4 ) = 10
−4
mol·L−1 , α(I− ) = 0.1
−1 − −1
plex but stronger than bromine, chlorine, thiocyanates, mol·L , and α(I3 )=0.1 mol·L , the chemical potentials
and cyanates [13]. The gold dissolution chemical reactions of reactions (6) and (7) are 0.169 and 0.013 V, respec-
in iodine-iodide solution are shown as follows. tively. The reactions could proceed spontaneously under
I2 (s) = I2 (l) (1) this condition. Therefore, leaching gold from the ore using
I2 (l) + I− = I−3 (2) iodine-iodide solution is feasible in theory.
Anode reaction: The electric potential-pH values (Eh -pH) diagram of
Au + 2I− = AuI− 2 + e
−
(3) the Au-I2 -I− -H2 O system also indicated that gold dissolu-
−
Au + 4I = AuI4 + 3e−
−
(4) tion in iodine-iodide solution was feasible in theory. Li et
Cathode reaction: al. [16-17] pointed out that (1) iodine-iodide solution was
I−
3 + 2e
−
= 3I− (5) suitable for gold dissolution; (2) gold-iodine complex ions
Total reaction: AuI− −
2 and AuI4 were stable in water or hydrogen peroxide
2Au + I− + I− 3 = 2AuI2
−
(6) solution; (3) because of high oxidation potential, hydrogen
− −
2Au + 3I3 = 2AuI4 + I− (7) peroxide as a auxiliary oxidant was good for gold dissolu-
Standard Gibbs free energies of the above-mentioned tion; and (4) the pH value of iodine-iodide solution should
species at 25◦ C and 0.1 MPa are shown in Table 1. be controlled as acid or neutral.

Table 1. Standard Gibbs free energy of species at 3. Experimental

25◦ C and 0.1 MPa [14] 3.1. Material source and properties
Formula State Δ f GΘ
m / (kJ·mol
−1 )
The flotation gold concentrate used in this study came
Au Solid 0
from Shuangqishan, Fujian Province, China. Pyrite was
I− Aqueous −51.67
I− Aqueous −51.51 the major metallic mineral; calcite and quartz were the
3
AuI−2 Aqueous −47.99 major gangue minerals. Gold minerals were distributed
AuI−4 Aqueous −41.00 nonuniformly and native gold was the main form. The
dissemination size of gold was very fine (several microns).
In reaction (3), Δf GΘ m = [−47.99 − 2 × (−51.67)] Most of the gold was filled in the cavities of pyrite in
kJ·mol−1 = 55.35 kJ·mol−1 . xenomorphic granular textures and filled in the fracture
Reaction (3) is a half-reaction that loses electrons; as short vein or granular textures. Little was distributed
thus, ΔfGΘ Θ
m = nF ϕ− [15], in quartz as xenomorphic granular textures or vein.
Θ
Δ G
f m 55.35 × 103 The chemical analysis of the gold concentrate showed
ϕΘ− = = V = 0.574 V.
nF 1 × 96485 that it consisted of 60.62 g/t Au, 102 g/t Ag, 0.13wt% As,
Similarly, for reaction (4), ϕΘ
− = 0.572 V. 21.54wt% Fe, and 22.48wt% S.
In reaction (5), Δf GΘm = −103.5 kJ·mol
−1
. For the mineral leaching process, when the size of
Reaction (5) is a half-reaction that receives electronic; ground products becomes finer, more valuable minerals are
thus, Δf GΘ Θ Θ
m = nF ϕ− [15], ϕ+ = 0.536 V. exposed, which benefits to the contact of gold and leach-
Because that E = ϕ+ − ϕΘ
Θ Θ
−, E
Θ
= −0.038 V in ing solution. Therefore, the finer size of ground products
reaction (6). could reach a higher leaching rate, but fine grinding of the
Similarly, E Θ = −0.036 V in reaction (7). ore would increase costs. Therefore, based on the leaching
The Nernst equations of reactions (6) and (7) are theory and plant actual situation, the size of ground prod-
shown as follows: ucts in this study was controlled at 99% passing 200 mesh
0.05917   −    2   and 80% passing 325 mesh.
E = −0.038+ lg α I3 · α I− α AuI− 2
2 3.2. Reagents and methods
(8)
0.05917  3  −  2    −  Reagents used in this study included iodine, potassium
E = −0.036+ lg α I3 α AuI− 4 ·α I iodide, hydrochloric acid, sodium hydroxide, and hydrogen
6
(9) peroxide (30%). All the reagents were analytically pure,
The standard electric potentials of reactions (6) and and water used in the experiment was tap water in Beijing.
(7) are -0.038 and -0.036 V, respectively. Due to Δf Gm = The leaching experiment was carried out in a 500 mL
−nF E, Δf Gm > 0, the reactions could not proceed sponta- beaker, and the sample per test was 50 g. The solution was
neously in the standard condition. However, their Nernst mixed with an MY3000-6 intelligent stirrer, timed with a
Eqs. (8) and (9) show that the concentrations of I− , I− 3 , chronograph. The pH value of the solution was adjusted
AuI−2 , or AuI −
4 are changed, Δ f Gm could become negative by hydrochloric acid or sodium hydroxide and checked by
and the reactions could proceed spontaneously. For exam- Mettler Toledo Delta 320.
H.X. W ang et al., Study on gold concentrate leaching by iodine-iodide 325

The pregnant solution was filtered after leaching and ists in the leaching solution. The oxidant and complexing
kept for extracting of gold or rebirth of iodine. The grade agent existing together is an essential condition to gold
of gold in tailings was analyzed for calculating the leaching dissolution. It is better for gold dissolution when the oxid-
rate of gold. ability of the oxidant is strong and the stability constant
of complexes between gold and ligands is big. During gold
4. Results and discussion extraction in iodine-iodide solution, I2 is the oxidant and
A series of experiments were performed under vari- I− is the ligand [18-19]. The effect of iodine-to-iodide mole
ous process conditions. The process condition variables ratio on the gold leaching rate is described in Fig. 2. The
included initial iodine concentration, iodine-to-iodide mole iodine-to-iodide mole ratio is 1:4, 1:6, 1:8, 1:10, and 1:12,
ratio, solution pH values, liquid-to-solid mass ratio (L/S), respectively. Other experiment parameters were as fol-
stirring intensity, leaching time and temperature, and lows: the initial iodine concentration was 1%, the solution
dosage of hydrogen peroxide. Their effects on gold leaching pH value was 7, the L/S ratio was 4:1, the leaching time
rate are discussed as follows. was 4 h, the stirring intensity was 600 r/min, and the tem-
4.1. Effect of initial iodine concentration on perature was 25◦ C. As shown in Fig. 2, the gold leaching
gold leaching rate rate increases as the iodine-to-iodide mole ratio decreases.
Hence, the iodine-to-iodide mole ratio should be as low as
The gold extraction rate is different when the initial
possible in practice. However, the gold leaching rate has no
iodine concentration changes. In iodine-iodide solution,
obvious change when the iodine-to-iodide mole ratio was
the iodine that exists in the form of I−
3 is more than 99%
lower than 1:8. Considering the costs, all further experi-
[10]. Based on thermodynamics analysis, the gold leach-
ments were performed at the iodine-to-iodide mole ratio of
ing rate is higher and higher with the increase of iodine
1:8.
concentration. The effect of initial iodine concentration on
the extraction of gold was investigated from 0.4% to 1.4%
at 25◦ C for 4 h at an iodine-to-iodide mole ratio of 1:8, a
solution pH value of 7, a L/S ratio of 4:1, and a stirring
intensity of 600 r/min. The results are shown in Fig. 1. As
indicated in Fig. 1, when the initial iodine concentration
changes from 0.4% to 0.8%, the gold leaching rate quickly
increases at first and then slightly changes from 0.8% to
1.4%. This presents that a proper initial iodine concentra-
tion is of benefit to leaching, but too much dosage is not
necessary. Consequently, the further tests were carried out
by keeping the initial iodine concentration fixed at 1.0%.

Fig. 2. Effect of iodine-to-iodide mole ratio on gold

leaching rate.

4.3. Effect of pH value on gold leaching rate

The adjusting agents of pH values in this study were
hydrochloric acid (1%) and sodium hydroxide (10%). The
experiment conditions were shown as follows: the pH value
was varied from 4 to 10 (the interval was 1.5), the initial
iodine concentration was 1%, the iodine-to-iodide mole ra-
tio was 1:8, the L/S ratio was 4:1, the leaching time was
4 h, the stirring intensity was 600 r/min, and the tem-
Fig. 1. Effect of initial iodine concentration on gold
perature was 25◦ C. The experimental results are shown in
leaching rate. Fig. 3. As presented in Fig. 3, the leaching rate of gold
keeps at a high level and increases before the solution pH
value reaches 8.5. However, it decreases quickly when the
4.2. Effect of iodine-to-iodide mole ratio on pH value is higher than 8.5. In the Au-I2 -I− system, gold
gold leaching rate dissolution is the coefficient result of I− −
3 and I , which are
Gold can be oxidized when a complexing agent ex- both irreplaceable. However, when the pH value is in a rel-
326 Int. J. Miner. Metall. Mater., V ol. 20 , No. 4 , Apr. 2013

atively high level, the I−3 concentration decreases and the crease of leaching time. When the reaction time reaches 4
gold dissolution rate also decreases; thus, the gold leach- h, the leaching rate reaches up to a relatively high level.
ing rate will reduce [20]. Therefore, the proper condition of However, when the time is varied from 4 to 10 h, the leach-
gold leaching in iodine-iodide solution is neutral or acidic, ing rate has almost no change. In this case, 4 h is selected
but considering the equipment corrosion and safety pro- as the optimum value in the following study.
duction of a plant, the value of 7 is adopted as the solution
pH value.

Fig. 4. Effect of L/S ratio on gold leaching rate.

Fig. 3. Effect of solution pH values on gold leaching

rate.

4.4. Effect of L/S ratio on gold leaching rate

To study the effect of L/S ratio on the gold extraction,
the L/S ratio was varied from 2:1 to 6:1. Other variables
were as follows: the initial iodine concentration was 1%,
the iodine-iodide ratio was 1:8, the solution pH value was
7, the leaching time was 4 h, the stirring intensity was 600
r/min, and the temperature was 25◦ C. The experimental
results are shown in Fig. 4. It can be observed that the
gold leaching rate gradually increases with the increase of Fig. 5. Effect of leaching time on gold leaching rate.
L/S ratio. The reason is that a lower pulp density means a
lower pulp viscosity, and in this condition, diffusion veloc- 4.6. Effect of stirring intensity ratio on gold
ity from the reagent to the surface of gold becomes much leaching rate
faster, thus the dissolution speed of gold increases, then the
The main purpose of stirring is to increase the con-
extraction rate of gold increases. However, a higher L/S
tact frequency between the ore and leaching solution to
ratio means a more reagent consumption, a more invest-
enhance the leaching rate. Maintaining the initial iodine
ment of equipment, and a more difficulty of the recovery
concentration of 1%, the iodine-to-iodide mole ratio of 1:8,
of iodine. Considering these factors, 4:1 is used as the L/S
the L/S ratio of 4:1, the solution pH value of 7, the leach-
ratio.
ing time of 4 h, and the temperature of 25◦ C, the stirring
4.5. Effect of leaching time on gold leaching intensity was varied from 200 to 800 r/min. The results
rate shown in Fig. 6 indicate that gold leaching rate gradually
The effect of leaching time on the gold leaching rate decreases with the increase of stirring speed. It is possible
is shown in Fig. 5. The leaching time was 2, 4, 6, 8, and that the ore and liquid will rotate together in the con-
10 h, respectively. Other experimental parameters were tainer when the mixing speed is higher. Then, the ore and
as follows: the initial iodine concentration was 1%, the liquid could not mix uniformly, and the leaching solution
iodine-to-iodide mole ratio was 1:8, the L/S ratio was 4:1, on the ore surface could not be updated. Therefore, the
the solution pH value was 7, the stirring intensity was 600 reaction proceeding will be influenced [21]. When the stir-
r/min, and the temperature was 25◦ C. As shown in Fig. 5, ring speed is 200 r/min, the leaching rate is the highest.
the gold leaching rate is higher and higher with the in- However, when the stirring speed was less than 200 r/min,
H.X. W ang et al., Study on gold concentrate leaching by iodine-iodide 327

there was sediment that appeared in the ore pulp based on shown in Fig. 8, when the hydrogen peroxide consumption
the experiment phenomenon. Therefore, 200 r/min was is 1%, the leaching rate is the highest. It indicates that a
adopted as the stirring intensity in the further study. proper concentration of hydrogen peroxide can accelerate
the dissolution of gold. However, if it is too much, such as
2%, the leaching rate starts to decrease. The reason is that
the ions of I− and I− 3 in the solution will be oxidized by
the excessive hydrogen peroxide. Thus, the leaching reac-
tion will be destroyed; the gold leaching rate will decrease.
Therefore, 1% of the hydrogen peroxide consumption is
adopted in the experiments.

Fig. 6. Effect of stirring intensity on gold leaching

rate.

4.7. Effect of leaching temperature on gold

leaching rate
Temperature has an important impact on the chemical
reaction and the diffusion rate for most leaching processes. Fig. 7. Effect of leaching temperature on gold leaching
When the energy stored in the mineral grain increases, the rate.
power of destroying the mineral chemical bond enhances,
and the number of molecules whose kinetic energy greater
than activation energy increases; therefore, the leaching
process is accelerated [21]. Fig. 7 shows the effect of tem-
perature on the gold leaching rate. Other experimental
parameters were as follows: the initial iodine concentra-
tion was 1%, the iodine-to-iodide mole ratio was 1:8, the
solution pH value was 7, the L/S ratio was 4:1, the leach-
ing time was 4 h, and the stirring intensity was 200 r/min.
As presented in Fig. 7, the gold leaching rate increases as
the temperature increases from 15◦ C to 45◦ C. When the
temperature reaches 25◦ C, the leaching rate reaches up to
a relatively high level. However, the leaching rate changes
slowly from 25◦ C to 45◦ C. Meanwhile, in view of the con-
venience of the experiment process, 25◦ C is chosen for the
Fig. 8. Effect of hydrogen peroxide consumption on
leaching temperature.
gold leaching rate.
4.8. Effect of hydrogen peroxide consumption
on gold leaching rate
Because the leaching reaction can be accelerated by 5. Conclusions
adding an auxiliary oxidant in the leaching solution, hy- (1) Thermodynamic calculations show that the gold
drogen peroxide was selected as an auxiliary oxidant in this leaching reactions could not proceed spontaneously in the
study. The effect of hydrogen peroxide concentration on standard condition. However, if the concentration of ions
the gold leaching rate was examined from 0 to 4%, whereas changes appropriately, the reactions can proceed sponta-
the initial iodine concentration, iodine-to-iodide mole ra- neously. Therefore, gold leaching from the ore in iodine-
tio, solution pH value, L/S ratio, leaching time, stirring iodide solution is feasible in theory.
intensity, and leaching temperature were kept constant as (2) Experimental results prove that the theory of gold
1%, 1:8, 7, 4:1, 4 h, 200 r/min, and 25◦ C, respectively. As leaching using iodine-iodide solution is also suitable for
328 Int. J. Miner. Metall. Mater., V ol. 20 , No. 4 , Apr. 2013

treating the practical flotation gold concentrate. Through [7] G.C. Li and S.C. Lu, Research on iodine leaching of gold,
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