Dissolution Behavior of Cu, Fe and Zn from Gold Sulfide

Concentrate during Pre-oxidation using Ozone in Neutral

Media

Kurniawana, M. Zaki Mubarok

Metallurgical Engineering Department, Faculty of Mining and Petroleum Engineering, Institut Teknologi Bandung
Jalan Ganesha, Nomor 10, Bandung 40132, Indonesia
a
Corresponding Author : Kurniawan.280795@gmail.com

Abstract. The aim of this work was to observe the dissolution behaviour of Cu, Fe and Zn from gold sulfide concentrate
during preoxidation with ozone as the oxidant and distillation water as the media. The preoxidation experiments were carried
out in five-necked reactor with variations of retention time, percent solid, particle size and oxygen dosage injected to ozone
generator. The retention time was varied at 6 hours, 8 hours, 12 hours and 24 hours. The percent solid was varied at 10%,
20% and 30% while the particle size was varied at P80 -75 mesh dan P80 -20 mesh. The dosage of oxygen injection to ozone
generator was varried at 1 liter per minute and 2 liter per minute. The ozone gas was produced by using ozone generator type
OZ-03 and injected to the slurry by using Mazzei injector. The soluble Cu, Fe and Zn were measured by using Atomic
Absorption Spectrophotometry (AAS). The concentrates were characterized by X-Ray Diffraction (XRD), mineragraphy, fire
assay and Inductively Coupled Plasma (ICP). Fire assay, ICP and XRD were used to analyse the residues and froth. The
solubilition of metals (Cu, Fe and Zn) was obtained through the formation of sulphate ion and H + which decreased the pH,
released a number of heat and then was continued by the formation of elemental sulphur (So). The interaction of particles and
gas yielded the formation of froth. The highest dissolution percentage of Cu, Fe and Zn was achieved through 24 hours
oxidation at 20% (w/w), P80 -20 mesh and one liter per minute of oxygen injection dosage by 83.016%, 24.7303% and
91.6808%, respectively.

INTRODUCTION
Refractory ores is a difficult type of gold ore to process and yields less than 90% through conventional
cyanidation [1-4]. The amount of refractory ore is about 60% of the world’s total gold reserves so it can be an
alternative to meet the demand for gold [5-6]. One type of refractory ores is a sulfide gold ore in which fine-sized
gold particles are trapped in sulfide minerals thereby impede the contact between the gold particles and the leach
reagents [7,8]. Research on the extraction of gold from sulfide gold ores has been widely practiced, such as leach
with leachate reagents other than cyanide (thiourea, thiosulfate, chloride) or by pre-oxidizing refractory gold ores
prior to the cyanidation process [8-13]. Pre-oxidation such as roasting, oxidation at high temperature and pressure in
autoclave, as well as oxidation using bacteria has been done and found problems associated with SO2 gas emissions
and other gases such as mercury and arsenic, high investment costs for procurement of autoclaves, difficulties to
control the bacterial behavior and the process which takes a relatively long time [8-14]. Another alternative
developed is the use of ozone gas as an oxidizer [14-16].
The ozone gas was chosen because it has a high reduction potential (2.07 V), higher than hydrogen peroxide
(1.77 V) and chlorine gas (1.36 V) [14]. The developed injection system of ozone gas is a direct and indirect [14-
16]. A study by Sukamto (2016) suggested an association between the size of the ozone gas which is in contact with
minerals to the success of the oxidation process [17]. Sukamto compared two injection systems: difusser system and
Mazzei injector for the oxidative leaching of the sphalerite concentrate (ZnS) and yielded zinc recovery as 99%
using Mazzei injector [17]. The Mazzei injector system allows the formation of micro-bubble ozone gas which
increases the surface area of ozone gas [17]. In this system, the slurry is passed in a narrow gas that exhaled ozone
gas so that the contact between ozone gas and minerals becomes more intensive. This Mazzei injector system was
then used in this study and was expected to liberate gold particles from its sulfide matrix (mainly pyrite, chalcopyrite
and sphalerite). The dissolution behavior of Cu, Fe and Zn was observed during pre-oxidation. Distillation water
was chosen as the media of the pre-oxidation associated with low cost and environmentally friendly. Moreover, the
effect of retention time, percent solid, particle size and the dosage of oxygen injected to ozone generator were
examined.

EXPERIMENTAL

Materials. This study used sulfide gold concentrates which was obtained from gold mining in North Sulawesi. The
concentrates was stored in a refrigerator to prevent oxidation. X-Ray Diffraction (XRD) showed that the
concentrates mainly consisted of quartz, pyrite, chalcopyrite and chovelit. Chemical analysis indicated that it
contained Au (6.69 ppm), Ag (15 ppm), Cu (2,720 ppm), Fe (20.1%), Zn (66 ppm) and S total (32.2%). Meanwhile,
mineragraphy pointed out that the gold grains in the form of electrum were mostly trapped in sphalerite.

Experimental. Pre-oxidation experiments were carried out in a five-necked glass reactor with a volume of 2.5 liters
and an output hole below it. A total of 200 grams of concentrate was used in each of the pre-oxidation experiments.
The fixed parameters were the media used (distilled water), the rotation speed of 500 rpm and conducted at room
temperature. The set-up of the pre-oxidation experiments is schematically shown in Figure 1. Meanwhile, the
parameter tested were the retention time which was varied at 6 hours, 8 hours, 12 hours and 24 hours. Percent solid
was set at 10% (w/w), 20% (w/w) and 30% (w/w). The particle size was varied at P80 -75 µm dan P80 -20 µm. The
dosage of oxygen injection to ozone generator was varried at 1 liter per minute and 2 liter per minute.

FIGURE 1. Schematic diagram of pre-oxidation experiment

Analytical Techniques. The concentrate was characterized using XRD at Hydrogeology Laboratory, Mining
Engineering Department, ITB, mineragraphy which was done at Laboratorium Geoteknik LIPI Bandung while fire
assay and Inductively Coupled Plasma (ICP) analysis were conducted at PT Geoservices Cikarang. Fire assay and
ICP were also done to analyze the residues of the pre-oxidation experiments and the froth. Meanwhile, oxygen gas
was purchased from PT. Trijaya Gasindo Bandung. Dissolved metals were measured by using Atomic Adsorption
Spectrophotometry (AAS) at Hydro-electrometallurgy, Metallurgical Engineering Department, ITB. Moreover, pH
was measured with a pH meter (HI 8424 HANNA) while temperature was determined by using thermometer.

RESULTS AND DISCUSSION

pH and Temperature Profile during Pre-oxidation. The pH value profile during pre-oxidation in the various
variables is shown in Figure 2 while the temperature profile shown in Figure 3. The pH value decreased from the
 initial conditions in all conditions of the pre-oxidation experiments. This is because the release of H+ during sulfide
mineral oxidation [8,18]. The mechanism of the oxidation reaction of sulfide minerals at neutral media (pH ~6) is
described by Marsden (2006) as follows:
FeS2 + 11H2O  Fe(OH)3 + 2SO42- + 19H+ + 15e (1)
CuFeS2 + 10H2O  Cu(OH)2 + Fe + 2SO4 + 17H + 16e
2+ 2- +
(2)
ZnS + 6H2O  Zn(OH)2 + SO42- +10H+ + 8e (3)

The increase of temperature is due to the oxidation of sulfide minerals is an exothermic reaction [20].

8 8
6 hrs 10%
7 7
8 hrs 20%
6 6
12 hrs 30%
5 5
24 hrs
pH

pH
4 4
3 3
2 2

1 (a) 1 (b)
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

8 8
P80 -20 1 lpm
7 7
mikron 2 lpm
6 6
P80 -75
5 5
mikron
pH

pH

4 4
3 3
2 2
1 (c) 1 (d)
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

FIGURE 2. Profile of pH during pre-oxidation with variable: (a) retention time, (b) percent solid, (c) grain size, (d) oxygen dosage

Dissolution Analysis of Cu, Fe and Zn during Pre-oxidation. Dissolved Cu, Fe and Zn profiles are shown in
Figure 4-6. It can be seen that by the time of pre-oxidation experiments, more Cu, Fe and Zn dissolved which
indicated that the oxidation reaction occurred. Equation 1-3 shows the mechanism of oxidation reaction of sulfide
minerals at neutral pH. However, neutral conditions did not occur continuously due to the formation of H + ions so
that the pre-oxidation environment became more acidic. This triggered the occurrence of other oxidation reaction
mechanisms. The mechanism of oxidation reaction of sulfide minerals in acidic conditions by Marsden (2006) is
described as follows:
 FeS2  Fe2+ + 2So + 2e (4)
CuFeS2  Cu2+ + Fe2+ + 2So + 4e (5)
ZnS  Zn2+ + So + 2e (6)
6Fe2+ + O3 + 6H+  6Fe3+ + 3H2O (7)

The presence of elemental sulfur (So) was evidenced by the formation of froths which will be discussed later.
The reaction mechanism of 4-6 was supposed to involve not only ozone gas but also Fe 3+ ions [8]. The formation
Fe3+ ion is described by equation 7 in which the reaction mechanism occurred at the low pH conditions [8]. The
presence of this ions can accelerate the process of dissolving the elements of the compounds since this ions is strong
oxidizer [2,8,16,19]. Unfortunately, there was no Fe 3+ ions presence analysis in this study. These two steps oxidation
mechanisms then predicted to occur during pre-oxidation.
XRD showed that the residues of the pre-oxidation experiments still consisted of quartz and pyrite. This
indicated that the pre-oxidation process could dissolve both Cu and Zn while Fe was dissolved with a smaller
percentage than the two elements. This was probably due to the high content of Fe in the concentrate (in the form of
pyrite). In addition, elemental sulfur was found in the residue which ensures that the Reaction 4-6 occurred.

40 40

35 35

30 30
6 hrs 10%
Temperature (C)
Temperature (C)

25 25
8 hrs 20%

20 12 hrs 20 30%

24 hrs
15 15

10 10

5 5
(a) (b)
0 0

0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

40 40

35 35

30 30
1 lpm
Temperature (C)
Temperature (C)

25 25
2 lpm
P80 -20
20 mikron 20
P80 -75
15 15
mikron

10 10

5 5
(c) (d)
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

FIGURE 3. Profile of temperature during pre-oxidation with variable: (a) retention time, (b) percent solid, (c) grain size, (d) oxygen
dosage
 30% 60%

25% 50%

Dissolved Percentage
Dissolved Percentage

20% 40%
10%
6 hrs
15% 30% 20%
8 hrs
30%
10% 12 hrs 20%
24 hrs
5% 10%
(a) (b)
0% 0%
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

80% 90%
70% 80%
70%
Dissolved Percentage

60% Dissolved Percentage

50%
60%
1 lpm
50%
40%
P80 -20 2 lpm
40%
30% mikron
30%
20% P80 -75
mikron 20%
10%
(c) 10% (d)
0% 0%
0 5 10 15 20 25 30
0 5 10 15 20 25 30
Time (hr)
Time (hr)
FIGURE 4. Profile of dissolved Cu percentage during pre-oxidation with variable: (a) retention time, (b) percent solid, (c) grain size, (d)
oxygen dosage

Effect of Retention Time. Pre-oxidation experiments with variation of retention time were performed by
maintaining percent solid at 20%, P80 -75 µm grain size and oxygen dosage of 2 liters per minute. The effect of the
retention time (pre-oxidation time) on the dissolution of Cu, Fe and Zn elements is shown in Figure 4-6 (a). It can be
seen that over time, the higher the elements were dissolved. Cu, Fe and Zn dissolved as 25.773%, 20.292% and
52.964% respectively on pre-oxidation with 24 hours retention time. This result is in accordance with the results
obtained by Sukamto (2016) in which dissolved Zn was greater along with the length of time of pre-oxidation [17].

Effect of Percent Solid. Pre-oxidation experiments with variation of percent solid were conducted by setting
retention time at 24 hours, P80 -75 µm grain size and oxygen dosage of 2 liters per minute. The effect of the percent
solid on the dissolution of Cu, Fe and Zn elements is shown in Figure 4-6 (b). Significant difference occurred in Fe
element where the highest was reached at percent solid 10% (w/w), ie 26.4273% while for Cu, there was no
significant difference between percent solid as 10% and 20%. Zn element showed the highest end-dissolved
percentage was achieved at percent solid 20%. Percent solid 30% gave the lowest dissolved percentage for all the
elements. The same results were also obtained by Sukamto (2016) [17]. This is due to the tendency of diffusion film
formation [20]. Percent solid 20% then was chosen to next experiments due to operational reasons.
 25% 30%

25%
20%

Dissolved Percentage
Dissolved Percentage

20%
15% 6 hrs 10%
8 hrs
15% 20%
12 hrs
10% 24 hrs 30%
10%
5%
5%
(a) (b
0% 0% )
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (hr)
Time (hr)

25% 30%

20%
25%
Dissolved Percentage

Dissolved Percentage
P80 -20 1 lpm
mikron 20%
15% 2 lpm
P80 -75
mikron 15%
10%
10%
5%
5%
(c) (d)
0% 0%
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (hr) Time (hr)
FIGURE 5. Profile of dissolved Fe percentage during pre-oxidation with variable: (a) retention time, (b) percent solid, (c) grain size, (d) oxygen
dosage

Effect of Grain Size. Pre-oxidation experiments with variation of grain size were performed with retention time of
24 hours, percent solid 20% and oxygen dosage of 2 liters per minute. The effect of the grain size is shown in Figure
4-6 (c). The results obtained showed an increase of dissolved percentage for all elements at concentrates with fine
grain size (-20 µm). These results are similar to the results obtained by Sukamto (2016) [17]. The highest soluble
percentage for Cu, Fe and Zn is 66.7927%, 19.8897% and 73.741%, respectively.

Effect of Oxygen Dosage. Pre-oxidation experiments with variation of oxygen dosage were done with retention
time of 24 hours, percent solid 20% and oxygen dosage of 2 liters per minute. The effect of oxygen dosage is shown
in Figure 4-6 (d). The highest soluble percentage for Cu, Fe and Zn is 83.016%, 24.7303% and 91.6808%,
respectively. This result was obtained by using a dose of oxygen of 1 liter per minute. Sukamto (2016) also got
similar results, ie the fewer doses of oxygen used, the greater the percent of recovery [17]. This is related to the
amount of ozone gas formed. In the ozone generator used by Sukamto, the ozone gas formed decreased along with
the increase of dose of oxygen injected into the generator [Figure 7]. The same ozone generator was used in this
study.
 70% 70%

60% 60%

Dissolved Percentage
Dissolved Percentage

50% 50%
6 hrs 10%
40% 40%
8 hrs 20%
12 hrs 30%
30% 30%
24 hrs
20% 20%

10% 10%
(a) (b)
0% 0%
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

80% 100%
70% 90%
80%

Dissolved Percentage
Dissolved Percentage

60% 1 lpm
70%
50% 2 lpm
60%
40% P80 -20 50%
30% mikron 40%
P80 -75 30%
20% mikron 20%
10% (c) 10% (d)
0% 0%
0 5 10 15 20 25 30 0 5 10 15 20 25 30

Time (hr) Time (hr)

FIGURE 6. Profile of dissolved Zn percentage during pre-oxidation with variable: (a) retention time, (b) percent solid, (c) grain size, (d)
oxygen dosage

Froths Formation. Froths became side products which were formed during pre-oxidation. Froths also formed in the
study conducted by Sukamto (2016) [17]. However, the formation of froths in that study occurred from the
beginning of the oxidation process, while the froths in this study generally formed after 4 hours since the pre-
oxidation began or when the pH was ~2 (Fig. 2). The difference is because Sukamto used sulfuric acid as the
medium of the oxidation. Moreover, this also confirms the previous discussion that different reactions mechanisms
occurred during the pre-oxidation experiments.
Analysis of the froths showed that it contained high elemental sulfur (Table 1). This was due to the formation of
elemental sulfur during pre-oxidation (Equation 4-6). This product floated because of the interaction with the gas
that did not dissolve and try to exit and was characterized by the formation of bubbles on the surface at the
beginning of the formation of the froths (Figure 8). In this case, the gasses were ozone and oxygen. Sukamto
confirmed that as pH decreased, the ozone solubility diminished [17]. In addition, it is known that elemental sulfur is
a stable species at low pH and hydrophobic [8,19].
TABLE 1. Elemental sulfur content of the froths formed during pre-oxidation experiments of various variables (in percent)

P80 -20 P80 -75

6 hrs 8 hrs 12 hrs 24 hrs 10% 20% 30% 1 lpm 2 lpm
mikron mikron
NA NA NA 29.1 57.145 65.705 65.725 26.9 65.705 29.2 26.9
* NA: Not analyzed
 FIGURE 7. Profile of ozone gas formed by the variation of oxygen dosage

FIGURE 8. Froths formation

CONCLUSIONS

The solubilition of metals (Cu, Fe and Zn) was obtained through the formation of sulphate ion and H + which
decreased the pH, released a number of heat and then was continued by the formation of elemental sulphur (S o). he
highest dissolution percentage of Cu, Fe and Zn was achieved through 24 hours oxidation at 20% (w/w), P 80 -20
mesh and one liter per minute of oxygen injection dosage by 83.016%, 24.7303% and 91.6808%, respectively. The
interaction of particles and gas yielded the formation of froths.

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