Solid State Phenomena Submitted: 2019-04-29

ISSN: 1662-9779, Vol. 298, pp 116-120 Revised: 2019-05-02

doi:10.4028/www.scientific.net/SSP.298.116 Accepted: 2019-05-14
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-10-18

Two-Stage Agitation Leaching of Old Flotation Tailings

Aleksandr Bulaev1,a*, Vitaliy Melamud1,b and Anna Boduen2,c
1
Winogradsky Institute of Microbiology, Research Center of Biotechnology of the Russian
Academy of Sciences, 33 bld. 2 Leninsky Ave., Moscow 119071, Russia
2
Saint-Petersburg Mining University, 2 21st Line, St Petersburg 199106, Russia
bulaev.inmi@yandex.ru, bvmelamud.inmi@yandex.ru, cbodyen-anna@mail.ru
a

Keywords: old flotation tailings, acid leaching, copper, zinc, ferric iron, copper-zinc sulfide
concentrates.

Abstract. The goal of the present work was to develop hydrometallurgical approaches based on acid
leaching for selective extraction of base metals from the sample of old flotation tailings as well as
obtaining solution, which can be used for leaching of substandard copper-zinc concentrate. Old
flotation tailings contained 23.2% of iron, 0.36% of copper, and 0.23% of zinc. Copper-zinc
concentrate contained 23.8% of iron, 16% of copper, and 5.3% of zinc. Agitation leaching of old
flotation tailings with distilled water and sulfuric acid solutions (of 0.5 to 10% H2SO4) for 3 h at
pulp density of 20% made it possible to extract of 26 to 34% and of 58 to 70% of copper and zinc,
respectively. Concentrations of copper and zinc in the pregnant solutions were of 0.19 to 0.25 g/L
and of 0.27 to 0.32 g/L, respectively. The increase in H2SO4 concentration up to 10% did not lead to
significant increase in base metals extraction but led to significant increase in iron ions
concentration in the pregnant solutions. Pregnant solution obtained during the leaching with water
contained less than 1 g/L of iron ions, while that obtained during the leaching with 10% sulfuric
acid contained about 9 g/L of iron ions. Therefore, two-stage acid leaching with water and 10%
sulfuric acid was proposed for selective extraction of non-ferrous metals in the first stage and
obtaining of ferric iron solution in the second stage. Two-stage leaching at pulp density of 40% with
water made it possible to extract 31 and 64% of copper and zinc, respectively. It was shown, that
second stage did not allow to increase non-ferrous metals extraction but made it possible to obtain
solution containing 11g/L of ferric iron. This pregnant solution was used for oxidative leaching of
copper-zinc concentrate. Leaching at 80°C made it possible to extract 13 and 48% of copper and
zinc, respectively.

Introduction
Decline in metal content in ores as well as deficiency of conventional ores result in the need to
extract metals from low-grade raw materials including low grade ores, substandard sulfide
concentrates, and different wastes [1–7].
Tailings of flotation of sulfide ores containing non-ferrous (for example, copper and zinc) and
noble metals may be considered as technogenic source of metals [5–7]. Flotation tailings pose an
environmental problem as their long-term storage results in formation of acid mine drainage (AMD)
caused by biotic or abiotic oxidation of sulfide minerals contained in the tailings [8].
Therefore, development of approaches for extraction of valuable metals from flotation tailings is
relevant issue as it may allow not only producing valuable metals from waste materials but also
decreasing harmful effect on environment. Different methods including bioleaching and acid
leaching were proposed to extract metals from different samples of flotation samples [5–7, 9–11]. It
was shown that non-ferrous and noble metals can be successfully extracted from flotation tailings,
but peculiarities of tailings composition often leads to the obtaining of pregnant solution with iron
ions concentrations, which can be by an order of a magnitude higher than concentrations of base
metals, that has negative effect on further extraction of base metals [9–11]. Thus, the methods,

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 Solid State Phenomena Vol. 298 117

which may provide selective extraction of valuable metals from flotation tailings and obtaining
solutions appropriate for further extraction of non-ferrous metals, are required.
It was shown that pregnant solutions obtained during treatment of flotation tailings can be used
for oxidative leaching of copper from slags as these solutions contain high concentrations of ferric
iron ions, strong oxidants [11]. Leaching with ferric iron solutions is promising method for
treatment of different raw materials including slags and substandard concentrates [9, 11, 12]. Thus,
flotation tailings may be used not only as source of metals but also for obtaining ferric iron ions,
which can be used for treatment other products.
The goal of the present work was to develop hydrometallurgical approaches based on acid
leaching for selective extraction of base metals from the sample of old flotation tailings as well as
obtaining solution, which can be used for leaching of substandard copper-zinc concentrate.

Materials and Methods

Samples of old pyrite flotation tailings and copper-zinc concentrate obtained at an industrial
concentrators in Russia were used. The main elements contents in the samples are presented in
Table 1. Old flotation tailings contained pyrite, cuprite, gypsum, jarosite as well as chalcopyrite and
sphalerite. Copper was observed as chalcopyrite and oxidized compounds, and zinc was observed
as sphalerite and oxidized compounds. The concentrate contained pyrite, chalcopyrite, tennantite,
sphalerite, and scorodite.
Acid leaching of old flotation tailings was carried out using bottle agitator at ambient
temperature for 3 h. Pulp densities during agitation leaching (S : L) were 1 : 5 and 1 : 2.5. Sulfuric
acid solutions with concentrations from 0.5 to 10% (0.5, 1.0, 2.5, 5.0, and 10.0%) and distilled
water were used for leaching.
Pregnant solution obtained during acid leaching of old flotation tailings was used as leach
solution for concentrate treatment. Ferric leaching of copper-zinc concentrate was carried out in a
300 mL reactors containing 200 mL of pulp at 40°С for 6 h and 80°C for 3 h. Pulp density (S : L)
was 1 : 10. The stirring speed was set at 750 rpm. The leaching was carried out batchwise.
During the leaching, the parameters of the liquid phase (pH, Eh, concentrations copper and zinc
as well as ferric and ferric iron) were constantly determined. The concentrations of the Fe3+ and Fe2+
ions in the liquid phase were determined by reacting a sample from the liquid phase with potassium
thiocyanate and measuring the resulting absorption using a photometer with a wavelength of
λ=475 nm. The concentrations of copper and zinc were determined using a Perkin Elmer
3100 flame atomic absorption spectrometer (USA). Copper and zinc recovery rates were calculated
based on the results of the measurements.
Table 1. Content of the main components in old flotation tailngs and concentrate
Content, [wt. %]
Сomponent Copper-zinc
Old flotation tailings
concentrate
Si 13.6 0.91
Stot 25.3 36.0
Fetot 23.2 23.8
As - 1.36
Cu 0.36 16.0
Zn 0.23 5.3
118 Metallurgy Technology and Materials VII

Results and Discussion

The concentrations of metals in pregnant solutions of the acid leaching are presented in Fig. 1 A.
Recovery of copper and zinc reached of 26 to 34% and of 58 to 70%, respectively. Concentrations
of copper and zinc in the leachates were of 0.19 to 0.25 g/L and of 0.27 to 0.32 g/L, respectively
(Fig. 1A). The increase of H2SO4concentration up to 10% did not lead to increase in base metals
extraction (Fig. 1 B) but led to significant increase of iron ions concentration in the pregnant
solutions.

Figure 1. Concentrations of the metals in pregnant solutions of the acid leaching with sulfuric acid
solutions (A) and extraction of base metals (B) (3 h, S : L 1 : 5). 1 – Cu2+, 2 – Zn2+, 3 – Fe3+,
4 – Fetotal
In the pregnant solution obtained during the leaching with distilled water copper, zinc, and ferric
iron concentrations were 0.31, 0.32, and 0.29 g/L. In the same time, in the pregnant solution
obtained during the leaching with 10% H2SO4, copper, zinc, and ferric iron concentrations were
0.25, 0.32, and 8.01 g/L. Thus, leaching with distilled water provided comparatively high copper
and zinc extraction and made it possible to obtain pregnant solutions with low ferrous and ferric
iron concentrations that may be significant to further extraction. In the same time, leaching with
10% sulfuric acid did not allow to increase copper and zinc extraction in comparison to distilled
water but allowed to obtain pregnant solution with high ferric iron concentration that can impede
non-ferrous metals extraction from the solution but may be used for oxidative leaching.
Increase in pulp density up to 1 : 2.5 (S : L) allowed to reach almost the same extraction of
copper and zinc and increase concentrations of non-ferrous metals in the solution (Fig. 2).

Figure 2. Concentrations of the metals in pregnant solutions of leaching with water (A) and
extraction of base metals (B) (3 h, distilled water). 1 – Cu2+, 2 – Zn2+, 3 – Fe3+, 4 – Fetotal
 Solid State Phenomena Vol. 298 119

Two-stage leaching was performed to obtain pregnant solutions with low iron concentration
appropriate for non-ferrous metals extraction as well as pregnant solution with high ferric extraction
for further oxidative leaching. In the first stage, acid leaching was performed with distilled water. In
the second stage, its solid residue was leached with 10% H2SO4. Results of the experiments are
shown in Fig. 3.

Figure 3. Concentrations of the metals in pregnant solutions of leaching with water and 10%
sulfuric acid solution (A) and extraction of base metals (B) (3 h, S : L 1 : 2.5). 1 – Cu2+, 2 – Zn2+, 3
– Fe3+, 4 – Fetotal
The second stage of the leaching did not allow to increase copper and zinc extraction and their
concentration in the solution obtained during the stage were extremely low (0.06 and 0.05 g/L of
copper and zinc, respectively). In the same time, this pregnant solution contained about 11.3 g/L of
ferric iron ions and therefore was used in the further experiments.
Results of ferric leaching of copper-zinc concentrate at 40°C and 80°C using pregnant solution
obtained during two-stage leaching are shown in Table 2.

Table 2. Parameters of pregnant solutions obtained during acid leaching of old flotation tailings and
ferric leaching of the concentrate
Eh, Fe3+, Fe2+, ∑Fe, Cu2+, Zn2+,
Solution pH
[mV] [g/L] [g/L] [g/L] [g/L] [g/L]
Second stage of acid 11.27 1.16 11.93 0.062 ± 0.049 ±
0.23 687
leaching ± 0.56 ± 0.61 ± 0.67 0.003 0.002
Ferric leaching at 9.74 3.29 13.03 0.96 1.37
0.42 672
40°C (6 h) ± 0.68 ± 0.52 ± 1.25 ± 0.03 ± 0.09
Ferric leaching at 1.98 12.98 14.97 2.22 2.55
0.49 596
80°C (3 h) ± 0.80 ± 1.36 ± 1.28 ± 0.13 ± 0.19

It was shown that concentrations of both copper and zinc were higher in pregnant solution
obtained during leaching at 80°C despite longer residence time of leaching at 40°C. Leaching at 40°
and 80°C made it possible to extract 6 and 25% and 13 and 48% of copper and zinc, respectively.
Solid residues yields were 89.5 and 83.7% at 40 and 80°C, respectively. Copper and zinc content in
the residues obtained during the leaching at 40 and 80°C comprised 17.0% and 4.0% and 16.4% and
2.5%, respectively. Thus, ferric leaching made it possible to decrease zinc content in copper-zinc
concentrate that may increase quality of copper-zinc concentrates that was demonstrated previously
by the example of other copper-zinc products and ferric sulfate solution [12].
120 Metallurgy Technology and Materials VII

Conclusions
Results of the present work demonstrated that two-stage leaching may be a promising method for
treatment of this type of mining wastes since it may provide selective leaching of valuable metals
from old flotation tailings at the first stage as well as obtaining solutions with high ferric iron
concentrations. Thus, old flotation tailings may be used not only as source of non-ferrous metals but
also for obtaining ferric iron solutions, which can be used for oxidative leaching of different raw
materials.

Acknowledgments
The reported study was funded by RFBR according to the research project 18-29-24103

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