225

Received January 31, 2014

Original Accepted for Publication July 29, 2014
©2014 Soc. Mater. Eng. Resour. Japan

Copper Upgrading and Recovery Process from Mine Tailing of Bor Region,
Serbia Using Flotation

Baisui HAN※, Batnasan ALTANSUKH※, Kazutoshi HAGA※, Zoran STEVANOVIC※※, Jonovic RADOJKA※※,
Radmila MARKOVIC※※, Ljiljana AVRAMOVIC※※, Ljubisa OBRADOVIC※※, Yasushi TAKASAKI※※※,
Nobuyuki MASUDA※※※, Daizo ISHIYAMA※ and Atsushi SHIBAYAMA※
※
Graduate School of Engineering and Resource Science, Akita University, 1-1Tegata gakuen-cho Akita 010-8502, Japan
※※
Mining and Metallurgy Institute Bor, 35 Zeleni Bulevar, 1920 Bor, Serbia
※※※
International Center for Research and Education on Mineral and Energy Resources, Akita University,
1-1Tegata gakuen-cho Akita 010-8502, Japan
E-mail : sibayama@gipc.akita-u.ac.jp

A process for concentration of Cu from a Cu mine tailing by flotation has been investigated in this study.
The flotation studies were carried out under varying conditions of pH (3.5~12), flotation time (0~20 minutes)
and sulfurizing reagent (0, 1000 g/t) using two different pH regulators (NaOH, Ca(OH)2). The results showed
that the grade of Cu in froth concentrate was increased from 0.24 mass% to 0.81 mass% with the enrichment
ratio of 4, whereas the Cu recovery reached 60% under the conditions (pH 10, sulfurizing reagent: 1000 g/t,
collector of PAX: 100 g/t, frother of MIBC: 200 g/t and flotation time: 5 minutes). At the condition, the grade
of Al and Fe were reached to 0.6 mass% and 6.6 mass% from 3.45 mass% and 3.51 mass%, respectively.

Key Words : Copper, Flotation, Mine tailing, Chalcopyrite, Flotation reagent

and recovery of Cu using MS (Mineral Separation) type flotation

1　INTRODUCTION
machine for the purpose of upgrading and recovery of Cu.
　Mineral resources are non-renewable and most important
2　EXPERIMENTAL
resources of which utilization has increased in many industries.
Today, since high grade mineral resources are fewer with long- 2.1 Experimental sample
term mining activities and human usage [1], the problems related 　In this experiment, the mine tailing sample (from Copper Mine
to rapid depletion of existing ore deposits, high impurities, lower in Bor Serbia) was ground by a mill until the top particle size
grade of ore and increasing of refractory ore and industrial wastes
(such as mine tailings) are happened. About 5 billion tons of
tailings are discharged a year all over the world [2]. On the other Table 1　Chemical compositions of the mine tailing.
hand, the content of useful components especially copper and
precious metals in the tailings is few times higher than the primary
copper ores. Therefore, mine tailings present a very important
resource, which could be processed in the future [3]. Research
attitude on the development of economic efficiency treatment of
mine tailings is main attention.
　Chalcopyrite is highly hydrophobic and floats easily among
other sulphide minerals, but its enrichment or concentration
by flotation is not always simple due to surface change during
exposure to environment, poor liberation, impurity and so on.
　According to the data for 2002, 207 Mt of flotation tailings,
450 Mt of overburden and 23 Mt of slag were disposed of on the
territory of Bor municipality (Serbia), in there is 11333.3 t of waste
per inhabitant of the municipality. Over 68% of the Bor mining
area has been ruined by waste dumps and tailings ponds [4].There
is low grade (about 0.24 mass% on the average) of Cu contains
in those mine tailings [4]. In this study, we had investigated the
effect of pH, flotation time and sulfurizing reagent on the grade Figure 1　XRD pattern of the mine tailing.

Int. J. Soc. Mater. Eng. Resour. Vol.20, No.2, (Oct. 2014)

226 Baisui HAN et al.

became 100 micro meter. Table 1 shows the grade of each metal in
the mine tailing in which were Fe (3.51 mass%), Cu (0.24 mass%),
and Al (3.45 mass%), respectively. As shown in Figure 1, XRD
pattern of the mine tailing confirmed that mineral composition of
the mine tailing are SiO2, FeS2, and Al2O3.

2.2　Experimental procedure
　Experiments were carried out by using the MS type floating
machine (see Figure 2). At first, 10 g mine tailing introduced
into the cell with water and adjusted the pulp density to 40 g/L
at agitation speed of 1000 rpm and mixing time of 5 minutes. After
the pH of the slurry fixed from pH 3.5~12 using NaOH or Ca(OH)2,
a sulfurizing reagent (NaHS) was added under constant agitation
and conditioned for 5 minutes. After that, appropriate amount of
Figure 3　The effect of pH (controlled by NaOH) on Cu grade and
collector (PAX: Potassium amyl xanthate (C5H11OCSSK)) was
recovery.
added into the cell and conditioned for 5 minutes. Flotation was
(pH: 3.5~12, Pulp density: 40 g/L, PAX: 100 g/t, MIBC:
performed during 5~20 min after frother (MIBC) was added into
200 g/t, Flotation time: 5 min)
the cell. Table 2 shows the conditions of flotation studies. The
mineral and chemical composition analyses are carried out with
X-ray diffraction and ICP (Inductively Coupled Plasma) after
recovery decreased with increasing the pH to 12. Due to the results
prepared the froth concentrate.
obtained, pH 10 as optimum condition can be used to concentrate
Cu from the mine tailing.
3.1.2　Effect of pH regulator (Ca(OH)2 ): The effect of pH on
Cu grade and recovery was examined at the conditions such as
pulp density of 40 g/L, collector (PAX) of 100 g/t, frother (MIBC)
of 200 g/t, flotation time of 5 min. pH was changed from 3.5 to
12 with addition of Ca(OH)2. As shown in Figure 4, the grade
of Cu reached about 0.57 mass% with increasing pH to 6, and it
became stable further even rise the pH up to 12. The recovery of
Cu decreased up to 4% with increasing of pH to 12. These results
are in accordance with the references [5-9]. Junzo et.al found that
multiply charged ion such as Ca2+ have an active action which
reverse the potential of SiO2 to plus due to the adsorption. It was
reported that anion type collector is adsorbed on SiO2 surface
which has been plus charged. It can be considered as one of the
reason of why Cu grade become stable with increasing pH whereas
Figure 2　MS type flotation machine recovery of Cu decreased.

Table 2　Flotation conditions

Cu grade in conc.

3　RESULTS AND DISCCUSION

3.1　Effect of pH
3.1.1　Effect of pH regulator (NaOH): The effect of pH on Cu
grade and recovery was examined at the conditions of pulp density
of 40 g/L, collector (PAX) of 100 g/t, frother (MIBC) of 200 g/t
and initial flotation time of 5 minutes when pH controlled from 3.5 Figure 4　The effect of pH (controlled by Ca(OH)2) on Cu grade and
(nature pH) to 12 by NaOH. The results are shown in Figure 3. It recovery.
was revealed that both the grade and recovery of Cu increased with (pH: 3.5~12, Pulp density: 40 g/L, PAX: 100 g/t, MIBC:
increasing of pH. At pH 10, grade and recovery of Cu reached to 200 g/t, Flotation time: 5 min)
0.68 mass% and 40%, respectively, whereas both the grade and

Int. J. Soc. Mater. Eng. Resour. Vol.20, No.2, (Oct. 2014)

 Copper Upgrading and Recovery Process from Mine Tailing of Bor Region, Serbia Using Flotation
3.2　Effect of flotation time
　The effect of flotation time on Cu recovery was examined at the
conditions such as pulp density of 40 g/L, collector (PAX) of 50 g/t
and frother (MIBC) of 200 g/t with varying flotation time from 0 to
20 minutes. In order to prevent from the recovery of other mineral
(except chalcopyrite) such as pyrite, the pH of slurry was adjusted
at pH 10 with alkaline pH regulator (NaOH). As the results shown
in Figure 5, the effect of flotation time on Cu recovery from the
mine tailing was significant because the recovery of Cu increased
up to 40% at 5 minutes, and it increased further with increasing of
the flotation time. The Cu recovery reached 65% when flotation
time was 20 minutes. However, the grade of Cu increased to
0.68 mass% when flotation time is 5 minutes, and it decreased with
increasing flotation time up to 20 minutes. The flotation time of
5 minutes was chosen as the optimum flotation time for recovery of
Cu from the mine tailing.
Figure 5　The effect of flotation time on Cu grade and recovery.
(Flotation time: 0~20 min, pH: 10, Pulp density: 40 g/L,
PAX: 100 g/t, MIBC: 200 g/t)
3.3　Effect of sulfurization
3.3.1　Effect of sulfurizing reagent and pH regulator (NaOH):
The effect of sulfurizing reagent on Cu grade and recovery was
examined under the conditions with fixed the pulp density of 40 g/L,
sulfurizing reagent (NaHS) of 1000 g/t, collector of 100 g/t, frother
of 200 g/t, and flotation time of 5 minutes while the pH was
controlled from 3.5 to 10 using NaOH as a pH regulator.
Experimental results are shown in Figure 6. The sulfurizing
reagent has highly significant effect on the Cu recovery process
as shown in Figure 6. The grade of Cu increased with addition of
the sulfurizing reagent and it reached to 0.81 mass% at pH of 10.
It can be seen that the recovery of Cu increased depending on the
sulfurizing reagent. The sulfurizing reagent was efficacious in the
Cu recovery from the mine tailing by flotation. The recovery of
Cu reached about 60% with addition of sulfurizing reagent at pH
of 10 when the flotation time was 5 minutes. It can be considered
as one reason due to Cu recovery percentage become low. The
surface of chalcopyrite in mine tailing may be oxidized with
rainwater naturally in the air, loading metals oxides (CuO, CuSO4)
which change the floating characteristics. Research on the effect
Int. J. Soc. Mater. Eng. Resour.
227
of sulfurizing reagent on flotation has been widely discussed in
literature [9-12]. It can be seen from Figure 7, in there shows
the effect of sulfurizing reagent (NaHS) on flotation. Generally,
a sulfurizing reagent (NaHS) as a feed led to sulfurize the oxide
layer of the minerals forming HS - and S 2- ion on the surface.
Sulphidisation enables oxide mineral of copper activation or the
formation of a metal sulphide or elementary sulphur on their
surfaces [13~15] for rendering them amenable to flotation using the
collecting properties of thiol. Xanthates are made of heteropolar
molecules that react with the activated minerals surfaces based on
the chemical reactions. As the matter of fact, xanthate ions (X-)
liberated in solution by thiol collectors adsorb, via chemisorption
or an electrochemical process, on the activated minerals surfaces
in the form of hydrophobic species. These species enable the
attachment of the mineral particles to air bubbles within the
agitated pulp submitted to flotation [13, 16] and causes to improve
Cu flotation kinetics due to an increment of froth stability.
(No sulfurizing)
(Sulfurizing)
(No sulfurizing)
(Sulfurizing)
Figure 6　The effect of sulfurizing reagent and pH (controlled by NaOH)
on Cu grade and recovery.
(pH: 3.5~10, Pulp density: 40 g/L, NaHS: 0 and 1000 g/t, PAX:
100 g/t, MIBC: 200 g/t, Flotation time: 5 min)
Float
(Cp : Chalcopyrite)
Figure 7　The model of NaHS effect on flotation.
3.3.2　Effect of sulfurizing reagent and pH regulator (Ca(OH)2 ):
The effect of sulfurizing reagent on Cu grade and recovery was
examined with the conditions of pulp density (40 g/L), sulfurizing
reagent (NaHS , 1000 g/t), collector of PAX (100 g/t), frother
of MIBC (200 g/t), flotation time for 5 minutes when pH was
controlled from 3.5 to 10 by Ca(OH) 2. Experimental results
are shown in Figure 8, respectively. As shown in Figure 8, the
sulfurizing reagent has highly significant effect on the Cu grade.
The grade of Cu increases from 0.30 mass% to 1.53 mass% with
Vol.20, No.2, (Oct. 2014)
228 Baisui HAN et al.
(No sulfurizing)
(Sulfurizing)
(No sulfurizing)
(Sulfurizing)
Figure 8　The effect of sulfurizing reagent and pH (controlled by Ca(OH)2)
on Cu grade and recovery.
(pH: 3.5~10, Pulp density: 40 g/L, NaHS: 0 and 1000 g/t, PAX:
100 g/t, MIBC: 200 g/t, Flotation time: 5 min)
increasing of pH from 3.5 to 10 when adding the sulfurizing
reagent. It can be seen that the recovery of Cu was increased
depending on the sulfurizing reagent, but the recovery was lower
(20%) even grade of Cu reached 1.53 mass% when pH is 10.
Therefor the pH regulator Ca(OH)2 is not suitable in flotation of
mine tailing.
3.4　Application of the optimum conditions
　The optimum flotation conditions are summarized in Table 3.
Chemical composition of the froth concentrate obtained under
optimum flotation conditions and results of XRD measurement are
shown in Table 4 and Figure 9, respectively. As shown in Table 4,
Cu grade in the froth concentrate increased from 0.24 mass% to
0.81 mass% as enrichment ratio of 4 under the optimum conditions
obtained in the flotation, whereas the grade of Al and Fe were
0.64 mass% and 6.62 mass%, respectively. It was observed that
the forth concentrate consists of chalcopyrite (CuFeS2) as main Cu
components, and quarts (SiO2), pyrite (FeS2) and Al2O3 are gangue
minerals.
4　CONCLUSION
In this study, flotation for upgrading and recovery of Cu from
Table 3　The optimum flotation conditions.
Table 4　Chemical compositions of froth concentrate.
Int. J. Soc. Mater. Eng. Resour.
Figure 9　XRD pattern of froth concentrate.
copper mine tailing was tested. The effects of pH, pH regulator
and flotation time on Cu grade and recovery have been discussed.
The results showed that the grade of Cu reached to 0.81 mass% as
enrichment ratio of 4, while recovery of Cu became 60% under the
controlled condition at pH of 10, sulfurizing reagent (NaHS) of
1000 g/t, collector (PAX) of 100 g/t, frother (MIBC) of 200 g/t and
flotation time for 5 minutes. It was revealed that both of the grade
and recovery of Cu increased with addition of sulfurizing reagent
which cause to improve Cu flotation kinetics due to an increment
of froth stability.
Acknowledgment―This study was undertaken as a program
of dispatch of Science and Technology Researches named
"Management of mining waste-tailing dump in the Bor region"
supported by the Japan Society for the Promotion of Science and
Japan International Cooperation Agency. This study would not
have been possible without the generous cooperation and logistic
support of the Ministry of Environment, Mining and Spatial
Planning of the Serbian Government, RTB Bor and Mining &
Metallurgy Institute Bor. Also this work was supported by JSPS
KAKENHI Grant Number 24360370, JSPS leading program "New
Frontier Leader Program for Rare-metals and Resources" and JST/
JICA, SATREPS (Science and Technology Research Partnership
for Sustainable Development). And we gratefully acknowledge
their financial support.
References
[1] Yingbo Dong, Hai Lin; "Influences of flotation reagents on
bioleaching of chalcopyrite by Acidthiobacillus ferrooxidans",
Minerals Engineering, 32, 27-29 (2012).
[2] Li Lin, Lv Xianjun, Qiu Jun, Li Peng; "The Study on the
Flotation of Tailings of Molybdenum Minerals for the
Reclamation of Iron", Procedia Environmental Sciences, 12,
453-458 (2012).
[3] Rodoljub D. Stanojlović , Jovica M. Sokolović , Novica
Milosević ; "Integrated environmental pollution by wastes
from copper MINE BOR, SERBIA", Environmental
engineering and Management Journal
[4] M.M. Antonijević, M.D. Dimitrijević, Z.O. Stevanović, S.M.
Serbula, G.D. Bogdanovic; "Investigation of the possibility of
copper recovery from the flotation tailings by acid leaching",
Journal of Hazardous Materials, 158, 23-34 (2008).
[5] Junzo SHJMOIIZAKA, Katsuto MAKATSUKA, Isao
MATSUOKA; "Principles of Non-sulphide Mineral
Vol.20, No.2, (Oct. 2014)
 Copper Upgrading and Recovery Process from Mine Tailing of Bor Region, Serbia Using Flotation
Flotation", UDC 622.765.01: 549.5
[6] J. M. W. Mackenzie: Trans. AIME, 235, 82 (1966).
[7] J. M. W. Mackenzie and R. T. O' Brien: Trans. AIME, 244,
172 (1969).
[8] M. C. Fuerstenau and D. A. Elgillani: Trans. AIME, 235, 405
(1966).
[9] Ryoji ITO, Gjergj DODBIBA, Jun SADAKI, Ji Whan AHN
and Toyohisa FUJITA; "Recovery of Heavy Metals by
Flotation from Incinerated Automobile Shredder Residues",
The Resources Processing Society of Japan, 54, 152-157
(2007).
[10] A.J.H. Newell, D.J. Bradshaw; "The development of a
sulfidisation technique to restore the flotation of oxidised
pentlandite", Minerals Engineering, 20, 1039-1046 (2007).
[11] Li Pang Wang, Josiane Ponou, Seiji Matsuo, Katsunori
Okaya, Gjergj Dodbiba, Tatsuki Nazuka, Toyohisa Fujita;
"Integrating sulfidization with neutralization treatment for
selective recovery of copper and zinc over iron from acid
mine drainage", Minerals Engineering, 45, 100-107 (2013).
[12] W.J. Bruckard, G.J. Sparrow, J.T. Woodcock; "A review of the
Int. J. Soc. Mater. Eng. Resour.
229
effects of the grinding environment on the flotation of copper
sulphides", International Journal of Mineral Processing, 100,
1-13 (2011).
[13] J. Drzymala; Mineral Processing, Foundations of Theory
and Practice of Minerallurgy, 1st English edition, Oficyna
Wydawnicza PWr, Wroclaw University of Technology, 2007,
pp. 344, 357, 361, 362
[14] M.S. Davidson; "An Investigation of Copper Recovery from
a Sulphide Oxide Ore with a Mixed Collector System", A
thesis submitted to the Department of Mining Engineering
in conformity with the requirements for the degree of Master
of Science in Engineering, Queen's University, Kingston,
Ontario, Canada, 2009, pp. 1-32
[15] K. Kongolo, M. Kipoka, K. Minanga, M. Mpoyo; "Improving
the efficiency of oxide copper–cobalt ores flotation by
combination of sulphidisers", Miner. Eng, 16, 1023-1026
(2003).
[16] S.M. Bulatovic; Handbook of Flotation Reagents, Chemistry,
Theory and Practice: Flotation of Sulfide Ores, Elsevier
Science & Technology Books, 2007, pp. 177-178 105-109.
Vol.20, No.2, (Oct. 2014)