Acid leaching of oxide–sulfide copper ore prior the flotation – A way for

an increased metal recovery

Miroslav D. Sokić1, Vladan D. Milošević1, Velizar D. Stanković2, Vladislav Lj. Matković1,
Branislav R. Marković1
1
Institute for Technology of Nuclear and Other Mineral Raw Materials, Belgrade, Serbia
2
University of Belgrade, Technical Faculty, Bor, Serbia

Abstract
The copper mine Cerovo – East Serbia, as well as the other ore bodies in its vicinity, con- PROFESSIONAL PAPER
tains a significant amount of oxide copper minerals in their uper layers (>40%). Processing
of such mixed ores by the existing concentration technologies leads to a substantial copper UDC 622:622.765(497.11–11):
losses (<60%). Reduction of “oxide copper”, by acid leaching prior the flotation concentra- 66.061.34
tion, can increase the overall copper efficiency up to more than 70% in the single-stage
leaching, achieving an efficiency in the flotation concentration stage higher than 75%.
Based on the performed experimental results, the flow sheet for processing of the mixed Hem. Ind. 69 (5) 453–458 (2015)
oxide-sulfide copper ore is proposed.
Keywords: oxide–sulfide copper ore, leaching, flotation, increase of copper recovery. doi: 10.2298/HEMIND140509061S

Available online at the Journal website: http://www.ache.org.rs/HI/

Many copper mines contain, beside sulfide ore as a be 18000 t of cooper, including a part that is already
main quantity in deeper layers, a certain amount of extracted during the ten years of C1 ore body (Open pit
oxide deposit in upper layers, as well as oxide–sulfide Cerovo) exploitation [1].
blend in the middle of an ore body. In order to recover Three sources of cooper losses are noticed during
the copper metal oxide ore parties are usually pro- the exploitation of C1 ore body, which also generates
cessed by leaching, followed by solvent extraction, and technical and environmental problems that will appear
electrowinning, while the rest of ore deposit is pro- in each of the other ore bodies:
cessed by flotation, having considerable technological − Barren surface layer and associated gangue
problems, and usualy a low percent of copper recovery material, with cooper content below 0.2%;
may be achieved. Hence, the major fraction of oxide − Oxide–sulfide ore from the current ore excav-
and a part of sulfide minerals may be lost and thus ation containing various percentages of oxide and sul-
making the process economy less advantageous. Such fide minerals, in a range from few percents up to 60%
case is found in the copper ore deposit “Kraku Buga- of oxide.
resku”, an ore field in Eastern Serbia, a property of − Mine water collected at the open pit bottom, as
Mining and Smelting Copper Co., Bor, Serbia. This ore well as the one drained as an acid mine drainage
field contains several smaller ore bodies, named (AMD), due to a spontaneous self-leaching of the out of
“Cerovo – C1–4”, having oxide cap on the top, followed balance ore stored as a dump at the open pit edge, as is
by a layer of oxide-sulphide mixture, before cominig illustrated in Figure 1.
deeper into the main sulfide ore deposit. So far, only
the ore body C1-Copper Mine Cerovo is opened, this
body is under exploitation. The majority of oxide–sul-
fide batches from “Cerovo – C1–4” ore bodies contain
carbonate minerals, with some cuprite and chrysocolla
which may easily leach. From all ferrous minerals the
hematite and limonite are predominant, including
some parts of lodestone. The oxide batches are placed
on the surface, and upon the body opening they are
the first to be excavated. Potential content of cooper
oxide batches in the C1 to C4 ore bodies is estimated to
Figure 1. A photograph of the dump, formed of out of balance
Correspondence: M.D. Sokić, Institute for Technology of Nuclear and ore (top part), and the pond (lower part of the photo), formed
Other Mineral Raw Materials, 86 Franchet d'Esperey Street, 11000
by collecting the AMD.
Belgrade, Serbia.
E-mail: [email protected]
Paper received: 9 May, 2014 Each of these cooper sources needs a different
Paper accepted: 17 July, 2014 approach related to their technological treatment. Flo-

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tation of sulfide minerals from copper ore, containing a teflon mechanical stirrer, the condenser, the thermo-
high percent of oxide copper, generates technical prob- meter, the glass funnel for feeding a solid sample and
lems in the concentration process, decreasing the level the sampling device. Such set-up provides stable her-
of cooper content, which is already low. In order to inc- metic conditions, and allows leaching at the chosen
rease the overall efficiency of cooper concentration constant temperature as well as at the constant stirring
process from such ore blend it is necessarily to treat rate.
the part of cooper oxide either by leaching of grinded
ore prior the flotation or by leaching the flotation
tailing coming out from the concentrator.
Direct leaching process of copper oxides or complex
ores attracts considerable scientific and engineering
attention, which plays an important role in the sus-
tainable development of copper industry. Sulphuric,
hydrochloric and nitric acid, as well as the ammonia are
usually used as the leaching agents in a various copper
ore leaching processes [2–12]. Copper oxides easily
react with sulphuric acid solutions at the room tempe-
rature producing Cu2+ in the aqueous phase. Energy Figure 2. Experimental set-up for the leaching process at
consumption can also become an important factor of atmospheric pressure: 1 – electrical heater, 2 – glass reactor,
3 – glass funnel, 4 – mechanical stirrer, 5 – contact
economy when the leaching process occurs, consider- thermometer, 6 – cut off relay, 7 – condenser, 8 – absorber.
ing the heating and agitation of the input suspension.
The kinetics of copper minerals leaching was recently Sulphuric acid, analytical grade was used to prepare
published by several authors, for example Sokić at al. the leach solution by dissolving it in distilled water.
kinetics of copper leaching from chalcopyrite [7], Bingol Since the initial H2SO4 concentration was the key para-
and Canbazoglu kinetics of copper leaching from mala- meter of leaching, the stock solution with the concen-
chite [10,11], while Quast has published the kinetics of tration of 0.3 M was prepared and further diluted to
copper leaching from atacamite [12]. Also some res- get the desired initial concentration of H2SO4.
earchers studied the processing of copper oxides wrap- In flotation concentration of the leaching residue
ped by silicate and limonite [13,14]. This kind of ore is standard chemicals were used, save as in the concen-
usually processed by mill running and then smelting, tration plant Veliki Krivelj. These are the potassium-
and the copper recovery is about 35% during the mill ethyl-xanthate (PEX) as the collector, and the DOW 250
running process. Sun at al. [14] performed the copper as the frothing agent. These chemicals were of a tech-
leaching from low grade copper oxide ore by sulphuric nical grade. Lime milk (technical grade) was used for
acid, and they have obtained leaching percent of cop- adjusting the pH value of suspension before the flot-
per over 90%. Compared with the copper leaching effi- ation.
ciency of about 35% in the mill running technology the Time was measured by a chronometer. Atomic abs-
leaching process has achieved a better economic result. orption spectrophotometer (AAS – Perkin Elmer, model
In the present study the leaching of oxide-sulfide Analyst 300) was used for chemical analysis of the
copper ore was considered, and a modification of the leaching samples. Chemical analysis of the ore samples,
existing process was performed by inserting the leach- as well as of the leaching residue, the concentrate, and
ing process between the ore milling and the flotation the flotation tailing were all analyzed in laboratories of
sections. Therefore, a higher overall efficiency of the the Institute of Mining and Metallurgy Bor.
copper removal, from such minerals blend, was obtained.
Through this study, the influence of some parameters, Leaching procedure
affecting the leaching process, and the flotation pro- Ore samples, at first were disintegrated and then
cess of the leach residue were defined. Finally, the sieved through a set of standard laboratory sieves. The
oxide–sulfide copper ore, used in the experimental fraction <74 µm was used in the leaching experiments.
part, was taken from the current mine works in the Prior the leaching the chemical analysis was done in
Copper Mine Cerovo. order to determine the initial concentrations of oxide,
sulfide and total copper. Also, the percent of moisture,
EXPERIMENTAL the contents of Fe, S, and SiO2 were determined.
The measured volume of the leaching solution with
Equipment and chemicals a chosen initial H2SO4 concentration was poured into
The leaching experiments were carried out in a the reactor. The weighted mass (1372 g) of disinteg-
glass reactor, presented in Figure 2, equipped with the rated and sieved ore was joined to the leaching solu-

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tion (2.5 dm3), and the time of leaching was measured. Leaching of oxide-sulfide copper ore
The solution samples were taken in a predetermined The influence of time and H2SO4 concentration on
time intervals for chemical analysis on Cu2+, Fe2+ and the leaching degree of oxide copper, leached out from
Zn2+. After completing the leaching process, solid resi- the ore sample, was determined and presented in
due was filtered, than washed and further processed by Figure 3.
flotation in order to separate and concentrates copper
sulfide minerals from gangue minerals.
Leaching time was in a range of 20 to 240 min,
while the initial H2SO4 concentration in the leaching
solution varied from 0.05 M to 0.3 M. The particle size
was 90% –74 μm; stirring velocity 300 rpm, while the
phase ratio was S:L = 1:2. These three process para-
meters were kept constant in all experiments. All expe-
riments were performed at the room temperature.
The leach residue, that followed each of leach expe-
riments, was conducted in the laboratory flotation cell
of the following characteristics: Denver DR12, 1350
rpm, a small impeller and average air consumption. All
experimental parameters were scaled down, adding
the same flotation agents to the conditioned suspen-
sion, and the proportional quantities as they are used
at the industrial scale. Also, the process time of each Figure 3. Leaching efficiency vs. process time for different
flotation stage was the same as it is on the industrial H2SO4 concentrations in the leaching solution.
scale in the concentrator “Veliki Krivelj”. The aim was
to get an insight how high is the copper recovery from As expected, a copper extraction increases with the
the ore, liberated from oxide minerals, in the leaching process time, tending to achieve a plateau value after
stage. Potassium ethylxanthate (PEX) was used as a approximately two hours for all here used initial con-
flotation reagent, while as an aero promoter AP 3418 centrations of H2SO4 in the leaching solution. The
was used, both as collectors, while as a frothing agent higher concentrations the higher copper leaching per-
DOW 250 was used. After completing both leaching centages were obtained. The highest extraction per-
and flotation processes, chemical analysis of the centage of 73.8% was achieved at the H2SO4 concen-
obtained products – leach solution, concentrate and tration of 0.3 M. One can see that after 180 min inc-
flotation tailing, was carried out and the mass balance rement of leaching degree is almost negligible and the
was evaluated. Finally, the copper distribution along process occurs very slowly. From an engineering point
the both stages was determined. of view, the optimal process time could be chosen
between 1.5 and 3 h, depending on the used initial con-
RESULTS AND DISCUSSION centration of H2SO4. However, increasing the concen-
tration of H2SO4 over 0.2M is not justified due to its
Oxide–sulfide copper ore was sampled from the ore higher consumption in undesired reactions with earth-
body Cerovo C1 (south deposit) and used in this study. -alkali carbonates present in the ore, as well as with
The chemical composition of the ore sample is pre- higher acidity of the leach solution. The leash solution
sented in Table 1. From Table 1, it can be seen that the has to be adjusted to a desired value (pH 2), to be pre-
high copper concentration is in the sample, as well as pared for further processing by ion exchange and/or
the high copper oxide content, while the sulfide copper solvent extraction [15].
concentration is lower. The iron concentration is also The chemical composition of the leach liquor and
high, what may be related to the presence of hematite leach residue, obtained after leaching of the ore
and other iron oxides. Low sulphur content indicates a sample at 120 min and 0.2 M of H2SO4, is presented in
low content of pyrite. Also, the content of impurities in Table 2.
the ore, such as zinc, lead, arsenic and cadmium is low, Obtained copper concentration in the leach solu-
which is very convenient for its processing. tions was usually in the range 1.2–1.7 g/dm3, for other
experimental conditions. Concentration of leached fer-

Table 1. Chemical composition of the ore sample (%)

Cu Cuox Cusulf Fe Zn Pb As Cd S SiO2

0.68 0.45 0.23 4.37 0.016 0.023 0.004 <0.0025 1.33 60.36

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Table 2. Chemical composition of the leach liquor and leach residue

Leach part Cu Cuox Cusulf Fe Zn Moisture

Liquor 1.62 g/l – – 1.39 g/l 7.75 mg/l –
Residue 0.41% 0.176% 0.23% 4.06% 0.013% 22.24%

rous/ferric ions is approximately equal to the copper The chemical composition of the sulfide copper
ions concentration, while the concentration of zinc ions concentrate and the flotation outflow are presented in
was for more than two orders of magnitude less. Table 3. Base concentrate with a 5% of Cu was
obtained, and after a three-stage rinsing the final con-
Flotation of the leach residue
centrate with over 20% of Cu, for smelting process, was
In the residual solid part, after completing the obtained. In the base concentrate total copper reco-
leaching process and phase separation by filtration, very, during the ore processing (leaching and flotation),
lime milk was added in order to adjust the pH value up is approximately 75%.
to 9.5. Than after, the residue was processed by
flotation in order to separate the cooper sulfide mine- Table 3. Chemical composition (%) of the flotation products
rals from the gangue and produce the concentrate. obtained at the content of 30 g/t PEX
Frothing agent D 250 was used as needed while the Flotation product Cutotal Cuox Cusulf
consumption of PEX collector was 40 g/t. Figure 4 pre-
Base concentrate 5.06 0.6 4.46
sents the influence of flotation time on the flotation
Outflow 0.23 0.16 0.07
efficiency of sulfide copper, for five experiments with
the different amount of the PEX collector of 15, 20, 25 Process proposal
30 and 35g/t. The maximum sulfide copper removal in
Based on these, preliminary, experimental results,
the flotation process was 78%, for 20 min of treating,
on an enlarged laboratory scale the schematic flow
and amount of the PEX collector of 30 g/t. Similar
sheet of mixed oxide-sulfide copper ore processing was
results were obtained by Chen et al. [16]. They have
proposed and presented in Figure 5. Also, the copper
studied chalcopyrite recovery from cleaner flotation as
distribution and its recovery, along some particular
a function of collector dosage, and their result showed
stages, are shown.
that with the increase of collector, chalcopyrite reco-
very slightly increase and then decrease. Besides the
valorization of oxide copper, the utilization of sulfide
copper in flotation process increases 2–4% by intro-
ducing the leaching process, because it has a positive
effect on the surface of the sulfide mineral grains.

Figure 4. Influence of the time of treatment on the sulfide

copper flotation efficiency, from leach residue, for five
experiments with the different amount of the PEX collector.
Figure 5. Schematic flow sheet of the oxide-sulfide copper ore
processing.

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CONCLUSION chloride and sulphate-nitrate process options, Hydro-

metallurgy 140 (2013) 163–180.
Copper Mine Cerovo, as well as the other ore [4] Y. Li, N. Kawashima, J. Li, A.P. Chandra, A.R. Gerson, A
bodies in its vicinity, contains significant amount of review of the structure, and fundamental mechanisms
oxide copper minerals (>40%) in the upper layers. Pro- and kinetics of the leaching of chalcopyrite, Adv. Colloid
cessing of such mixed ores by the existing concen- Interface Sci. 197–198 (2013) 1–32.
tration technologies leads to the oxide copper losses. In [5] D. Dreisinger, Copper leaching from primary sulfides:
order to increase an overall degree of cooper utiliz- Options for biological and chemical extraction of cop-
per, Hydrometallurgy 83 (2006) 10–20.
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[6] F. Arslan, G. Bulut, M. Kangal, K. Perek, A. Gul, S.
oxide–sulfide ore followed by flotation of cooper sul-
Gurmen, Studies on leaching of massive rich copper ore
phide minerals from the leach residue was presented. in acidic ferric sulfate solutions, Scand. J. Metall. 33
Maximum copper oxide extraction during the single (2004) 6–14.
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solution and after 180 min. Maximum sulfide copper pyrite leaching by sodium nitrate in sulphuric acid, Hyd-
extraction in the flotation process was 78% for 20 min rometallurgy 95 (2009) 273–279.
and amount of the PEX collector of 30 g/t. Achieved [8] M. Sokić, V. Matković, B. Marković, N. Štrbac, D. Živ-
total copper recovery in the ore leaching and flotation ković, Pasivizacija halkopirita tokom luženja rastvorom
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–165.
Acknowledgement [11] M. Bingöl, M. Canbayoğlu, Dissolution kinetics of
malachite in ammonia/ amonium carbonate leaching,
The presented research was financially supported
Hydrometallurgy 76 (2005) 55–62.
by Ministry of Education, Science and Technological
[12] K.B. Quast, Leaching of atacamite (Cu2(OH)3Cl) using
Development, Republic of Serbia, Grants No. 34023 and dilute sulphuric acid, Miner. Eng. 13 (2000) 1647–1652.
33007. [13] K. Lee, D. Archibald, M.A. Mclean, Flotation of mixed
copper oxide and sulphide minerals with xanthate and
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IZVOD

KISELO LUŽENJE OKSIDNO–SULFIDNE RUDE BAKRA PRE FLOTACIJE – NAČIN ZA POVEĆANJE ISKORIŠĆENJA METALA
Miroslav D. Sokić1, Vladan D. Milošević1, Velizar D. Stanković2, Vladislav Lj. Matković1, Branislav R. Marković1
1
Institut za tehnologiju nuklearnih i drugih mineralnih sirovina, Beograd, Srbija
2
Univerzitet u Beogradu, Tehnički fakultet, Bor, Srbija
(Stručni rad)
Rudnik bakra Bor, lokalitet Cerovo, sadrži više rudnih tela koja sadrže značajnu Ključne reči: Oksidno–sulfidna ruda
količinu oksidnih minerala bakra u svojim površinskim slojevima (> 40%). To su bakra • Luženje • Flotacija • Povećanje
najvećim delom karbonatni minerali, uz nešto kuprita i hrizokole, a od minerala iskorišćenja bakra
gvožđa preovlađuju hematit, limonit i nešto magnetita. Prerada mešanih sulfidno-
oksidnih ruda stvara tehnološke probleme pri flotiranju, smanjujući ionako nizak
stepen iskorišćenja, pa ukupni gubici na bakru dostižu i do 60%. U cilјu povećanja
ukupnog stepena iskorišćenja bakra, prilazani su rezultati luženja oksidnog bakra
iz oksidno-sulfidne rude i flotacije sulfidnog bakra iz čvrstog ostatka luženja.
Maksimalno iskorišćenje oksidnog bakra tokom jednostepenog luženja sa 0,3 M
rastvorom H2SO4 i vremenu od 180 min je 73%, a sulfidnog bakra u procesu
flotacije je 78%, za 20 min i dodatak PEX kolektora od 30 g/t koncentrata. Ukupno
iskorišćenje bakra u procesima luženja i flotacije rude iznosi oko 75%. Koncen-
3
tracija bakra u lužnom rastvoru iznosi 1,2–1,7 g / dm , a sadržaj bakra u koncen-
tratu nakon flotacije je oko 5%. Na osnovu izvršenih eksperimentalnih rezultata
predložena je tehnološka šema za preradu mešovite oksidno-sulfidne rude bakra.

458