International Journal of Mining Science and Technology 23 (2013) 4146

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International Journal of Mining Science and Technology

journal homepage: www.elsevier.com/locate/ijmst

Improvement of coppermolybdenum ore beneciation using a combined

otation and biohydrometallurgy method
Irina Pestryak a,, Valery Morozov a, Jamsranjav Baatarhuu b
a
Chemistry Department, Moscow Mining University, Moscow 119991, Russia
b
Erdenet Mining Corporation, Erdenet, Orkhon Aimag 213900, Mongolia

a r t i c l e i n f o a b s t r a c t

Article history: The authors present the results of analysis of material composition and experimental investigations of
Received 4 May 2012 acid and biohydrometallurgical leaching of middlings on grain size, pH level, leaching process duration,
Received in revised form 2 June 2012 temperature and slurry density. The rational parameters of otation and acid-bacterial leaching of mid-
Accepted 2 July 2012
dlings providing an efcient release of valuable components from mineral complexes and recovery to o-
Available online 6 February 2013
tation concentrate and leaching solution have been determined. A combined owsheet and a
beneciation process for bulk otation middlings of coppermolybdenum ore have been suggested,
Keywords:
which include middlings grinding, sulde minerals otation, bacterial leaching of sulde otation tail-
Coppermolybdenum ore
Beneciation of middlings
ings, liquid-phase extraction of dissolved copper and electrolysis of re-extraction eluates. The suggested
Flotation combined method of cleaning of middlings of coppermolybdenum ores beneciation provides the total
Bioleaching copper recovery increase by 0.8% with a reduction of the cost price of saleable material by 0.5%.
Combined owsheet 2013 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

1. Introduction sizing, regrinding and otation allows to produce saleable concen-

A signicant part of copper and molybdenum losses (about 15%)
during coppermolybdenum ores beneciation is associated with
the middlings cycle where mineral fractions with a comparatively
high content of valuable components and low oatability are accu-
mulated [1,2]. Middlings fractions are considered as the most suit-
able product for the application of a combined otation and
biohydrometallurgy method due to the possibility to recover valu-
able components both as highly-oatable loose grains and as liber-
ated and locked aggregates of valuable minerals with pyrite and
minerals of enclosing rock which are not recovered by otation [3].
2. Study of composition and properties of otation middlings
The middlings from bulk otation at the processing plant of
Erdenet Mining Corporation (Fig. 1) contain the otation under-
ow of cleaner otation and froth product of recleaner otation.
The fractions of intermediate oatability are accumulated in the
middlings, as it has been shown that they are characterized by low-
er otation rate constants [4]. According to a standard owsheet,
the middlings are recirculated which results in the accumulation
of fractions of intermediate oatability and overloading of otation
circuit. Cleaning of middlings in a separate cycle which includes
Corresponding author. Tel.: +7 4992309421.
E-mail address: dchmggu@freemail.ru (I. Pestryak).
trate and nal tailings from ores of simple mineral composition.
This objective has not been achieved in the beneciation of complex
coppermolybdenum ores at the processing plant of Erdenet
Mining Corporation [5].
The results of mineralogical analysis of raw ore, middlings and
nal tailings show that the middlings accumulate secondary sul-
de and oxidized copper minerals as well as the aggregates of
copper minerals with pyrite. The mass fraction of secondary sulde
copper minerals in the middlings increases by 1060% compared to
raw ore. The mass fraction of oxidized copper minerals is 5 times
higher. The total mass fraction of sulde minerals in the middlings
is 2.5 times higher than that in raw ore and 3.4 times higher than
that in nal tailings. The higher content of oxidized and secondary
sulde copper minerals allows for and justies the application of
acid leaching.
Higher sulde content of middlings favors efcient activity of
bacteria such as Thiobacillus ferrooxidans and Thiobacillus thiooxi-
dans [68].
Another particular characteristic of the investigated middlings
is 4-time reduction of mass fraction of carbonate rock-forming
minerals (Table 1), which also favors the use of acid-bacterial
leaching [9].
The quantitative mineralogical analysis was performed using an
optical microscope Axioplan (Carl Zeiss Jena, Germany) with semi-
automatic system of image analysis (MOP Videoplan) on transpar-
ent polished sections of products. On average at least 1000
measurements of grains in each product were made.

2095-2686/$ - see front matter 2013 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
http://dx.doi.org/10.1016/j.ijmst.2013.01.007
42 I. Pestryak et al. / International Journal of Mining Science and Technology 23 (2013) 4146

Feed Copper-glance and covellite form aggregates, the intergrowths

with chalcopyrite make up 2% and intergrowths with pyrite make
up 5.4%. The intergrowths with nonmetallic minerals make up
Bulk rougher flotation about 19.6% (Table 2).
Molybdenite occurs as liberated and locked aggregates mainly
with nonmetallic minerals, and the size of its liberated grains in
First cleaner flotation First control flotation aggregates is almost at all times over 40 lm. Less often it occurs
as poor intergrowths with other suldes.
Pyrite mainly occurs as liberated grains and to a limited extent
Second cleaner flotation Second control flotation
it intergrows with copper suldes (4.7%) and nonmetallic minerals
(4.7%).
The microscopic analysis shows that at 7275% of 74 lm par-
Middlings ticles the major part of copper minerals (73.14%) is in a free state.
Copper-molybdenum Final tailings However, the recovery level of these minerals by otation is not
concentrate
sufcient (6275%). The results of microscopic examination show
Fig. 1. Flowsheet of bulk coppermolybdenum otation at processing plant of that the other reason of low recovery of copper minerals, namely,
Erdenet Mining Corporation. secondary suldes, is formation of surface lms on these minerals
and a signicant slimes content ( 10 lm size) that are difcult to
recover by otation [2].
Table 1 A signicant part of copper mineral is found in liberated (26.3%)
Mineral composition of ore and main beneciation products. and locked (2.24%) aggregates that makes it impossible to produce
No. Mineral Mineral content (%)
a rich concentrate and leads to important copper loss in nal
tailings.
Middlings Ore Final
(absolute/ tailing
Thus, the investigations performed have demonstrated that the
relative) middlings from bulk otation cycle of coppermolybdenum ores
1 Chalcosine 0.060/12.900 0.04 0.017
are characterized by higher content of secondary sulde and oxi-
2 Covellite 0.030/6.400 0.02 0.008 dized copper minerals (57.1%), higher content of pyrite (18.3%),
3 Copper pyrite 0.20/42.900 0.86 0.100 lower content of carbonaceous rock-forming minerals (up to
4 Bornite 0.060/12.900 0.05 0.020 0.8%) and a signicant part of aggregates (up to 28%), including
5 Tennantite 0.016/3.500 0.01 0.003
locked intergrowths with pyrite. It makes it possible to recom-
6 Oxidized copper minerals 0.100/21.400 0.02 0.017
7 Molybdenite 0.015 0.03 0.012 mend using of combined otationbiohydrometllurgical process
8 Piryte 18.300 3.70 3.500 for coppermolybdenum ore beneciation that allows to efciently
9 Oxidized ferrous minerals 0.300 0.30 0.330 recover mineral fractions with essentially different physicochemi-
10 Quartz 24.400 35.70 36.600 cal properties [10,11].
11 Feldspar 41.500 45.00 45.500
12 Sericite 15.000 11.50 10.900
13 Calcite, magnesite, 0.800 2.80 3.000 3. Experimental studies of leaching process of bulk otation
dolomite middlings
Total 100.000 100.00 100.000

The experimental studies were carried out in a hydrometallur-

The quantitative mineralogical analysis of middlings otation
tailings demonstrated that a great part of chalcopyrite (65%) occurs
in the form of aggregates (Table 2). Chalcopyrite mainly intergrows
with nonmetallic minerals (12.7% abs.) and to a lesser degree with
pyrite (5.8%) and secondary copper suldes (2.5%).
gical laboratory of the Technological Institute n. a. Sh. Otgonbileg
afliated with Erdenet Joint Venture. Leaching was performed
under conditions of natural (unforced) aeration. To prepare the
slurry, the raw product with 7275% of 74 lm fraction was
mixed with acid or regenerated bacterial solution at a specied so-
lid-to-liquid (S:L) ratio. During the test the specied pH and tem-

Table 2
Mineral composition of bulk otation feed.

No. Mineral Size distribution (%)

In the product In grain-size classes (lm)
010 1044 44100 100300
Chalcopyrite 1 Liberated grains 65.0 90.9 60.4 37.6 21.4
2 Intergrowths with secondary copper suldes 2.5 0.7 3.2 6.0 8.1
3 Intergrowths with pyrite, liberated 4.0 0.5 6.5 8.5 10.2
4 Intergrowths with pyrite, locked 1.8 0.3 1.5 2.6 5.6
5 Intergrowths with rock-forming minerals, liberated 12.7 1.2 10.9 15.3 19.4
6 Intergrowths with rock-forming minerals, locked 4.0 0.7 3.9 5.3 7.4
Secondary copper suldes 7 Liberated grains 62.5 88.9 58.4 38.6 20.1
8 Intergrowths with chalcopyrite 2.0 0.8 3.0 5.1 7.6
9 Intergrowths with pyrite, liberated 3.5 0.4 6.2 7.5 8.8
10 Intergrowths with pyrite, locked 1.9 0.3 1.6 2.7 5.9
11 Intergrowths with rock-forming minerals, liberated 14.8 2.0 12.9 18.8 24.4
12 Intergrowths with rock-forming minerals, locked 4.8 0.8 4.6 6.3 8.4
Pyrite 13 Liberated grains 90.6 94.4 77.7 58.3 37.04
14 Intergrowths with copper sulde minerals 4.7 0.2 4.1 11.2 22.3
15 Intergrowths with nonmetallic minerals 4.7 0.3 4.2 11.3 21.0
 I. Pestryak et al. / International Journal of Mining Science and Technology 23 (2013) 4146 43

perature were maintained and chemical and phase analyses of so-
lid and liquid phases were made separately. At the initial stage,
nutritive salts were added to the process to maintain the biomass.
The use of effective biomass and provision of the optimal condi-
tions for its growth at the beginning of the process allowed to
achieve cells concentration of 2.5  109 cell/mL.
The following leaching methods were tested: leaching by sulfu-
ric acid alone and by sulfuric acid after bacterial oxidation, leach-
ing by ammonium sulfate alone and by ammonium sulfate after
bacterial oxidation, combined bacterial and sulfuric acid leaching
(Fig. 2). Prior to leaching the middlings were additionally ground
to 75% of 74 lm particles and subjected to rougher and recleaner
bulk otation of suldes at pH 10.310.4.
A comparative study of the results of leaching of middlings o-
tation tailings demonstrated that the investigated processes should
be arranged in the following order according to the rate of copper
transfer into solution and nal recovery of copper into solution
(Fig. 3a). The analysis of medium alkalinity showed that bacterial
leaching is accompanied by acidication of solutions that prevents
precipitation of iron ions as hydroxides and enhances leaching
(Fig. 3b). The pH drift to the acid direction also increases nal cop-
per recovery into solution.
The best results of leaching are obtained at a temperature of
3235 C and slurry density of 50% (S:L ratio is 1:1, Fig. 4a). It
should be noted that in acid-bacterial leaching the best results
are obtained at relatively lower temperature values than in acid
leaching (Fig. 4b) that allows to recommend the use of acid-bacte-
rial leaching at processing plants operated in a cold climate.
4. Experimental studies of regrinding and otation processes
Grinding and otation characteristics are an important factor
determining the overall efciency of a combined method. The o-
tation characteristics of chalcopyrite and pyrite fractions were se-
lected as criteria for evaluation of otation efciency. The

Sample Sample

Desliming Desliming
Biomass Acid
pH =1.7 - 2.2 pH =2.1 - 2.5
Biooxidation Acid leaching

Decantation Decantation

Copper -bearing Leaching Copper -bearing Leaching

solution cake solution cake
(a) Acid leaching with preliminary biooxidation (b) Direct acid leaching

Sample Sample
Ammonium
Desliming sulphate Desliming
Acid
pH =5.6 - 6.5 Biomass pH =2.1 - 2.2 Biomass
Bioleaching Acid bioleaching

Decantation Decantation

Copper -bearing Leaching Copper -bearing Leaching

solution cake solution cake
(c) Bacterial-ammonium leaching (d) Combined acid and bacterial leaching

Fig. 2. Schemes of leaching tests of middlings from bulk otation cycle.

a 70 b 7

60 6
pH level of the medium
Copper recovery (%)

50 5

40 Ammonium leaching 4
Bacterial and ammonium
30 leaching 3
Bacterial oxidation
20 Sulfuric acid leaching 2
10 Acid-bacterial leaching 1

0 1 2 3 4 0 1 2 3 4
Duration (day) Duration (day)

Fig. 3. Copper recovery into solution and pH level variation as a function of test duration.
44 I. Pestryak et al. / International Journal of Mining Science and Technology 23 (2013) 4146

68 70

Recovery into solution (%)

Recovery into solution (%) 66 65
64
60
62
55
60 Acid-bacterial
Acid (at acid consumption 50
58 of 15 g/kg and leaching
time of 4 days) 45
56

54 40
20 30 40 50 60 20 30 40 50 60
(a) Slurry density (%) (b)Slurry temperature ( )

Fig. 4. Copper recovery into solution during leaching as a function of slurry density and temperature.

80 80
75 75
Recovery into concentrate (%)

Recovery into concentrate (%)

70 70
65 65

60 Chalcopyrite fraction 60
55 Pyrite fraction 55
50 50
45 45
40 40
10 10.2 10.4 10.6 10.8 11 65 70 75 80 85
pH of slurry Content of -74 m fraction (%)

Fig. 5. Mineral fractions recovery into otation concentrate as a function of the slurry pH and middlings particle size.

conditions of efcient otation of chalcopyrite fraction correspond
to complete otation of other copper sulde minerals [12,13].
The inhibition of pyrite fraction otation allows obtaining bulk
coppermolybdenum concentrate of high quality. In addition, it in-
creases the total sulde content in the feed of bacterial leaching
[14].
The analysis of results of otation tests allows to recommend
using of pH range from 10.2 to 10.5 at 7275% of 74 lm particles
as boundary conditions that assure efcient depth of middlings
cleaning by otation followed by biohydrometallurgical treatment
of otation tailings. As it can be seen from Fig. 5, the optimal selec-
tivity of chalcopyrite and pyrite otation is assured in this range:
chalcopyrite is recovered to concentrate, and pyrite is accumulated
in otation tailings.
5. Larger scale studies of combined method
The further stage of the study was the selection and justication
of acid-bacterial leaching owsheet. Testing was performed at a
larger laboratory facility allowing to maintain the specied tem-
perature and other process variables during leaching.
Testing started by mixing the slurry with bacterial nutritive
medium composed of iron vitriol solution in a concentration of
3 g/L and the culture of T. ferrooxidans. During leaching continuous
regeneration of Fe3+ by the biomass was observed, and its content
was maintained at the maximum level. Test duration was up to
168 h.
During the tests, the specied solid-to-liquid ratio, pH level of
medium and temperature were maintained. The chemical and
phase analysis of solid and liquid phases were made separately.
Nutritive salts were added to the process to maintain the biomass.
The use of the biomass and provision of the optimal conditions for
its growth allowed to maintain cells concentration at 0.9  109
2.1  109 cell/mL.
The owsheet of biohydrometallurgical treatment of middlings
includes the agitation leaching after which the copper-enriched
solution is sent to a collecting pond and the copper-depleted
underow is sent to a tailing dump. The copper-enriched solution
with copper content of 1.6 g/L collected in the pond is sent to two-
stage extraction. After the second stage of extraction a rich eluate
with copper content of 2.1 g/L is obtained and sent to re-extraction.
A rich sulfuric acid solution with sulfuric acid content of 178 g/L ta-
ken from the nite electrolysis baths is used as re-extractant.
The re-extraction eluate is sent to electrolysis. As a result of
electrolysis primary cathodes with copper mass fraction of
99.95% are produced. If it appears to be nancially reasonable,
these cathodes can be rened by electrolysis to produce high-qual-
ity cathodes with copper mass fraction of 9999.
Testing results (Table 3) conrmed the results of laboratory
investigations and demonstrated that the best results were
achieved using acid-bacterial leaching with simultaneous feeding
of biomass and acid at a slurry density of 50% (solid-to-liquid ra-
tio = 1:1) and at a higher temperature (3236 C). This method
was applied during further testing aimed at the selection and jus-
tication of a combined owsheet of middlings fraction treatment.
When choosing the principal owsheet for otationbiohydro-
metallurgical treatment of middlings three options were consid-
ered. The rst owsheet (Fig. 6a) provided for leaching of tailings
from middlings otation after additional grinding of underow.
The material in which 72% of particles were of 74 lm size was
sent to otation, and the product in which 67% of particles were
 I. Pestryak et al. / International Journal of Mining Science and Technology 23 (2013) 4146 45

Table 3
Results of middlings tailings leaching conditions.

Temperature No. Leaching condition SL ratio Initial pH of solution Final pH of solution Copper recovery
(C) to solution (%)
3236 1 Acid-bacterial with simultaneous feeding of biomass and acid 1:3 2.41 2.20 63.1
1:2 2.32 2.15 65.2
1:1 2.23 2.12 65.4
2 Acid-bacterial with preliminary feeding of biomass 1:3 2.32 2.92 62.1
1:2 2.21 2.64 64.1
1:1 2.02 2.50 65.0
3 Sulfuric acid 1:3 2.44 2.95 58.1
1:2 2.30 2.82 60.2
1:1 2.18 2.73 61.4
2024 1 Acid-bacterial with simultaneous feeding of biomass and acid 1:3 2.36 2.18 54.1
1:2 2.28 2.14 56.2
1:1 2.18 2.10 57.4
2 Acid-bacterial with preliminary feeding of biomass 1:3 2.28 2.88 51.1
1:2 2.20 2.61 52.2
1:1 2.00 2.45 53.4
3 Sulfuric acid 1:3 2.41 2.91 50.1
1:2 2.30 2.80 52.2
1:1 2.18 2.71 53.4

Middlings Middlings Middlings

Sizing
Sizing Sizing

Flotation M Flotation
Flotation Thickening

Bulk concentrate Desliming Bulk concentrate Thickening

Bulk concentrate Leaching
Leaching Leaching
Extraction-elution-
Extraction -elution- electrolysis Extraction -elution-
electrolysis electrolysis

Cathode copper Waste product Waste product Cathode copper Cathode copper Waste product

(a) With additional grinding of underflow (b) With leaching of underflow (c) With leaching of underflow fraction and
fraction of middlings fraction of middlings flotation tailings of slime fraction of middlings

Fig. 6. Flowsheets of combined otationhydrometallurgical treatment of middlings from bulk otation cycle.

of 74 lm size was sent to leaching. In the second owsheet
(Fig. 6b) the classication underow which contained 60.5% of par-
ticles of 74 lm size was sent to leaching.
The third scheme (Fig. 6c) assumed direction of the leaching of
the mixed product, including oatation tailings and gravel fraction
operations of classication, with 62.5% of size class 74 lm.
While selecting a owsheet for otation and biohydrometallur-
gical treatment of middlings three options were considered. The
rst option provided for leaching of tailings of middlings otation
after regrinding of underow. The material containing 72% of
74 lm particles was cleaned by otation, and the product con-
taining 67% of 74 lm particles was treated by leaching. The sec-
ond option provided for leaching of underow containing 60.5% of
74 lm particles.
The third owsheet included leaching of mixed product com-
posed of otation tailings and sizing underow containing 62.5%
of 74 lm particles.
The comparison of efciency of these options was made at a pi-
lot scale using the acid-bacterial leaching method (Table 4). The
tests demonstrated that the best results can be achieved using
the owsheet with regrinding of middlings underow and leaching
of tailings of middlings otation.
The results of the mineralogical analysis of copper minerals in
the feed and nal tailings of leaching showed that the recovery

Table 4
Technical and economic indices of a combined otation and biohydrometallurgical method of coppermolybdenum ores beneciation (%).

Ore dressing owsheet characteristics Recovery into saleable otation Recovery by leaching and Total recovery
concentrates electrolysis
Cu Mo Cu Mo Cu Mo
Flotation owsheet (original) 84.22 44.50 84.22 44.50
Combined owsheet with middlings regrinding and leaching of otation tailings 84.02 44.30 1.40 0.20 85.42 44.50
Combined owsheet with underow leaching 83.45 44.10 1.60 0.25 85.05 44.35
Combined owsheet with leaching of underow and otation tailings 83.60 44.05 1.53 0.22 85.13 44.27
46 I. Pestryak et al. / International Journal of Mining Science and Technology 23 (2013) 4146
Raw feed
Bulk rougher flotation
First and second
First cleaner flotation recleaner flotation
Second cleaner flotation Sizing
Middlings flotation M
Cleaner middlings Recleaner middlings
flotation flotation
Desliming
Concentrate
Bioleaching
Decantation
Copper bearing solution treated
by sorptionor extraction Tailings
Fig. 7. Flowsheet of coppermolybdenum ore beneciation using a combined
otation and biohydrometallurgical method.
of grains with transformed surface and locked aggregates of sul-
de, secondary and oxidized copper minerals by leaching could
be 7085% [15].
6. Pilot-scale testing of combined method
Pilot-scale testing was performed at an enlarged otation and
hydrometallurgy plant of Erdenet Joint Venture. The owsheet
of combined treatment of bulk otation middlings shown in
Fig. 7 includes sizing and regrinding of middlings to 7275% of
74 lm particles, rough, cleaner and recleaner otation of copper
and molybdenum suldes, desliming and biohydrometallurgical
treatment of otation tailings at simultaneous feeding of biomass
and acid.
Flotation was performed at a relatively high pH levels (10.2
10.5) exceeding the pH value in control experiments, without the
application of bioleaching technology (9.810.1). The underow
of middlings recleaner otation was thickened during desliming
to a density of 50% of solid (solid-to-liquid ratio = 1:1) that pro-
vided the minimization of capacity of equipment used and reduc-
tion in sulfuric acid consumption.
Acid-bacterial leaching was performed at a temperature of 32
35 C for 35 days that assured the maximum possible oxidation of
copper-pyrite aggregates (by 8590%) and transition of copper
minerals as ions into solution. The pH level during leaching was
maintained in the range of pH 2.12.3 that provided favorable con-
ditions for bacterial activity and chemical leaching.
After leaching, the ltered liquid phase was sent to liquid-phase
extraction, acid re-extraction and eluate electrolysis that provided
98.599% copper recovery to the nal product, that is, the cathodes
[16].
The results of pilot-scale testing demonstrated that the sug-
gested combined method of cleaning of middlings of copper
molybdenum ores beneciation provides the total copper recovery
increase by 0.8% with a reduction of the cost price of saleable mate-
rial by 0.5%. The method is being implemented at the plant of the
MongolianRussian Erdenet Joint Venture. The benets from the
implementation of a combined method of coppermolybdenum
ore beneciation are estimated at 12.2 mln of rub/year.
7. Conclusions
It is shown that the middlings from bulk otation cycle of cop-
permolybdenum ores are characterized by higher content of sec-
ondary sulde and oxidized copper minerals, higher content of
pyrite, lower content of carbonaceous rock-forming minerals and
a signicant part of aggregates, including locked intergrowths with
pyrite. It is recommended to use the combined otationbiohydro-
metallurgical process for coppermolybdenum ore beneciation
for efciently recover mineral fractions with essentially different
physicochemical properties. A combined method of cleaning of
coppermolybdenum ore beneciation middlings which includes
ore grinding to 7275% of 74 lm size, otation of sulde miner-
als at pH of 10.310.5 and bacterial leaching of sulde otation
tailings at pH from 2.1 to 2.3 at a temperature of 3235 C during
3 days and guarantees the total copper recovery increase by 0.8%
with reduction of cost price of saleable material by 0.5% has been
developed. The method and the owsheet of coppermolybdenum
ore beneciation are being implemented at the plant of the Mon-
golianRussian Joint Venture Erdenet Mining Corporation.
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