Professional Documents
Culture Documents
Investigation of Cu-S intermediate species during electrochemical dissolution
and bioleaching of chalcopyrite concentrate
Weimin Zeng, Guanzhou Qiu, Miao Chen
PII:
DOI:
Reference:
S0304-386X(13)00046-7
doi: 10.1016/j.hydromet.2013.02.009
HYDROM 3683
To appear in:
Hydrometallurgy
Received date:
Revised date:
Accepted date:
21 November 2012
31 January 2013
11 February 2013
Please cite this article as: Zeng, Weimin, Qiu, Guanzhou, Chen, Miao, Investigation
of Cu-S intermediate species during electrochemical dissolution and bioleaching of chalcopyrite concentrate, Hydrometallurgy (2013), doi: 10.1016/j.hydromet.2013.02.009
This is a PDF le of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its nal form. Please note that during the production process
errors may be discovered which could aect the content, and all legal disclaimers that
apply to the journal pertain.
ACCEPTED MANUSCRIPT
Investigation of Cu-S intermediate species during electrochemical
dissolution and bioleaching of chalcopyrite concentrate
IP
School of Minerals Processing and Bioengineering, Central South University, Changsha, China
SC
R
NU
MA
formation process of these species was analysed. It was shown that the oxidation of
chalcopyrite can only produce CuS, but CuxS and Cu2S were mainly formed due to the
reduction reaction of copper ion and sulphur. Furthermore, it was found that the addition of
copper ion could greatly affect the formation of Cu-S intermediate species. Therefore, during
TE
CE
P
was low, it was hard to form Cu-S species in the ore residue. However, as the increase of
copper concentration, the formation of Cu-S intermediate species also increase and could be
detected by X-ray diffraction.
AC
1. Introduction
Chalcopyrite is the most important copper sulphide due to it takes about 70% of
copper resource in the world (Dutrizac 1978). As it has higher lattice energy than
other copper sulfides, the bioleaching of chalcopyrite by mesophilic microorganisms
would lead to slow kinetics and poor extraction and its industrial application is still a
major challenge in the biohydrometallurgy field (Rawlings 2002). Since the end of
last century, more and more researchers in hydrometallurgy field focus on the use of
moderate thermophiles during bioleaching of chalcopyrite. This is mainly due to that
ACCEPTED MANUSCRIPT
using moderate thermophilies compared with mesophiles to bioleach chalcopyrite can
greatly improve the leaching reaction kinetics, avoids excessive chalcopyrite
passivation and finally improve the total copper extraction percentage (Cancho et al.,
IP
SC
R
and copper depending on the leaching parameters (Nicol et al., 1984). The oxidation
of iron ion was simple and its valence was from Fe2+ to Fe3+. The oxidation of copper
was mainly performed among Cu0, Cu+ and Cu2+, while the oxidation of sulphur was
NU
very complex (from S2- to S6+). Due to these, there were several potential intermediate
species during dissolution of chalcopyrite, such as Cu2S, Cu1.92S, Cu1.6S, Cu1.4S and
MA
In the electrochemistry researches, cyclic voltammetry was often used to detect the
intermediate species during dissolution of chalcopyrite (Li et al., 2006; Lopez -Juarez
TE
et al., 2006). Nava and Gonzalez (2006) investigated the oxidation of chalcopyrite by
cyclic voltammetry and found that Cu1-rFe1-sS2-t, Cu1-xFe1-yS2-z, CuS and Fe2(SO4)3
CE
P
(solid) were the oxidation products of chalcopyrite when the applied potential of
cyclic voltammetry was from 0.411 to 0.961V (vs Ag/AgCl). Mikhlin et al. (2004)
found that S0, Cu1-xFe1-yS2-z and CuS were the intermediate species during oxidation
of chalcopyrite when the applied potential was from 0.4 to 0.8V (vs Ag/AgCl). But
AC
Yin et al. (1995) did not find the evidence of S0 on the chalcopyrite surface and they
proposed the formation of a copper sulphide CuS2 when the potential was from 0.4 to
0.5V (vs Ag/AgCl). Furthermore, Hiroyoshi et al. (2002) found that the addition of
copper ion would promote the dissolution of chalcopyrite, so they considered Cu2S
would formed due to the reaction of chalcopyrite with copper ion when the potential
was from 0.4 to 0.5V (vs Ag/AgCl). It can be seen that although there were many
researchers attempted to identify the process involved in the formation of intermediate
species by cyclic voltammetry, many inconsistencies existed compared with their
reports. These may be due to that the reactions of chalcopyrite would change mainly
according to the type of impurities or because of variations in stoichiometry or
depending on the leaching parameters (Shuey 1975; Prosser 1970).
ACCEPTED MANUSCRIPT
Although the Cu-S intermediate species could be analysed successfully by cyclic
voltammetry in this study, it was difficult to use normal XRD or EDX to detect these
species during bioleaching process, which had two possible reasons: 1) the amounts
of these species produced by bioleaching were small; 2) these species were very easy
IP
SC
R
NU
MA
TE
CE
P
The chalcopyrite used in the electrochemistry experiments was obtained from Yushui
Copper Sulphide Mine in Meizhou, Guangdong, China. XRD analysis indicates that
AC
The chalcopyrite used in the bioleaching experiment was also obtained form Yushui
Copper Sulphide Mine. This ore sample was a chalcopyrite concentrate, and the XRD
analysis indicates that the sample mainly includes chalcopyrite (64%), pyrite (17%),
galena (15%), and gangue (4%). This chalcopyrite concentrate had been used for
culture moderate thermophiles for more than 2 years and thus the bioleaching
microorganisms were very adaptive to this concentrate (Zhou et al., 2009).
The chalcopyrite electrodes were made by the pure chalcopyrite. The pure
chalcopyrite was cut with a work surface of approximately 0.2 cm2 and, as far it was
3
ACCEPTED MANUSCRIPT
possible, with no visible imperfections. The specimens were placed on an epoxy resin
and were connected to a copper wire by silver paint on the back face. Preparation of
electrode surface after coarse grinding was completed on 1200-grit silicon carbide
paper. Furthermore, after each experiment, the electrode was taken out from the
IP
electrolyte and then repeats to grind on 1200-grit silicon carbide paper to get a fresh
SC
R
surface.
For the electrochemistry experiment, a three-electrode system was used. The cell
consisted of the chalcopyrite working electrode, a platinum counter electrode and an
NU
MA
were carried out at 48 C and pH 2.0, using a PARSTAT 2273 Potentiostat with
Power-Suite Software of the same company. Cycles were performed from 0 to 800
mV (vs Ag/AgCl), then to -800 mV (vs Ag/AgCl), and back to 0 mV (vs Ag/AgCl).
All tests were carried out at a scan rate of 30 mV/s (vs Ag/AgCl). In the paper, all
TE
potential values are expressed vs. the Ag/AgCl electrode (3M KCl).
CE
P
The mineral surface was characterised by SEM and EDX, which were performed on
an FEI Quanta 400 field emission, environmental scanning electron microscope
(ESEM) under high vacuum conditions. Secondary electron imaging was performed
using beam energies of 15 kV and probe currents of approximately 140 to 145 pA.
AC
Acid Mine Drainages (AMD) samples from several chalcopyrite mines in China were
collected. The samples were mixed and then inoculated into the culture medium for
enrichment of moderate thermophiles. This medium was modified 9K consisted of the
following compounds: (NH4)2SO4 3.0 g/L, Na2SO4 2.1 g/L, MgSO47H2O 0.5 g/L,
K2HPO4 0.05 g/L, KCl 0.1 g/L, Ca(NO3)2 0.01 g/L. And 10 g/L chalcopyrite
concentrate (with diameter of the particles less than 75 m) was added as the energy
source. The moderate thermophiles were enriched at 48C and initial pH of 2.0 in a
stirred tank reactor (shown as 2.4.).
4
ACCEPTED MANUSCRIPT
IP
cylindrical reactor with a mechanic stirrer operating at 500 r/min. About 1950 mL
modified 9K medium was added into the reactor; 50 mL seed culture (no soluble
SC
R
NU
copper sulphate was added into the bioleaching solution to obtain the different
MA
The reactor was placed in a thermostatic bath to keep the constant temperature at 48
0.2C. Sterile air was introduced into the base of the reactor at an approximate rate of
360 mL/min. The experiments were performed at initial pH 2.0. The acid
TE
CE
P
to compensate for evaporation losses. The levels of Cu2+, Fe2+, total iron in solution
were analysed at the end day of bioleaching experiment, while the cell density, pH
value and redox potential was analysed every day. The ore residue bioleached after 10
days was filtered to remove some of the water and then dried under vacuum (for 24
AC
The components of the mineral sample and ore residue were analysed by XRD.
Copper and total iron concentrations in solution were determined by ICP-AES.
Ferrous iron concentration in solution was assayed by titration with potassium
dichromate. Ferric iron concentration is the concentration of total iron minus the
concentration of ferrous irons. The redox potential (or Eh) was measured using a
platinum electrode with an Ag/AgCl reference electrode. Free cells in solution were
observed and counted under an optical microscope.
ACCEPTED MANUSCRIPT
Cyclic voltammetry tests were performed to characterize the oxidation and reduction
reactions during dissolution of chalcopyrite. Fig.1 shows the results of cyclic
voltamperometry of chalcopyrite electrodes in the modified 9K electrolyte. There are
five anodic peaks (A1, A2, A3, A4 and A5) and four cathodic peaks (C1, C2, C3 and
IP
C4). A4 and A5 are the very common anodic peaks during the study of chalcopyrite
electrochemical behaviour, which has been reported by many authors (Biegler and
SC
R
Swift, 1979; Biegler and Horne, 1985; Gomez et al., 1996). There was a selective
dissolution of iron from the crystal lattice of chalcopyrite (peak A4) according to Eq.
(1) and Eq. (2). They reported that a blue layer was observed obviously on the
NU
chalcopyrite surface after this reaction. This was associated with the formation of
covllite shown in Eq. (2). When at potential values more than 0.6 V (vs Ag/AgCl), the
MA
2+
2+
(1)
(2)
(3)
TE
CuS S + Cu + 2e
CE
P
However, Hiroyoshi et al. (2001, 2002) considered that the dissolution of chalcopyrite
during potential 0.40.5 V (vs Ag/AgCl) was related to the production of Cu2S.
Because they found that after addition of 0.1 mol/L copper ion into the electrolyte, the
(4):
AC
peak A4 would increase in a large scale and they proposed the reaction model as Eq.
(4)
Furthermore, Yin et al. (1995) also did not agree with Eq(2), because they did not find
the evidence of S0 on the chalcopyrite surface and they proposed the formation of a
copper sulphide according to Eq(5). It can be seen from these that the oxidation
reaction of chalcopyrite at 0.40.5 V (vs Ag/AgCl) was different according to the
different authors reports. Therefore, it is necessary to investigate which of the Cu-S
intermediate species such as CuS, Cu2S and CuS2 was the oxidation product of
chalcopyrite in the experiment.
ACCEPTED MANUSCRIPT
CuFeS2 CuS2 + Fe2+ + 2e-
(5)
At potential values more than 0.7 V (vs Ag/AgCl), it is reported as the oxidation of
ferrous iron to ferric iron and the oxidation of sulphur to sulphuric acid (Biegler and
IP
Horne, 1985; Nava et al., 2002). But Lopez-Juarez et al. (2006) considered that the
oxidation of ferrous iron should be favoured (Eq. (6)), because a large quantity of S0
SC
R
was still observed on the chalcopyrite surface with scanning electron microscope
(SEM) and energy dispersive x-ray analysis (EDX).
(6)
NU
MA
In the inverse scan, there was series reduction peaks appeared especially from -0.2 to
0.2 V (vs Ag/AgCl) of potential value. These peaks could be attributed to the
reduction of some species produced during the anodic scan like Cu2+ and Fe3+ (Eq. (7),
Fe3+ + e- Fe2+
(7)
(8)
CE
P
TE
Eq. (8) and Eq. (9)), according to Holliday and Richmond (1990).
(9)
When the potential value was lower than -0.3 V (vs Ag/AgCl), peak C3 and C4 were
AC
observed. Arce and Gonzalez (2002) and Biegler and Horne (1985) attributed these
peaks to reduction of covellite and chalcopyrite, respectively (Eq. (10) and Eq. (11)).
Furthermore, Wood et al. (1987) considered that the reduction of covellite would
produce several kinds of Cu-S intermediate species such as Cu1.04S, Cu1.38S, Cu1.67S,
Cu1.83S, Cu1.93S and Cu1.96S.
2CuS + 2H+ + 2e- Cu2S + H2S
(10)
(11)
While Velasquez et al. (2001) recognized there was the reduction of chalcocite in
peak C4 according to Eq. (12). The reverse of this reaction accounts for the process
associated with anodic peak A1 (from -0.4 to -0.3 V, vs Ag/AgCl).
ACCEPTED MANUSCRIPT
Cu2S + H2O + 2e- 2Cu + HS- + OH-
(12)
In the anodic scanning, peaks A1, A2 and A3 were reported not much during the
IP
chalcocite and bornite (Velasquez et al., 2001; Arce and Gonzalez, 2002; Lu et al.,
2000). Furthermore, according to cathodic reaction shown as above, peaks A1 and A2
SC
R
were considered as the oxidation of copper (Eq. (13)) and chalcocite (Eq. (14)).
2Cu + HS- + OH- Cu2S + H2O + 2e-
(13)
(14)
NU
2+
MA
While the reaction about peak A3 was relatively complicated, Arce and Gonzalez
(2002) reported that peak A3 maybe associate with the oxidation of CuxS (1<x<2)
mainly included djurleite and geerite (Eq. (15) and (16)), which were the intermediate
TE
(15)
(16)
CE
P
AC
and sulphur (i.e. S2-, S0) in the chalcopyrite structure. In the anodic scanning (from 0.8 V to 0.8 V, vs Ag/AgCl), the states of copper and sulphur are from Cu0 to Cu2+,
and S2- to S0, respectively, while in the cathodic scanning (from 0.8 V to -0.8 V, vs
Ag/AgCl), the states of copper and sulphur are from Cu2+ to Cu0, and S0 to S2-,
respectively. The potential intermediate species during dissolution of chalcopyrite
mainly include Cu2S, Cu1-xS (1<x<2) and CuS.
3.2 The Cu-S intermediate species during electrochemistry experiments
The detailed oxidation process of chalcopyrite was not clear till now. But there were
some reports recognized that the oxidation of chalcopyrite would remove iron and
then became CuxS (1x2), which were the Cu-S intermediate species (Nava and
Gonzalez, 2006; Mikhlin et al., 2004; Yin et al., 1995; Hiroyoshi et al., 2002). There
8
ACCEPTED MANUSCRIPT
are many kinds of Cu-S intermediate species, such as CuS, Cu2S and Cu1.96S (Lee et
al., 2008). The investigation about their formation process and relations is very
IP
3.2.1 CuS
SC
R
The Fig.1 showed that CuS could be produced by the oxidation of chalcopyrite when
the potential was from 0.4 to 0.5V (vs Ag/AgCl), but it was difficult to detect the
existence of CuS on the electrode surface by XRD or EDX, which was due to that the
NU
production amount was very small and easy to be oxidized at higher potential than
0.5V (vs Ag/AgCl). For confirming the formation of CuS during the potential 0.4
MA
electrode surface.
TE
CE
P
EDX. After the 60s anodic potentiostatic experiment, a blue layer on the electrode
surface could be observed (Fig.2). The EDX result showed that the amount of S and
Cu produced by the oxidation of chalcopyrite were large, but the amount of Fe was
AC
very small. This indicated that the oxidation of chalcopyrite firstly removed Fe and
formed a blue layer which should be the complex substances of CuS and S0.
3.2.2 Cu2S
ACCEPTED MANUSCRIPT
It can be seen from Fig.1 that the oxidation potential of chalcopyrite was much higher
than Cu2S, and this suggested that it is difficult to form Cu2S during the oxidation of
chalcopyrite. For further proving this suggestion, linear votalmmetry of chalcopyrite
electrode was carried out from the different start potential (-0.2V, -0.2V, -0.3V, -0.5V
IP
and -0.75V, vs Ag/AgCl) to the end potential 0.65V (vs Ag/AgCl, the electrodes were
not taken out from the electrolyte after the 1st scan, but continue to be used for the
SC
R
next scan). The experiment principle was that if Cu2S was the product of chalcopyrite
oxidation at potential 0.40.5V (vs Ag/AgCl) (Fig.1), the oxidation peak of Cu2S
NU
would be detected at the next linear scan at potential -0.20V (vs Ag/AgCl).
Otherwise, Cu2S should be the reduction products of copper ion or CuS (at potential
MA
lower than -0.3V, vs Ag/AgCl), or the oxidation production of Cu0 (at potential -0.4
0.3V, vs Ag/AgCl).
It can be seen from Fig.3 that in the 1st scan, the potential range was from -0.2V to
TE
0.65V (vs Ag/AgCl) and the chalcopyrite was oxidized during this scan. After this,
the second scan was carried out and the potential range was same as the 1st one. In the
CE
P
2nd scan, the scan plot was rather similar with the 1st one and the oxidation peak of
Cu2S still did not appear during the potential -0.20 V (vs Ag/AgCl). This indicated
AC
that Cu2S did not form by the chalcopyrite oxidation at the potential 0.40.5 V (vs
Ag/AgCl). When the start potential decreased to -0.3 V (vs Ag/AgCl, in the 3rd scan),
a slightly oxidation peak was observed at potential -0.20 V (vs Ag/AgCl) and this
was due to that Cu2S began to form by the reduction of CuS (which formed as Eq(7)
from -0.2 to 0.2 V, vs Ag/AgCl). In the 4th scan, the decrease of start potential to -0.5
V (vs Ag/AgCl) led the increase of reduction of CuS, and thus the oxidation peak of
Cu2S became more obvious. In the 5th scan, when the start potential decreased to -0.75
V (vs Ag/AgCl), the oxidation peak of Cu2S increased due to another reduction
reaction (Eq. (10)). These concluded that Cu2S here was the reduction production of
CuS or chalcopyrite when the potential was lower than -0.3V (vs Ag/AgCl), but not
the oxidation product of chalcopyrite at potential 0.40.5V (vs Ag/AgCl).
10
ACCEPTED MANUSCRIPT
3.2.3 CuxS (1<x<2)
It is reported that CuxS (1<x<2) includes several intermediate species during
IP
(Nava and Gonzalez, 2006; Lee et al., 2008). Their oxidation peaks in cyclic
SC
R
voltammetry are between the oxidation peak of Cu2S and CuFeS2, generally from
potential 00.4 V (vs Ag/AgCl). However, in this cyclic voltammetry experiment,
there was only one obvious oxidation peak of CuxS (1<x<2) in Fig.1 (peak A3). The
production of CuxS (1<x<2) was reported to have two potential ways: the oxidation of
NU
Cu2S and the reduction of CuS. Therefore, according to Eq.(8) , the addition of copper
ion would promote the production of CuS and thus would benefit the formation of
MA
(1<x<2) during the dissolution of chalcopyrite electrode, copper ion was added into
TE
the electrolyte to promote the formation of CuxS (1<x<2) and the linear voltammetry
of chalcopyrite electrode was carried out. It can be seen from Fig.4 that the addition
CE
P
of copper ion greatly affected the anodic peak current and potential. As the increase of
addition of copper ion concentration, oxidation peak current increased as well and the
AC
When the addition of copper ion was 1 g/L, three oxidation peaks was obtained. One
peak was at about potential 0.1V and considered as the oxidation of CuxS (B1)
(1<x<2) (Eq.(16)). One peak was at potential 0.40.5V (vs Ag/AgCl) and considered
as the oxidation of chalcopyrite (Eq.(2)). The other one peak was at potential 0.7V
(vs Ag/AgCl) and considered as the oxidation of CuS (Eq.(3)). Furthermore, a tight
blue layer could be observed as CuS when the linear voltammetry potential was lower
than 0.6 V (vs Ag/AgCl). The formation of CuS was due to the oxidation of
chalcopyrite and reduction of Cu2+ and S0 (Eq(8)). When the concentration of copper
addition increased to 3 g/L, the oxidation peak of chalcopyrite disappeared, which
maybe due to the CuS layer covered on the chalcopyrite electrode surface and block
the oxidation of chalcopyrite. But then one new oxidation peak was obtained at
potential -0.05V (vs Ag/AgCl). According to Fig.1 and Fig.3 this peak was related
11
ACCEPTED MANUSCRIPT
with the oxidation of Cu2S. When the concentration of addition copper increased to 6
g/L, another new oxidation peak at about potential 0.3V (vs Ag/AgCl) was observed
slightly, this should be the oxidation of another kind of CuxS (B5) (1<x<2). In this
case, four Cu-S intermediate species were obtained, and they were Cu2S (B4), CuxS-1
IP
(B5), CuxS-2 (B1) and CuS (B3). When the concentration of addition copper
increased to 12 g/L, the reduction products increased in a large scale, covered on the
SC
R
chalcopyrite electrode surface, and the anodic peak potential moved positively, thus
the oxidation peak of CuS disappeared below potential 1.0 V (vs Ag/AgCl).
NU
MA
The results of electrochemistry experiment (section 3.2.3) showed that the high
concentration of copper ion would promote the reduction reaction and thus the
amount of reduction products increased, such as Cu2S and CuS. Therefore, during
bioleaching of chalcopyrite, when the concentration of copper was very high, the
TE
intermediate species may be promoted and increase in a large scale. In the experiment,
different concentration of copper ion was added into the bioleaching solution and the
CE
P
AC
of copper ion was 0 g/L (A), copper extraction from chalcopyrite concentrate could
reach 4.32 g/L and the ferric iron concentration was 1.83 g/L. As the increase of
copper addition, the concentration of both ferric iron and ferrous iron decreased. In
addition, the redox potential value and cell density also decreased. Especially when
the addition of copper ion was 36 g/L (E), the ferric iron concentration decreased
remarkably to about 0.94 g/L, which accompanied with a very low redox potential
value (477 mV, vs Ag/AgCl). At high concentration of copper ion, the cell density of
moderate thermophiles for bioleaching of chalcopyrite concentrate was relatively low
and this would lead to the low copper and iron extraction.
The ore residues after bioleached for 10 days were analysed by XRD. It can be seen
from Fig.5 that the high concentration of copper ion in the bioleaching system greatly
affected the component of ore residue. The results showed that during bioleaching of
12
ACCEPTED MANUSCRIPT
chalcopyrite concentrate, the major components of ore residue were chalcopyrite,
pyrite, lead sulphate, jarosite and chalcanthite (the formation of chalcanthite was due
to that copper sulphate crystallized with water when the ore residue was drying under
vacuum). In the experiment A and B, when the addition of copper ion was only 0 and
IP
6 g/L (Table 1), it was hard to find any Cu-S intermediate species by XRD analysis.
But when the addition of copper ion increased to 12 g/L (C), the XRD result showed
SC
R
that Cu2S and CuS were produced in the ore residue. When the addition of copper ion
increased to 24 g/L (D), the other intermediate species like Cu34S32 and Cu1.96S could
be found. However, when the concentration of total copper ion increased to about 36
NU
g/L (E), only Cu2S was detected, but its amount increased in a large scale (data not
shown). This may be due to that when the copper concentration was the highest (E),
MA
the redox potential was only 477mV (vs Ag/AgCl), and then the formation of Cu2S
would be easier than any other intermediate species (Lee et al., 2008; Woods et al.,
1987).
TE
CE
P
copper concentration was relatively low, the reduction reaction in the bioleaching
system was not obvious and Cu-S intermediate species were very difficult to be
detected by XRD. However, when the copper concentration increased, the reduction
reaction would be accelerated and the amount of reduction products increased. There
AC
were several intermediate species formed, but CuS and Cu2S were the majority. When
the copper concentration was very high, such as in the experiment E, the Cu-S species
became simple and only Cu2S was the reduction product, but its amount increased in a
large scale than before.
However, in our previous studies and other authors reports, it was hard to detect CuS intermediate species in the ore residue by XRD during bioleaching of chalcopyrite.
There were two possible reasons: 1) in the previous studies, the ore residue sample
after bioleached was dried in the oven at 50-75C, and in this case the Cu-S
intermediate species were very easy to be oxidized; 2) when the copper concentration
in the solution was low, the amount of Cu-S intermediate species was small and easy
to be dissolved by acid or bioleaching microorganisms, and thus it was hard to detect
them by XRD. These results indicate that during dissolution of chalcopyrite, the
13
ACCEPTED MANUSCRIPT
oxidation and reduction reactions were performed simultaneously, but at many cases,
such as when the copper concentration was low, the oxidation reaction was the
dominant reaction.
IP
4. Conclusions
SC
R
The analysis of the formation process of Cu-S intermediate species indicated that the
oxidation of chalcopyrite can only produce CuS, but not CuxS (1<x<2) and Cu2S, and
the later two species were mainly produced due to the reduction reaction of copper ion
NU
and sulphur. During bioleaching of chalcopyrite, when the copper concentration was
high, the reduction reaction of copper ion and sulphur could be promoted and the Cu-
MA
S intermediate species such as CuS and Cu2S formed largely. However, when the
copper concentration was relatively low (lower than 10 g/L); these intermediate
species amounts were very low and easy to be oxidized, and thus hard to be detected
CE
P
Acknowledgements
TE
by XRD.
This work was supported by the China National Basic Research Program (No.
2010CB630901), the National Natural Science Foundation of China (No. 31200382),
Postdoctoral Science Foundation of Central South University (No. 1332-
AC
References
14
ACCEPTED MANUSCRIPT
Cancho, L., Blzquez, M.L., Ballester, A., Gonzlez, F., Muoz, J.A., 2007. Bioleaching of
chalcopyrite concentrate with moderate thermophilic microorganisms in a continuous
reactor system. Hydrometallurgy 87(3-4), 100-111.
Crundwell, F.K., 1988. The influence of the electronic structure of solids on the anodic
IP
155-190.
SC
R
Dutrizac, J.E, 1978. The kinetics of dissolution of chalcopyrite in ferric ion media.
Metallurgical and Materials Transactions B 9B, 431439.
Gmez, C., Figueroab, M., Muoza, J., Blzqueza, M.L., Ballestera A., 1996.
Electrochemistry of chalcopyrite. Hydrometallurgy 43 (1-3), 331-344.
NU
Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M., 2001. Enhancement of chalcopyrite
leaching by ferrous iron in acidic ferric sulphate solutions. Hydrometallurgy 60(3), 185-
MA
197.
Hiroyoshi, N., Arai, M., Miki, H., Tsunekawa, M., Hirajima, T., 2002. A new reaction model
for the catalytic effect of silver ions on chalcopyrite leaching in sulfuric acid solutions.
TE
Lee, M. S.,
CE
P
AC
Electrochemistry. 38:363369.
Li, H.X., Qiu, G.Z., Hu, Y.H., Cang, D.Q., Wang, D.Z., 2006. Electrochemical
behavior of chalcopyrite in presence of Thiobacillus ferrooxidans. Transactions of
Nonferrous Metals Society of China 16(5), 1240-1245.
Lopez-Juarez, A., Gutierrez-Arenas, N., Rivera-Santillan, R.E., 2006. Electrochemical
behavior of massive chalcopyrite bioleached electrodes in presence of silver at 35C.
Hydrometallurgy 83(1-4), 63-68
Lu, Z.Y., Jeffrey, M.I., Lawson, F., 2000. An electrochemical study of the effect of chloride
ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy 56(2), 145155.
Mikhlin, Y. L., Tomashevich, Y. V., Asanov, I. P., Okotrub, A.V., Varnek, V. A., Vyalikh,
D.V., 2004. Spectroscopic and electrochemical characterization of the surface layers of
chalcopyrite (CuFeS2) reacted in acidic solutions. Applied Surface Science 225(1-4), 395409.
15
ACCEPTED MANUSCRIPT
Nava, J.L., Oropeza, M.T., Gonzalez, I., 2002. Electrochemical characterisation of sulfur
species formed during anodic dissolution of galena concentrate in perchlorate medium at
pH 0. Electrochimica Acta 47(10), 1513-1525.
Nava, D., Gonzlez, I., 2006. Electrochemical characterization of chemical species
the electrochemical treatment
of
in
sulfuric
acid
IP
chalcopyrite
formed during
SC
R
Nicol, M. J., in: Robinson, P.E., Srinivasan, E. S., Wood, R., (Eds), 1984. Processing of the
Cincinatti Ohio meeting of the electrochemical society. The Electrochemical Society.
Pennington, NJ, 1984, p152.
Prosser, A., in: Jones, M.J.(Ed.), proceeding of the ninth commonwealth minning and
NU
Rawlings, D.E., 2002. Heavy metal mining using microbes. Annual review of microbiology
MA
56: 65-91.
Shuey, R.T., 1975. Semiconducting ore minerals. Developments in economic geology series,
Elsevier, Amsterdam, p242.
Velasquez, P., Leinen, D., Pascual, J., Ramos-Barrado, J.R., Cordova, R., Gomez, H.,
Schrebler, R., 2001. XPS, SEM, EDX and EIS study of an electrochemically modified
510(1-2), 20-28.
TE
CE
P
Woods, R., Yoon, R.H., Young, C.A., 1987. Eh-pH diagrams for stable and metastable phases
in the copper-sulfur-water system International Journal of Mineral Processing. 20(12),109-120.
AC
Wu, C.B., Zeng, W.M., Zhou, H.B., Fu, B., Huang, J.F., Qiu, G.Z., Wang, D.Z., 2007.
Bioleaching of chalcopyrite by mixed culture of moderately thermophilic microorganisms.
Journal of Central South University Technology 14, 474-478.
Yin, Q., Kelsall, G.H., Vaughan, D.J., England, K.E.R., 1995. Atmospheric and
electrochemical oxidation of the surface of chalcopyrite (CuFeS2). Geochimica et
Cosmochimica Acta 59(6), 1091-1100.
Zeng, W.M., Qiu, G.Z., Zhou, H.B., Liu, X.D., Chen, M., Chao, W.L., Zhang, C.G., Peng
J.H., 2010. Characterization of extracellular polymeric substances extracted during
16
ACCEPTED MANUSCRIPT
Zhou, H.B., Zeng, W.M., Yang, Z.F., Xie, Y.J., Qiu, G.Z., 2009. Bioleaching of chalcopyrite
concentrate by a moderately thermophilic culture in a stirred tank reactor. Bioresource
AC
CE
P
TE
MA
NU
SC
R
IP
17
ACCEPTED MANUSCRIPT
Table 1 The bioleaching parameters during bioleaching of chalcopyrite concentrate
after addition of different concentration of copper ion in the stirred tank reactor after
10 days. A: without addition of copper ion, B: addition of 6 g/L copper ion, C:
addition of 12 g/L copper ion, D: addition of 24 g/L copper ion, E: addition of 36 g/L
Total copper
Ferric iron
Ferrous iron
(g/L)
(g/L)
(mg /L)
pH
Redox
Cell density
value
potential
(108cells/mL)
SC
R
Experiments
IP
copper ion.
(mV)
4.32
1.83
151
1.66
584
7.9
10.28
1.82
144
1.67
582
7.8
16.04
1.79
148
1.67
579
7.2
27.73
1.72
143
1.7
562
5.6
37.58
0.94
84
1.84
477
0.4
AC
CE
P
TE
MA
NU
18
A5
A4
IP
A3
SC
R
3.5
3.0
2.5
2.0
1.5
A2
1.0
0.5
A1
0.0
-0.5
-1.0
C2
-1.5
-2.0
C3
-2.5
-3.0
C4
-3.5
-1.0 -0.8 -0.6 -0.4 -0.2
C1
NU
I / mA
ACCEPTED MANUSCRIPT
0.0
0.2
0.4
0.6
0.8
1.0
MA
E / V vs Ag/AgCl
AC
CE
P
TE
19
ACCEPTED MANUSCRIPT
B
SC
R
IP
MA
NU
Fig.2. the formation of CuS and S0 on the electrode surface during dissolution of chalcopyrite
when the constant potential pulse was 0.45 V in the electrochemistry experiments. A: the
TE
AC
CE
P
20
TE
MA
NU
SC
R
IP
ACCEPTED MANUSCRIPT
E/V vs Ag/AgCl
Fig.3. The linear voltammetry of chalcopyrite from different start potential (-0.2V, -0.2V, -
CE
P
0.3V, -0.5V and -0.75V) to the end potential 0.65V in the modified 9K medium at sweep rate
AC
21
ACCEPTED MANUSCRIPT
2.0
0.25
1 g/L
3 g/L
6 g/L
12 g/L
B3
1 g/L
0.20
1.5
B2
B1
0.10
0.05
B1
B5
Current / A
0.15
0.0
0.2
0.4
0.6
0.8
IP
-0.2
1.0
E/ V
B1
B3
B5
B4
0.5
B4
B4
B3
B1
B1
B2
0.0
0.2
B3
NU
0.0
-0.2
SC
R
Current / A
0.00
0.4
0.6
0.8
1.0
MA
E / V vs Ag/AgCl
Fig.4. the effect of different concentration of Cu2+ (1, 3, 6, 12 g/L) on the electrochemistry
behaviour of chalcopyrite electrode in the modified 9K medium at sweep rate = 30 mV/s.
AC
CE
P
TE
22
ACCEPTED MANUSCRIPT
NU
SC
R
IP
AC
CE
P
TE
MA
23