Review
Department of Mining & Metallurgical Engineering, Amirkabir University of Technology, Hafez St., Tehran, Iran
School of Mining Engineering, College of Engineering, University of Tehran, Tehran, Iran
A R T I C L E I N F O
Article history:
Received 29 October 2016
Received in revised form 10 December 2016
Accepted 18 December 2016
Available online xxx
Keywords:
Mineral processing
Pyrite
Flotation
Electrochemical potential
Surface chemistry
A B S T R A C T
Metal suldes are usually semiconductor and cause electrochemical reactions. This phenomenon plays
an important role in sulde otation. Pyrite as the most abundant sulde mineral is often associated with
valuable sulde minerals, coal and gold. It is very important to study its electrochemical behavior in the
otation process. This review focuses on researches carried out over the past several decades that have
studied electrochemical processes associated with pyrite occurring during otation. The mechanism of
processes such as oxidation, activation, depression, and interactions of activated and non-activated
surfaces with collectors as well as factors affecting them are described. Moreover, the effect of
electrochemical conditions during grinding on the otation process is also discussed. It has been found
that moderately oxidizing conditions are favorable for collector-less otation of pyrite while strongly
reducing or oxidizing potentials lead to its depression. Increasing the electrochemical potential not only
has a deleterious effect on the activation of pyrite by copper, but also facilitates its depression by
depressants. In the case of the adsorption of xanthate whether on activated or non-activated surfaces, a
great increase or decrease in the potential has adverse effects and it is necessary to optimize the
electrochemical conditions. Various factors such as pH, solid percentage, particle size distribution,
otation time, type and concentration of reagents and oxygen content as well as grinding conditions can
affect the intensity of these electrochemical interactions. It is proposed that further researches using
advanced chemical analysis techniques are needed to understand the electrochemical processes involved
in otation systems.
2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidation of pyrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of oxidation on pyrite oatability . . . . . . . . . . . . . . . . .
Effect of pyrite origin on the oatability due to oxidation
Effect of oxidation on pyrite depression . . . . . . . . . . . . . . . . .
Effect of pH on pyrite depression . . . . . . . . . . . . . . . . . . .
Effect of dissolved oxygen content on pyrite depression .
Removal of depressing effect of oxidation . . . . . . . . . . . .
Pyrite activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pyrite activation by copper . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pyrite activation by lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Collector adsorption on pyrite surface . . . . . . . . . . . . . . . . . . . . . .
Collector adsorption on non-activated surface . . . . . . . . . . . .
....
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* Corresponding author.
E-mail addresses: hoseinn_moslemi@yahoo.com, h.moslemi@aut.ac.ir
(H. Moslemi), gharabaghi@ut.ac.ir, m.gharabaghi@gmail.com (M. Gharabaghi).
http://dx.doi.org/10.1016/j.jiec.2016.12.012
1226-086X/ 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
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G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
Introduction
Demand for base metals has been increasing continuously due
to the development of industries worldwide; therefore, it is
necessary to improve processing of sulde ores which are the
major sources of base metals. Pyrite (FeS2, iron disulde), which is
the most common sulde mineral on the Earth [15], is the main
gangue of sulde ores [16]. The pyrite presence in the concentrate
of valuable minerals leads to a decrease in grade and an increase in
sulfur and iron contamination resulting in an increase in smelting
costs [1,4,7]. Moreover, if pyrite contains potentially hazardous
elements such as arsenic, hazardous dusts and fumes will be
produced during the smelting process [812]. Pyrite is also found
in coal deposits [13]. The burning process of coal containing a high
content of pyrite leads to the atmospheric emission of sulfur oxides
[1419] which are the major cause of acid rain [1421]. The
primary aim of the processing of sulde ores and coal is to remove
the pyrite content [22]. However, occasionally, pyrite may contain
signicant amounts of valuable metals such as gold [2330], and
thus, it may be concentrated to gain these valuable metals [23].
Froth otation is widely used in mineral industry to selectively
separate minerals from each other [31]. Annually, more than
109 tons of various materials are processed by this method
worldwide [32]. The process strongly depends on the physicochemical surface properties of minerals [14,33] and is controlled by
modifying these properties through addition of otation reagents
[14].
Since most metal suldes are semiconductor [3437], various
electrochemical reactions occur in the sulde mineral otation
system. Extensive researches have shown that there is a strong
correlation between otation of pyrite and electrochemical
reactions [38]. Electrochemical mechanisms are often known to
be responsible for various phenomena, occurring in a otation
system containing pyrite, such as changes in pyrite surface
chemistry due to oxidation, the interaction of pyrite with other
components, adsorption of collector and precipitation of metals on
the surface [39]. The most important factor which affects
electrochemical processes is the electrochemical potential of
mineral/solution interface [40,41]. This potential is a mixed
potential in which the rates of anodic and cathodic reactions,
occurring on the mineral surface, are exactly equal to each other
[40,4244]. The electrochemical potential controls formation of
not only surface species responsible for the otation of the mineral
(such as polysuldes, elemental sulfur and xanthate), but also
surface species responsible for its depression (such as ferric oxide/
hydroxide and sulfate) [45].
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(1)
(2)
(3)
(4)
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
(5)
(6)
(7)
Fig. 1. Eh-pH diagram for FeS2H2O system at 25 C and for 105 M dissolved
species [84].
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
Table 1
Relationship between pulp electrochemical potential and pyrite otation recovery
in collector-less conditions.
Pulp potential
(mV vs. SHE)
Pulp pH
Reference
Increased
Was observed
Maximum
Increased
Maximum
Was observed
Maximum
[89]
[90]
[49]
[89]
[54]
[90]
[91]
Alkaline
Acidic
0
100 to 800
400
100
280
300 to 400
200 to 250
Recovery
4.6
4.6
4.67
9.2
9.2
9.2
9.2
(8)
(9)
(10)
(11)
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
Fig. 2. Lattice structures of four types of pyrite; perfect (a), As-substituted (b), Co-substituted (c) and intercrystalline Au (d) [106].
(12)
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
(13)
(14)
(15)
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
(16)
4
5
6
7
8
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
(17)
(18)
(19)
(20)
E0X/X2
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
(21)
1/2
(22)
11
10
12
Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
Ind. Eng. Chem. (2016), http://dx.doi.org/10.1016/j.jiec.2016.12.012
G Model
JIEC 3218 No. of Pages 18
10
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry xxx (2016) xxxxxx
Fig. 3. Dissolution of surface ferric hydroxide and dixanthogen formation on non-activated pyrite surface [208].
13
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+x
+ x(CN)
(23)
(24)
11
(25)
(26)
(27)
However, it has been found that these reactions are slow, and
thus do not appear to have an important role in suppressing the
xanthate oxidation through lowering the mixed potential [181].
Enhancing the anodic reactions by cyanide may also be due to
the formation of soluble iron cyanide compounds instead of the
insoluble oxide/hydroxide species. Since these iron cyanide
compounds, unlike the oxide/hydroxide species, are soluble, they
cannot inhibit the pyrite oxidation, and thus the anodic reactions
are enhanced [181,188]. This nding was conrmed by voltammetry studies conducted by Wang and Forssberg which showed a
linear relationship between the concentration of cyanide and the
peak current of the pyrite oxidation [188]. Although these studies
showed that cyanide suppresses xanthate oxidation through
decreasing the mixed potential, it was found that the xanthate
oxidation in the presence of cyanide is not enhanced by increasing
mixed potential by adding an oxidizing agent [173]. Therefore, the
decrease in the mixed potential does not appear to be the main
cause for suppressing the xanthate oxidation.
Several other causes such as high consumption of oxygen in the
cyanide oxidation reactions and direct reduction of dixanthogen to
xanthate by cyanide have also been reported [188]. The most
acceptable explanation for the inhibition of the xanthate oxidation
by cyanide has been found to be the formation of insoluble
cyanoferrate complexes on the pyrite surface [50,99]. It has been
found that iron hexacyanide compounds can be formed by the
reduction of the surface ferric hydroxide layer in the presence of
cyanide [50] according to Reaction (28) [99].
5Fe(OH)3 + 12CN + 15H+ + 3e = Fe3[Fe(CN)6]2 + 15H2O
(28)
(29)
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Table 2
Mechanisms of depression of pyrite otation by cyanide ions in different conditions.
Condition
Mechanism
Reference
Collector-less otation
In the presence of xanthate
In the presence of copper ions
Removing hydrophobic sulfur species from the surface by the formation of thiocyanate compounds
Replacing surface adsorption sites for dixanthogen by insoluble cyanoferrate complexes
Reducing concentration of the free copper ions in the pulp and inhibiting the formation of
coprous xanthate by the formation of cyano-copper species
Cyanide is not able to depress the pyrite otation.
[188]
[50,99]
[188]
(30)
(31)
(32)
(33)
These experimental ndings have been conrmed by thermodynamic calculations [188] and also by XPS analysis [68]. Table 2
summarizes the mechanisms of depression of the pyrite otation
by cyanide ions in different conditions.
Sulfoxy reagents such as sulfur dioxide, sodium sulte or
sodium metabisulte are also widely used as depressants for pyrite
[50,146,202]. Studies have shown that these reagents suppress the
adsorption of xanthate by reducing the mixed potential to below
the potential required for the oxidation of xanthate to dixanthogen
[50,202,230] and enhancing formation of hydroxide species on the
pyrite surface [146].
Organic depressants
Although various inorganic reagents (e.g., cyanide and sulfoxy
species) have been found to be effective in the depression of pyrite,
there are problems associated with the use of these reagents such
as high cost and environmental concerns [3,91,231]. In order to
overcome such problems, some researchers have focused on
developing alternative cheap and environmental friendly organic
depressant.
Natural polysaccharides, such as starch, dextrin and guar gum,
are used as depressant. These organic compounds are polymers
[228,229]
14
15
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16
DETA: diethylenetriamine.
13
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Table 3
Effect of electrochemical activity of media grinding on various processes in pyrite otation.
Process
Reference
Collector-less otation
Xanthate adsorption
Activation by copper
Activation by lead
[259]
[185,201]
[259263]
[122]
(34)
(35)
(36)
2HO = H2O2
(37)
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Table 4
Relationship between electrochemical conditions and processes in pyrite otation.
Electrochemical process
Electrochemical conditions
Explanation
Flotation of pyrite by
oxidation
Depression of pyrite by
oxidation
With Increasing potential, the oxidation rate Cu(I) to Cu(II) increases, and as a result
the concentration of Cu(I) ions which are responsible for the activation decreases.
At high potentials, since extensive oxidation of the surface occurs, the surface is
covered by iron oxides/hydroxides. Thus, the available surface area for the copper
adsorption decreases.
At high potentials, hydrophilic copper carbonate/hydroxyl species are formed and
precipitated on the Cu activated surface.
Xanthate adsorption on non- A great decrease or increase in the potential has A great decrease in potential leads to a decrease in the xanthate oxidation to
activated surface of pyrite adverse effects. The potential must be optimized.
dixanthogen.
A great increase in potential leads to an increase in the surface oxidation and the
formation of iron oxide/hydroxide species on the surface. These species, in addition
to being hydrophilic, prevent electron transfer across the mineralsolution
interface, and thus, reduce the xanthate adsorption on the surface.
A great decrease or increase in the potential has A great decrease in potential leads to a decrease in the xanthate oxidation to
Xanthate adsorption on
copper activated surface of adverse effects. The potential must be optimized.
dixanthogen.
A great increase in potential leads to the formation of copper carbonate/hydroxyl
pyrite
species, in addition to iron oxide/hydroxide species, which are precipitated on the
Cu activated surface. These species, in addition to being hydrophilic, prevent
electron transfer across the mineralsolution interface, and thus, reduce the
xanthate adsorption on the activated surface.
Depression of pyrite by
depressants
In the case of cyanide, it has been found that it is an effective depressant only when
the surface is oxidized.
In the case of organic depressants, it has been found that increasing potential and
increasing oxidation products density on the surface is often favorable for
depressants adsorption.
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Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
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JIEC 3218 No. of Pages 18
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Please cite this article in press as: H. Moslemi, M. Gharabaghi, A review on electrochemical behavior of pyrite in the froth otation process, J.
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