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Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

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Journal of Industrial and Engineering Chemistry


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Review

A review on electrochemical behavior of pyrite in the froth flotation


process
Hossein Moslemia,* , Mahdi Gharabaghib
a
Department of Mining & Metallurgical Engineering, Amirkabir University of Technology, Hafez St., Tehran, Iran
b
School of Mining Engineering, College of Engineering, University of Tehran, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Article history:
Received 29 October 2016 Metal sulfides are usually semiconductor and cause electrochemical reactions. This phenomenon plays
Received in revised form 10 December 2016 an important role in sulfide flotation. Pyrite as the most abundant sulfide mineral is often associated with
Accepted 18 December 2016 valuable sulfide minerals, coal and gold. It is very important to study its electrochemical behavior in the
Available online 24 December 2016 flotation process. This review focuses on researches carried out over the past several decades that have
studied electrochemical processes associated with pyrite occurring during flotation. The mechanism of
Keywords: processes such as oxidation, activation, depression, and interactions of activated and non-activated
Mineral processing surfaces with collectors as well as factors affecting them are described. Moreover, the effect of
Pyrite
electrochemical conditions during grinding on the flotation process is also discussed. It has been found
Flotation
that moderately oxidizing conditions are favorable for collector-less flotation of pyrite while strongly
Electrochemical potential
Surface chemistry 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,
flotation 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 flotation systems.
© 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Oxidation of pyrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Effect of oxidation on pyrite floatability . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Effect of pyrite origin on the floatability due to oxidation ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Effect of oxidation on pyrite depression . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Effect of pH on pyrite depression . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Effect of dissolved oxygen content on pyrite depression . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Removal of depressing effect of oxidation . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Pyrite activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Pyrite activation by copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Pyrite activation by lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Collector adsorption on pyrite surface . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Collector adsorption on non-activated surface . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

* 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.
2 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

Effect of pH on collector adsorption . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9


Effect of oxygen content on collector adsorption . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Effect of pyrite surface oxidation products on collector adsorption .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Effect of pyrite type and origin on the collector adsorption . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Collector adsorption on activated surface . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Collector adsorption on copper activated surface . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Collector adsorption on lead activated surface . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Inorganic depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Organic depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Effect of grinding environment on pyrite electrochemical properties . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Effect of grinding media type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Effect of oxygen content in grinding system . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Effect of water quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Effect of reactions occurred in the grinding system . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Summary and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Introduction Since electrochemical potential is known as the key factor in


pyrite flotation process, the present study was performed to
Demand for base metals has been increasing continuously due provide a comprehensive review of the effects of electrochemical
to the development of industries worldwide; therefore, it is conditions on pyrite surface chemistry and also electrochemical
necessary to improve processing of sulfide ores which are the processes occurring on the pyrite surface in the flotation system.
major sources of base metals. Pyrite (FeS2, iron disulfide), which is Oxidation of pyrite and its effects on the flotation, activation of
the most common sulfide mineral on the Earth [1–5], is the main pyrite, depression of pyrite, are also discussed in detail in this
gangue of sulfide ores [1–6]. The pyrite presence in the concentrate review. In addition, interactions between pyrite and collectors and
of valuable minerals leads to a decrease in grade and an increase in interactions between pyrite and grinding media with emphasis on
sulfur and iron contamination resulting in an increase in smelting the electrochemical reactions were focused. There are some
costs [1,4,7]. Moreover, if pyrite contains potentially hazardous researches which investigate various interactions in the pyrite
elements such as arsenic, hazardous dusts and fumes will be flotation, so this review is intended to provide further insights into
produced during the smelting process [8–12]. Pyrite is also found the pyrite flotation process and to address important points for the
in coal deposits [13]. The burning process of coal containing a high control of the process and its optimization in order to enhance the
content of pyrite leads to the atmospheric emission of sulfur oxides product quality and to reduce process costs.
[14–19] which are the major cause of acid rain [14–21]. The
primary aim of the processing of sulfide ores and coal is to remove Oxidation of pyrite
the pyrite content [22]. However, occasionally, pyrite may contain
significant amounts of valuable metals such as gold [23–30], and Pyrite is oxidized in aqueous solutions through an electro-
thus, it may be concentrated to gain these valuable metals [23]. chemical mechanism. The oxidation rate is influenced by various
Froth flotation is widely used in mineral industry to selectively factors such as solution pH, solution electrochemical potential,
separate minerals from each other [31]. Annually, more than oxidant type and concentration, particle size, temperature and
109 tons of various materials are processed by this method agitation speed [46–53]. Different samples of pyrite exhibit
worldwide [32]. The process strongly depends on the physico- different electrochemical reactivity [23] due to various reasons
chemical surface properties of minerals [14,33] and is controlled by such as differences in iron to sulfur ratio, crystal structure and
modifying these properties through addition of flotation reagents surface morphology [54–56].
[14]. If pyrite is completely oxidized, ferrous iron and sulfate ions are
Since most metal sulfides are semiconductor [34–37], various produced [57,58]. The complete oxidation of pyrite occurs
electrochemical reactions occur in the sulfide mineral flotation according to Reaction (1) [59–61].
system. Extensive researches have shown that there is a strong
FeS2 + 3.5O2 + H2O ! Fe2+ + 2SO42 + 2H+ (1)
correlation between flotation of pyrite and electrochemical
reactions [38]. Electrochemical mechanisms are often known to Experimental observations indicate that the pyrite oxidation
be responsible for various phenomena, occurring in a flotation does not completely occur and elemental sulfur is also produced in
system containing pyrite, such as changes in pyrite surface addition to the ferrous iron and the sulfate ions as a result of
chemistry due to oxidation, the interaction of pyrite with other incomplete oxidation (Reaction (2)) [62–69].
components, adsorption of collector and precipitation of metals on
FeS2 + 2.9O2 + 0.6H2O ! Fe2+ + 0.4S0 + 1.6SO42 + 1.2H+ (2)
the surface [39]. The most important factor which affects
electrochemical processes is the electrochemical potential of The ferrous iron produced by Reactions (1) and (2) undergoes
mineral/solution interface [40,41]. This potential is a mixed Reactions (3) and (4) and forms ferric hydroxide [70,71].
potential in which the rates of anodic and cathodic reactions,
occurring on the mineral surface, are exactly equal to each other Fe2+ + 0.25O2 + H+ ! Fe3+ + 0.5H2O (3)
[40,42–44]. The electrochemical potential controls formation of
not only surface species responsible for the flotation of the mineral
(such as polysulfides, elemental sulfur and xanthate), but also Fe3+ + 3H2O ! Fe(OH)3 + 3H+ (4)
surface species responsible for its depression (such as ferric oxide/ The formed ferric hydroxide can be precipitated as a coating on
hydroxide and sulfate) [45]. the pyrite surface of and inhibits further oxidation of pyrite. This
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 3

phenomenon occurs at higher rates with increasing solution pH


[72,73].
The electrochemical oxidation of pyrite, producing ferrous and
sulfate ions, involves removal of seven electrons from each sulfur
atom to oxidize S1 in the pyrite, to S6+ in the sulfate ions. Since
only one or at most two electrons can be removed at any one time,
the oxidation process is quite complex, involving several key
intermediate electrochemical reactions with the formation of
various sulfoxy species [74]. The presence and abundance of these
species on the surface depends strongly on the electrochemical
conditions [4].
The most important step in the pyrite oxidation process is the
breaking of strong bond between sulfur and iron atoms, and
formation of thiosulfate ion as intermediate product (Reaction (5))
[51].
FeS2 + 1.5O2 ! Fe2+ + S2O32 (5)

The produced thiosulfate ion is unstable, especially in acidic


conditions [51], and decomposes to elemental sulfur and
tetrathionate ion through Reaction (6) [69].

S2O32 + 1.2H+ ! 0.4S0 + 0.4S4O62 + 0.6H2O (6) Fig. 1. Eh-pH diagram for FeS2–H2O system at 25  C and for 105 M dissolved
species [84].
The formed tetrathionate ion, which is also an unstable
intermediate product [51], is further oxidized to form sulfate
ion as a final product according to the Reaction (7) [69].
potential and to study their effects on the pyrite flotation
S4O62 + 3.5O2 + 3H2O ! 4SO42 + 6H+ (7) recovery.
Tao et al. [89] conducted studies to measure the pyrite flotation
Despite extensive studies conducted on the oxidation of pyrite,
recovery in a micro-flotation electrochemical cell at pH 4.6 and pH
there is little agreement on the details of oxidation processes
9.2. The collector-less flotation obtained results – recovery as a
particularly surface composition of the oxidized pyrite [55]. Using
function of pulp potential- showed that the recovery began to
spectroscopic surface and electrochemical analysis, some
increase at potential values close to 0 and 100 mV (SHE1 ) at pH
researchers have found that mild oxidation resulted in the
values 4.6 and 9.2, respectively.
formation of an iron-deficient surface layer on pyrite [65–
In another study, they observed that, in the absence of collector
67,75,76] while a number of researchers believe the oxidation
at pH 9.2, maximum flotation of pyrite occurred at potentials
product of pyrite is iron polysulfide [77–80]. On the other hand,
slightly above 0.28 V (SHE) [54].
using linear sweep voltammetry, it was observed that a monolayer
Results of collector-less flotation tests performed by Yoon et al.
or multiple layers of sulfur (depending on solution pH) were
[90] showed that the pyrite flotation occurred in potential ranges
formed on the surface of oxidized pyrite [57]. It was also found that
of 0.1 to 0.8 V and 0.3 to 0.4 V (SHE) at pH 4.6 and 9.2, respectively.
sulfur forms vary from disulfide ion (in pyrite) on the internal
The results also showed that the flotation recovery at pH 4.6 was
surface to elemental sulfur (which is suitable for electrochemical
considerably higher than recovery at pH 9.2.
reaction) on the outer surface [81].
Hicyilmaz et al. [49] measured pyrite contact angle in the
In general, most of these studies have shown that the
absence of collector in the potential range of 505 to +595 mV
concentration of sulfur in a pyrite oxidized layer increases from
(SHE) and at different pH values. The maximum measured contact
the internal to the outer surface while the concentration of iron
angle was 25 at the potential of +400 mV (SHE) at pH 4.67. The
decreases in this direction [81]. However, under strongly oxidizing
variation trend of the contact angle as a function of potential was
conditions where sulfate is the main oxidation product [57,62–
similar at all pH values.
64,82,83], it has been observed that the sulfur concentration on the
Guler et al. [91] investigated floatability of pyrite in the
surface is reduced relative to iron [54].
collector-less conditions in a wide potential range involving
Fig. 1 shows the Eh-pH diagram for FeS2-H2O system at 25  C.
reducing (400 mV, 100 mV (SHE)), slightly oxidizing
The fields of thermodynamic stability of various species of iron and
(+200 mV (SHE), around open circuit potential) and highly
sulfur in terms of pH and electrochemical potential (Eh) are
oxidizing (+500 mV, +800 mV (SHE)) potentials in borate buffer
presented in this diagram [84].
solution at pH 9.2. Results showed that the recovery increased with
potential increasing and reached its maximum (approximately
Effect of oxidation on pyrite floatability 18%) at about 200250 mV (SHE) and then decreased at more
oxidizing potentials.
Pyrite is naturally floatable under specific conditions and a The relationship between the pulp electrochemical potential
proportion of it can be recovered without use of any flotation and pyrite flotation recovery in the collector-less conditions from
reagent [31,45,85]. Small changes in the surface chemistry of various investigations are summarized in Table 1.
pyrite may significantly affect its floatability [86]. These changes The results of these electrochemical studies on pyrite flotation
can be due to the anodic oxidation of the mineral surface and systems clearly show that the flotation recovery in the collector-
the cathodic reduction of oxygen dissolved in the pulp [62]. less conditions is a function of the mineral/solution interface
Electrochemical properties such as redox potentials of the system
and rest potentials of the mineral are used to describe the changes
in the surface composition of pyrite [87,88]. Some researchers
have attempted to measure the variation in the flotation pulp 1
SHE: standard hydrogen electrode.
4 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

Table 1 significant difference between the recovery values of 5 min (50%)


Relationship between pulp electrochemical potential and pyrite flotation recovery and 10 min (93%) of flotation, Ekmekci and Demirel [63] also
in collector-less conditions.
suggested that in this time interval, the hydrophobic surface
Pulp potential Pulp pH Recovery Reference species are slowly produced by the electrochemical reaction.
(mV vs. SHE)
Acidic Alkaline Effect of pyrite origin on the floatability due to oxidation
0 4.6 Increased [89] There are differences between mineral-pyrites and coal-pyrites
100 to 800 4.6 Was observed [90] in the floatability and electrochemical properties. It was reported
400 4.67 Maximum [49]
100 9.2 Increased [89]
that coal-pyrite could be floated over a wide range of pH values
280 9.2 Maximum [54] while mineral-pyrite could only be floated at acidic pH. It was also
300 to 400 9.2 Was observed [90] observed that in the absence of xanthate collectors and at a pH
200 to 250 9.2 Maximum [91] above 6.5, coal-pyrite exhibited significantly higher floatability
than mineral-pyrite [90]. In contrast, Yoon et al. [90] observed that
flotation recovery of coal-pyrite was lower than mineral-pyrite.
electrochemical potential [92]. Cyclic voltammetry studies of Electrochemical studies showed that coal-pyrite produces a higher
freshly created pyrite surfaces indicate that the potentials at which, concentration of oxide species on its surface. This can be due to the
pyrite begins to float correspond to the potentials at which, the fact that coal-pyrite is poorly crystalline and has a higher surface
freshly created pyrite surfaces begin to oxidize [89]. Therefore, it area. Therefore, its oxidation occurs faster than mineral pyrite
can be concluded that the initial oxidation of pyrite occurs at [101–103] and its metastable hydrophobic sulfur-rich species are
potentials slightly more positive than the stable potential, results more readily transformed to the hydrophilic oxidation species
in an increase in pyrite floatability [39]. (The stable potential is the which decreases its floatability [101,102].
potential at which, the surface of pyrite is neither oxidized nor In addition to the floatability differences between mineral-
reduced) [54]. pyrite and coal-pyrite, there are also differences in the floatability
Tao et al. [89] using XPS2 and electrochemical studies proposed of pyrites from different geographical locations. For example,
that metal-deficient sulfides (Fe1xS2, x < 1) and iron polysulfides Gebhart et al. [104] observed that the pyrite collector-less flotation
(FeSn, n > 2) are the sulfur oxidation product(s) and are responsible was maximum at potentials of approximately +85 mV (Ag/AgCl),
for the pyrite flotation. The reactions producing these species can whereas Chandurya et al. [105] obtained maximum pyrite flotation
be represented by Reactions (8) and (9). at 700 mV (Ag/AgCl) without collector at pH 9.2. This difference
FeS2 + 3x(OH) = Fe1xS2 + xFe(OH)3 + 3xe (8) in the pyrite flotation behavior may be due to the presence of
lattice defects in the pyrite bulk due to the lattice substitution of Fe
and S by impurities such as As, Co, Ni, Pb, Cu, Se, Zn, Au and Ag
nFeS2 + 3(n  2)OH = 2FeSn + (n  2)Fe(OH)3 + 3(n  2)e (9) which influences the electrochemical properties of pyrite [106–
112]. Xian et al. [106] conducted flotation studies on four types of
XPS studies conducted by Buckley and Woods [67] showed that pyrite, including perfect pyrite, As-substituted pyrite, Co-substi-
moderate oxidation of pyrite released iron preferentially from tuted pyrite and intercrystalline Au pyrite. In the perfect pyrite
normal lattice sites and resulted in creating a metal-deficient bulk, each S atom was coordinated to three Fe atoms and one S
surface through formation of soluble iron compounds. Since the atom in a tetrahedral configuration, whereas in the bulk of As-
floatability of pyrite is influenced by the relative amount of substituted pyrite an As atom substituted for one of S atoms, in the
hydrophobic sulfur to insoluble oxide/hydroxides species present bulk of Co-substituted pyrite a Co atom substituted for one Fe atom
on the surface [89], a decrease in the amount of iron hydroxide and in the bulk of intercrystalline Au pyrite an Au atom filled in the
results in an increase in the floatability [54]. The role of the interstitial positions. Fig. 2 shows the lattice structures of the four
polysulfides and the metal-deficient sulfides as the oxidation types of pyrite proposed by Xian et al. [106].
products responsible for the hydrophobicity of pyrite has been The flotation results showed that the floatability of co-
confirmed by researchers [78–80,93–96]. substituted and intercrystalline Au pyrites increased with pulp
In addition to the polysulfides and the metal-deficient sulfides, aeration time, whereas floatability of pure and As-substituted
it has been found that the elemental sulfur can also be responsible pyrites decreased with pulp aeration time. Using electronic
for the collector-less floatability [31,57,67,97,98]. Ekmekci and structure and band structure studies of the four types of pyrites,
Demirel [63] obtained a pyrite recovery over 90% after 10 min of Xian et al. [106] observed that the stability of the pyrites was
flotation at pH 4.6. Their studies showed that this high recovery influenced by the impurity defects and the electronic structures.
was due to the formation of the hydrophobic elemental sulfur on The stability of the pyrites increased in the following order:
the surface. The elemental sulfur is believed to be a critical factor in As-substituted < perfect < Co-substituted < intercrystalline Au.
collector-less flotation [38,88]. Researchers have reported that the Therefore, it was concluded that the observed difference in the
elemental sulfur is formed on the pyrite surface by the oxidation of flotation behavior was due to the difference in the stability of the
pyrite and its decomposition (Reaction (10)) [63], pyrites and their oxidation intensity. The effect of the presence of
FeS2 = Fe2+ + 2S0 + 2e (10) such impurities in the pyrite lattice on the oxidation process has
also been confirmed by other researchers [113–115]. It has been

or by the oxidation of HS ions on the pyrite surface (Reaction (11)) demonstrated that the electrochemical properties and the flotation
[88,99,100]: behavior of pyrite is also significantly influenced by vacancy
HS = S0 + H+ + 2e (11) defects due to loss of anions or cations in the pyrite lattice [116].

The HS ion may be produced by the cathodic reduction of the Effect of oxidation on pyrite depression
oxidation products on the pyrite surface [47]. This ion is expected
to be formed at neutral and alkaline pH values [99]. Based on the Several investigations have been conducted in order to evaluate
the influence of the electrochemical potential on the surface
properties of pyrite leading to its depression. Hicyilmaz et al. [49]
2
XPS: X-ray photoelectron spectroscopy. measured contact angles of pyrite in the absence of collector in a
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 5

Fig. 2. Lattice structures of four types of pyrite; perfect (a), As-substituted (b), Co-substituted (c) and intercrystalline Au (d) [106].

potential range of 505 to +595 mV (SHE) and observed that extensive oxidation products such as SO32, S2O32 and SO42 and
increasing pulp potential from +400 to +595 mV (SHE), decreased the iron hydroxide species on the pyrite floatability have also been
contact angles. Similar results were also obtained in other study reported by various researchers [22,58,63,93,99,123,124].
[91]. The decrease in the contact angles and floatability of pyrite It is possible to minimize the floatability of pyrite by modifying
with increasing pulp potential was found to be due to the evolution the pulp potential at an appropriate value in order to oxidize the
and precipitation of the hydrophilic species such as iron hydroxide hydrophobic sulfur species to sulfate [54]. On this basis, oxidation
at high potentials [63,117,118]. The performed studies have shown at the anode has been considered as the key step for electrochem-
that since ferrous ions released by oxidation of pyrite have low ical desulfurization of coal [125]. On the other hand, it was found
stability, these ions are then oxidized to the ferric oxy-hydroxide that reduced pyrite is more hydrophobic than pyrite. Therefore, in
species at highly oxidizing potentials. These final products of the case of coal, grinding and flotation under moderate reducing
oxidation are hydrophilic, and thus decrease the pyrite floatability potentials have also been proposed as an effective method for
and eventually cause its depression [91]. Another reason for the preventing pyrite oxidation and improving coal desulfurization
loss of the hydrophobicity at high potentials can also be the [89,126]. It was reported that galvanic coupling of pyrite with
oxidation of the hydrophobic elemental sulfur into the hydrophilic active metals such as manganese, zinc and aluminum can be a
species such as sulfate [119–121] according to following reaction practical technique for creating a reducing environment. Using this
[49]: technique, decreasing the potential of pyrite to values that were
negative enough to inhibit the oxidation of pyrite and to reduce the
S + 4H2O = SO42 + 8H+ + 6e (12)
hydrophobic oxidation products that were already present on the
The percentage of various elements on the pyrite surface at surface was successfully performed [90]. The result of flotation
electrochemical potential values of 60 and +130 mV (SHE) was experiments performed on coal samples conditioned with an
measured by XPS surface analysis [45]. The results showed that at active metal powder obviously showed that the separation
positive potential values, percentage of the surface oxidation efficiency was significantly improved by the galvanic coupling.
species (%O) was more than the sulfur species while the opposite For example, the pyrite rejection increased from 45% in the absence
was true at the negative potential value. The results of zeta of manganese to 75% in the presence of manganese.
potential measurements and XPS studies also supported this fact
that the concentration of these surface oxidation species which Effect of pH on pyrite depression
were formed on the pyrite surface increases with an increase in the It has been found that the pyrite flotation recovery decreases
electrochemical potential [122]. The adverse effects of the with an increase in pH [54,63,89,122,127–130]. This inverse
6 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

relation between the recovery flotation and pH is associated with Removal of depressing effect of oxidation
the relative abundance of the hydrophilic hydroxide to the The adverse effects of the extensive oxidation products on the
hydrophobic sulfur species [97]. The relative abundance of the pyrite flotation can be eliminated or reduced through various
hydrophilic to the hydrophobic species is expected to be largely methods. It has been reported that reducing agents are able to
dependent on the solubility of the oxidation products [54]. It has restore the potential to the optimum level and to reduce the
been found that as the pyrite surface is oxidized, ferrous ions oxidation products [140]. These products which formed on the
move from the mineral lattice to the surface due to their high surface, however, may be not completely removed by this method
mobility. In the alkaline environments, released ferrous ions because of the irreversibility of their reactions [53,140,141].
undergo further reactions to form ferrous hydroxides. The EDTA3 solutions have also been found to be effective for removing
produced ferrous hydroxides are then oxidized to the ferric the iron hydroxide films from the pyrite surface in the range of pH
hydroxides and precipitated on the pyrite surface [63,83,131]. The 6–11 [90,142,143]. Since the iron hydroxide species are thermo-
formation rate and stability of the hydrophilic products of dynamically unstable in EDTA solutions of this pH range
oxidation increase with increasing pH [63,72,132–134]. The [45,117,131], these species dissolve in EDTA solutions through
hydrophobic species such as sulfur are also formed by the forming EDTA-iron complexes according to bellow reactions
pyrite oxidation, but they are covered by the hydrophilic species [131]:
such as ferric hydroxides [131]. The coverage of the pyrite
Fe(OH)3(s) + EDTA4 = FeEDTA + 3(OH) (13)
surface by the stable iron oxy-hydroxide species during the
oxidation process has also been confirmed by various researchers
[49,50,72,135,136].
Fe(OH)3(s) + EDTA4 = FeEDTA(OH)2 + 2(OH) (14)
Measurement of pyrite contact angles as a function of pH
showed that the highest values were obtained at slightly acidic
pH [49]. It was also found that with increasing pH and passing
from acidic to neutral and alkaline conditions, hydrophobicity of Fe(OH)2(s) + EDTA4 = FeEDTA2 + 2(OH) (15)
the pyrite surface significantly decreased. Peng et al. [122] In addition, the amount of the iron hydroxide species dissolved
conducted flotation studies in the absence of collector at pH 9 and in EDTA solutions increases with increasing Eh [45,144]. In the
in the potentials of 185, 10 and +260 mV (SHE) and obtained acidic pH range, however, the different results are obtained in the
very low recovery values (around 8 wt. %) at the completion of presence of EDTA. In this pH range, due to the adsorption of EDTA
8 min of flotation. They concluded that in the alkaline conditions, and/or Fe-EDTA complexes on the pyrite surface, the dissolution
the electrochemical potential has no significant effect on the rate of the iron hydroxide species decreases dramatically. It has
flotation recovery. As it was stated previously, at alkaline pH also been noted that EDTA concentration should be optimum. The
values, formed iron oxy-hydroxide species are electrochemically presence of excess EDTA causes destroying sulfur-rich layers on the
very stable and cause extensive passivation of the pyrite surface. pyrite surface after removing the iron hydroxide species which
This surface passivation in the alkaline solutions causes the results in decreasing the pyrite floatability [131]. To create the
mineral to exhibit no response, or a negligible response, to the optimum conditions and to completely eliminate the undesired
changes in the pulp potential [63,137,138]. Cyclic voltammetry oxidation products, the use of non-oxidizing gas such as nitrogen
studies by Hicyilmaz et al. [49] on pyrite samples in the strongly as a more effective method has been proposed by several
alkaline solution (i.e. pH 11) also supported this finding, where no researchers [53,63,140].
apparent cathodic or anodic peaks were observed in the obtained It has been found that in industrial flotation processes, pyrite
voltammograms. shows stronger floatability compared to experimental processes.
The studies indicated that vigorous pulp stirring and high solids
Effect of dissolved oxygen content on pyrite depression content in industrial flotation cells cause generating intensive
The effect of dissolved oxygen content in the pulp on the particle–particle abrasion. This results in removing the hydrophilic
variation of the pulp potential and the formation of the oxidation species from the pyrite surface and the exposure of the
hydrophilic species on the pyrite surface has also been underlying hydrophobic sulfur-rich layer, thereby increasing the
investigated by various researchers. Owusu et al. [139] measured floatability of pyrite [90].
pH, pulp potential (Eh) and dissolved oxygen content of pyrite
pulp after various aeration times of the pulp. Initially, the pulp Pyrite activation
was purged with air for 3 min and the dissolved oxygen content
was then measured with time. They observed that the dissolved It has been obviously observed that pyrite can float in the
oxygen concentration of the pulp reduced from 5.5 to 0.06 mg/ presence of lead and copper minerals, even in alkaline solutions
dm3 during 5 min. This showed that the oxygen dissolved in the [63,122,145,146]. This is due to the fact that pyrite can be activated
pulp was nearly completely consumed by pyrite. However, with by lead or copper ions released from lead or copper containing
increasing aeration time, it was observed that the residual minerals [93,122,147]. The activation is one of the most important
dissolved oxygen content increased to 5.21 mg/dm3. On the other phenomena associated with the flotation of sulfides. In this
hand, it was also observed that with increasing the dissolved process, metal species are precipitated or adsorbed on the mineral
oxygen content of the pulp, the pulp pH decreased considerably surface, to create suitable sites for adsorption of the collector [85].
and the pulp Eh changed from a reducing to more oxidizing value.
These changes in pH and Eh of the pulp were found to be favorable Pyrite activation by copper
for the pyrite oxidation and the oxygen consumption. Therefore, it
was concluded that by increasing aeration time, formation of iron Several studies have been conducted on adsorption mecha-
oxy-hydroxide species and also coating the surface with these nisms of copper ions on the pyrite surface. Some researchers have
species increase. Then, however, because of the coverage of most proposed an ion exchange mechanism between ferrous ions and
of the pyrite surface by these species, a significant decrease in the
surface reactivity with oxygen occurs. In other words, with a
further increase in aeration time, the pyrite surface is more
passivated [139]. 3
EDTA: ethylene diamine tetra acetic acid.
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 7

cupric ions in a system involving pyrite and copper ions (Reaction alkaline conditions, the copper concentration on the surface was
(16)) [49,145,148,149]. independent of the electrochemical potential. They observed no
changes in the chemical state of sulfur on the pyrite surface by
FeS2 + Cu2+ = CuS + Fe2+ + S0 (16)
potential changing [153].
Although the Fe surface species have been known to be The concentration of various copper species at different
energetically favorable for surface redox processes, it has been electrochemical potentials at pH 9 was measured by Peng et al.
reported that these species do not appear to have an electrochem- [122]. They found that the concentration of copper species strongly
ical role in the Cu activation process of pyrite [150]. Chandra et al. depended on the electrochemical potential. It was observed that at
[150] studied Cu activated pyrite in slightly acidic conditions using the potential of 185 mV (SHE) almost all aqueous copper (>99 wt.
PEEM4 analysis and found that Cu is adsorbed onto the pyrite %) was present as cuprous ion while at the potential of 10 mV
surface in Cu+ form. It was also observed that greater amounts of (SHE) this decreased to 28 wt.% and at the potential of +260 mV
Sn2 and S–OH species and smaller amounts of S2 and S22 are (SHE), no aqueous Cu was present as cuprous ion. Moreover, it was
present on activated pyrite relative to non-activated pyrite. It was also found that if it was possible to form Cu(OH)2 precipitation,
suggested that this may be due to the presence of O2/H2O or the almost all the copper could precipitate as Cu(OH)2 at potentials of
adsorption processes of cupric ions [150] which cause oxidation 10 mV and +260 mV (SHE), while at the potential of 185 mV
during conditioning and activation of pyrite [150–152]. Their (SHE), only a small amount of the copper could precipitate as Cu
findings confirmed the fact that the ion exchange is performed (OH)2. According to these observations, it was concluded that
along with the spontaneous reduction of cupric ions into cuprous increasing pulp electrochemical potential caused an increase in the
ions and the oxidation of sulfur [148–150,153–156]. The reduction formation of Cu(OH)2 and a decrease in the concentration of Cu+ on
of cupric ions to cuprous ions has been known to be responsible for the pyrite surface. On this basis, it has been suggested that since
a small increase in the pulp potential that is observed during the the pyrite activation by copper ions strongly depends on the
activation of pyrite by copper [40,154]. It has been suggested that formation of Cu+-sulfide species, reducing conditions which
covellite was the major compound on the surface of the Cu prevent oxidation of cuprous species to cupric species, are more
activated pyrite [49,145,148,153,157–159]. This was confirmed by favorable for the activation process [161,164]. Peng et al. [122] also
the results of XPS analysis [153] and voltammetry studies which noted that it can be possible to control the pyrite flotation in the
conducted on the activated pyrite [49]. It has also been reported presence of copper ions through the addition of reducing or
that copper is adsorbed only on the surface and does not penetrate oxidizing agents.
into the bulk of pyrite [45,146,160]. Hicyilmaz et al. [49] performed contact angle measurements on
Studies conducted by Richardson et al. [161] showed that in the copper activated pyrite in a potential range of 505 to +595 mV
slightly acidic pH conditions, activation of pyrite by cupric ions is (SHE) and at pHs of 4.67, 6.97 9.2 and 11. They observed that
strongly influenced by the electrochemical potential of the pulp. activation by copper resulted in a significant increase in the
They observed that by increasing the electrochemical potential, the hydrophobicity of the pyrite at all Eh and pH values. The pyrite
adsorption of cupric ions decreases. This finding is in agreement surface appeared to be similar to that of chalcopyrite when
with studies by Wang et al. [158] who reported that O2 purging activated with copper sulfate. It was reported that this was due to
causes a decrease in the available surface area for the copper the formation of CuS, Cu2S, and an iron deficient surface layer
adsorption because of an increase in the oxidation of the pyrite [118,136,148,153,159]. In this study, a slightly acidic pH that
surface. resulted in the highest contact angles at all potentials was known
The activation of pyrite by copper in alkaline conditions has also to be favorable for the flotation of pyrite. The contact angles
been investigated. It was found that in alkaline pH conditions, Cu2+ decreased gradually with increasing pH and passing from slightly
is first adsorbed on the surface as copper hydroxide [162]. Then, acidic to neutral and alkaline conditions. The contact angle
the copper hydroxide reacts with sulfide (S22) at the pyrite surface measurements also showed that the pyrite surface was hydropho-
and is subsequently reduced to form Cu(I)S species through bic even at the potential of 505 mV (SHE). This could be attributed
oxidation of sulfide to S21 or Sn2 (polysulfide). It was also noted to the presence of the elemental sulfur on the surface. Hicyilmaz
that under alkaline conditions and for a strongly oxidized pyrite et al. [49] suggested that when copper ions interact with pyrite, the
surface, the rate of the copper adsorption is low because copper elemental sulfur species are formed on the pyrite surface, and since
has to penetrate into the surface hydroxide layer. these species are reduced very slowly, the sulfur may still be
Weisener and Gerson [148] studied the activation of pyrite at present on the surface in its elemental form at the potential of
high electrochemical potentials using ToF-SIMS5 , EXAFS6 , XPS and 505 mV (SHE). With increasing the potential to +385 mV (SHE), it
angle resolved XPS and reported that at alkaline pH values, the was observed that the contact angles first decreased and then
pyrite surface, is initially rapidly activated by forming the Cu+- increased. The decrease in the contact angles was known to be due
sulfide species but these species are then covered by precipitates of to the formation of HS and H2S and the increase in the contact
cupric carbonate/hydroxyl. Although it has been suggested that the angles was explained by oxidation CuS into Cu2+ and S0. With a
cupric hydroxyl/carbonate species can form cuprous xanthate further increase in the potential to +595 mV (SHE), a slight
upon the addition of xanthate collector to enhance the pyrite decrease in the contact angles was also observed that could be
flotation [159,163], it is clear that these species are not able to react attributed to the formation of copper oxide/hydroxide species [49].
significantly with the xanthate within the time frame of the As mentioned above, under alkaline conditions and at high
flotation process, and thus the flotation recovery will decrease electrochemical potentials, cupric species can depress the pyrite
[122]. flotation by precipitation of the copper carbonate/hydroxyl.
The effects of the electrochemical potential on the pyrite Therefore, the overall adsorption of copper ions necessarily does
activation by copper ions at pH 9 and in the potential region from not mean that the activation of pyrite has effectively occurred
100 to +400 mV (SHE) was studied and it was found that in [122]. Based on XPS, IR7, UV–vis8 and flotation studies, Shen et al.
[165] proposed an electrochemical mechanism for the depression

4
PEEM: photoemission electron microscopy.
5 7
ToF-SIMS: time of flight secondary ion mass spectrometry. IR: infrared spectroscopy.
6 8
EXAFS: extended X-ray absorption fine structure. UV–vis: ultraviolet–visible spectroscopy.
8 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

of pyrite involving the formation of copper hydroxide on the of xanthates [85], the results of flotation studies conducted by
copper activated surfaces of pyrite by reduction of oxygen, which Trahar [184] using ethyl xanthate as collector showed that pyrite
leads to a decrease in the solution potential (Reactions (17) and can be floated by xanthates at potentials much more cathodic than
(18)). the equilibrium potentials of the xanthate/dixanthogen couples.
Thus, dixanthogens cannot be solely responsible for the flotation of
H2O(aq) + 2e + 1/2O2(aq) = 2OH(aq) (17)
pyrite. Using the Eh-pH stability diagram of the Fe–EX–H2O
system, it was clearly found that the potential of flotation
commencement is approximately equal to potential for formation
Cu2+(aq) + 2OH(aq) = Cu(OH)2(surface) (18)
of ferric xanthate compounds [181,185–187]. Therefore, it can be
Under such conditions, oxygen conditioning has been found to concluded that the formation of the ferric xanthate compounds
have an important effect on the rate of the pyrite depression by Cu2 and adsorption of ethyl xanthate ions may be the reason why the
+
species [165]. pyrite flotation occurs at more cathodic potentials than the
Formation of the copper hydroxide on the surface may also potential required for the dixanthogens formation from xanthates
occur through galvanic interactions between the pyrite mineral [185,188,189]. FTIR9 studies showed that the adsorption of both
surface and copper sulfide layer formed on the pyrite surface [165]. ferric xanthate compounds and dixanthogens occurs on the pyrite
On this basis, cupric ions are produced by oxidation of the copper surfaces reacted with xanthates [85,99,146,150,159,185,186,190,
sulfide layer and then, react with hydroxide ions which are 191], but the amount of adsorbed ferric xanthates is much less than
produced by reduction of oxygen on the pyrite surface. that of adsorbed dixanthogens [85,99,159,169,185,192,193]. It was
also found that ferric xanthates form a monolayer on the surface,
Pyrite activation by lead whereas dixanthogens are adsorbed as multiple layers [186,194]. In
addition to ferric xanthates and dixanthogens, a minor amount of
The effect of the electrochemical potential on the activation of monothiocarbonates was also found on the surface by voltam-
pyrite by lead ions has also been investigated. Peng and Grano metry studies conducted by Harris and Finkelstein [195]. They
[154] measured the pulp potential during the lead activation of identified them as intermediate products of the ferric xanthates
pyrite but observed no changes in the pulp potential. Peng et al. formation during interaction between pyrite and xanthates.
[122] conducted zeta potential measurements on the lead- Using FTIR studies, four main steps in the adsorption process of
activated pyrite and found that the lead-activated pyrite displays xanthate collectors on the pyrite surface were identified. These
similar zeta-potential properties at different electrochemical steps include [186]:
potentials. They also found that the lead-activated pyrite has an
iso-electric point similar to lead hydroxides, oxides or carbonates 1 - Surface oxidation of pyrite.
[166,167]. On the other hand, it was observed that almost all the 2 - Xanthate ions adsorption on pyrite surface and formation of
lead ions added during the activation process were extractable by ferric xanthates.
EDTA solutions. These findings obviously show that the activation 3 - Xanthate ions oxidation and dixanthogen formation.
of pyrite by lead occurs mainly through the formation of lead 4 - Dixanthogen adsorption on pyrite through ferric xanthates
surface complexes such as hydroxides and, unlike the activation present on the surface.
process by copper, new metal sulfide phase does not form [154].
Therefore, since the activation of pyrite by lead ions does not Based on the literatures, it was found that pure dixanthogen
appear to occur through an electrochemical mechanism, in order cannot be effectively adsorbed on pyrite without the existence of
to control pyrite flotation in the presence of lead ions, other suitable adsorption sites on the surface [177,186]. The ferric
methods apart from the methods based on the electrochemical xanthate compounds are believed to be one of the suitable sites for
processes have to be sought [122]. the adsorption. Thus, their formation on the pyrite surface appears
to be necessary for the effective adsorption of dixanthogens [186].
Collector adsorption on pyrite surface Xanthates are reducing agents [11,177,181]. Due to the
equilibrium potential of the xanthate/dixanthogen couple, as
Due to semiconducting properties of sulfide minerals, adsorp- more cathodic than the mixed potential of pyrite, the xanthate
tion of collectors on their surface is usually electrochemical in addition causes a decrease in the mixed potential of the pulp
nature and affected by the electrochemical conditions of the [40,181]. The magnitude of this decrease in the potential indicates
flotation pulp [39,92,99,168–170]. Collector adsorption is influ- that the intensity of interaction of the xanthate with pyrite [40].
enced not only by oxygen, but also by all the oxidizing and reducing Dixanthogen is formed on the mineral surface only when the
agents present in the pulp and collector adsorption mechanism mixed potential of the pulp rises above the xanthate/dixanthogen
depends on activity of the mineral surface [171,172]. equilibrium potential [128,181,196]. Pyrite is the most noble among
the sulfide minerals. Therefore, more dixanthogen is expected to
Collector adsorption on non-activated surface be formed on the pyrite surface compared to other sulfide minerals
[99]. The oxidation potential of dixanthogen (EhX2) can be
The general proposed mechanism for hydrophobisation of the calculated by the Nernst equation (Relation (20)) [85].
pyrite surface in the presence of xanthate collectors is the
EhX2 = E0X/X2  0.059log[X] (20)
oxidation of xanthates to hydrophobic dixanthogens and their
adsorption on the surface [173–178] according to Reaction (19) Where E0X/X2
is the standard potential of the half-cell reaction
[179,180]. expressed by Equation (19) and [X] is the molar concentration of
xanthate. It was demonstrated that there is an inverse relationship
2X = X2 + 2e (19)
between the equilibrium potential of the xanthate/dixanthogen
Charge balance for the oxidation reaction of xanthate to redox reaction and length of the hydrocarbon chain. An increase in
dixantogen is preserved by the cathodic reduction of adsorbed the length of the hydrocarbon chain causes a decrease in the
oxygen according to Reaction (17) [181–183].
Although dixanthogens have been known as the main
hydrophobic products formed on the pyrite surface in the presence 9
FTIR: fourier transform infrared spectroscopy.
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 9

equilibrium potential of the xanthate/dixanthogen couple and xanthate are cathodically shifted by an increase in the pulp pH
[185,186]. and xanthate concentration, respectively. However, the shift
The rate of the xanthate adsorption by pyrite from aqueous caused by increasing xanthate concentration by an order of
solutions can be expressed as Relation (21) [174,187,197]. magnitude is greater than that by increasing pH by a unit. These
results showed that it is possible to find a relationship between the
(dcX/dt) = kcX-a  cO2bcH+g (21)
pulp pH and the concentration of a xanthate collector during a
1/2
where k = (1/V)k'(AaAc) ,V is the liquid volume, k' is the rate flotation process. For example, they represented the general
constant, Aa and Ac are the surface areas of sites over which the Relation (22) for the ethyl xanthate collector.
oxidation and reduction reactions take place, respectively, cX-, cO2
[C2H5OCS2]/[OH]0/8 = Constant (22)
and cH+ are the xanthate ion, dissolved oxygen and hydrogen ion
concentrations in the solution, respectively, and a, b, and g are
reaction orders. For example, on pyrite at a constant oxygen Effect of oxygen content on collector adsorption
concentration, a = 0.5 and g = 0 in neutral solution and a = 0.75 and Some researchers have studied the effect of oxygen on the
g = 0.25 in alkaline solution [187]. xanthate adsorption on the pyrite surface. It was found that the
Apart from xanthates, other collectors such as DTPI10 are also presence of oxygen improves the xanthate adsorption by pyrite
used in the sulfide minerals flotation [62,198–200]. Flotation [174,202,203]. An increase in the dissolved oxygen concentration
studies in the presence of these collectors have shown that the in the pulp causes an increase in the pulp potential and
electrochemical conditions have significant influence on their consequently an increase in the oxidation rate of xanthate to
performance [198,199]. Güler [47] and Hicyilmaz et al. [48], dixanthogen on the pyrite surface [174,202,204,205]. Furthermore,
performed spectroscopic and electrochemical studies and found it was also suggested that oxysulfides and also ferric ions produced
that DTPI dimer can only be formed on the pyrite surface at highly by the pyrite oxidation can facilitate dixanthogen formation
oxidizing conditions. Despite these studies, the electrochemical [53,85,190,206,207]. Investigations showed that the xanthate
behavior of pyrite in the presence of these types of collectors is still adsorption on the non-activated pyrite surface was along with
not well understood [62]. an increase in ferrous iron concentration in the pulp [208]. It was
In another study, researchers have conducted flotation tests on found that the reduction of ferric hydroxide to ferrous ions and
pyrite using two different types of collectors, including PAX and a development of dixanthogen occur simultaneously on the pyrite
trithiocarbonate. The results of the flotation experiments showed surface [146,208]. This finding is in agreement with results of FTIR
that lower recoveries were obtained by trithiocarbonate collector studies conducted by Leppinen et al. [135]. Fig. 3 shows this
type compared to PAX [201]. These differences in the flotation process schematically.
results could be due to the differences in the electrochemical Although it is believed that oxygen is necessary for the pyrite
properties of these two types of collectors. It was found that the flotation in the presence of xanthate, the findings of some studies
standard reduction potentials of xanthate type collectors are about have shown that the recovery of pyrite may be improved when
90 mV more negative than that of their corresponding trithiocar- nitrogen is used instead of oxygen as flotation gas [53,209,210].
bonate homologues. On this basis, it could be concluded that during Flotation experiments in the presence of 50 g/t PAX11 collector by
flotation, pulp electrochemical potential was high enough for air and nitrogen during the conditioning step and as flotation gas
xanthate oxidation to dixanthogen and its adsorption on the pyrite showed that the pyrite recovery increased from 31.4% to 94.1%
surface, whereas this value of potential was probably not enough for when air was replaced by nitrogen [53]. Using DRIFT12 analysis,
the trithiocarbonate type collector oxidation. Therefore, adsorption they found that the xanthate adsorption and the dixanthogen
of trithiocarbonate oxidation products did not occur on the pyrite formation increased in the nitrogen atmosphere. Pulp potential
surface, leading to the recovery reduction. These results clearly measurements showed that this increase in the formation of
indicated that it is necessary to consider the electrochemical nature dixanthogen was due to lowering the pulp potential and
of collectors used in the flotation processes of pyrite. consequently inhibiting the formation of the hydrophilic oxidation
products on the pyrite surface because of the presence of nitrogen.
Effect of pH on collector adsorption Similar results were also obtained in experiments performed by
The effect of pH on the xanthate oxidation and formation of Miller et al. [211]. On the basis of XPS analysis, they reported that
dixanthogen has also been studied. The results showed that, at the nitrogen atmosphere not only inhibited the formation of
lower pH levels, pyrite surface is oxidized at more positive hydrophilic oxidation products on the pyrite surface, but also
potentials than the equilibrium potential for the dixanthogen caused reduction of the surface compounds on pyrite and as a
formation. Under such conditions, the oxygen reduction and the result, the xanthate adsorption on pyrite surface was facilitated.
xanthate oxidation are the dominant electrochemical reactions in
the system and as a result, the pyrite surface will be hydrophobic Effect of pyrite surface oxidation products on collector adsorption
through adsorption of dixanthogen. By increasing pH, the required Electrochemical polarization method was used to determine
potential for oxidation of pyrite decreases. At higher pH levels, the the effect of the pyrite surface composition on the xanthate
oxidation of the pyrite surface occurs at lower potentials than the adsorption in a flotation system. The results of flotation on the
potential required for the dixanthogen formation from xanthate. electrochemically polarized pyrite samples (at polarization poten-
Therefore, the major electrochemical reactions in the system tials of +250 and 250 mV (SHE)) in the alkaline environment (pH
include the oxidation of pyrite and the reduction of oxygen. In such 9.18) showed that the anodic polarization decreased pyrite
a state, rate of the xanthate oxidation decreases and the pyrite recovery by 12%, whereas the cathodic treatment increased the
surface will remain hydrophilic [50]. recovery by 4–5% [212]. Using laser scanning microscopy, it was
It has been suggested that the negative effect of pH increasing found that the adsorption of xanthate on the anodically polarized
on the xanthate adsorption can be reduced by increasing xanthate sample significantly decreased due to severe oxidation of surface
concentration. The results of voltammetry studies conducted by and its coverage by iron oxidation products. In contrast, in the case
Janetski et al. [50] revealed that the oxidation potentials of pyrite

11
DRIFT: diffuse reflectance infrared fourier transform spectroscopy.
10 12
PAX: potassium amyl xanthate. DTPI: dithiophosphinate.
10 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

Fig. 3. Dissolution of surface ferric hydroxide and dixanthogen formation on non-activated pyrite surface [208].

of the cathodically treated sample, analysis of the microimages the addition of KEX13 collector at the end of the period of the
showed that not only was no new phase due to the iron oxidation activation with copper ions [150]. It was also observed that the
formed on the surface, but the iron oxidation products present on it amount of this precipitate increased by increasing collector
were also dissolved. Instead, it was observed that the formation of dosage. Moreover, the yellow precipitate was found not to be
dixanthogen phases on the pyrite surface increased after contact- removed, even by washing with a sulfuric acid solution (pH 5). FTIR
ing the sample with xanthate. This finding that the electrochemical studies revealed that this precipitate was comprised mainly of
adsorption of xanthate on the pyrite surface occurs effectively only cuprous xanthate along with a small proportion of dixanthogen.
in slightly oxidizing or reducing environments can be attributed to The formation of cuprous xanthate on the copper-activated pyrite
facilitation of electron transfer across the interface between the surfaces in the presence of xanthate has been reported by other
slightly oxidized or the unoxidized surface and solution. The researchers [45,146,153,159,162].
results of these studies and similar results clearly indicate the The proposed mechanism for the xanthate adsorption is a two-
importance of the pyrite oxidation products in the adsorption of step process, including a surface electrochemical reaction which
xanthate on the surface and its floatability. produces copper ions and a chemical reaction that produces the
cuprous xanthate compound [85]. The cuprous xanthate com-
Effect of pyrite type and origin on the collector adsorption pound is formed as a monolayer on the pyrite surface and known as
It has been found that a defect in the pyrite lattice influences the the main hydrophobic product of the interaction of xanthate with
adsorption process of xanthate on the pyrite surface. Electronic the copper-activated surfaces [45,146,153,159,162].
structure and band structure studies on four types of pyrite including It was reported that, during conditioning of pyrite at pH 7, if
perfect, Co-substituted, As-substituted, and intercrystalline Au equal dosage of xanthate collector and copper are used, the
pyrites was performed by Xian et al. [106] and it was found that cuprous xanthate will be the only formed compound. However, if
there is a relationship between the amount of xanthate adsorbed on unequal amounts of xanthate and copper are used, considerable
the pyrite surface and band-gap value. The results of the studies amounts of dixanthogen will also be formed in addition to the
showed that a pyrite with a lower band-gap transfers an electron cuprous xanthate [146]. The studies have shown that, at higher
from a xanthate collector to an oxidant more quickly (such as oxygen concentrations of copper, cupric xanthate is also formed from
or ferric iron). As a result, the oxidation of xanthate collector to combining aqueous Cu2+ ions with xanthate, but due to its unstable
dixanthogen occurs more readily. Moreover, they found that the nature, it is then oxidized to dixanthogen [150,163].
stability of the electrochemically adsorbed oxidation products on the Xanthates show a strong affinity to copper and their adsorption
surface increases with a decrease in the band-gap of pyrite [116,213]. on the copper- activated pyrite surfaces increases with increasing
It was also observed that intercrystalline Au and co-substituted Eh. However, it has been found that if Eh highly increases, the
pyrites adsorbed more xanthate compared to perfect and As- extensive pyrite oxidation will occur and the surface will be
substituted pyrites due to having lower band-gap values [106]. covered with iron hydroxide/oxide films. As a result, due to the
Xanthate collectors are also used to separate coal-pyrite in the hydrophilic nature of these products, the pyrite floatability will
coal desulfurization process by flotation. Adsorption experiments decrease [45].
and rest potential measurements conducted by Miller et al. [214]
showed that coal-pyrite has more adsorption ability for xanthate in Collector adsorption on lead activated surface
comparison to pure pyrite. It appears that the rest potential of coal- In the case of lead activated pyrite surfaces, it was found that
pyrite is influenced by other electrochemical processes such as lead has a catalytic effect on the dixanthogen formation. The
oxidation of electrochemically active components present in coal. proposed mechanism for the dixanthogen precipitation includes
three steps. First, xanthate adsorbs on the activated sites as
Collector adsorption on activated surface
Pb(OH)X. Then, the xanthate ions adsorption occurs to form

Collector adsorption on copper activated surface


During conditioning of pyrite, it was observed that a yellow
precipitate was formed on the pyrite surface immediately after 13
KEX: potassium ethyl xanthate.
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 11

Pb(OH)X.X. Finally, the adsorbed xanthate is oxidized and inhibit the surface reduction reactions [181]. However, no evidence
dixanthogen is precipitated [85]. has been found that cyanide inhibits the reduction reaction of
oxygen [173]. Another possibility is to enhance oxidation reactions
[181]. Since cyanide has a strong reducing nature, it is oxidized to
Depressants
cyanate and/or cyanogen according to relations (25)–(27) [188].
Inorganic depressants 2CN + O2 = 2CNO (25)

Cyanide, mainly as potassium cyanide (KCN) and sodium


cyanide (NaCN) has been known as one of the most common 2CN + H2O + 1/2O2 = (CN)2(g) + 2OH (26)
depressants for pyrite in flotation process [215]. Simple cyanide
compounds are dissolved in water and produce ionic species
according to the following reaction [216]: (CN)2 + 1/2O2 + 2OH = 2CNO + H2O (27)
+x 
A(CN)x = A + x(CN) (23) However, it has been found that these reactions are slow, and
where A is an alkali metal and X is the valence of the alkali metal thus do not appear to have an important role in suppressing the
and it is equal to the number of cyano groups present in the xanthate oxidation through lowering the mixed potential [181].
compound. Enhancing the anodic reactions by cyanide may also be due to
The released cyanide anion, CN, hydrolyzes through abstract- the formation of soluble iron cyanide compounds instead of the
ing a proton from water to produce aqueous hydrogen cyanide insoluble oxide/hydroxide species. Since these iron cyanide
[217]: compounds, unlike the oxide/hydroxide species, are soluble, they
cannot inhibit the pyrite oxidation, and thus the anodic reactions
CN + H2O = HCN + OH (24) are enhanced [181,188]. This finding was confirmed by voltam-
metry studies conducted by Wang and Forssberg which showed a
Hydrogen cyanide is a volatile substance and can easily
linear relationship between the concentration of cyanide and the
evaporate from the solution as a very toxic gas [218–220]. The
peak current of the pyrite oxidation [188]. Although these studies
concentrations of cyanide ion and hydrogen cyanide are governed
showed that cyanide suppresses xanthate oxidation through
by pH of the solution. These concentrations are at equilibrium
decreasing the mixed potential, it was found that the xanthate
when the pH is equal to pKa of HCN (acid–base dissociation
oxidation in the presence of cyanide is not enhanced by increasing
constant) [216]. At pH values higher than the pKa value, cyanide
mixed potential by adding an oxidizing agent [173]. Therefore, the
ion concentration in solution increases while at pH values lower
decrease in the mixed potential does not appear to be the main
than the pKa value, volatile hydrogen cyanide concentration
cause for suppressing the xanthate oxidation.
increases [220]. Since pKa value depends on various factors such as
Several other causes such as high consumption of oxygen in the
the concentration of dissolved solids in the solution, reported
cyanide oxidation reactions and direct reduction of dixanthogen to
values for pKa is often inconsistent [216]. Although a value equal to
xanthate by cyanide have also been reported [188]. The most
9.31 has been frequently quoted as pKa in several reports [221–
acceptable explanation for the inhibition of the xanthate oxidation
224]. Therefore, it is necessary to keep the solution pH above
by cyanide has been found to be the formation of insoluble
9.31 to avoid volatilization of cyanide as hydrogen cyanide gas
cyanoferrate complexes on the pyrite surface [50,99]. It has been
[225].
found that iron hexacyanide compounds can be formed by the
It has been found that electrochemical interaction of xanthates
reduction of the surface ferric hydroxide layer in the presence of
is strongly affected by the presence of cyanide ions [173]. Results of
cyanide [50] according to Reaction (28) [99].
voltammetry studies conducted by Janetski et al. [50] revealed that
at constant xanthate concentration and pH, increasing cyanide ion 5Fe(OH)3 + 12CN + 15H+ + 3e = Fe3[Fe(CN)6]2 + 15H2O (28)
concentration causes a shift in the oxidation potential of xanthate
to more positive values. Based on these results, they reported that It has also been reported that, in the presence of cyanide,
insoluble ferric xanthate compounds formed on the pyrite surface,
cyanide ions appear to have an inhibiting effect on the oxidation
process of xanthate. It was also found that, at constant xanthate which act as suitable adsorption sites for dixanthogen, become
unstable. These compounds are then replaced by Fe(CN)64 and
concentrations, the anodic shift in the oxidation potential of
xanthate due to increasing the cyanide ion concentration is also Fe(CN)63 at higher electrochemical potentials (Reaction (29))
[188].
gradually reduced with decreasing the solution pH. These findings
have been confirmed by other studies [181,194]. Fe(OH)2EX(s) + 6CN = Fe(CN)63 + EX + 2OH (29)
De Wet et al. [181] by electrochemical impedance measure-
ments, observed that in a low frequency range, the electrochemical Consequently, the dixanthogen adsorption on the surface is
impedance of the pyrite electrode in the presence of NaCN was reduced. The presence of these species on the surface has been
considerably higher than in its absence. This shows that the confirmed by zeta and redox potential measurements and also
presence of cyanide increases polarization resistance. An increase thermodynamic calculations [226]. In addition, it has also been
in polarization resistance means a decrease in the electrochemical found that since these species are hydrophilic, their formation on
reaction rates on the pyrite surface. De wet et al. [173] observed the surface results in a decrease in the hydrophobicity due to the
that the mixed potential of pyrite decreased from +195 to +125 mV adsorbed dixanthogen [50]. It has been noted that cyanide
(SHE) after adding 200 mg/l cyanide to the flotation pulp in the effectively acts as a depressant only when the pyrite surface
presence of 50 g/ton of xanthate. Since by decreasing mixed undergoes extensive oxidation [50,227].
potential, the oxidation rate of xanthate to dixanthogen decreases, Studies have shown that, even in the presence of copper ions,
it was concluded that suppressing the xanthate oxidation in the cyanide is able to depress pyrite. It has been observed that, in
presence of cyanide can be due to decreasing the mixed potential alkaline conditions and in a potential range of approximately
[173,181,188]. 300 to +450 mV (SHE), addition of cyanide to the flotation pulp
There are two possibilities that can cause a decrease in the causes the formation of cyano-copper species such as insoluble
mixed potential in the presence of cyanide. One possibility is to CuCN and Cu(CN)32 at low and high CN/Cu concentration ratios,
12 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

Table 2
Mechanisms of depression of pyrite flotation by cyanide ions in different conditions.

Condition Mechanism Reference


Collector-less flotation Removing hydrophobic sulfur species from the surface by the formation of thiocyanate compounds [188]
In the presence of xanthate Replacing surface adsorption sites for dixanthogen by insoluble cyanoferrate complexes [50,99]
In the presence of copper ions Reducing concentration of the free copper ions in the pulp and inhibiting the formation of [188]
coprous xanthate by the formation of cyano-copper species
In the presence of lead ions Cyanide is not able to depress the pyrite flotation. [228,229]

respectively. The formation of these species leads to a significant with high molecular weights composed of monosaccharide units.
reduction in the free copper ions concentration in the pulp and Natural polysaccharides depress the pyrite in the flotation through
consequently, inhibition of the coprous xanthate formation. It has selective adsorption on pyrite surface [232]. It was found that both
also found that, even if the coprous xanthate compounds are natural polysaccharides and xanthats adsorb on the pyrite surface,
formed on the surface, the addition of cyanide will dramatically but hydrophobic molecules of dixanthogen are enveloped by large
reduce the stability of these compounds and will dissolve them hydrophilic molecules of natural polysaccharides, resulting in the
(Reactions (30) and (31)) [188]. pyrite depression [232–234]. Due to the heterogeneous nature of
the oxidized pyrite surface, their adsorption occurs at different
CuEX(s) + CN = CuCN(s) + EX (30)
sites on the surface. Xanthate ions adsorb on non-oxidized sites on
the pyrite surface, while these organic depressants adsorb on
oxidized sites [233]. The adsorption of natural polysaccharides on
CuEx(s) + 3CN = Cu(CN)32 + EX (31)
oxidized sites was found to be due to the existence of two hydroxyl
It has been reported that cyanide, even at relatively high groups on C-2 and C-3 carbon atoms in each unit of the
concentrations, is not able to depress the lead activated pyrite polysaccharides, which enable polysaccharides to form complexes
because the cyanide anion cannot form complex with the lead with hydroxide species present on the surface. Therefore,
cations [228]. This finding has been used to improve performance adsorption of these organic compounds on pyrite surface resulting
of N2TEC flotation technology applied at Newmont's Lone Tree in pyrite depression depends on level of surface oxidation and
Plant in Nevada, where it was observed a loss in the auriferous density of metal oxidation species on the surface [232].
pyrite recovery, due to the presence of cyanide in the flotation mill CMC14 is another organic compound which acts as depressant
water. It has been found that higher recovery can be obtained at in pyrite flotation process. It is a cellulose derivative being
lower xanthate concentrations in reducing conditions by the produced by etherification process. The presence of negatively
activation with lead ions [229]. charged carboxyl groups in CMC structure in addition to hydroxyl
In collectorless flotation, the elemental sulfur and polysulfides groups, causes increasing CMC’s selectivity compared to natural
have been found to be responsible for the pyrite floatability. In the polysaccharides. Unlike the carboxyl groups, which is able to
presence of cyanide, these species are unstable [188]. It has been interact with various forms of metallic species, the hydroxyl groups
found that cyanide is able to react with the elemental sulfur and is only able to interact with metal hydroxyl species. Therefore,
polysulfides to form thiocyanate and to remove the hydrophobic similar to natural polysaccharides, adsorption of this depressant on
species from the surface in the range of low potentials (Reactions the pyrite surface is also affected by intensity of the surface
(32) and (33)). oxidation and presence of oxidation products on the surface [232].
PAM15 (a synthetic polymer with general chemical formula
S + CN = SCN (32)
–CH2CHCONH2) is another organic compound which, similar to
natural polysaccharides and CMC. PAM adsorption on the surface
depends on the presence of metal oxyhydroxy species which are
(x  1)CN + Sx2 = (x  1)SCN + S2 (33) produced from oxidation process. Studies conducted in laboratory
These experimental findings have been confirmed by thermo- showed ability of PAM and its derivatives to depress pyrite in
dynamic calculations [188] and also by XPS analysis [68]. Table 2 flotation process [232].
summarizes the mechanisms of depression of the pyrite flotation Lignosulfonates, or sulfonated lignins (water-soluble anionic
by cyanide ions in different conditions. polyelectrolyte polymers) are also used as organic depressants for
Sulfoxy reagents such as sulfur dioxide, sodium sulfite or pyrite flotation. Depression mechanism of pyrite flotation by these
sodium metabisulfite are also widely used as depressants for pyrite organic compounds has been investigated in both non-activated
[50,146,202]. Studies have shown that these reagents suppress the and Cu-activated states [232]. Electrochemical studies conducted
adsorption of xanthate by reducing the mixed potential to below on non-activated pyrite flotation showed that the biopolymers,
the potential required for the oxidation of xanthate to dixanthogen after adsorption on pyrite, passivate surface and suppress
[50,202,230] and enhancing formation of hydroxide species on the electrochemical reactions occurring on the pyrite surface, includ-
pyrite surface [146]. ing oxidation and reduction reactions of pyrite itself and also
oxidation of xanthate on the surface [232,235–237]. It was found
Organic depressants that this was due to form insulator layers on the surface, resulted in
a reduction in pyrite conductivity and an increase in the difficulty
Although various inorganic reagents (e.g., cyanide and sulfoxy in electrons transferring between pyrite-solution and pyrite-
species) have been found to be effective in the depression of pyrite, xanthate interfaces [232,236,237]. In the flotation of Cu-activated
there are problems associated with the use of these reagents such pyrite, studies showed that the biopolymers was able to accelerate
as high cost and environmental concerns [3,91,231]. In order to cuprous sulfide and xanthate compounds to form complexes with
overcome such problems, some researchers have focused on extracted cuprous ions from the sulfide and xanthate forms
developing alternative cheap and environmental friendly organic
depressant.
Natural polysaccharides, such as starch, dextrin and guar gum, 14
CMC: carboxymethyl cellulose.
are used as depressant. These organic compounds are polymers 15
PAM: polyacrylamide.
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 13

[232,238]. In these conditions, the pyrite depression occurs as a have an important role in depressing the pyrite flotation [245–257].
result of the formation of Cu-biopolymer and Cu(OH)2 hydrophilic It has also been reported that the use of the electrochemically active
species on the pyrite surface [232]. grinding media causes a decrease in the xanthate oxidation rate in
DETA16 is another organic compound which is used as a pyrite the flotation process [185,201]. This is due to the dissolved oxygen
depressant in the flotation process. In the case of Cu-activate pyrite consumption in pulp during the grinding media oxidation, which
flotation, it was found that DETA causes depression of the pyrite results in a reduction in Eh of the pulp [146,201,258].
surface through promoting oxidation of Cu(I) to Cu(II) and The extent of the galvanic interaction occurring during grinding
removing Cu(I)-S species from the surface resulting in a substantial and consequently the magnitude of change in the electrochemical
reduction in xanthate adsorption. DETA also increases hydrophilic potential of pulp has been found to be directly related to the
oxidation products such as Fe-Ox, Cu(OH)2 and Cu-DETA. Depres- difference in the electrochemical properties between grinding
sion mechanism of Pb-activate pyrite by DETA has also been media and sulfide minerals [72,128,245]. It was reported that a
investigated. Electrochemical studies indicated that DETA sup- conventional mill produces a reducing grinding environment with
presses xanthate oxidation, probably by reducing rest potential of a low electrochemical potential while a porcelain or an autogenous
Pb-activated pyrite [232]. mill produces a non-reducing grinding environment with a high
Ovalbumin (chicken egg albumin), which is a high molecular electrochemical potential [252]. Moreover, it was found that the
weight monomeric glycoprotein was proposed by Guler et al. [91] use of grinding media with more electrochemical activity results in
as another organic reagent. Ovalbumin, due to having four more reducing grinding conditions [93,147]. Chen et al. [259]
sulfhydryl ( SH) bonds in cysteine groups and one disulfide conducted flotation tests on two samples containing pyrite that
(SS) bond in cysteine, has been found to be electrochemically were ground with two types of grinding media, including mild
active in aqueous solutions [239–242]. steel and stainless steel media. The results showed that the
Flotation studies at pH 9.2 and in a potential range of 400 to flotation recovery of pyrite for the sample ground with less active
+800 mV (SHE) by ovalbumin as depressant showed that in grinding media (stainless steel media) was significantly higher
reducing conditions, adsorption of ovalbumin on the pyrite surface than that with more active grinding media (mild steel media).
occurred at lower rates. Since, in the alkaline conditions and at Based on the XPS analysis, they found that the amount of oxidation
potentials lower than the pyrite open circuit potential, both pyrite species on surfaces of the pyrite particles increased after grinding,
and ovalbumin have negative surface charges, it was concluded and this increase was significantly greater in the case of the sample
that the lower rates of the adsorption are due to the electrostatic ground with mild steel media. These results were in good
repulsion between them. In slightly oxidizing conditions, a slight agreement with the results of EDTA extraction tests reported by
increase was observed in the adsorption rate, which was found to Peng et al. [93].
be due to the hydrophobic interaction of ovalbumin with the Studies have shown that different grinding media also have
hydrophobic oxidation products formed on pyrite. Results showed different effects on the activation process of pyrite. It has been
that the depressing effect of ovalbumin reaches its maximum at found that grinding with more active grinding media results in
oxidizing potentials around +500 mV (SHE) [91], where the surface more pyrite activation by copper ions [259–263]. In contrast, it has
is intensely oxidized and the ferric species [58,63,99,243], being been observed that electrochemically inert grinding media, which
favorable for the electrostatic interaction of the surface with produce a strong oxidizing grinding condition, have an enhancing
ovalbumin molecules [3,240,244], are formed on the pyrite surface. effect on the activation of pyrite by lead ions [122]. This difference
The adsorption rate has been found to remain approximately in the activation by copper and lead ions is attributed to the
constant in the highly oxidizing environment. Results of cyclic different mechanisms of the pyrite activation by these ions. The
voltammetry and FTIR spectroscopy showed that in these activation of pyrite by copper ions occurs through an electro-
conditions, the pyrite depression occurs by the formation of chemical mechanism, which is enhanced in reducing conditions,
ovalbuminmetal chelates mainly by the electrochemical pro- while the activation of pyrite by lead ions is independent of the
cesses [91]. electrochemical potential [154]. Since in an operating mineral
processing plant, it is impractical to adjust the electrochemical
Effect of grinding environment on pyrite electrochemical condition during grinding by replacing the existing mill and
properties grinding media, the addition of oxidizing or reducing agents has
been proposed by researchers as an alternative solution for
Effect of grinding media type controlling the activation process of pyrite during grinding [122].
The effect of the electrochemical activity of media grinding on the
It has been found that grinding has significant effects on the various processes in pyrite flotation is summarized in Table 3.
electrochemical potential at the mineral/solution interface and the
nature of reactions occurring in a mill is considerably influenced by Effect of oxygen content in grinding system
the type of grinding media [122]. The use of electrochemically
active grinding media causes galvanic interaction between pyrite It is well known that oxygen plays an important role in the
and the grinding media during grinding, which results in an effect galvanic interaction during grinding. Huang and Grano [261]
on the electrochemical behavior of pyrite. In this galvanic studied the floatation recovery of pyrite as a function of galvanic
interaction, pyrite due to having a higher rest potential acts as a current during grinding in the presence of copper ions under
cathode and results in the oxygen reduction on its surface and the different atmospheres including nitrogen, air and oxygen. Results
production of hydroxide ions. In contrast, the grinding media, showed that nitrogen purging produced the lowest galvanic
which act as an anode, are oxidized and release ferrous ions. The currents as expected. In this condition, with increasing the galvanic
produced ferrous ions undergo further oxidation to ferric ions and current, the pyrite recovery increased which appeared to be
then react with the hydroxide ions and are precipitated as ferric associated with the increased rate of the cupric ion reduction on
hydroxide on the pyrite surface [72,245]. The iron oxidation the pyrite surface. When air was purged during grinding, higher
species emanating from the grinding media have been found to galvanic currents were recorded. This was mainly due to an
increase in the reduction rates of ferric ion and oxygen. An increase
in the pyrite recovery was still observed with the galvanic current
16
DETA: diethylenetriamine. and the copper ions addition. This increase was found to be
14 H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18

Table 3
Effect of electrochemical activity of media grinding on various processes in pyrite flotation.

Process Effect of increasing electrochemical activity of media grinding Reference


Collector-less flotation A decrease in pyrite floatability [259]
Xanthate adsorption A decrease in xanthate adsorption rate [185,201]
Activation by copper An increase in activation rate [259–263]
Activation by lead A decrease in activation rate [122]

because of the increased pulp potential due to air purging, increased production of ferrous iron. The results also showed that
resulting in an increase in the adsorption of xanthate in the more hydrogen peroxide was produced during grinding under a
conditioning stage. In the oxygen purging, the galvanic currents nitrogen atmosphere than under an air atmosphere, which was
were the highest because of very high rates of the reduction of explained to be due to a change in Eh and pH of the pulp in the
ferric ion and oxygen. In this case, it was found that the amount of nitrogen atmosphere, resulting in producing more ferrous iron
the iron oxidation species on the pyrite surface increased while [246].
copper sulfide formed on the surface was oxidized. This resulted in
a decrease in the floatability of pyrite with the galvanic current. On Summary and recommendations
the basis of these results, Huang and Grano suggested that it may
be possible to predict and optimize the floatation behavior of pyrite In this review, the various electrochemical processes associated
through the measurement of the galvanic current during grinding. with pyrite occurring in a flotation system as well as the key factors
affecting them have been discussed. Pyrite as the most abundant
Effect of water quality sulfide mineral on the Earth has little economic value and in
flotation processes it is often rejected to tailings, unless it contains
The quality of water used in grinding is another important significant amounts of valuable metals to be recovered.
factor affecting the galvanic interaction and consequently flotation Over several decades, extensive studies have been conducted on
of pyrite. Moslemi et al. [128] studied effect of presence of sulfate the electrochemical behavior of pyrite in the flotation process to
and chloride ions in water on the rest potentials of pyrite and provide the basic knowledge required for optimizing the process.
grinding media. They found that the presence of these ions causes The results of these studies need to be integrated with each other
an increase in the potential difference between pyrite and grinding to be more effectively applicable to the mineral processing plants.
media, resulting in an increase in the galvanic interaction during Due to the electrochemical nature of pyrite, the studies show
grinding. that any change in the electrochemical potential may have
significant effects on the pyrite flotation results, whether pyrite
Effect of reactions occurred in the grinding system is a gangue or a desired mineral. Table 4 summarizes the
relationship between the electrochemical conditions and process-
It peroxide hydrogen which is a strong oxidizing agent es related to pyrite flotation.
[246,264] can greatly reduce floatability of pyrite [265,266], even These electrochemical processes are affected by various factors
in the presence of xanthate collectors [206], by enhancing the such as pulp pH, pulp solid percent, particle size distribution, pulp
surface oxidation of pyrite and also by oxidizing xanthates to form oxygen content, conditioning and flotation time, type and
perxanthates [199,267,268] which do not have collector properties concentration of reducing or oxidizing agent and electrochemical
[267,269,270]. Studies have shown that hydrogen peroxide can be properties of collector.
produced during grinding of pyrite [271–276] both in the presence Grinding also has significant effects on these processes and
[277–282] and absence of oxygen [278–282]. In the presence of therefore it is necessary to pay special attention to it. Type of mill,
oxygen, superoxide anion, which is generated by ferrous iron, grinding time, grinding atmosphere, surface area of solid particles,
reacts further with the ferrous iron to form hydrogen peroxide electrochemical activity of grinding media and also type of
(Reactions (34) and (35)) [246,264,278]. grinding method (dry or wet) are important factors associated
with the grinding process, affecting the electrochemical inter-
Fe2+ + O2 = Fe3+ + (O2) (34)
actions.
The presence of various impurities in the water used in the
flotation, which is probably due to dissolution of various minerals
Fe2+ + (O2) + 2H+ = Fe3+ + H2O2 (35)
and also due to flotation reagents remaining in recycled water may
In the absence of oxygen, hydrogen peroxide is formed by change the intensity of the electrochemical interactions and result
combining two hydroxyl radicals which are generated by reacting in unwanted depression or flotation of pyrite. Therefore, the
ferric iron with water (Reactions (36) and (37)) [246,264,278]. quality of water used in the flotation circuit should be regularly
monitored and maintained at a optimum level.
Fe3+ + H2O = HO + H+ + Fe2+ (36) It is important to consider the geographical origin of pyrites.
Pyrites from different geographical regions, due to having different
chemical and physical properties such as iron to sulfur ratio, crystal
2HO = H2O2 (37) structure and surface morphology exhibit different electrochemi-
Nooshabadi et al. [246] studied some factors affecting the cal properties, which may result in a various oxidation, depression,
production of hydrogen peroxide during grinding and found that activation, collector adsorption and flotation behaviors.
the amount of formed hydrogen peroxide increases with increas- It is well known that the electrochemical interactions do not
ing grinding time and solids concentration due to the increased occur uniformly throughout the pyrite surface and their intensity
surface area of solids in contact with water. In addition, they found may vary significantly even between adjacent points. This can lead
that an increase in the electrochemical activity of grinding media to the formation of different products on the surface of different
[246,281] as well as a decrease in the pH of the pulp [281,282] leads particles. Therefore, it is important to conduct a comprehensive
to an increase in the formation of hydrogen peroxide because of the study to fully identify the factors causing such variations in the
H. Moslemi, M. Gharabaghi / Journal of Industrial and Engineering Chemistry 47 (2017) 1–18 15

Table 4
Relationship between electrochemical conditions and processes in pyrite flotation.

Electrochemical process Electrochemical conditions Explanation


Flotation of pyrite by Moderately oxidizing potentials are favorable.  At these potential values, hydrophobic sulfur-rich species are produced on the
oxidation surface.
 At these potential values, iron species produced by the oxidation are soluble.

Depression of pyrite by Strongly oxidizing potentials are favorable.  In these conditions, hydrophobic sulfur species are oxidized into hydrophilic
oxidation species.
 In these conditions, hydrophilic iron oxide/hydroxide species are formed and
precipitated on the surface.

Strongly reducing potentials are favorable.  At strongly reducing potentials, hydrophobic sulfur species present on the surface
are reduced to hydrophilic species.

Activation of pyrite by copper Increasing potential has an adverse effect.  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 mineral–solution
interface, and thus, reduce the xanthate adsorption on the surface.

Xanthate adsorption on A great decrease or increase in the potential has  A great decrease in potential leads to a decrease in the xanthate oxidation to
copper activated surface of adverse effects. The potential must be optimized. dixanthogen.
pyrite  A great increase in potential leads to the formation of copper carbonate/hydroxyl
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 mineral–solution interface, and thus, reduce the
xanthate adsorption on the activated surface.

Depression of pyrite by Oxidizing potentials are favorable.  In the case of cyanide, it has been found that it is an effective depressant only when
depressants 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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