Mu-2016-The Depression of Pyrite in Selective Flotation by Different Reagent Systems - A Literature Review

Minerals Engineering 96-97 (2016) 143–156
Contents lists available at ScienceDirect
Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng
The depression of pyrite in selective flotation by different reagent

systems – A Literature review
Yufan Mu a,⇑, Yongjun Peng a,⇑, Rolf A. Lauten b
a
School of Chemical Engineering, The University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
b
Pionera, P.O. Box 162, NO-1701 Sarpsborg, Norway
a r t i c l e i n f o a b s t r a c t
Article history: Pyrite is a gangue mineral widely associated with valuable minerals. It is problematic to deal with in dif-
Received 17 December 2015 ferential flotation because it easily reports to flotation concentrates. Pyrite may float due to natural or
Revised 13 June 2016 self-induced hydrophobicity or collector-induced hydrophobicity. Its flotation can also be enhanced by
Accepted 16 June 2016
the activation of copper or lead ions emanating from other minerals. Depressants are generally required
Available online 22 June 2016
to selectively depress pyrite. In this article, a comprehensive review of the fundamental studies of depres-
sion mechanisms and effectiveness of commonly used reagent systems to depress pyrite is presented. It
Keywords:
includes inorganic reagents (hydroxyl ions, oxygen conditioning, cyanide, sulfoxyl reagents, etc.), organic
Pyrite
Flotation
reagents such as polysaccharides (starch, dextrin, carboxymethyl cellulose etc.), polyacrylamides, wood-
Depression extracted biopolymers, diethylenetriamine and a combination of these methods. Overall, the action of
Inorganic depressants pyrite depressants is either to desorb the collector or activator from pyrite surface, deactivate the activat-
Organic depressants ing ions, prevent collector adsorption on pyrite, or make the pyrite surface hydrophilic. The mechanisms
of some non-xanthate collectors such as dithiophosphate, dithiophosphinate and thionocarbamate in
rejecting pyrite were also briefly reviewed.
Ó 2016 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2. Inorganic depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2.1. pH modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2.2. Oxidants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2.3. Cyanide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
2.4. Sulfur-oxy species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3. Organic depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.1. Polysaccharides polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.1.1. Starch, dextrin and guar gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.1.2. Carboxymethyl cellulose (CMC). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.1.3. Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2. Lignosulfonate-based biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3.3. Polyacrylamide polymers (PAM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3.4. Diethylenetriamine (DETA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4. Non-xanthate collectors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
⇑ Corresponding authors.
E-mail addresses: [email protected] (Y. Mu), [email protected] (Y. Peng).
http://dx.doi.org/10.1016/j.mineng.2016.06.018
0892-6875/Ó 2016 Elsevier Ltd. All rights reserved.
144 Y. Mu et al. / Minerals Engineering 96-97 (2016) 143–156
1. Introduction 100
2×10-4 M
Pyrite (FeS2, iron disulfide), is the most abundant sulfide min-
80 2×10-5 M
eral and commonly associated with valuable minerals such as
Flotaon recovery (%)

sphalerite, chalcopyrite, galena, gold as well as coal (Wang and
Forssberg, 1991; Wang, 1995; Dimitrijevic et al., 1996; Jiang 60
et al., 1998). Pyrite has very low economic significance and is usu-
ally removed from the valuable components by flotation and pro-
40
cessed as a waste material (Wang and Forssberg, 1991; Chandra
and Gerson, 2009; Bulut et al., 2014). However, its presence has
an impact on the handling and utilizing of the valuable compo- 20
nents. In the differential flotation of multiple sulfide minerals, 1×10-5 M
the misplacement of pyrite into concentrates dilute concentrate
0
grades and reduce the economic value (Wang and Forssberg,
0 2 4 6 8 10 12 14
1991; Chandra and Gerson, 2009; Huang et al., 2013). It also has pH
an adverse effect on the efficiency of pyro metallurgical processes
(Ahmadi et al., 2012). Combustion of pyrite-bearing coal may lead Fig. 1. Flotation recovery of pyrite as a function of pH with various additions of
to the release of sulfur dioxides causing acid rain (Cheng et al., ethyl xanthate adapted from Fuerstenau et al. (2007).
2013). Therefore, there are significant economic and environmen-
tal advantages to separate pyrite from valuable minerals at an early
stage of processing. flotation presents two maximums at around pH 4 and 8 with
Xanthate (ROCSS) is the most extensively used collector in the depression around pH 7. The high flotation yield at pH 4 is due
flotation of base metal sulfide minerals (Janetski et al., 1977; Wang to the formation of sulfur-rich products and dixanthogen
and Forssberg, 1991). Adsorption of xanthate collectors on sulfide (Leppinen, 1990; Wang and Forssberg, 1991; López Valdivieso
mineral surfaces has been considered as an electrochemical pro- et al., 2005). The yield at pH 8 has been explained to be due to
cess, involving charge transfer in the chemisorption of xanthate the formation of iron hydroxide-xanthate complexes on pyrite sur-
ions (Eq. (1)), oxidation of xanthate to dixanthogen (Eq. (2)) and/ face (Fornasiero and Ralston, 1992). The depression of pyrite
or the formation of metal xanthate (Eq. (3)) (Ralston, 1991; around pH 7 has been explained to be due to a high density of ferric
Miller et al., 2002). Anodic oxidation in flotation is generally cou- hydroxide on pyrite, which, however, disappears with the increase
pled with cathodic reduction of oxygen (Eq. (4)) (Miller et al., of xanthate concentration. This has been interpreted to be due to
2002; Guo et al., 2014). the reduction of ferric hydroxides to ferrous species resulting from
the oxidation of xanthate to dixanthogen (López Valdivieso et al.,
X ! Xads þ e ð1Þ 2005). Depression of pyrite observed below pH 2 is due to decom-

2X X2 þ 2e ð2Þ position of xanthate, while the depression above pH 11 is due to
MS þ 2X ! MX2 þ S þ 2e ð3Þ the thermodynamic instability of dixanthogen and the formation
of ferric hydroxide islands on pyrite surface (Leppinen, 1990;
1=2O2 þ H2 O þ 2e ! 2OH ð4Þ
Fuerstenau et al., 2007). While it is clear that flotation or depres-
sion depends upon the balance of hydrophobic and hydrophilic
In Eqs. (1)–(4) X , Xads, X2, MS and MX2 represent xanthate ions,
the adsorbed xanthate, dixanthogen, sulfide mineral and metal species on the surface, the finding above indicate that several ionic
xanthate, respectively. S represents elemental sulfur or polysulfide. equilibria can modify pyrite surfaces only by a change in pH (He
Traditional theories consider that dixanthogen is the predomi- et al., 2005; López Valdivieso et al., 2005). In real ore systems,
nant species responsible for the hydrophobicity of pyrite, which many ionic species can modify the surface properties of pyrite
has been confirmed by means of IR spectroscopy, UV and cyclic and change its flotation behavior.
voltammetry techniques (Fuerstenau et al., 1968; Majima and In alkaline solutions, the separation of pyrite from other base
Takeda, 1968; Janetski et al., 1977; Richardon and Walker, 1985; metal sulfides (Pb/Cu/Zn) is difficult due to the inadvertent activa-
Miller et al., 2002). Dixanthogen is only formed if the mineral sur- tion of pyrite by metallic species such as Cu2+ and Pb2+, either dis-
face reaches a mixed potential higher than the X/X2 equilibrium solved from complex sulfide minerals due to galvanic interactions
value (Allison et al., 1972). The reversible potential for the X/X2 or present as contaminants in process water (Ekmekçi and Demirel,
couple can be computed from the Nernst equation Eq. (5) (Miller 1997; Zhang et al., 1997; Boulton et al., 2001b; Dichmann and
et al., 2002; Guo et al., 2015). Some researchers have suggested Finch, 2001; He et al., 2005; Pecina et al., 2006; Barker et al.,
that for pyrite, the coupled cathodic reaction may also be due to 2014; Owusu et al., 2014). Copper activation of pyrite is an electro-
the reduction of ferric hydroxide to ferrous ions via Eq. (6) chemical process that involves a single fast step of Cu2+ adsorption
(López Valdivieso et al., 2005; Guo et al., 2014). The standard onto the reactive sulfur surface sites. During adsorption Cu2+ is
half-cell potential E0 for the amyl xanthate/di-amyl dixanthogen reduced to Cu+ to form Cu(I)-sulfide species accompanied by the
couple is 0.158 V vs. SHE, and becomes progressively more posi- oxidation of the surrounding S atoms (Weisener and Gerson,
tive with decreasing the length of hydrocarbon chain in xanthate 2000a,b; Chandra et al., 2012; Peng et al., 2012). At alkaline pH
molecules (Winter and Woods, 1973). The formation of ferric xan- above 8.5, copper hydroxide may precipitate over the Cu(I) acti-
thate is also reported to contribute to pyrite flotation (Taggart vated surface (Weisener and Gerson, 2000a). The activation of pyr-
et al., 1934; Leppinen, 1990; Wang and Forssberg, 1991). ite by Pb2+ follows a different mechanism which does not involve
an electrochemical process. It occurs via the precipitation of lead
E ¼ E0 0:059 log½X ð5Þ complexes such as hydroxides or carbonates (Finkelstein, 1997).
þ 2þ The formation of lead complexes depends upon pH. Copper or lead
2FeðOHÞ3 ðsÞ þ 6H þ 2e 2Fe þ 6H2 O ð6Þ
species adsorbing/precipitating onto pyrite surface have significant
Fuerstenau et al. (2007) studied the flotation of pyrite at differ- chemical affinity for xanthate collectors and this interaction
ent pH conditions with various xanthate concentrations, and the enhances pyrite flotation (Leppinen, 1990; Pecina et al., 2006;
results are shown in Fig. 1. At low xanthate concentrations, pyrite Chandra et al., 2012; Barker et al., 2014).
Y. Mu et al. / Minerals Engineering 96-97 (2016) 143–156 145
Various reagents, including inorganic depressants (hydroxyl ite surface, which hinders the oxidation of pyrite and the formation
ions, oxygen, cyanide, sulfoxyl reagents, etc.), organic depressants of dixanthogen. In contrast, when OH is used as a pH regulator
(polysaccharides, polyacrylamides, modified lignosulfonate instead of lime, OH- extracts electrons from the surface providing
biopolymers, diethylenetriamine, etc.) and a combination of two less inhibition to the formation of dixanthogen compared with
or more have been used to depress the flotation of pyrite. Non- Ca(OH)+ (Li et al., 2012). Hu et al. (2000) suggested that the forma-
xanthate collectors, such as dithiophosphate, dithiophosphinate tion of hydrophilic surface species like Ca(OH)2, CaSO4 and Fe(OH)3
or thionocarbamate type collectors, are frequently used in the accounted for the depression of pyrite flotation at higher pH. The
flotation of sulfide minerals to control pyrite flotation. Despite number of adsorption sites of dixanthogen on pyrite surface were
extensive studies, there is a lack of reviews to summarize the reduced due to adsorption/precipitation of Ca2+, Ca(OH)+ and Ca
depression of pyrite in the flotation of various sulfide mineral sys- (OH)2 species depending on pH. Li et al. (2012) assessed the effi-
tems. Herein, the fundamental mechanisms underpinning the roles ciency of copper activation on pyrite surface and found that pyrite
of commonly used depressants for both un-activated and Cu2+/ flotation was depressed by OH and Ca(OH)+. They reported that
Pb2+-activated pyrite as well as non-xanthate collectors are pyrite surfaces were less prone to copper-activation in the pres-
reviewed. Challenges and advantages with their application in ence of lime than NaOH. They proposed that sulfur sites on pyrite
industrial flotation and further development trends are discussed. surfaces for Cu adsorption and activation were covered by Ca in the
This study also provides a guideline for choosing the suitable form of Ca(OH)+, which explains the strong depression of pyrite
reagent system for particular circumstance and sheds light on flotation by lime (Li et al., 2012). Ca(OH)2 may also cover pyrite
the development of potential depressants for pyrite flotation. surface restricting copper activation of pyrite.
However, the depression of pyrite flotation through pH modula-
tion causes some problems in industry. Boulton et al. (2001a)
2. Inorganic depressants pointed out that the increased selectivity of chalcopyrite over pyr-
ite by adjusting pH was at the expense of a decrease in copper
2.1. pH modifiers flotation rate and recovery. This is because that with increasing
pH copper/iron hydroxides may also precipitate on chalcopyrite
It is known that the fate of pyrite in flotation circuits is strongly surface inhibiting the adsorption of collector (Leppinen, 1990). A
pH dependent. Without activation, pyrite exhibits poor floatability large amount of lime addition not only increases the plant operat-
under alkaline conditions (Leppinen, 1990). Thus, using alkalies ing cost but also reduces the plant performance if gypsum precip-
(e.g. NaOH, Na2CO3 and lime) for regulating the solution pH to itation occurs (Shen et al., 1998).
make pyrite unfloatable is one of the most widely applied methods
in sulfide mineral flotation. Several mechanisms have been pro- 2.2. Oxidants
posed to explain the depressing action of hydroxyl ions.
It is commonly believed that the interaction between hydroxyl Extensive studies have confirmed a correlation between the
ions and surface species results in hydrophilic iron hydroxyl on flotation of sulfide minerals and pulp potential (Eh). Fig. 2 shows
pyrite surface preventing the adsorption of xanthate (Fuerstenau the flotation recovery of sulfide minerals as a function of pulp
et al., 1985). With a relatively high concentration of hydroxyl ions, potential with ethyl xanthate (EX) as the collector. Flotation is gen-
reactions (2) and (4) proceed to the left with the decomposition of erally observed in restricted ranges of pulp potential (Trahar, 1984;
dixanthogen to less powerful xanthate ions (Fuerstenau et al., Ralston, 1991). The Eh influences the surface composition of sulfide
1985). Another view suggests that the depressing mechanism is minerals by superficial oxidation (Tolley et al., 1996; He et al.,
through the competitive adsorption of hydroxyl and xanthate 2005). This surface oxidation may enhance the flotation of sulfide
anions. OH may exchange with X leading to the desorption of minerals by forming elemental sulfur, metal-deficient or sulfur-
X from the pyrite surface (Wark and Cox, 1934; Gaudin, 1957). rich species facilitating collectorless flotation (Luttrell and Yoon,
Janetski et al. (1977) studied the depression of pyrite flotation from 1984; Trahar, 1984; Tolley et al., 1996). The potential at which
an electrochemical viewpoint and found that an increase in pH minerals start to float corresponds to the formation of elemental
facilitated pyrite oxidation. It was suggested that oxidation of pyr- sulfur (Fig. 2) (Ralston, 1991). However, extensive oxidation gener-
ite replaced oxidation of xanthate as the dominant anodic process. ally reduces mineral floatability by forming hydrophilic and stable
Thus, the formation of dixanthogen is inhibited at high pH.
Boulton et al. (2001a) indicated that effective separation of pyr-
ite and chalcopyrite was achieved by increasing the pH value to 12. 100
As pyrite is more cathodic than chalcopyrite at these conditions,
surface oxidation products are more likely to form on pyrite, lead-
80
Flotation recovery (%)
ing to depression. At alkaline conditions, the stability of X2 is

reduced which lowers its propensity towards flotation. As a layer Cu2S Cu2FeS4
of iron hydroxide normally is present at the surface, copper ions 60
are less likely to adsorb on the pyrite surface and associate with CuFeS2 FeS2
sulfur, reducing the extent of copper-activation.
40
Lime (CaO) is more effective in rejecting pyrite in flotation than
NaOH at lower pH levels (pH < 11) (Fuerstenau et al., 1985; Rao
and Leja, 2004; Li et al., 2012). It is worth noting that calcium ions 20
from lime also contribute to the depression of pyrite flotation. The
dissolution of lime in water produces two main components, Ca2+ 0
and OH. At alkaline pH below 12.5, Ca(OH)+ is the main compo- -0.2 0 0.2 0.4
nent in solution. Ca(OH)+ has a higher affinity for the pyrite surface Potential (V vs. SHE)
than OH- and adsorbs readily by electrostatic attraction, since the
Fig. 2. Flotation recovery as a function of potential for chalcocite (Cu2S), bornite
surface of pyrite is negatively charged at high pH (Fornasiero (Cu2FeS4), chalcopyrite (CuFeS2) and pyrite (FeS2) at pH 9.2; [EX] = 1.44 105 M
et al., 1992; Chen et al., 2011; Li et al., 2012). Ca(OH)+ loses elec- for chalcocite and 2 105 M for other sulfide minerals adapted from Ralston
trons to the surface resulting in accumulation of electrons on pyr- (1991).
metallic oxide/hydroxide coatings (Martin et al., 1991; Senior and reported that grinding with chromium media yielded higher chal-
Trahar, 1991; Smart, 1991). The Eh also influences the adsorption of copyrite recovery and lower pyrite recovery than with mild steel
xanthate collectors on mineral surfaces since the mineral-collector media. This was attributed to the more electrochemically active
interaction is potential dependent (Eqs. (2) and (5)) (Trahar, 1984; mild steel that increased the formation of iron hydroxides on chal-
Tolley et al., 1996). Therefore, a specific sulfide mineral displays a copyrite surface. Additionally, the electrochemical potential has a
strong flotation performance only above certain potential values as significant effect on the activation of pyrite by copper ions. This
shown in Fig. 2 (Ralston, 1991). Miller et al. (2006) reported that in is an electrochemical process involving the formation of cuprous
a 1 103 M potassium amyl xanthate (PAX) solution, a hydropho- sulfide species on pyrite surface (He et al., 2005; Peng et al.,
bic pyrite surface state was established at potentials higher than 2012). Reducing grinding conditions generated by mild steel grind-
0.19 V (vs. SHE) which corresponds to the reversible potential of ing media or reducing agents, added intentionally, favors reduction
the xanthate/dixanthogen couple. Therefore, depending upon the of Cu2+ to Cu+ on pyrite surface, leading to pyrite activation. In con-
Eh, the mineral surface may facilitate collector adsorption leading trast, an oxidizing condition generated by chromium media or oxy-
to flotation. Alternatively, strong surface oxidation may facilitate gen purging inhibits copper activation of pyrite (Peng et al., 2003a,
depression. 2012). Thus, utilization of chromium media achieves better separa-
Another electrochemical factor influencing the separation of tion of chalcopyrite against pyrite than the mild steel media.
pyrite from other valuable minerals is the galvanic interaction The control of pulp electrochemistry by adjusting redox poten-
between grinding media and minerals as well as the mineral- tial (Eh) or oxygen purging in the flotation of multiple sulfide min-
mineral interaction during grinding and conditioning, which may erals has been an industry practice (Owusu et al., 2013). However,
influence the floatability of coupled minerals (Ekmekçi and Boulton et al. (2001a) noted that the flotation of iron sulfide min-
Demirel, 1997; Peng et al., 2003b,a; Huang and Grano, 2005, erals was only depressed after oxygen conditioning time greater
2006; Huang et al., 2006). Fig. 3 shows a galvanic cell formed by than 20 min, which is time-consuming. Oxygen purging is also
chalcopyrite and pyrite. Pyrite with the higher rest potential acts found to promote galvanic interactions between minerals and
as a cathode and is galvanically protected, while chalcopyrite with grinding media and thus lowers the floatability of valuable miner-
a lower rest potential acts as an anode (Ekmekçi and Demirel, 1997; als (Yelloji Rao and Natarajan, 1989). Therefore, an optimal condi-
Liu et al., 2007; Owusu et al., 2013). Hence, the oxidation of chal- tion must be identified to achieve the greatest recover of value
copyrite is accelerated with electrons flowing from chalcopyrite components. It is also found that a combination of oxygen condi-
to pyrite accompanied by the reduction of oxygen on pyrite surface tioning and additional usage of other depressants can significantly
(Ekmekçi and Demirel, 1997). Simultaneously, the activation of pyr- reduce the conditioning time and the dosage of depressants
ite surface may also occur due to the adsorption of copper ions dis- (Boulton et al., 2001b; He et al., 2006).
solved from chalcopyrite (Ekmekçi and Demirel, 1997). As a result,
the flotation of pyrite is enhanced while the flotation of chalcopy-
rite is weakened after the two minerals are galvanically coupled. 2.3. Cyanide
Oxygenation of the pulp can considerably alter the flotation
results by changing the electrochemical atmosphere (Houot and Cyanide species have commonly been used to depress the flota-
Duhamet, 1990). An optimum level of oxygenation, on one hand, tion of iron sulfide minerals (Prestidge et al., 1997; Guo et al.,
improves chalcopyrite recovery because the presence of oxygen 2015). The depression of pyrite flotation by cyanide may result
facilitates the interaction between collector and chalcopyrite sur- from one or more of the following mechanisms: (1) Cyanide may
face (Boulton et al., 2001a; Owusu et al., 2015). On the other hand, depress pyrite flotation by replacing xanthate ions on pyrite sur-
it reduces pyrite recovery due to the preferential reduction of oxy- face, similar to hydroxyl ions (Wark and Cox, 1934; Prestidge
gen on pyrite surface. This again leads to the formation of hydro- et al., 1993). (2) The adsorption of cyanide on pyrite surface leads
philic species such as copper/iron hydroxide and sulfate (Owusu to the formation of insoluble iron cyanide compounds, which pre-
et al., 2013) and these species may prevent or reduce the adsorp- cipitate on pyrite surface making the surface hydrophilic and
tion of collector and copper ions on pyrite (Shen et al., 1998). inhibiting the adsorption of xanthate ions (Elgillani and
Improved separation of pyrite from sphalerite, galena and gold Fuerstenau, 1968; Wang and Forssberg, 1996; Guo et al., 2014).
may also be achieved under oxidizing conditions (Monte et al., (3) Cyanide may also react with sulfur or polysulfides produced
1997; Boulton et al., 2001b; Peng et al., 2003b). by surface oxidation to form thiocyanate thereby removing surface
The type of grinding media can also modify the pulp electro- hydrophobic entity (Leja, 1981; Guo et al., 2015). Thiocyanate is
chemistry and thus influence the flotation recovery and selectivity hydrophilic, and if adsorbed, can depress pyrite flotation
of sulfide minerals (Martin et al., 1991). Peng et al. (2003a) (Prestidge et al., 1993). (4) The addition of cyanide may reduce
the mixed potential and inhibit the electrochemical activity on
the pyrite surface, which interferes with the chemisorption and
Fe(OH)3 oxidation of xanthate (Janetski et al., 1977; De Wet et al., 1997;
OH- Guo et al., 2015). (5) In copper-activated pyrite flotation, cyanide
S is employed as a deactivating agent which removes cuprous ions
from activated pyrite via the formation of strong cuprous cyanide
Pyrite SO42- complexes such as CuCN, CuðCNÞ2 3
Chalcopyrite 3 and CuðCNÞ4 by selectively dis-
(noble) solving cuprous-xanthates, -sulfides and -oxides (Bulatovic, 2007).
(acve)
H2O e Although cyanide is an effective depressant for pyrite flotation,
CuS it is highly toxic and its use continues to raise environmental con-
cerns and health hazards (Boulton et al., 2001a; Agorhom et al.,
Cu2+ + S 2014). In excessive quantities, cyanide can be poisonous to humans
O2
and animals. When deposited in tailing dumps, it contaminates the
Cathodic Anodic surrounding water sources (Mehrabani et al., 2011). Further, the
Cu(OH) 2
use of cyanide may depress the flotation of precious minerals in
Fig. 3. A model of galvanic interaction between chalcopyrite and pyrite adapted some conditions (De Wet et al., 1995). Therefore, its use to depress
from Ekmekçi and Demirel (1997). the flotation of pyrite should be discouraged.
2.4. Sulfur-oxy species conditioning was performed and the time interval between addi-
tions of sulfite and xanthate was short. The selective depression
A range of sulfur-oxy species, such as sulfite (SO2
3 ), bisulfite
of pyrite was attributed to the formation of more copper hydroxide
(HSO 2 species on copper-activated pyrite surface through the consump-
3 ), metabisulfite (S2 O5 ) and sulfur dioxide (SO2) as well as
sulfide (S2), have been used in flotation as pyrite depressants in tion of oxygen (Shen et al., 2001). Galvanic interactions may occur
neutral or mildly alkaline pH conditions to replace cyanide between the cuprous sulfide layer on pyrite or sphalerite surface
(Khmeleva et al., 2002; Chandra and Gerson, 2009). Except S2, and the mineral itself. The cuprous sulfide being less cathodic is
oxidized to form cupric ions while oxygen is reduced at the pyr-
the sulfur-oxy species function mainly through SO2 3 (Dávila-
ite/sphalerite surface forming hydroxyl ions. Pyrite is the most
Pulido et al., 2011). Since dixanthogen is the main species respon-
cathodic mineral, thus a higher proportion of copper hydroxides/
sible for pyrite flotation, any reagents that are more reducing than
oxides forms on pyrite than on sphalerite inhibiting collector
the X-/X2 couple are supposed to act as pyrite depressants by pre-
adsorption on pyrite (Shen et al., 2001; Chandra and Gerson, 2009).
venting oxidation of xanthate (Fuerstenau et al., 1985). The reduc-
Zinc sulfate has been tested in the separation of chalcopyrite
ing agents, sulfide/sulfite ions, are readily oxidized following Eqs.
from pyrite (He et al., 2006). It only acts as a depressant in the
(7) and (8), the half-cell potentials of which are much lower than
presence of hydroxyl ions (Bulatovic, 2007). He et al. (2006) indi-
that of X/X2 couple.
cated that the selective depression of pyrite in the flotation of chal-
S2 þ 2e S0 E0 ¼ 0:48 V ð7Þ copyrite was due to the selective adsorption of zinc hydroxide on
pyrite surface via electrostatic interactions between zinc hydrox-
SO2
3 þ 2OH SO2
4 þ H2 O þ 2e E0 ¼ 0:93 V ð8Þ
ide and ferric hydroxide in mildly alkaline pH conditions. Olsen
Janetski et al. (1977) studied how sodium sulfide depressed et al. (2012) also indicated that zinc sulfate can induce sulfoxyl
pyrite flotation by cyclic voltammograms and found that the pres- and hydroxide species on mineral surfaces that inhibit collector
ence of sodium sulfide introduced an additional anodic reaction. adsorption. However, the depression of pyrite flotation by zinc sul-
The new anodic reaction was assigned to the oxidation of dissolved fate is Eh dependent and zinc sulfate cannot function well at lower
sulfide species (S2 or HS) taking place at potentials cathodic rel- Eh values because there are less hydroxide groups formed on pyrite
ative to xanthate oxidation. In other words, sodium sulfide con- surface for zinc hydroxide attachment (He et al., 2006).
sumed oxygen and reduced the mixed potential, which In practice, high dosages of sulfoxyl reagents are usually
prevented dixanthogen formation and pyrite flotation. required for the depression of pyrite flotation (Bulut et al., 2011).
The depression of pyrite by sulfoxyl species is rather complex The relative cost of these reagents and the increase in storage
and a number of mechanisms have been proposed. Khmeleva and operation costs are still a problem limiting their application.
et al. (2002) investigated the effect of sulfite ions on the flotation
of copper-activated pyrite induced by xanthate with nitrogen or
air purging and found that the depression effect was more pro- 3. Organic depressants
nounced with air purging. This may be because more oxidation
products formed on pyrite surface in the presence of air. Sulfite Inorganic depressants, though effective, are found to be detri-
can interact with both pyrite and collector in solution and at sur- mental to the environment and cause additional cost during han-
face. It was suggested that sulfite decomposed xanthate ions in dling. Organic depressants, with rich sources, biodegradable
solution and those present on pyrite surface via the formation of nature and relatively inexpensive price are attracting great atten-
perxanthate (ROCSSO) as shown in Eq. (9) (Yamamoto, 1980; tion and possess the potential to function as alternative depres-
Khmeleva et al., 2002). Yamamoto (1980) and Misra et al. (1985) sants (López Valdivieso et al., 2004; Bicak et al., 2007; Bulut
indicated that the presence of oxygen was necessary for the et al., 2011; Sarquís et al., 2014). The commonly investigated
decomposition of xanthate by sulfoxyl species. The presence of sul- organic depressants for pyrite flotation include polysaccharides
fite may also lead to desorption of dixanthogen from pyrite surface polymers (starch, dextrin, guar gum, carboxymethyl cellulose and
(Eq. (10)) (Miller, 1970; Khmeleva et al., 2002, 2003). Moreover, chitosan), polyacrylamides (PAM), wood extracts (lignosulfonate-
the presence of sulfite consumes dissolved oxygen leading to a based biopolymers), diethylenetriamine (DETA), etc. The chemistry
drop of the pulp potential. This lowers the amount of dixanthogen and interaction modes of these polymeric compounds is highly
formed due to the lower amount of oxygen available (Illyuvieva complex. Differences in the composition of the raw material and
et al., 1984; Khmeleva et al., 2002). In addition, sulfite ions pro- the manufacturing processes can significantly impact the function-
mote the formation of iron/copper hydroxides on copper- ality of the final product (Bulatovic, 1999). However, organic
activated pyrite as a result of oxygen consumption rendering the depressants have the following similar features in their structures:
surface hydrophilic (Shen et al., 2001; Khmeleva et al., 2002, (1) a hydrocarbon backbone or segment which is able to adsorb on
2003). Alternatively, sulfite species can interact with the hydrophobic mineral surfaces; (2) in most instances, large num-
hydrophobic species such as elemental sulfur (S0) forming thiosul- bers of hydroxyl groups which are distributed throughout the poly-
mer structures capable of ionization or hydrogen bonding; (3)
fate (S2 O2
3 ) which may further oxidize to sulfate, leading to a
decrease of surface hydrophobicity (Li et al., 1995; Khmeleva strongly hydrated polar groups like SO2 3 , COO , etc. which are also
et al., 2005, 2006; Dávila-Pulido et al., 2011). Some researchers frequently dispersed through the molecule (Pugh, 1989). Gener-
reported depression of pyrite via the formation of a hydrophilic ally, the polymer is thought to adsorb onto the mineral surface
metal sulfite surface layer. For instance, sulfite and copper may via various interactions. Hydrophilic functionalities enhance the
form copper sulfite precipitates that limit the extent of activation hydrophilic character of the surface, facilitating depression of min-
of pyrite (Peres, 1979; Misra et al., 1985). eral via reduced possibility of bubble-particle attachment
(Beaussart et al., 2009; Kar et al., 2013).
ROCSS þ HSO3 þ SO2 2
3 þ O2 ! ROCSSO ! ROH þ 2S2 O3 þ CO2 The interactions between polymers and mineral surfaces are
ð9Þ complicated due to both complex polymer structures and hetero-
geneous mineral surfaces. Several interactions can account for
FeðC4 H9 OCSSÞ2 þ HSO3 ! 2C4 H9 OCSS þ FeSO3 þ H ð10Þ
adsorption or association with mineral surfaces as shown in
Shen et al. (2001) achieved the maximum separation of copper- Fig. 4. Firstly, there is electrostatic attraction between oppositely
activated sphalerite from pyrite by sodium sulfite when oxygen charged polymers and mineral surfaces. Secondly, hydrophobic
(1) Electrochemical attraction (2) Hydrophobic interaction

Hydrophobic carbon chain
- - - - - - - - - - - -
- - - - -
++++++++++++++++
Hydrophobic sites
(3) Hydrogen bonding (4) Chemical interaction
H H H H
C OH HO C OH O C OH C O
Me H Me Me
+ + HO Me
C OH HO C OH O C C C O
COOH
H
H H OH H O
Fig. 4. Possible interaction mechanisms of organic polymers with mineral surface: electrochemical attraction (1), hydrophobic interaction (2), hydrogen bonding (3) and
chemical interaction (4) adapted from Mu et al. (2015).
interactions between non-polar segments of polymer chains and structure of starch is shown in Fig. 5. Starch consists of two frac-
hydrophobic areas of mineral surfaces can drive the accumulation tions, a linear amylose which contains the a-D-glucose monomers
of polymers. Thirdly, hydrogen bonds may form via an interaction jointed through C-1, 4 connections, and a branched amylopectin
between hydroxyl groups and hydrated metallic sites on mineral which contains the a-D-glucose monomers jointed through both
surfaces, particularly at basic pH values. Finally, chemical bonds C-1, 4 and C-1, 6 connections (Laskowski et al., 2007). a-D-
between the anionic functional groups (such as carboxylate or sul- glucose monomers are predominant. Starch has a molecular
fonic groups) and the metallic cations on mineral surfaces may weight of up to 150,000 (Bulatovic, 1999).
drive the binding of polymers (Boulton et al., 2001c; Gregory and Dextrin is derived from starch by partial thermal degradation
Barany, 2011). under acidic conditions. This process causes break down of the
Polymer-induced mineral depression depends very much on the chain and reconnection to the fragments of existing chains forming
chemical characteristics of the polymers, such as polymer func- low molecular weight molecules that are more branched (Pugh,
tionality, steric configuration of functional groups, charge density 1989; Liu et al., 2000; López Valdivieso et al., 2004). The structure
and molecular weight (Bulatovic, 2007). The flotation conditions of dextrin is similar to amylopectin, as shown in Fig. 5, and the
(i.e., pH, ionic strength of aqueous phase, composition of solids, molecular weight ranges from 800 to 70,000 (Laskowski et al.,
dissolved ions, etc.) also significantly affect their effectiveness 2007).
(Bulatovic, 1999). In this section, the structures and adsorption/ Guar gum is a branched polysaccharide in which galactoman-
depression mechanisms of organic depressants are reviewed. nan is the basic unit as shown in Fig. 6. Structurally galactomannan
is made of a linear chain of b-D, 1, 4-linked mannoses to which a
3.1. Polysaccharides polymers galactose is 1, 6-linked at every second mannose, forming short
side-branches (Liu et al., 2000; Laskowski et al., 2007).
3.1.1. Starch, dextrin and guar gum It can be seen that starch, dextrin and guar gum all contain two
Natural polysaccharides are condensation polymers with high hydroxyl groups on C-2 and C-3 carbon atoms in each unit. There-
molecular weights and the basic structural units are monosaccha- fore, these polysaccharides all have the ability to form complexes
ride (sugar) monomers (Liu et al., 2000; Laskowski et al., 2007). with metal hydroxides/ions possibly through hydrogen bonding
Polysaccharides produced from different sources offer significantly which are strongly pH dependent (Rath and Subramanian, 1999;
different polymer properties, like chain lengths, chain configura- Liu et al., 2000; Laskowski et al., 2007). It has been suggested that
tion, molecular weights and impurity contents (Laskowski et al., selection of depressants with the correct spacing between hydro-
2007). Starch ((C6H10O5)n), the most abundant natural polysaccha- xyl groups greatly enhance selectivity. The mineral lattice spacing,
ride, can be derived from corn, tapioca, rice, potato, wheat, sago, and hence placement of metal hydroxide groups at high pH may
arrowroot, maize, etc. (Pugh, 1989; Kar et al., 2013). The general differ between minerals. By selection of the correct polysaccharide,
Fig. 5. Structural units of starch and dextrin adapted from Laskowski et al. (2007).
β Polysaccharides
R R R
O O O
C C C
S S S S S S Dixanthogen
S S S S S S
C C C
O O O
R R R
α
Pyrite surface
Enveloping the adsorbed X2
Fig. 7. Co-adsorption of polysaccharides and dixanthogen on pyrite surface.

Fig. 6. Structural unit of guar gum adapted from Laskowski et al. (2007).
enveloped inside the macromolecules and the polar hydroxyl

separation of otherwise similar minerals can be achieved. The groups of adsorbed polymers create a hydrophilic surface coating
depression of pyrite flotation by polysaccharides is due to the on pyrite lowering the stability of bubble-particle aggregate and
selective adsorption of polysaccharides polymers on pyrite surface. therefore facilitating the depression of pyrite flotation (Bulatovic,
Bulut et al. (2011) investigated the depression effect of starch 1999; López Valdivieso et al., 2004). Studies have shown that
on pyrite flotation and found that starch was effective at a low polysaccharides are poor depressants at elevated collector concen-
dosage (1.7 mg L1) and more pronounced at alkaline pH (10) than trations and the order of addition of xanthate and polysaccharides
natural pH (6.5). This confirms the adsorption of starch on mineral also impact the adsorption of either agent on mineral surface
surfaces through the interaction with metal-hydroxylated species. (Steinberg and Harris, 1976; Bulatovic, 1999).
However, when applied on a pyritic copper ore, starch depressed It has been widely reported that the addition of bivalent cations,
the copper flotation as well (Bulut et al., 2011). for instance calcium ions, increases the adsorption or depression
Kydros et al. (1994) showed that dextrin effectively depressed function of starch and dextrin (Liu et al., 2000; Bulatovic, 2007).
pyrite flotation at pH higher than 4 with metal hydroxides formed This is because calcium ions act as ‘‘bridges” between mineral sur-
in the presence of ethyl xanthate and selective separation of faces and these polysaccharides (Laskowski et al., 2007). Calcium
copper-activated sphalerite from pyrite was achieved. López ions are found in the form of Ca2+, Ca(OH)+ and Ca(OH)2 at basic
Valdivieso et al. (2004) reported similar results and attributed pH. Once adsorbed/precipitated on mineral surfaces they signifi-
the adsorption of dextrin to the interaction between dextrin and cantly enhance the bonding between the hydroxyl groups on both
ferric oxyhydroxide on pyrite surface. Pyrite depression with dex- polysaccharides and mineral surfaces (Liu et al., 2000; Bicak et al.,
trin in flotation with xanthates has been shown to be dependent on 2007). However, the presence of calcium ions has no influence on
the level of pyrite surface oxidation (Lopez Valdivieso et al., 2007). either adsorption densities or depression effects of guar gum on
Bogusz et al. (1997) also indicated that metal oxidation species pyrite at pH 9 where Ca2+ and Ca(OH)+ predominates (Bicak
were required on pyrite surface for dextrin adsorption. The opti- et al., 2007). This may be because guar gum exhibits high adsorp-
mum pH for dextrin adsorption occurs around 6, close to the pHiep tion affinity towards pyrite surface with good depression on pyrite
(isoelectric point) of pyrite due to ferric oxyhydroxide (López flotation irrespective of the presence of calcium ions (Bicak et al.,
Valdivieso et al., 2004). Dextrin is as effective depressant of pyrite 2007).
as cyanide. It is commercially used for the depression of carbona- The predominant perception regarding the application of
ceous pyrite at the Mount Isa copper concentrator and cross- polysaccharides as pyrite depressants is that their adsorption in
linked low molecular-weight dextrin shows good depression on differential flotation is not specific, or not as specific as inorganic
pyrite flotation (Bulatovic, 1999, 2007). depressants (Liu et al., 2000). This is further complicated by sub-
Bicak et al. (2007) investigated the effect of guar gum on pyrite stantial cross-contamination of mineral surfaces in flotation pulp
flotation and found that the addition of as low as 0.1 mg L1 guar where metal ions from different minerals are present (Bogusz
gum caused a dramatic decrease of pyrite recovery. An optimum et al., 1997). Also the organic reagents may form colloidal particles
dosage of 10 mg L1 was recommended. The difference in molecu- at higher concentrations in the pulp which deposit on mineral sur-
lar weight (MW) of guar gum did not show any difference in faces. This will cause the non-specific depression of minerals pre-
depressing pyrite flotation; however, the effect of pH was signifi- sent following a similar manner as slime coatings (Bulut et al.,
cant. Pyrite depression with guar gum was more efficient at high 2011).
pH due to the formation of hydrophilic iron oxyhydroxy coating It is suggested to combine the use of polysaccharides with other
(Bicak et al., 2007). metal selective chelating agents, organic or inorganic, to improve
Polysaccharides act as depressants on pyrite flotation due to the the selectivity of polymers towards target mineral by selectively
formation of a hydrophilic surface coating. Unlike inorganic removing contaminating metal ions (Bogusz et al., 1997). One
depressants which act by changing the pyrite surface and thus pre- example is to use a combination of dextrin with a selective metal
vent xanthate adsorption, the adsorption of natural polysaccha- complexing agent, e.g., diethylenetriamine (DETA), which is selec-
rides has no influence on xanthate adsorption (Steinberg and tive for copper ions (Bogusz et al., 1997).
Harris, 1976; López Valdivieso et al., 2004). Dixanthogen forms The chemical modification of polysaccharides may enhance the
on pyrite surface through an electrochemical process and is an oily specific adsorption and depression effect of polysaccharides (Liu
compound spreading on hydrophobic surface area by physical et al., 2000; Bulatovic, 2007). Foreign functional groups (e.g., COO)
means (Haung and Miller, 1978). Polysaccharides adsorb on pyrite can be incorporated to polysaccharides chains through various
surface through an interaction with iron hydroxides. Due to the modification processes like oxidation, substitution, etherification
heterogeneous nature of pyrite surface, co-adsorption of polysac- or esterification reactions with hydroxyl groups, resulting in ‘‘mod-
charides and xanthate occurs on pyrite surface as shown in ified” polysaccharides (Bulatovic, 2007; Laskowski et al., 2007). In
Fig. 7. The dixanthogen formed by xanthate adsorption is however, each monomer, three hydroxyl groups at the C-2, C-3 and C-6 posi-
tions are inclined to undergo the modification reactions and the that the pyrite surface becomes less negative with the addition
reactivity of the three hydroxyl groups follows the order of C- of Ca2+, due to the adsorption of the positively charged Ca(OH)+
6 > C-2 > C-3 (Laskowski et al., 2007). The number of substituted on pyrite surface (Bicak et al., 2007). As a result, the electrostatic
functional groups per monomer is called the degree of substitution repulsive force between negatively charged CMC and pyrite surface
(DS). For example, the introduction of anionic functional groups to is diminished. Electrostatic attraction between the CMC and the Ca
starch chains may cause the conformation of starch molecules at (OH)+ spots on pyrite surface greatly promotes CMC adsorption. In
mineral surfaces being more stretched out thereby making starch addition to electrostatic effects, calcium hydroxide species precip-
more effective as depressant (Bulatovic, 2007). Cross-linked starch itating on pyrite surface increase the amount of metal hydroxide
and dextrin have shown a more effective and selective depression sites facilitating hydrogen bonding between hydroxyl groups on
action at a lower reagent dosage (Pugh, 1989). The ideal polysac- both CMC and pyrite surface. The carboxylic acid groups can also
charide will have the correct chain length, optimum molecular size react with Ca2+ and CaOH+ through chemical bonding (Bicak
and degree of substitution which often vary with the pulp compo- et al., 2007). Meanwhile, a high ionic strength of solution will cause
sition. Simultaneously, the substituted groups will dominate the the coiling of CMC chains and increase the adsorbed amount of
adsorption process which overrides the less specific adsorption CMC on mineral surface because its charge is screened (Bicak
resulting from unsubstituted hydroxyl groups (Liu et al., 2000; et al., 2007; Laskowski et al., 2007). Unlike starch and dextrin,
Bulatovic, 2007). the depression of pyrite flotation by CMC proceeds through the
competitive adsorption of CMC and xanthate (Fig. 9) (Feng et al.,
3.1.2. Carboxymethyl cellulose (CMC) 2013). Results have shown that the adsorption of xanthate on pyr-
CMC is an anionic polymer produced from the etherification of ite surface is significantly decreased in the presence of the pre-
cellulose. Cellulose is a linear polysaccharide with the basic unit b- adsorbed layer of CMC (Feng et al., 2013). The coiled CMC formed
in the presence of Ca2+ acts as a better blinding agent which blocks
D-glucose monomers joined by the C-1, 4 connections (Liu et al.,
the mineral surface and inhibits the collector adsorption
2000). The carboxymethyl groups replace the protons in some of
(Laskowski et al., 2007).
the hydroxyl groups in the cellulose forming the CMC as shown
in Fig. 8 (Laskowski et al., 2007). The maximum degree of substitu-
tion of CMC is 3, however, the DS of commercial CMC is much 3.1.3. Chitosan
lower, typically around or lower than 1 (Laskowski et al., 2007). Chitosan is a linear polysaccharide composed of b-(1,4)-linked
The molecular weight of CMC ranges from 50,000 to 800,000 amino-2deoxy-D-glucosamine monomers, the deacetylated deriva-
(Bulatovic, 1999). The main difference between CMC and natural tive of the chitin, containing amine, hydroxyl and acetamide
polysaccharides is the presence of negatively charged carboxyl groups (Gylienė et al., 2015). The structure of chitosan is shown
groups in CMC structure that may increase CMC’s selectivity. The in Fig. 10. Its structure is usually characterized by the deacetylation
hydroxyl groups only interact with metal hydroxyl species, while degree (DD) and molecular weight (MW) which determine the
the carboxyl groups can interact with various forms of metallic number of functional groups in chain (Gylienė et al., 2015). Chi-
species on mineral surfaces (Liu and Laskowski, 1999; Bicak tosan and its derivatives have been commonly used as adsorbents
et al., 2007). Both groups take part in the interaction of CMC with to remove heavy metal ions from industrial wastewater, due to the
surface metallic sites. chelating ability of chitosan with metal ions resulting from the
Bicak et al. (2007) tested the effect of two types of CMC with a amine and hydroxyl groups (Huang et al., 2013; Gylienė et al.,
high degree of substitution (HDS, 0.86) and a low degree of substi- 2015).
tution (LDS, 0.47) as pyrite depressants at pH 9 and found that the Huang et al. (2013) used chitosan to selectively separate pyrite-
LDS CMC was more effective than HDS CMC due to the lower elec- galena mixtures (weight ratio 1:1) in flotation with potassium
trostatic repulsion between the less negatively charged CMC and
pyrite surface allowing more CMC adsorbed on pyrite. However, Xanthate ions Dixanthogen
S
CMC requires a rather high dosage (500 mg L1 LDS CMC) to

O
S
achieve sufficient pyrite depression. The solution pH influences R R

R
-
R
C
O
the CMC adsorption as it affects the dissociation of carboxyl O O

-
O
S
C C
R
groups, hydroxylation of mineral surfaces as well as the charge

S
C
-
of mineral surface. Adsorption isotherms show that the adsorption S S S S

CMC
S
density of CMC decreases slightly when the pH is over 9 and higher S S S S

due to the increased electrostatic repulsion between CMC and neg-
- C - C
atively charged pyrite surface (Bicak et al., 2007). O O
Similar to the case with starch and dextrin, the presence of cal- - R - R -
cium ions strengthens the adsorption and depression capability of Pyrite surface
CMC on pyrite, particularly the HDS CMC at pH 9 (Bicak et al.,
2007; Laskowski et al., 2007). Zeta potential measurements show Inhibiting the adsorption of X-
Fig. 9. Inhibition of the adsorption of xanthate on pyrite surface by the pre-

adsorbed CMC.
Fig. 8. Structural unit of cellulose and carboxymethyl cellulose adapted from

Laskowski et al. (2007). Fig. 10. Structure of chitosan adapted from Huang et al. (2013).
ethyl xanthate (KEX) as collector. The single mineral flotation accompanied by the reduction of oxygen or ferric hydroxides on
results showed that chitosan depressed both pyrite and galena pyrite surface. Cyclic voltammograms of a pyrite electrode show
flotation at a dosage of 0.67 mg L1 but pyrite flotation was more that the biopolymers can passivate the pyrite surface and reduce
severely depressed. The recoveries of both pyrite and galena the extent of electrochemical oxidation of both pyrite itself and
decreased with the increase of solution pH. However, in the flota- xanthate (Mu et al., 2015). This maybe because these biopolymers
tion of pyrite-galena mixtures chitosan selectively depressed pyr- adsorb on pyrite surface and act as an insulator that reduces the
ite while galena was floated and the optimum separation result efficiency of the charge transfer between the electrode-
was observed around pH 4 (Huang et al., 2013). The difference electrolyte and electrode-xanthate interfaces. This inhibits the
indicated that when both minerals were present, chitosan pre- electrochemical oxidation and reduction of pyrite surface required
ferred to adsorb on pyrite, which was confirmed by ToF-SIMS mea- for formation of dixanthogen and flotation. Further, hydrophilic
surement. The ToF-SIMS results also showed that more chitosan functional groups of adsorbed biopolymers enhance the
adsorbed onto pyrite and galena at pH 6 than at pH 4. However, hydrophilicity of pyrite surface, which facilitates the depression
there was still more chitosan adsorbed on pyrite. XPS spectra indi- of pyrite flotation. In the flotation of copper-activated pyrite,
cated that both amine and hydroxyl groups in chitosan structure cuprous xanthate is the predominant hydrophobic entity enabling
reacted with pyrite surface to form a complex, probably through pyrite flotation. Cuprous sulfide and xanthate complexes are easily
a chemisorption mechanism (Huang et al., 2013). The preferential oxidized in the presence of biopolymers (Mu et al., 2016a). The
adsorption of chitosan on pyrite over galena was probably due to complexing strength of biopolymers is sufficient to extract the
the higher affinity of the lattice metal ions of pyrite (Fe3+/Fe2+) than cuprous ions from its sulfide or xanthate forms, tentatively linked
galena (Pb2+) towards chitosan (Huang et al., 2013). to the chelating ability of biopolymers. It is supposed that the
interaction of biopolymer with Cu(I) can form a multiple six-
3.2. Lignosulfonate-based biopolymers member-ring complex which is more stable than the complex
formed between Cu(I) and the single coordination ligand, S2 or
Lignin is the natural biopolymer second to polysaccharides in X. The hydrophilic species, Cu-biopolymer complex and Cu
abundance (Lebo et al., 2000). Lignosulfonates, or sulfonated lig- (OH)2, on pyrite surface contribute to the depression of copper-
nins are water-soluble anionic polyelectrolyte polymers, produced activated pyrite.
as byproducts from the sulfite pulping process in the production of The depression performances of the three biopolymers (DP-
cellulose (Lebo et al., 2000; Ouyang et al., 2010). They are used as 1775, DP-1777 and DP-1778) have been compared to delineate
depressants, dispersants and flocculants in mineral processing the effect of polymer chemistry on their depression role (Mu
(Bulatovic, 1999). The unmodified lignosulfonates are not effective et al., 2016b). The molecular weight of biopolymers determines
depressants in sulfide flotation, while the function of specific ligno- the adsorption density on pyrite surface with a higher molecular
sulfonates can be significantly enhanced after modification weight leading to a higher adsorption capacity and more pyrite
(Bulatovic, 2007). The depression effect of lignosulfonates depends depression. A higher content of functional groups plays a signifi-
on the degree and type of modification (Bulatovic, 2007). The cant role in decreasing surface hydrophobicity and inhibiting xan-
molecular structure of sulfonated-lignins is shown in Fig. 11. The thate adsorption. The bivalent cation, Ca2+, is also found to enhance
modified lignosulfonate biopolymers are highly cross-linked, con- the depressing effect of biopolymers by increasing the adsorbed
taining both hydrophilic groups, such as sulfonic and carboxylic amount of biopolymers, especially the highly negatively charged
acid groups in addition to various hydroxyl groups, all grafted to biopolymers, on pyrite surface. The presence of Ca2+ also enhances
a hydrophobic carbon skeleton (Ouyang et al., 2006). the biopolymers’ ability to inhibit xanthate adsorption on un-
A study conducted by Mu et al. (2014) demonstrated that three activated pyrite possibly through the adsorption of Ca(OH)+ on
lignosulfonate-based biopolymers (DP-1775, DP-1777 and DP- pyrite surface (Li et al., 2012). However, the role of Ca2+ was not
1778) differing in molecular weight and polymer chemistry observed in the flotation of copper-activated pyrite with the same
depressed the flotation of un-activated pyrite (at pH 5), copper- biopolymers (Mu et al., 2016a). In contrast, the presence of Ca2+ in
activated pyrite (at pH 9) and chalcopyrite (at pH 9). Recoveries large quantities may weaken the biopolymers’ ability to inhibit
of pyrite and chalcopyrite decreased with the dosage of the three xanthate adsorption due to the stronger complexing affinity of
biopolymers but the depression of chalcopyrite was less significant biopolymers towards Ca2+ in solution.
at the same biopolymer dosage. However, large dosages were Liu et al. (2009) found that the selective depression of pyrite in
required to achieve effective depression of pyrite flotation. Another the flotation of chalcopyrite-pyrite mixtures was due to the prefer-
study conducted by Liu et al. (2009) showed that lignosulfonate ential adsorption of lignosulfonate calcium (LSC) on pyrite surface
calcium (LSC) depressed pyrite flotation in a wide pH range. and little adsorption on chalcopyrite based on the FTIR analysis.
The mechanism underpinning the depression role of The selective adsorption of LSC on pyrite occurred due to interac-
lignosulfonate-based biopolymers on the flotation of un-activated tions between the oxidized species Fe(OH)3 on pyrite surface and
pyrite and copper-activated pyrite has been investigated. In the the ASO 3 in LSC. The lower adsorption of LSC on chalcopyrite sur-
flotation of un-activated pyrite at pH 5, dixanthogen is the main face was due to the preferred reaction between cuprous and xan-
species responsible for pyrite flotation, the formation of which is thate ions instead of the reaction between iron on the
chalcopyrite surface and sulfonic groups (Liu et al., 2009). How-
ever, this is questionable since the adsorption of biopolymers on
pyrite surface decreases with pH due to electrostatic repulsion
between the increasingly negatively charged pyrite surface and
functional groups. The chelating complex formed through the
interaction between cuprous ions and biopolymers is more stable
than cuprous xanthate complex (Mu et al., 2016a). Given the gal-
vanic interaction between pyrite and chalcopyrite accelerating
the dissolution of chalcopyrite and activation of pyrite, the
biopolymers may preferentially adsorb on pyrite surface due to
Fig. 11. Molecular structure of sulfonated-lignin adapted from Ouyang et al. (2006). the complexing between the Cu(I) and biopolymer molecules.
3.3. Polyacrylamide polymers (PAM)
Polyacrylamide (PAM) is a water-soluble synthetic polymer

with general chemical formula ACH2CHCONH2A (Huang et al.,
2014). It is widely used as flocculants to flocculate fine and ultra-
fine particles in mineral processing industry (Zhang et al., 1999;
Tripathy and Singh, 2000). Recently, several attempts have been
conducted in laboratory to use PAM and its derivatives as depres-
sants for pyrite flotation. PAM possesses so-called ‘‘dual function-
ality” and is used as both flocculant and depressant, thereby Fig. 13. Two isomers for HPAM (a) and formation of five-member-ring Fe-HPAM
chelation adapted from Zhang et al. (2004).
lowering both true flotation and mechanical entrainment of
gangue particles (Huang et al., 2014).
Boulton et al. (2001c) used low molecular weight PAM poly- Fig. 13(b). Moreover, the test conducted by Boulton et al. (2001c)
mers to separate copper-activated sphalerite from pyrite with iso- showed that only PAM-T reacted with Cu2+, possibly forming a
butyl xanthate (IBX) as collector at pH 11. Various functional cuprous-PAM-T complex. This probably explains the fact that
groups like hydroxyl, carboxyl, sulfonate and thiourea groups were PAM-T displays the lowest selectivity of the PAMs (Boulton et al.,
grafted to polymer backbone to obtain PAMs with different charac- 2001c).
teristics. The chemical structures of the PAM and substituted PAM Competitive adsorption of PAM in favor of xanthate leads to
polymers are shown in Fig. 12. At the pH conditions examined, pyrite depression. Boulton et al. (2001c) indicated that when the
PAM-C and PAM-S are negatively charged, while PAM-H and PAMs were added before xanthate, better separation results were
PAM-T are neutral polymers (Boulton et al., 2001c). obtained. Zhang et al. (2004) also demonstrated that the adsorp-
Boulton et al. (2001c) found that all the PAMs depressed pyrite tion capability of xanthate on pyrite decreased with the increase
flotation with no or little depression of sphalerite. Among these of HPAM dosage.
PAMs, PAM-H showed the strongest depression effect while Boulton et al. (2001b) found that a combination of oxygen con-
PAM-C exhibited the best selectivity. At pH 11, the hydrophilic ditioning and polymer addition promoted the depression perfor-
copper/iron/zinc oxide/hydroxide species on the copper-activated mance. The flotation recovery obtained after 20 min oxygenation
sphalerite and pyrite surfaces electrostatically repelled the nega- was similar to that obtained by addition of 300 g t1 PAM-H. Alter-
tively charged polymers. This explains the greater depressing natively, 5 min oxygenation and 100 g t1 PAM-H gave the same
power of the nonionic PAM-H. Boulton et al. (2001c) concluded result. This has practical significance in industry by decreasing
that the predominant interaction mechanism between PAMs and the reagent and storage cost as well as the conditioning time.
mineral surfaces should be hydrogen bonding since the mineral In a parallel study on selective separation of copper and iron
surfaces were oxidized. Zhang et al. (2004) tested the depression minerals, effective depression of pyrite was also achieved by these
behavior of hydroxamic polyacrylamide (HPAM) on pyrite flotation modified PAMs (PAM-H, PAM-C and PAM-S). However, it is worth
at different pH and found that the depression ability of HPAM noting that these PAMs lowered the copper flotation rate to around
increased with the pH value. One reason may be the increased half its original value at the highest PAM concentration (Boulton
amount of iron hydroxides on pyrite surface confirming the hydro- et al., 2001a).
gen bonding between pyrite surface and HPAM (Zhang et al., 2004).
Thus the stronger interaction of PAMs with pyrite than with spha-
lerite is attributed to the more cathodic nature of pyrite resulting 3.4. Diethylenetriamine (DETA)
in more iron hydroxides formed on pyrite surface (Boulton et al.,
2001c). In addition, chemical interactions may also occur between DETA (NH2ACH2ACH2ANHACH2ACH2ANH2) is a polyamine
specific groups in polymer structure and surface metal ions, such with the molecular weight of 103.1 which has recently been intro-
as the interaction of carboxyl groups with iron ions, or thiourea duced as a depressant for pyrite and pyrrhotite flotation (Yoon
groups with copper ions (Boulton et al., 2001c). et al., 1995; Sui et al., 1998; Bulatovic, 2007). Similar to chitosan,
The selective interaction of these PAMs with metal ions (Zn2+, DETA and similar polyamine compounds are excellent complexing
Fe and Cu2+) was tested in solution and the results showed that
3+
or chelating agents. Liu et al. (2008) found that a DETA-
all the PAMs reacted with Fe3+, but with no visible interaction with functionalized polymeric adsorbent (P-DETA) bound copper or lead
Zn2+ (Boulton et al., 2001c). This indicates a specific interaction ions in the single metal species system. In the binary Cu–Pb metal
between ferric ions/hydroxides and the PAMs, independent of the species system, P-DETA exhibited a remarkable selectivity in the
type of polymer functional group (Boulton et al., 2001c). A similar uptake of copper ions over lead ions. Another study conducted
view was proposed by Zhang et al. (2004) who suggested that the by Xu et al. (1997) demonstrated that DETA complexed most
HPAM existed in two isomers as shown in Fig. 13(a). It was conjec- strongly with copper, followed by nickel and not at all with ferric
tured that adsorption of HPAM on pyrite surface took place via the ions. The nitrogen atoms in the amine groups of DETA can form
formation of a five membered chelation complex as indicated in coordination bonds with metal ions in solution (Kelebek and
Tukel, 1999; Liu et al., 2008). As shown in Fig. 14, each DETA mole-
Fig. 12. Chemical structure of the PAM and substituted PAM polymers adapted Fig. 14. Schematic representation of the complex formed between DETA molecule
from Boulton et al. (2001c). and Cu2+ in 1:1 molar ratio adapted from Kelebek and Tukel (1999).
cule donates three coordination bonds with Cu2+ generating a affinity towards specific metal ions, thus conferring them high
multi five-member-ring complex. DETA depresses mineral flota- selectivity (Pecina-Treviño et al., 2003).
tion via selective chelation with base metal ions and it can be Dithiophosphates are the most widely used collectors after xan-
applied in inadvertent activated system to deactivate pyrite thates. The general formula for dithiophosphates is shown in
surface. Fig. 15 and the key atom connecting the hydrocarbon chain is
The depression mechanism of DETA has been categorized to phosphorus instead of carbon as in xanthate (Bulatovic, 2007).
two aspects: (1) a ‘‘cleaning” mechanism which indicates that Dithiophosphate functions similarly in the pyrite system as xan-
DETA can remove the activating ions (Cu2+ or Pb2+) from pyrite sur- thate forming metal dithiophosphates or dithiophosphatogen
face; and (2) a ‘‘blocking” mechanism which means to form a (Valli et al., 1994; Fuerstenau et al., 2007). However, dithiophos-
hydrophilic Cu/Pb-DETA complex which adsorbs back to pyrite phate is more difficult to oxidize to its dimer, dithiophosphatogen
surface and competes with xanthate for adsorption sites (Sui than xanthate to dixanthogen. Diethyl dithiophosphatogen has
et al., 1998; Rashchi et al., 2004; Agorhom et al., 2014). been found experimentally to form at pH 4 and below in the pres-
Agorhom et al. (2014) studied the depression effect of DETA on ence of pyrite but not at pH 6 and above. Pyrite rejection in basic
the flotation of copper-activated pyrite with PAX as collector with medium when dithiophosphate is used as a collector is well known
or without aeration at pH 10. It was found that DETA depressed the (Fuerstenau et al., 2007).
flotation of Cu-activated pyrite at high dosages (500 g t1). The rest Dithiophosphinates are relatively new collectors for sulfide ore
potential was around 35 mV lower in the presence of DETA. flotation. The difference between dithiophosphates and dithio-
Though this is not enough to prevent xanthate oxidation, it may phosphinates is that the hydrocarbon groups are linked directly
reduce the oxidation rate. XPS, EDTA and UV–visible studies indi- to the phosphorus atom in the case of dithiophosphinates as
cated that DETA removed copper from the activated pyrite surface shown in Fig. 15 (Bulatovic, 2007). The studies on pyrite-DTPI
probably through the formation of a soluble Cu(DETA)2+ complex. interaction indicated that the adsorption of DTPI on pyrite surface
Displacement of xanthate and formation of Cu(I)-DETA complexes relied on chemical mechanisms rather than an electrochemical
on pyrite surface are also possible. Finally, under aeration, adsorp- interaction (Hicyilmaz et al., 2004). The dimer of dithiophosphi-
tion of DETA promotes the oxidation of Cu(I) to Cu(II) (Agorhom nate (DTPI)2 was also identified on pyrite surface at oxidizing
et al., 2014). As a result, the hydrophobicity of the pyrite surface potentials. The adsorption of DTPI exhibits high performance in
is reduced due to the removal of Cu(I)-S species, inhibition of xan- acid solution and decreases sharply under neutral and alkaline
thate adsorption and increase of the hydrophilic oxidation prod- conditions due to heavy surface oxidation at higher pH (Güler,
ucts such as Fe-Ox, Cu(OH)2 and Cu-DETA. This also indicates 2005). Dithiophosphinate is mainly recommended to float lead,
that DETA possesses higher affinity than xanthate to complex with copper and precious metals from minerals containing high levels
copper (Agorhom et al., 2014). Flotation tests showed that the of pyrite. The increased selectivity against pyrite is due to the more
DETA had a maximum depressing effect on pyrite under aerated pronounced affinity of dithiophosphinate towards metallic species
conditions (Agorhom et al., 2014, 2015). It may be because the acti- which constitute the matrix of the mineral than towards iron spe-
vation product Cu(I)-S is highly stable and inert towards DETA, but cies (Pecina-Treviño et al., 2003).
becomes reactive towards DETA when oxidized to copper oxides/ Thionocarbamate and thiourea type collectors are specific pro-
hydroxides (Agorhom et al., 2014). Similar observation was moter of copper sulfides which exhibit excellent selectivity for
reported by Yoon et al. (1995) that the depression of pyrrhotite copper sulfides against iron sulfides. The three important donor
flotation by DETA was more effective when the Cu-activated pyr- atoms, N, O and S are incorporated in the functional groups of these
rhotite surface was oxidized. collectors. The selectivity of these collectors for copper sulfides is
The effect of DETA on Pb-contaminated pyrite follows similar due to a metal ion specificity which interacts with cupric ions by
mechanisms as in the case of Cu-activated pyrite. In the study by forming an insoluble complex but not with ferrous, ferric or lead
Sui et al. (1998), dixanthogen was the only xanthate product on ions (Fairthorne et al., 1997). Examples of this type collector are
Pb-activated pyrite. Cyclic voltammetry indicated that DETA sup- O-isopropyl-N-ethyl thionocarbamate (C3H7O(C@S)NHC2H5), O-
pressed the formation of dixanthogen at large quantities (20– isobutyl-N-ethoxycarbonyl thionocarbamate (C4H9O(C@S)NH
40 ppm) (Sui et al., 1998). This may be due to a lower rest potential (C@O)OC2H5) and butyl ethoxycarbonyl thiourea (C4H9NH(C@S)
of Pb-contaminated pyrite in the presence of DETA, which lowers NH(C@O)OC2H5) which are commonly referred to as IPETC, IBECTC
the driving force for oxidation of xanthate. Although no trace of and BECTU, respectively. The difference between thionocarbamate
DETA on Pb-contaminated pyrite surface was detected using the and thiourea is that thiourea contains two N atoms in its structure,
IR spectra, the zeta potential measurement clearly showed the while thionocarbamate contains one N atom. These collectors pre-
adsorption of DETA on Pb-contaminated pyrite probably through cede xanthates and dithiophosphates due to their higher selectiv-
the formation of Pb-DETA complex (Sui et al., 1998). Therefore, ity against pyrite and higher stability at low pH (Buckley et al.,
the depression mechanism of DETA on Pb-activated pyrite is a 2014). Thionocarbamate is equal to or better than xanthates in col-
combination of the ‘‘blocking” mechanism and a decrease in poten- lecting power (O’Connor et al., 1990). Thionocabamate collectors
tial which retards xanthate oxidation. chemisorb on copper sulfides forming five/six-member chelate
ring by the bonding formed between collector S and O and surface
Cu (Fairthorne et al., 1997). However, some researchers suggested
4. Non-xanthate collectors that it would be the N rather than O involved in the interaction
Despite being a strong collector, xanthate cannot provide the

desired selectivity in a complex system involving pyrite. In this
respect, other collectors such as dithiophosphate (DTP), dithio-
phosphinate (DTPI) or thionocarbamate (TC) type collectors are
frequently used in flotation of sulfide minerals, alone or in combi-
nation with xanthates. They satisfy selectivity against iron sulfides
and have a strong collecting power similar to that of xanthate
(Bulatovic, 2007), These collectors are chelate-forming reagents Fig. 15. Chemical structure of dithiophosphate and dithiophosphinate adapted
whose structure possesses donor atoms endowed with chemical from Bulatovic (2007).
(Ackerman et al., 1987). While for pyrite, physisorption was pro- ship provided by the University of Queensland and China Scholar-
posed (Fairthorne et al., 1997). Unlike xanthates, the adsorption ship Council.
of thionocabamate collectors on pyrite did not remove sulfate-
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Minerals Engineering 96-97 (2016) 143–156

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The depression of pyrite in selective flotation by different reagent

Flotaon recovery (%)

ing to depression. At alkaline conditions, the stability of X2 is

(1) Electrochemical attraction (2) Hydrophobic interaction

(3) Hydrogen bonding (4) Chemical interaction

Enveloping the adsorbed X2

Fig. 7. Co-adsorption of polysaccharides and dixanthogen on pyrite surface.

enveloped inside the macromolecules and the polar hydroxyl

CMC requires a rather high dosage (500 mg L1 LDS CMC) to

achieve sufficient pyrite depression. The solution pH influences R R

the CMC adsorption as it affects the dissociation of carboxyl O O

groups, hydroxylation of mineral surfaces as well as the charge

of mineral surface. Adsorption isotherms show that the adsorption S S S S

density of CMC decreases slightly when the pH is over 9 and higher S S S S

Fig. 9. Inhibition of the adsorption of xanthate on pyrite surface by the pre-

Fig. 8. Structural unit of cellulose and carboxymethyl cellulose adapted from

3.3. Polyacrylamide polymers (PAM)

Polyacrylamide (PAM) is a water-soluble synthetic polymer

Despite being a strong collector, xanthate cannot provide the

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