Review of the flotation of molybdenite.
floatability

Part I: Surface properties and

S. Castro, A. Lopez-Valdivieso, J.S. Laskowski

PII:
DOI:
Reference:

S0301-7516(16)30003-5
doi: 10.1016/j.minpro.2016.01.003
MINPRO 2839

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International Journal of Mineral Processing

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12 September 2014
5 January 2016
11 January 2016

Please cite this article as: Castro, S., Lopez-Valdivieso, A., Laskowski, J.S., Review of
the otation of molybdenite. Part I: Surface properties and oatability, International
Journal of Mineral Processing (2016), doi: 10.1016/j.minpro.2016.01.003

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REVIEW OF THE FLOTATION OF MOLYBDENITE. PART I: SURFACE
PROPERTIES AND FLOATABILITY
S. Castro1, A. Lopez-Valdivieso2 and J.S. Laskowski3

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(1) Department of Metallurgical Engineering, University of Concepcin-Chile

(2) Instituto de Metalurgia, Universidad Autnoma de San Luis de Potos-Mxico
(3) NB Keevil Institute of Mining Engineering, University of British Columbia-Canada

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Corresponding author:
Sergio Castro
scastro@udec.cl
Phone: 56-9-98334829

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Abstract

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Molybdenite (MoS2) is a naturally hydrophobic mineral with anisotropic surface

properties. Its floatability is influenced by a number of factors such as, particle size and
shape, face/edge ratio, degree of crystallization, face heterogeneity, pH, etc. Molybdenite is
floated by using oily collectors, and its recovery is strongly affected by slime coating
phenomena. A number of hydrolyzable cations, such as Ca2+ and Mg2+, depress
molybdenite in alkaline solutions. Depression of molybdenite in seawater and saline waters
is mainly induced by the precipitation of colloidal magnesium hydroxide when pH is raised
to depress pyrite. Other metal cations present in recycled process water can also reduce the
flotation recovery of molybdenite (e.g., Al3+, Fe2+, Cu2+ ions). The native floatability of
molybdenite is highly depressed by natural polymers (starch, dextrin, guar gum, humic
acids, etc.) and synthetic polymers (e.g., flocculants of the polyacrylamide type). The
advances in understanding the surface chemistry of these systems are reviewed and
discussed in this paper.
Keywords: Molybdenite; Native floatability, Molybdenite depression; Cu-Mo sulfide ores.

1. Introduction
Common sulfide mineral collectors are known to adsorb onto molybdenite but these
reagents are not necessarily effective for molybdenite flotation. Flotation of molybdenite is
carried out with the use of hydrocarbons (e.g., diesel oil, kerosene, etc.). From this one
concludes that molybdenite must differ from other sulfides in that its surface is already
hydrophobic (Chander and Fuerstenau, 1972). Molybdenite, as all other inherently
hydrophobic minerals, cleaves by rupture of weak residual bonds (Gaudin et al., 1957)
revealing the surfaces that are hydrophobic since they interact with water only via
dispersion forces (Laskowski and Kitchener, 1969). Because of large differences between
the surface properties of molybdenite and other sulfides, molybdenite can be recovered
from Cu-Mo ores as a by-product with copper at levels as low as 0.01% Mo.
Approximately half of the worlds molybdenum production comes from porphyry CuMo
ores (Bulatovic, 2007; Guang-yi et al., 2012).
One of the most important publications in this area, edited by A. Sutulov, appeared
in 1979 (International Molybdenum Encyclopaedia). This volume also included two
reviews on molybdenite flotation (Castro, 1979; Shirley, 1979). We feel that considerable

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advances in understanding of the surface properties and floatability of molybdenite have
recently been made and this calls for a new review.

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2. Crystalline structure and natural floatability of molybdenite

The crystalline structure of molybdenite (MoS2) was first determined by Dickinson
and Pauling (1923). Molybdenite crystallizes in the hexagonal system as the common
polytype 2H and also in the trigonal system as the 3R polytype (less frequent).
Molybdenite (2H) has a hexagonal layer structure with a complete basal cleavage, showing
layers of trigonal prismatic coordination polyhedra, where each Mo atom is surrounded by
a trigonal prism of S atoms (Figure 1). The sulfur atoms form the upper and lower surfaces
with the smaller Mo atoms sandwiched between these layers. Sulfur-sulfur distances are
2.98 within the layers and 3.95 between the layers.

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Figure 1. Crystalline structure of molybdenite.

2.1. Hydrophobic minerals with anisotropic surface properties - molybdenite
A mineral with anisotropic surface properties is characterized by different surface
properties on different sides of the crystal. This is the case of the sheet structure of
inherently hydrophobic minerals, such as molybdenite, talc, graphite, etc. (Chander, et al.,
1975). In general, minerals with anisotropic surface properties do not have to be
hydrophobic, as in the case of clays, which are well recognized to have two types of
hydrophilic surfaces, faces and edges (Johnson et al., 2000; Laskowski, 2012). Molybdenite
particles exhibit two types of surfaces: (1) those that form by the break of the S-S bonds
(non-polar faces) and (2) those that are generated by rupture of the strong covalent Mo-S
bonds (polar edges). As a result, the faces are hydrophobic while edges are hydrophilic. It is
then reasonable to assume that crystal faces are responsible for the natural floatability of
molybdenite.
2.2. The effect of particle size and morphology on the floatability of molybdenite
Particle size is a very important factor affecting flotation properties of molybdenite.
In porphyry copper-molybdenite ores the flotation conditions (grinding, reagents, bubble
size, etc.) all are optimized with respect to Cu and not Mo. Figure 2 shows that the
optimum flotation particle size for molybdenite is around 20 m, and the size fraction 6.8
m exhibit the lowest recovery and flotation rate (Castro and Mayta, 1994). However, the
optimum particle size for copper sulfide minerals is around 15-100 m. Therefore, usually

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it is not economically attractive to grind a copper ore to the optimum liberation size of
molybdenite.
The natural floatability of molybdenite is also governed by textural features
(flatness, roundness, relative width, elongation ratio and surface roughness). Because of the
preferential cleavage along the weak SS bonds during grinding, platelet shaped fragments
exfoliating from larger particles, are produced (Figure 3). In the case of flat and elongated
particles, low particle-bubble collision efficiency explains its poor flotation recovery.
Hence, the flotation behavior of molybdenite is governed by a combination of: (a) the
native floatability (Chander and Fuerstenau, 1972; Chander et al., 1975; Arbiter et al.
1975); and (b) the particle morphology (shape and size) (Ametov et al., 2008; Nakhaei and
Irannajad, 2014). Molybdenite particles with a high aspect ratio (major axis over minor
axis) have higher probability of reporting to the concentrate, and coarse particles with high
perimeter to area ratio tend to report to the tailings (Triffett and Bradshaw, 2008; Triffett et
al., 2008).
Similarly, the shape characteristics of talc particles produced by ball, rod and
autogenous mills were investigated by Yekeler et al., (2004) using Scanning Electron
Microscope (SEM). Their results have shown that elongation and smoothness helped to
increase the hydrophobicity, while roundness and roughness caused a decrease in
hydrophobicity and floatability of talc. The grinding of talc powder decreased crystallinity
due to selective destruction of the (00l) plane and its hydrophobicity decreases by the
grinding effect (Terada and Yonemochi, 2004).
For molybdenite particles the faces-to-edges ratio is a function of particle size, it
decreases for fine particles which are therefore less hydrophobic than coarse ones (Castro
and Correa, 1995; Yang et al., 2014). Accordingly, small size particles show low
floatability (Figure 3). In addition, fine particles show slow flotation kinetics (Hsu, 1982;
Castro and Mayta, 1994). The flotation rate also depends on pH and is claimed to be faster
at pH 7.5 than at pH 11 (Hsu, 1982). The floatability of the overground molybdenite is
significantly reduced (Hsu, 1982).

Figure 2. The effect of particle size and of MIBC concentration on cumulative molybdenite
recovery after 12 min of flotation at pH 11 (NaOH) and IsopX=28 g/ton (Castro and Mayta,
1994).

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Figure 3. Native floatability of molybdenite of various particles size fractions as a function

of pH (Lopez-Valdivieso et al., 2006).

Figure 4. Photomicrographs of molybdenite particles separated from a flotation concentrate.

2.3. Floatability of molybdenite and degree of crystallization
The degree of crystallization is one of the relevant factors affecting molybdenite
flotation (Hernlund, 1961; Shirley, 1981; Podobnik and Shirley, 1982; Zanin et al., 2009).
Well crystallized molybdenite is considered fast floating, while almost amorphous variety
is either slow floating or non-floating (Hernlund, 1961).
Triffett et al., (2008) described two types of molybdenite: vein controlled and
disseminated. The vein controlled molybdenite is the most common and its occurrence
varies depending on the size of the vein in which it forms. Wider - quartz filled - veins tend
to form larger, cleaner crystals of molybdenite while narrow veins result in a coating of

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much finer molybdenite on fractured surfaces which can take on a smeared appearance due
to in situ movement within these fractures.
The main types of molybdenite in copper porphyry ores are: (1) coarse, clean
molybdenite with perfect basal cleavage which occurs in quartz veins, (2) fine-grained
scaly molybdenite which appears as fine coatings along the joints and fractures of breccia,
and (3) amorphous and dull variety (Sutulov, 1971; Hsu, 1982). Sutulov claimed that
problems in the recovery of molybdenite arise mainly from the amorphous and finely
disseminated molybdenite. According to Shirley (1979), molybdenite is commonly lost in
copper flotation circuits, as a result of the following problems: (a) lack of liberation; (b)
large flakes; and (c) oxide coatings. This author observed that large flakes are formed from
well crystallized veins, lack of liberation takes place with dispersed in quartz veins and
veinlets, and losses by sensitivity toward copper depressant is observed in sooty or smear
molybdenite types.

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2.4. Surface composition of molybdenite and its inherent hydrophobicity

Basal planes of molybdenite crystals are formed by rupture of the S-S week van der
Waals bonds, and are considered hydrophobic due to the surface content of S atoms.
According to Triffett et al. (2008), slower floating molybdenite shows decreasing S content.
Therefore, particles reporting to the tailings have a lower concentration of S than those
recovered with concentrates. Surface analysis of molybdenite particles by the Time of
Flight Laser Ionization Mass Spectroscopy (TOFLIMS) has indeed demonstrated that
surface S is depleted on slower floating particles, while surface oxidation (MoO3) and
calcium coating is increased.

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2.5. Atomic force microscopy of basal planes of molybdenite

Traditionally, the basal planes of molybdenite have been considered homogeneously
hydrophobic. However, this approach does not describe well various phenomena. Recent
atomic force microscopy (AFM) studies have revealed that the faces of molybdenite
particles are heterogeneous in nature and terraces and clusters of micro-crystals of
molybdenite having nano-edges and nano-faces (Figure 5) are observed on such faces. In
addition, these studies have shown that the faces possess a high level of roughness. Such
heterogeneity of the faces leads to both hydrophilic and hydrophobic areas on the basal
planes (Lopez-Valdivieso et al., 2012). These results are in good agreement with
Komiyama et al.s findings (2004) (in this work the atomic structure of the basal planes was
examined by Ultra-High Vacuum Scanning Tunneling Microscopy, UHV-STM, and crater
structures with diameters ranging from 5 to 9 nm were observed). These findings are
important because they offer further understanding for the adsorption of some inorganic
ions on faces, such as Ca and Mg ions, and of organic polymers such as dextrin and starch,
which strongly reduce molybdenite hydrophobicity. They showed that contact angle
measurements on crystal faces of molybdenite are performed on rough and anisotropic
surfaces composed of both hydrophobic and hydrophilic areas.

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Topographic image of a face-area of 2 m.

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Topographic image of a face-area of 5 m.

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Topographic image of face showing three

levels of depth in basal plane.

Profile of plane 1 to plane 3 showing the

depth of nano-faces and thickness of nanoedges in basal plane.

Figure 5. AFM images of different areas of MoS2 faces.

3. Molybdenite wettability
Contact angle studies performed on molybdenite have shown that faces are
hydrophobic while edges are hydrophilic. Natural crystals of molybdenite have been used
to obtain a contact angle around 80 for faces (Chander and Fuerstenau, 1972; Kelebek,
1988; Yang et al., 2014). However, Lopez-Valdivieso et al., (2006) found a contact angle of
61 at pH 5, which decreases slightly as pH increases (Figure 6). Figure 5 also shows that
calcium ions are able to reduce contact angle measured on the crystal faces. Arbiter et al.
(1975) have reported that contact angle depends on the method of preparation of the face.
For a face cleaved under water, they obtained a contact angle of 90o, while for a high luster
polished face the contact angle was 70o. The surface roughness and the anisotropic nature
of the face then are the main factors that affect the contact angle values.
Contact angle is also a function of the degree of surface oxidation. Roasting
molybdenite decreases contact angle from 80 to 30 depending on temperature (Chander
and Fuerstenau, 1972). Depressing reagents are able to reduce molybdenite hydrophobicity,
e.g., calcium ions decrease contact angle measured on faces (see Figure 6).

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Figure 6. Contact angle on edges and faces of molybdenite particles as a function of pH, in
the absence and presence of calcium ions (Lopez-Valdivieso et al., 2006).

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Wie and Fuerstenau (1974) also measured the contact angle between a free isooctane droplet in water (across water phase) on molybdenite surfaces. At pH 4, the contact
angle was determined to be about 150o, in alkaline solutions it decreased to 100o, and so
these measurements turned out to be much more sensitive to pH (to electrical charge at
solid/liquid interface). In further analysis of these data, Chander et al. (2007) demonstrated
an excellent correlation between molybdenite oil flotation recovery and oil/water contact
angle of molybdenite shown in Figure 7 (in oil flotation an oil phase is substituted for the
gaseous phase).

Figure 7. The effect of pH on the oil flotation of fine molybdenite without the addition of a
surfactant. Also plotted is the effect of pH on the oil/water contact angle of molybdenite,
expressed in terms of the flotation dewetting relation (1-cos) (Chander, et al., 2007).
In the thermodynamic criterion of flotation, G flot LV cos 1 , but for
correlation purposes, the parameter was needed that increases with increasing flotation
recovery, and that is why in Figure 7 the results were plotted in terms of the quantity

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(1 cos ) . Figure 7 shows a very good correlation between oil flotation of molybdenite
and the wettability of molybdenite surface by oil. Since these contact angle measurements
were carried out on freshly cleaved faces of a molybdenite crystal, these data seem to
indicate that the zero-point of charge of molybdenite faces is situated around pH 4.

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4. Zeta potential of molybdenite

Since in the case of the minerals with anisotropic surface properties the faces and
edges are formed by rupture of different bonds these faces and edges carry different
electrical charges. Electrical charge of solid particles suspended in water is commonly
estimated from the electrokinetic measurements and the value of the zeta potential. Microelectrophoretic equipment is utilized in such measurements and Smoluchowski equation is
used to calculate the zeta potential. However, this equation was derived for spherical
isotropic particles and it is not clear what is calculated if the particles used in the
experiment are non-spherical and carry different electrical charges on different sides of the
particles (Laskowski, 2012). Such experimental problems can result in misleading
conclusions as was demonstrated in the measurements with kaolinite (Johnson et al., 2000)
and talc (Burdukova et al., 2007; Lujie Yan et al., 2013).
In this paper we are dealing with the case of molybdenite, also an anisotropic
mineral, which has very hydrophobic faces. This results in a high natural floatability of this
mineral. However, since it is anisotropic, finding correlations between the measured
hydrophobicity and floatability, or zeta potential and floatability, is not an easy task.
Healy and Fuerstenau (2007) for zero field strength materials, i.e., nonpolar or
hydrophobic materials, propose that the pzc will be in the low acidic pH 13 region,
depending on the value assigned to water molecules or clusters at the interface; but for
molybdenite the experimental evidences presented show fluctuating values between pH 2
and 4. As summarized by Beattie (2007), almost all of the experimental evidence is
consistent with the idea that water at hydrophobic surfaces acquires a negative charge
above pH 3-4 from the preferential adsorption of hydroxide ions. Parreira and Schulman
(1961) in the electrokinetic experiments with very pure paraffin wax found that the zeta
potential of this solid exhibits i.e.p. value around pH 4 and that it is negatively charged in
distilled water. Zeta potential measurements for molybdenite give very negative values over
the whole pH range (Chander et al., 1975; Lopez-Valdivieso, 1980). This is shown by the
bottom curve after Lopez-Valdivieso et al. (2012) in Figure 7. It can be expected that for
anisotropic minerals both the charge of the faces and that of the edges contribute to the
overall zeta potential of molybdenite particles. As Figure 6 indicates, the point-of-zero
charge of molybdenite faces seems to be situated around pH 4. If we assume that the zeta
potential of the hydrophobic faces can be described by the Parreira and Schulmans data
(1961) obtained for a hydrophobic paraffin wax, then the obtained picture (Figure 8) can be
used to estimate the electrical charge of the edges.
Figure 8 indicates that at pH > 4 the zeta potential of molybdenite is very negative
since over this pH range both the faces and the edges are charged negatively. Below pH 4,
that is, below the i.e.p. for molybdenite faces, the charge on faces becomes positive while it
must still be very negative for the edges since the overall zeta potential data are still very
negative.

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Figure 8. Effect of pH on zeta potential of molybdenite (+, after Lopez-Valdivieso et al.,

2012) and of paraffin wax (, after Parreira and Schulman, 1961).

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The origin of the electrical charge at the edges is very different from the way the
charge is generated at the faces. The edges are chemically active and react with water or
oxygen to form oxidized surface species. The negative electric charge at edges has been
interpreted as a result of the formation and specific adsorption sites at the solid/solution
interface of HMoO4-/MoO42- ions, formed by oxidation of Mo(IV) to Mo(VI), and by the
subsequent hydrolysis reactions (Chander and Fuerstenau, 1972).

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4.1. Slime coating and hetero-coagulation

The generic term slime coating refers to the process in which slimy hydrophilic
gangue particles coat the surfaces of valuable minerals and make them hydrophilic (slime
coating can also take place between slimy molybdenite and coarse hydrophilic gangue).
The slime coating phenomenon has been identified as one of the factors affecting
molybdenite recovery. Low hydrophobicity and poor floatability of molybdenite can result
from slime coating on molybdenite. It is likely that fine particles of non-sulfide gangue
(quartz, feldspar, clays, etc.) adhere electrostatically to the molybdenite surface (Hsu, 1982;
Triffett et al., 2008). Lopez-Valdivieso (2004) has found that molybdenite fines are
attached to the surface of coarse quartz and pyrite in the feed of the rougher flotation of the
porphyry copper ore at Mexicana de Cobre (see Figure 9). Hernlund (1961) claims that
slime coating prevent the adsorption of collector on the surface of molybdenite and it
deteriorates its oatability. The mechanism of slime coating is widely believed to be a
coagulation of the oppositely charged mineral particles on the surface of molydenite. As it
is known, calcium ions are able to reduce or to reverse the zeta potential of quartz from
negative to positive values. Raghavan and Hsu (1984) reported that hetero-coagulation of
molybdenite and quartz takes place mainly in the aqueous dispersions containing lime.
They also found that coarse molybdenite particles (120-200 mesh) float extremely rapidly
and completely without being influenced by hetero-coagulation. But the flotation of fine
molybdenite particles (-200 mesh) was highly sensitive to hetero-coagulation.

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Figure 9. Slime coating of molybdenite on pyrite and quartz in the feed of rougher flotation
of porphyry copper ore at Mexicana de Cobre, pH 10.5 (Lopez-Valdivieso, 2004).

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Dispersing agents, such as sodium silicate and polyphosphates are recommended to

prevent the slime coating (Park and Jeon, 2010; Huynh et al., 2000). Figure 10 shows that
hexametaphosphate improves the recovery of molybdenite in the rougher flotation of
porphyry copper ore with 0.039% Mo. 7 g/ton thionocarbamate collector for copper and 5
g/ton non-polar collector for molybdenite were used in the flotation tests (LopezValdivieso, 2004).

Figure 10. Flotation recovery of Mo in copper rougher flotation of Mexicana porphyry

copper ore (0.039% Mo) without and with 10g/ton sodium hexametaphosphate in the ore
grinding. These are batch flotation tests with 7 g/ton thionocarbamate collector and 5 g/ton
non-polar oil, pH 10.5 (Lopez-Valdivieso, 2004).

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5. Molybdenite and flotation reagents

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5.1. Interactions with thiol collectors

Relatively few papers have been published on the interaction of molybdenite with
thiol collectors (xanthates, dithiphosphates, dithiocarbamates, etc.). Xanthates are weak
collectors for molybdenite and molybdenite is commonly floated with the addition of a
non-polar oily collector. Fine particles of molybdenite (6.8m) practically do not respond
to an increase in xanthate dose, but coarse particles (51.7 m) flotation recovery and rate
are significantly enhanced (Castro and Mayta, 1994). These results suggest that the
effectiveness of xanthate as collector increases with particle size due to its higher degree of
inherent hydrophobicity given by the larger faces/edges ratio.
In the presence of dissolved oxygen semi-conducting minerals (e.g. sulfides) are
able to electro-catalytically oxidize xanthate ions to form non-polar dimmer molecules (e.g.
dixanthogen, i.e., a dithiolate), which adsorb onto the faces sites, e.g. for graphite and
molybdenite (Afenya, 1982; Allison and Finkelstien, 1971; Allison et al., 1972). Pieces of
evidence of xanthate adsorption on molybdenite have been reported by Russian researchers,
as it was summarized by Castro (1979). However, no insoluble metal xanthate has been
detected on molybdenite. Allison and Finkelstein, (1971); and Allison et al., (1972)
confirmed by a spectrophotometric technique the formation of dixanthogen and another
not-identified product on molybdenite with different alkyl xanthates. The molybdenite rest
potential was +0.160 V (for 6.25 x 10-4M KEX and pH 7) and dixanthogen was the main
product identified. Atomic force microscopy (AFM) was applied to study in situ the
adsorption of potassium ethyl xanthate (KEX) on molybdenite at pH 11. AFM images show
a very sparse adsorption on the basal planes. Adsorbed species are much less on
molybdenite compared with chalcopyrite under similar conditions. Then, the obtained AFM
images show a low adsorption of KEX on the molybdenite basal planes, explaining why
KEX is not an efficient collector for molybdenite (Zhang and Zhang 2010). Potassium
trithiocarbonate (KTTC), a degradation product of potassium ethylxanthate, exhibits a
certain depressant activity on molybdenite. However, this depression effect was overcome
by small additions of fuel oil (Simpson et al., 1983).
Chander and Fuerstenau (1974a,b) studied the adsorption of potassium
diethyldithiophosphate (KDTP) on the surface of molybdenite as a function of pH. They
attributed the slight increase in contact angle to the physical adsorption of the oxidation
product of KDTP, i.e. (DTP)2. The adsorption of KDTP on the molybdenite surface may
proceeds through three mechanisms: (a) a reaction of ion exchange between the DTP- ions
and the HMoO4- or MoO42- adsorbed ions; (b) a catalytic oxidation of the collector with
formation of (DTP)2 ; (c) a cooperative adsorption of DTP- ions favored by (DTP)2. The
path (c) proceeds by electrochemical mechanisms.
5.2. Interaction with non-polar oils
Commonly oily collectors are used to promote molybdenite flotation (and all other
inherently hydrophobic minerals). For primary molybdenite ores a combination of sodium
silicate (Na2SiO3) and lime (CaO) is used at pH 911. Sodium silicate (water glass) is
employed as dispersant of the slime coating formed on the mineral particles, and as
depressant of gangue minerals (Park and Jeon, 2010). Another important factor is the use of
an emulsifying agent for the non-polar oil collector. It is well established that the addition
of the emulsifying agent Syntex-L improved molybdenite flotation at Climax mill,

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Colorado (Hoover and Malhotra, 1976). Nishkov et al. (1994) studied the use emulsifying
agents for diesel oil in the flotation of El Teniente Cu-Mo ore, reporting a significant
improvement in molybdenite recovery.
Hydrocarbon oils are the most common collectors for molybdenite, including
kerosene, diesel oil, transformer oil, etc. Petroleum hydrocarbons differed in their
effectiveness for enhancing the natural floatability of molybdenite. Hydrocarbon oils of
different aliphatic and aromatic content have been tested on various types of molybdenite
ores (Smith and Bhappu, 1971). They found that for an unaltered ore containing very little
or no clays, highly aromatic oils proved the most effective for all types of molybdenite
occurrence, crystalline, finely divided, and sooty. However, for altered ores, highly
saturated oils proved more effective than the highly aromatic oils (Hsu, 1982). Smith and
Bhasin, (1985) investigated in the AMAX plant a series of commercial oils which were
blended with diesel fuel to form different molybdenite non-polar collectors. A twocomponent blend of a high and low molecular-weight diluents oil demonstrated to be better
molybdenite collector than single-component oil. Furthermore, collector blended with
naphthenic oils gave superior flotation results to those blended with aromatic oils.
Kerosene is widely used as the conventional non-polar collector for molybdenite.
However, it is difficult to ensure its stable composition, which leads to a harmful effect on
the molybdenum production, particularly with difficult ores, i.e., lower-grade and finedisseminated ores (He et al., 2011). As a substitute, these authors studied the influence of
diesel oil from different manufacturers on the flotation of molybdenite and the influence of
pulp temperature on the dispersibility of diesel oil. In flotation pulp temperatures ranging
from 10 to 30C, the flotation recovery of molybdenite increases with increasing highboiling component in diesel oil. When pulp temperature is below 10C, the flotation
recovery of molybdenite is related to the dispersibility of diesel oil, i.e., the proportion of
high-boiling and low-boiling component in diesel oil. Therefore, a molybdenum flotation
plant should not blindly apply diesel oil instead of kerosene as the collector for
molybdenite, but should select diesel oil that is suitable for the properties of its ore.
Many studies (Crozier, 1979; Smit and Bhasin, 1985; Xia and Peng, 2007; Wang et al.,
2008; Song et al., 1999) have shown that the collecting ability of hydrocarbon oils enhance
as its carbon chain length increases, which contributes to the enhancement of collecting
ability for coarse molybdenite and intergrowths of molybdenite with gangue. However, too
long a carbon chain brings down the dispersibility of hydrocarbon oil in pulp, causing the
adverse effect and recovery decline of the valuable mineral. As summarized by Bulatovic
(2007) low-viscosity oils give lower recoveries than the high viscosity oils but at a
somewhat higher concentrate grade. Pine oil - and alkoxy paraffins give better MoS2
recovery than MIBC or polyglycol, and the use of emulsifier improves molybdenum
recovery significantly.
5.3. Interactions with methyl isobutyl carbinol (MIBC)
Methyl isobutyl carbinol (MIBC) (4-methyl-2-pentanol), a common frother, is a
partially soluble short-chain aliphatic alcohol commonly employed as a week but selective
frother in the flotation of Cu-Mo sulfide ores. For molybdenite MIBC is considered to be
an effective frother-collector. The adsorption of MIBC on molybdenite has been studied by
gas chromatography (Veliz and Molina, 1984). It was found that MIBC is strongly
adsorbed on fine molybdenite (6-9m), and in pH ranging from 8 to 12 adsorption
decreases as pH increases. Adsorption by hydrophobic interactions was suggested. These

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results agree with those reported by Castro et al. at pH 11 (1997). Castro and Mayta (1994)
reported that molybdenite recovery is significantly increased by increasing the dose of
MIBC for particle sizes from 6.8 m to 51.7 m, being higher for the 6.8 m size fraction
(the size with poorest flotation recovery) (Figure 9).
On the other hand, it has been found that MIBC is adsorbed on other inherently
hydrophobic minerals promoting their flotation. For example, Fuestenau and Pradip (1982)
and Miller et al., (1983) have shown that MIBC is adsorbed onto coal. They found that
oxidized coal is more hydrophilic and the adsorption of the non-ionic MIBC molecules is
reduced after oxidation. The results indicate that adsorption occurs through hydrophobic
interactions between the frother molecules and the coal surface. The adsorption of MIBC
on coal is closely related to coal floatability and combustible recovery increases with the
MIBC dose (Qu et al., 2013). Similarly, Kho and Sohn (1989) reported a good flotation of
talc with MIBC. In a more general view Hui et al. (2011) reported that weekly hydrophilic
compounds, like MIBC, are positively adsorbed on low energy surfaces by hydrophobic
attractive forces. This behavior includes plastics, coal, graphite, talc, molybdenite, etc.

Figure 11. Effect of MIBC concentration and of particle size on recovery of molybdenite;
flotation time 12 min at pH 11 (NaOH), and IsopX consumption of 28 g/ton (Castro and
Mayta, 1994).
6. Depression of molybdenite
6.1. Depression by polysaccharides and other natural polymers
Polysaccharides such as starch and dextrin have been used as molybdenite
depressants for a long time (Hernlund, 1961). The adsorption of dextrin occurs through
physical interactions with the molybdenite surface, possibly due to hydrophobic bonding
(Wie and Fuerstenau, 1974). Dextrin was found to be a very effective molybdenite flotation
depressant in the absence of a collector, whereas it does not effectively depress
molybdenite when oil is used as a collector. Recently, substituted dextrin has been studied
in more detail (Beaussart et al., 2012). The adsorption of three dextrins on molybdenite
(Wheat dextrin, dextrin TY, carboxymethyl (CM) dextrin, and hydroxypropyl (HP) dextrin)
were studied through Tapping Mode Atomic Force Microscopy (TMAFM) at plateau

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coverage. The isotherms revealed the importance of molecular weight (Beaussart et al.,
2012). Ansari and Pawlik (2007a,b) studied the adsorption and molybdenite depression by
lignosulfonate, and concluded that the high adsorption density of lignosulfonates on
molybdenite was primarily due to the adsorption of high molecular weight fractions.
Additionally, other natural polymers such as fulvic and humic acids - which are poorly
defined anionic polymers with phenolic and carboxylic groups (products of plant decay)
have also been shown to depress flotation recovery of molybdenite in acidic solutions
(Laskowski and Yu, 1994) similarly to other inherently hydrophobic minerals, such as
graphite (Wong and Laskowski, 1984); and coal (Pawlik et al., 1997).

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6.2. Depression by flocculants

Most of the commonly used flocculants depress molybdenite flotation. Therefore,
flocculants should not be utilized on middling thickeners in the copper circuits or in the
molybdenite plant feed thickener unless absolutely necessary (Shirley, 1979).
The main function of flocculants used in mineral processing circuits is to produce
large and strong flocs. It is generally accepted that polymers used as flocculants aggregate
suspensions of fine particles by a bridging mechanism. The bridging is considered to be a
consequence of the adsorption of the segments of the flocculant macromolecules onto the
surfaces of more than one particle. The optimum flocculation occurs at flocculant dosages
corresponding to a particle coverage that is significantly less than complete. Incomplete
surface coverage ensures that there is sufficient unoccupied surface available on each
particle for the adsorption of flocculant segments during collision of the particles.
Low molecular weight polymers are often used as depressant for naturally
hydrophobic minerals; South African platinum industry utilizes carboxymethyl cellulose,
and guar gum, to depress talc (Steenberg and Harris, 1984).
Polymer chains in solution can be irreversibly degraded by breaking of the polymer
chains by shearing forces (shear degradation) (Al Hashmi et al., 2013). Then, polymers
undergo chain scission and the overall result is a loss in its flocculation efficiency; this,
however, does not reduce depressing ability of these polymers (Castro and Laskowski,
2013).
The floatability of molybdenite - similarly to other naturally hydrophobic minerals is strongly depressed by polymers employed as flocculants for example by polyacrylamide
flocculants and non-ionic flocculants like poly(ethylene oxide) (PEO) (Castro and
Laskowski, 1997; Castro and Laskowski, 2004;; Castro and Laskowski, 2013; Castro and
Laskowski, 2015). Low molecular-weight shear-degraded polyacrylamides also depress
molybdenite.
7. Depression by hydrolyzable metal cations
Molybdenite floatability is highly affected by the presence of hydrolyzable metal
cations commonly found in process water. Similar effect is reported for talc, which has
identical anisotropic surface properties (Fuerstenau et al., 1988). The natural floatability of
talc is depressed within the pH range from the onset of the precipitation pH of metal
hydroxide to the i.e.p. of the metal hydroxide. Adsorption of hydrolyzable metal cations at
the mineral-solution interface depends not only on the ionic charge but also on these ions
hydrolysis (James and Healy, 1972c). James and Healy (1972a,b,c) studied the adsorption
of various metal cations as a function of pH on two oxides: SiO2 (low dielectric constant)

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and TiO2 (high dielectric constant) as model systems. These authors found that a qualitative
relationship exists between the pH where an abrupt rise in adsorption is observed and the
pH of hydrolysis of the metal cations. Hydration shells of the ions constitute a barrier to
adsorption of highly charged ions on the mineral surface; this makes direct adsorption of
un-hydrolyzed metal cations very difficult (in acid pH) in spite of the strong electrostatic
attraction forces between a cation and negatively charged solid surface. Figure 12 shows
the zeta potential of molybdenite in the absence and presence of the hydrolyzable metal
cations Fe3+, Al3+ and Mg2+.

Figure 12. Zeta potential of molybdenite in the absence and presence of Fe3+, Al3+
and Mg2+ cations (Lopez-Valdivieso, 1980).

7.1. Depression by calcium ions

An excess of lime can depress molybdenite flotation in cleaner circuits due to the
high pH needed to depress pyrite (pH 11-12). In some cases, the sensitivity of molybdenite
to lime appears to be reduced by using an oily collector (Shirley, 1979).
To understand the role of lime on the floatability of molybdenite the effect of
calcium ions has been studied (Lenkovskaya and Stepanov, 1968; Chander and Fuerstenau,
1972; Castro and Paredes, 1979; Hoover, 1980; Hsu, 1982; Raghavan and Hsu, 1984).
Calcium ions may act as both, a promoter or depressant of molybdenite flotation.
In acid media (pH 3.8 and 5.0), experimental evidence shows that the zeta potential
of molybdenite becomes less negative or reverses with increasing calcium ion
concentration. The adsorption mechanisms of calcium ions seems to be different to the
physical adsorption described by James and Healy (1972a,b,c). Specific adsorption of
calcium ions by chemical interactions with edges to form a surface coating of CaMoO4 has
been suggested (Chander and Fuerstenau, 1972). The adsorbed Ca2+ ions would neutralize
an equal amount of MoO42- ions, decreasing the negative surface charge and the value of
zeta potential. Over this acid pH range the flotation recovery is increased by calcium ions
becoming a maximum at the concentration of Ca2+ ions required for reversal of the zeta

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potential (PZR). Therefore, under conditions where the zeta potential is near zero, the
flotation is found to be the best (Figure 10). The subsequent adsorption of Ca2+ ions may
explain the loss of floatability observed at calcium concentration higher than the point of
PZR. Chander and Fuerstenau (1972) attributed this flotation depression in acid media to
the competition between compression of the double layer and specific adsorption of Ca2+
ions on the crystal faces.
However, in the alkaline pH range a strong molybdenite depression is usually
observed at pH>8 (Hoover, 1980). It is also reasonable to expect a chemical adsorption of
Ca(OH)+ species to form surface calcium molybdate, followed by adsorption of Ca(OH)+
species which increases the surface electrical charge. Then, adsorbed Ca(OH)+ species may
nucleate and co-precipitate as calcium hydroxide on edges, and in a small amount on faces.
The calcium speciation diagram shows that by increasing pH, Ca2+ ions hydrolyze to form
in a first step hydroxy species (CaOH+) with subsequent precipitation of colloidal calcium
hydroxide (Ca(OH)2(s)). The precipitation of calcium hydroxide depends on calcium
concentration and pH. Lopez-Valdivieso et al. (2006) for a total Ca ions concentration of
10-3M reported precipitation at a pH of 11.5. Other authors identified the precipitation zone
of calcium hydroxide at higher pH values (Fuerstenau and Palmer, 1976). Taking into
account that usually molybdenite depression takes place over the pH range from 8 to 12, it
seems that the depression mechanism not necessarily involves the precipitation of calcium
hydroxide.
Systematic studies revealed that Ca2+/Ca(OH)+ ions are strongly adsorbed on
molybdenite (see Figure 11) and that adsorption increases with increasing pH (Hoover,
1980; Lenkovskaya and Stepanov, 1968; Hsu, 1982). The depression mechanism assumes
that calcium species are adsorbed only onto the negatively charged edge surface sites.
Nevertheless, in order to understand molybdenite depression, the adsorption of calcium
species on the hydrophobic surface sites needs to be considered. Contact angles of edges
are approximately 0, i.e., they are initially hydrophilic before the adsorption of Ca(OH)+
ions. Additionally, it has been reported that basal planes are very heterogeneous and not
fully hydrophobic due to the presence of nano-edges, terraces and craters, where Ca2+ or
Ca(OH)+ ions can be adsorbed (Lopez-Valdivieso et al., 2012). Experimental evidence
shows that the adsorption of these hydroxy species decreases the contact angle of
molybdenite faces (Lopez-Valdivieso et al., 2012). Therefore, it can be expected that in
alkaline media Ca(OH)+ ions can be adsorbed not only on the edges of molybdenite
particles, but also on the basal planes. These basal planes as discussed in this paper
exhibit the pzc around pH of 4. If the i.e.p. for molybdenite faces is pH 4 then better
flotation of molybdenite at pH 3.8 than 5 (Figure 13) could be explained by the lack of the
electrical charge around pH 3.8 on the hydrophobic faces which are responsible for
molybdenite flotation.

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KOH Leached Molybdenite

48x65 Mesh
Ionic Strength
10-2 M KCl

PZR

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Relative Flotation Recovery, %

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Figure 13. Flotation recoveries of molybdenite as a function of calcium ion concentration at

an ionic strength of 10-2M KCl (without flotation reagents) (Chander and Fuerstenau,
1972).

Figure 14. Adsorption of calcium ions by radioactive tracer technique as a function of free
Ca(OH)2 content in slurry (mg/L) and pH (adjusted with H2SO4 and NaOH) (Lenkovskaya
and Stepanov, 1968; Hoover, 1980).

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7.2. Depression in seawater - effect of magnesium ions

Molybdenite is strongly depressed around pH 9.5-10.0 when Cu-Mo ores are floated
in seawater. The most important variable is pH and the depression takes place
approximately in the pH range where magnesium hydroxide (Mg(OH)2(s)) starts
precipitating (Castro, 2012; Castro et al., 2012; Laskowski and Castro, 2012; Laskowski et
al., 2013; Castro et al., 2014). In spite that MgMoO4 may be formed in aqueous solutions
(Essington, 1992), that does not seem to be relevant for molybdenite depression in seawater
and alkaline media. Castro et al., (2012) demonstrated that the native floatability of
molybdenite is not affected by the presence of anions, such as, SO42- and HCO3-, at
concentrations similar to those occurring in seawater (see Figure 15). However, a strong
depression of molybdenite at pH ranging from 9.5-10.0 is produced in seawater, and this
depressing effect of Mg2+ions is significantly stronger than the effect of Ca2+ ions.
Taking into account that the molar concentration of Mg in seawater is about four
times that of Ca (around 1,300 mg/L for Mg and 400 mg/L for Ca), and the lower Kps
(magnesium hydroxide Ksp(25oC) = 1.8x10-11, calcium hydroxide Ksp(25oC) = 6x10-6) and
lower critical pH of precipitation for Mg(OH)2(s), it is reasonable to expect that the
depressing effect of magnesium ions in seawater (and also in saline and hyper-saline
waters) should be much higher than that of calcium ions. The effect of Mg2+ ions on
molybdenite is related to its hydrolysis. As a first step MgOH+ hydroxy-complexes are
formed and adsorb on the surface of molybdenite; in a second step surface precipitation of
hydrophilic colloidal magnesium hydroxide takes place around pH 10. These species, as
shown in Figure 12, can reverse the zeta potential of molybdenite. According to Li and
Somasundaran (1991), the pH of precipitation of magnesium hydroxide varies from 9.2 to
11, for 10-2 and 10-5 M Mg concentrations, respectively. The hetero-coagulation of these
cationic colloidal species on the molybdenite surface forms a hydrophilic coating and
renders it hydrophilic as it has been recently suggested (Castro et al., 2014).

Figure 15. Effect of pH (lime) on the natural flotation (+200 mesh pure molybdenite) in
NaCl solutions (0.6 M) containing different ions (SO42-; CO32-; Mg2+; and Ca2+ ions),
without any collector and frother (Castro et al., 2012).

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7.3. Depression by other metal cations

Celik and Somasundaran (1986); and Somasundaran, Zhang and Fuerstenau (2000)
demonstrated that multivalent ions, such as, Ca2+, Fe3+, and Al3+ depressed coal in the
pH region of precipitation of metal hydroxides. Adsorption tests as a function of pH
showed that coal adsorbed these multivalent ions in a similar way to oxides. For example,
the adsorption of Ca2+ and Al3+ ions on coal is governed by the formation of the CaOH+ and
AlOH2+ species, which drastically reduce the hydrophobicity of coal, with good correlation
between its floatability and the precipitation of the metal hydroxy complexes. Molybdenite
is depressed by a number of hydrolyzable metal cations, such as, Al3+, Pb2+, Fe2+, Fe3+,
Cu2+, etc. (Lenkovskaya and Stepanov, 1968; Hoover, 1980). The effect of different ions on
molybdenite flotation at pH 7.5 is shown in Figure 16 for Fe3+, Al3+, Cu2+, and Cu+ ions.
It is to be pointed out that molybdenite case is different from other solids. MoO42surface sites at the edges may form insoluble salts with a number of metal cations. The
natural floatability of molybdenite in acid media seems to be affected by this phenomenon.
However, in alkaline media molybdenite behaves like an oxide (James and Healy,
1972a,b,c), the adsorption of the hydroxy species and the subsequent precipitation of the
colloidal metal hydroxide seems to explain the depression mechanism.

Figure 16. Effect of soluble salts on floatability of molybdenite by xanthates (25 mg/L) at
pH 7.5 (Lenkovskaya and Stepanov, 1968; Hoover, 1980).

SUMMARY
Most of the factors affecting molybdenite floatability depend on faces and edges
surface sites which carry different electrical charges. In this paper based on molybdenite
surface anisotropic properties we introduced the concept of various zeta potential-pH
curves for molybdenite faces and edges. Since for all hydrophobic surfaces the iso-electric

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points are reported to be in the range of pH 3-4, it is suggested that the zeta potential-pH
curve of molybdenite hydrophobic faces is similar to such a curve for hydrophobic paraffin
wax. Comparison with the measured zeta potential values for molybdenite particles gives
that the zeta potential of molybdenite hydrophilic edges is negative in the whole pH range.
This explains effect of pH on molybdenite floatability. AFM reveals that the molybdenite
faces are not homogeneous and contain craters and nano-size structures. Such surfaces are
then very heterogeneous not only because of the topography but also because of difference
in the electrical charge on these surface sites. This might explain a strong effect of slime
coatings, polycations, polysaccharides and flocculants on molybdenite floatability.
Likewise, this face heterogeneity seems to be an important factor in the interaction of
bubbles and oil droplets on molybdenite faces affecting the floatability of molybdenite
particles.
It is interesting to add that in the just published paper the zeta potential vs. pH
curves for molybdenite faces and edges, back calculated from the AFM measurements,
were provided by Zhenghe Lu et al. (2015). These experimentally determined values are
different from what we estimated (Fig. 8). The zeta potential values for the edges given by
Zhenghe Lu et al (2015) rather resemble our estimated curve for the faces. These
discrepancies seem to point out that the traditional picture of the molybdenite face as a
homogeneously hydrophobic surface is not necessarily correct (Komiyama et al., 2004;
Lopez-Valdivieso et al., 2012).

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The authors gratefully acknowledge the Water Research Center for Agriculture and
Mining (CRHIAM), University of Concepcion; and the Chilean Research Council
(CONICYT) for financial support through the FONDAP-15130015 Grant.

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GRAPHICAL ABSTRACT

Inorganic Depressants

Surface properties
Floatability
Zeta potential

Calcium ions
Lime
Mg hydroxide
Al3+; Fe2+; Cu2+

Organic Depressants

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Crystalline Structure

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MOLYBDENITE

Polysacharides (starch,
dextrin)
Flocculants (PAA)

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HIGHLIGHTS

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1. This paper reviews the surface chemistry and floatability of molybdenite, an inherently
hydrophobic mineral, usually by-product in Cu/Mo sulfide ores.
2. Oil collectors are used to improve molybdenite flotation and the comparison with thiol
collectors is discussed in this paper.
3. Some inorganic ions are strong molybdenite depressants, such as, calcium ions and
lime, usually employed as pH modifiers/pyrite depressants in Cu/Mo separation.
4. Magnesium ions are also strong depressants for molybdenite flotation when saline,
hypersaline or seawater are employed at pH>10.0, range of pH where magnesium
hydroxide precipitates.
5. The depressant effect of polymers on molybdenite flotation is discussed, and
particularly the detrimental effect of flocculants.