International Journal of Mineral Processing 148 (2016) 48–58

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Review of the flotation of molybdenite. Part I: Surface properties

and floatability
S. Castro a,⁎, A. Lopez-Valdivieso b, J.S. Laskowski c
a
Department of Metallurgical Engineering, University of Concepción, Chile
b
Instituto de Metalurgia, Universidad Autónoma de San Luis de Potosí, Mexico
c
NB Keevil Institute of Mining Engineering, University of British Columbia, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Molybdenite (MoS2) is a naturally hydrophobic mineral with anisotropic surface properties. Its floatability is in-
Received 12 September 2014 fluenced by a number of factors such as, particle size and shape, face/edge ratio, degree of crystallization, face het-
Received in revised form 5 January 2016 erogeneity, pH, etc. Molybdenite is floated by using oily collectors, and its recovery is strongly affected by slime
Accepted 11 January 2016
coating phenomena. A number of hydrolyzable cations, such as Ca2+ and Mg2+, depress molybdenite in alkaline
Available online 14 January 2016
solutions. Depression of molybdenite in seawater and saline waters is mainly induced by the precipitation of col-
Keywords:
loidal magnesium hydroxide when pH is raised to depress pyrite. Other metal cations present in recycled process
Molybdenite water can also reduce the flotation recovery of molybdenite (e.g., Al3+, Fe2+, Cu2+ ions). The native floatability of
Native floatability molybdenite is highly depressed by natural polymers (starch, dextrin, guar gum, humic acids, etc.) and synthetic
Molybdenite depression polymers (e.g., flocculants of the polyacrylamide type). The advances in understanding the surface chemistry of
Cu–Mo sulfide ores these systems are reviewed and discussed in this paper.
© 2016 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2. Crystalline structure and natural floatability of molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.1. Hydrophobic minerals with anisotropic surface properties — molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.2. The effect of particle size and morphology on the floatability of molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.3. Floatability of molybdenite and degree of crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4. Surface composition of molybdenite and its inherent hydrophobicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.5. Atomic force microscopy of basal planes of molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3. Molybdenite wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4. Zeta potential of molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.1. Slime coating and hetero-coagulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5. Molybdenite and flotation reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.1. Interactions with thiol collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.2. Interaction with non-polar oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.3. Interactions with methyl isobutyl carbinol (MIBC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6. Depression of molybdenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6.1. Depression by polysaccharides and other natural polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6.2. Depression by flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
7. Depression by hydrolyzable metal cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
7.1. Depression by calcium ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
7.2. Depression in seawater — effect of magnesium ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
7.3. Depression by other metal cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

⁎ Corresponding author.
E-mail address: scastro@udec.cl (S. Castro).

http://dx.doi.org/10.1016/j.minpro.2016.01.003
0301-7516/© 2016 Published by Elsevier B.V.
 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Common sulfide mineral collectors are known to adsorb onto mo-
lybdenite but these reagents are not necessarily effective for molybde-
nite 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 al-
ready hydrophobic (Chander and Fuerstenau, 1972). Molybdenite, as all
other inherently hydrophobic minerals, cleaves by rupture of weak re-
sidual bonds (Gaudin et al., 1957) revealing the surfaces that are hydro-
phobic 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 world's molybdenum
production comes from porphyry Cu–Mo ores (Bulatovic, 2007;
Guang-yi et al., 2012).
One of the most important publications in this area, edited by
Sutulov, appeared in 1979 (International Molybdenum Encyclopaedia).
This volume also included two reviews on molybdenite flotation
(Castro, 1979; Shirley, 1979). We feel that considerable advances in un-
derstanding of the surface properties and floatability of molybdenite
have recently been made and this calls for a new review.
2. Crystalline structure and natural floatability of molybdenite
The crystalline structure of molybdenite (MoS2) was first deter-
mined by Dikinson 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 hex-
agonal 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 (Fig. 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 Å
within the layers and 3.95 Å between the layers.
2.1. Hydrophobic minerals with anisotropic surface properties —
molybdenite
A mineral with anisotropic surface properties is characterized by dif-
ferent surface properties on different sides of the crystal. This is the case
of the sheet structure of inherently hydrophobic minerals, such as mo-
lybdenite, 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
Fig. 1. Crystalline structure of molybdenite.
49
56
57
57
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 re-
sponsible 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. Fig. 2 shows that the optimum flotation par-
ticle size for molybdenite is around 20 μm, and the size fraction 6.8 μm
exhibits the lowest recovery and flotation rate (Castro and Mayta,
1994). However, the optimum particle size for copper sulfide minerals
is around 15–100 μm. Therefore, usually 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 S–S
bonds during grinding, platelet shaped fragments exfoliating from larger
particles, are produced (Fig. 4). In the case of flat and elongated particles,
low particle-bubble collision efficiency explains its poor flotation recov-
ery. Hence, the flotation behavior of molybdenite is governed by a com-
bination of: (a) the native floatability (Chander and Fuerstenau, 1972;
Chander et al., 1975; Arbiter et al., 1975); and (b) the particle morphol-
ogy (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 crystallin-
ity 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 hy-
drophobic than coarse ones (Castro and Correa, 1995; Yang et al.,
2014). Accordingly, small size particles show low floatability (Fig. 3).
50 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
Fig. 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).
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).
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 con-
sidered 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 con-
trolled 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 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) amor-
phous 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
Fig. 3. Native floatability of molybdenite of various particles size fractions as a function of
pH (Lopez-Valdivieso et al., 2006).
Fig. 4. Photomicrographs of molybdenite particles separated from a flotation concentrate.
from well crystallized veins, lack of liberation takes place with dispersed
in quartz veins and veinlets, and losses by sensitivity toward copper de-
pressant is observed in sooty or smear molybdenite types.
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.
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 hav-
ing nano-edges and nano-faces (Fig. 5) are observed on such faces. In ad-
dition, 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
 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
Fig. 5. AFM images of different areas of MoS2 faces.
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 molybde-
nite are performed on rough and anisotropic surfaces composed of
both hydrophobic and hydrophilic areas.
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 (Fig. 6). Fig. 6
also shows that calcium ions are able to reduce contact angle measured
on the crystal faces. Arbiter et al. (1975) have reported that contact
Fig. 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).
51
angle depends on the method of preparation of the face. For a face
cleaved under water, they obtained a contact angle of 90°, while for a
high luster polished face the contact angle was 70°. The surface rough-
ness 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° depend-
ing on temperature (Chander and Fuerstenau, 1972). Depressing re-
agents are able to reduce molybdenite hydrophobicity, e.g., calcium
ions decrease contact angle measured on faces (see Fig. 6).
Wie and Fuerstenau (1974) also measured the contact angle be-
tween a free iso-octane droplet in water (across water phase) on mo-
lybdenite surfaces. At pH 4, the contact angle was determined to be
about 150°, in alkaline solutions it decreased to 100°, and so these mea-
surements 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
Fig. 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 − cosθ) (Chander et al., 2007).
52 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
molybdenite shown in Fig. 7 (in oil flotation an oil phase is substituted
for the gaseous phase).
In the thermodynamic criterion of flotation, ΔGflot = γLV(cosθ − 1),
but for correlation purposes, the parameter was needed that increases
with increasing flotation recovery, and that is why in Fig. 7 the results
were plotted in terms of the quantity (1 − cos θ). Fig. 7 shows a very
good correlation between oil flotation of molybdenite and the wettabil-
ity of molybdenite surface by oil. Since these contact angle measure-
ments were carried out on freshly cleaved faces of a molybdenite
crystal, these data seem to indicate that the zero-point of charge of mo-
lybdenite faces is situated around pH 4.
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 elec-
trokinetic measurements and the value of the zeta potential. Micro-
electrophoretic 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; Yan
et al., 2013).
In this paper we are dealing with the case of molybdenite, also an an-
isotropic 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 1–3 region, depending on the value assigned to
water molecules or clusters at the interface; but for molybdenite the ex-
perimental 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 adsorp-
tion of hydroxide ions. Parreira and Schulman (1961) in the electroki-
netic 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 neg-
atively charged in distilled water. Zeta potential measurements for mo-
lybdenite 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 Fig.8. 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 parti-
cles. As Fig. 7 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
Schulman's data (1961) obtained for a hydrophobic paraffin wax, then
the obtained picture (Fig. 8) can be used to estimate the electrical
charge of the edges.
Fig. 8 indicates that at pH N 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 molybde-
nite 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.
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 ac-
tive 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
Fig. 8. Effect of pH on zeta potential of molybdenite (+, after Lopez-Valdivieso et al., 2012)
and of paraffin wax (●, after Parreira and Schulman, 1961).
formation and specific adsorption sites at the solid/solution interface of
HMoO− 4 /MoO4
2−
ions, formed by oxidation of Mo(IV) to Mo(VI), and by
the subsequent hydrolysis reactions (Chander and Fuerstenau, 1972).
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 min-
erals and make them hydrophilic (slime coating can also take place be-
tween “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 mo-
lybdenite 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 at-
tached to the surface of coarse quartz and pyrite in the feed of the rough-
er flotation of the porphyry copper ore at Mexicana de Cobre (see Fig. 9).
Hernlund (1961) claims that slime coating prevent the adsorption of col-
lector on the surface of molybdenite and it deteriorates its floatability.
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 po-
tential 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 ex-
tremely rapidly and completely without being influenced by hetero-
coagulation. But the flotation of fine molybdenite particles (− 200
mesh) was highly sensitive to hetero-coagulation.
Dispersing agents, such as sodium silicate and polyphosphates are
recommended to prevent the slime coating (Park and Jeon, 2010;
Huynh et al., 2000). Fig. 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 (Lopez-Valdivieso, 2004).
5. Molybdenite and flotation reagents
5.1. Interactions with thiol collectors
Relatively few papers have been published on the interaction of mo-
lybdenite with thiol collectors (xanthates, dithiphosphates, dithiocarba-
mates, etc.). Xanthates are weak collectors for molybdenite and
molybdenite is commonly floated with the addition of a non-polar oily
 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
Fig. 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).
collector. Fine particles of molybdenite (6.8 μm) practically do not re-
spond to an increase in xanthate dose, but coarse particles (51.7 μm) flo-
tation recovery and rate are significantly enhanced (Castro and Mayta,
1994). These results suggest that the effectiveness of xanthate as collec-
tor increases with particle size due to its higher degree of inherent hy-
drophobicity 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 Finkelstein, 1971; Allison et al., 1972). Pieces of evi-
dence 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 spectro-
photometric 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 × 10−4 M KEX and
pH 7) and dixanthogen was the main product identified. Atomic force mi-
croscopy (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 molybde-
nite basal planes, explaining why KEX is not an efficient collector for mo-
lybdenite (Zhang and Zhang, 2010). Potassium trithiocarbonate (KTTC), a
degradation product of potassium ethylxanthate, exhibits a certain
Fig. 10. Flotation recovery of Mo in copper rougher flotation of Mexicana porphyry copper
ore (0.039% Mo) without and with 10 g/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).
53
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 potas-
sium 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 HMoO− 2−
4 or MoO4 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 electrochem-
ical 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 molybde-
nite ores a combination of sodium silicate (Na2SiO3) and lime (CaO) is
used at pH 9–11. Sodium silicate (water glass) is employed as disper-
sant of the slime coating formed on the mineral particles, and as depres-
sant 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 im-
proved molybdenite flotation at Climax mill, 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, in-
cluding kerosene, diesel oil, transformer oil, etc. Petroleum hydrocarbons
differed in their effectiveness for enhancing the natural floatability of mo-
lybdenite. 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 high-
ly aromatic oils (Hsu, 1982). Smit 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 two-
component blend of a high and low molecular-weight diluent oils dem-
onstrated to be better molybdenite collector than single-component oil.
Furthermore, collector blended with naphthenic oils gave superior flota-
tion 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, partic-
ularly with difficult ores, i.e., lower-grade and fine-disseminated ores
(He et al., 2011). As a substitute, these authors studied the influence
of diesel oil from different manufacturers on the flotation of molybde-
nite and the influence of pulp temperature on the dispersibility of diesel
oil. In flotation pulp temperatures ranging from 10° to 30 °C, the flota-
tion recovery of molybdenite increases with increasing high-boiling
54 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
component in diesel oil. When pulp temperature is below 10 °C, the flo-
tation 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 hy-
drocarbon 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 sul-
fide 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 (6–9 μm), and in pH ranging
from 8 to 12 adsorption decreases as pH increases. Adsorption by hydro-
phobic interactions was suggested. These results agree with those re-
ported by Castro et al. at pH 11 (1997). Castro and Mayta (1994)
reported that molybdenite recovery is significantly increased by in-
creasing the dose of MIBC for particle sizes from 6.8 μm to 51.7 μm,
being higher for the 6.8 μm size fraction (the size with poorest flotation
recovery) (Fig. 11).
On the other hand, it has been found that MIBC is adsorbed on other
inherently hydrophobic minerals promoting their flotation. For exam-
ple, Fuerstenau 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 re-
duced 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) re-
ported 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.
6. Depression of molybdenite
6.1. Depression by polysaccharides and other natural polymers
Polysaccharides such as starch and dextrin have been used as molyb-
denite depressants for a long time (Hernlund, 1961). The adsorption of
dextrin occurs through physical interactions with the molybdenite sur-
face, possibly due to hydrophobic bonding (Wie and Fuerstenau, 1974).
Dextrin was found to be a very effective molybdenite flotation depres-
sant in the absence of a collector, whereas it does not effectively depress
molybdenite when oil is used as a collector. Recently, substituted dex-
trin has been studied in more detail (Beaussart et al., 2012). The adsorp-
tion 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 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 con-
cluded that the high adsorption density of lignosulfonates on molybde-
nite 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).
6.2. Depression by flocculants
Most of the commonly used flocculants depress molybdenite flota-
tion. Therefore, flocculants should not be utilized on middling thick-
eners 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 poly-
mers 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 uti-
lizes 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 hydro-
phobic minerals – is strongly depressed by polymers employed as floc-
culants for example by polyacrylamide flocculants and non-ionic
flocculants like poly(ethylene oxide) (PEO) (Castro and Laskowski,
1997, 2013, 2004, 2015). Low molecular-weight shear-degraded poly-
acrylamides also depress molybdenite.
7. Depression by hydrolyzable metal cations
Molybdenite floatability is highly affected by the presence of hydro-
lyzable 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 hy-
droxide 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)
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 adsorp-
tion of highly charged ions on the mineral surface; this makes direct ad-
sorption 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. Fig. 12 shows the zeta potential of
 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
molybdenite in the absence and presence of the hydrolyzable metal cat-
ions Fe3+, Al3+ and Mg2+.
7.1. Depression by calcium ions
An excess of lime can depress molybdenite flotation in cleaner cir-
cuits 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 in-
creasing calcium ion concentration. The adsorption mechanisms of calci-
um 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 MoO2− 4 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 potential (PZR). Therefore, under conditions where the zeta poten-
tial is near zero, the flotation is found to be the best (Fig. 13). The subse-
quent 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 N 8 (Hoover, 1980). It is also reasonable to ex-
pect 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 nu-
cleate 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 de-
pends on calcium concentration and pH. Lopez-Valdivieso et al.
(2006) for a total Ca ions concentration of 10−3 M reported precipita-
tion 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 mech-
anism not necessarily involves the precipitation of calcium hydroxide.
Systematic studies revealed that Ca2+/Ca(OH)+ ions are strongly
adsorbed on molybdenite (see Fig. 14) 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. Never-
theless, 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 hydro-
philic before the adsorption of Ca(OH)+ ions. Additionally, it has been
reported that basal planes are very heterogeneous and not fully hydro-
phobic 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 spe-
cies 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
55
Fig. 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).
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 (Fig. 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
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 magne-
sium hydroxide (Mg(OH)2(s)) starts precipitating (Castro, 2012; Castro
et al., 2012, 2014; Laskowski and Castro, 2012; Laskowski et al., 2013).
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, SO2−
4 and HCO− 3 , at concentrations similar to those oc-
curring in seawater (see Fig. 15). However, a strong depression of mo-
lybdenite at pH ranging from 9.5–10.0 is produced in seawater, and
this depressing effect of Mg2+ ions is significantly stronger than the ef-
fect of Ca2+ ions.
Taking into account that the molar concentration of Mg in seawater
is about four times that of Ca (around 1300 mg/L for Mg and 400 mg/L
for Ca), and the lower Ksp (magnesium hydroxide Ksp = 1.8 × 10−11,
calcium hydroxide Ksp = 6 × 10−6) and lower critical pH of precipita-
tion 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 wa-
ters) 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 col-
loidal magnesium hydroxide takes place around pH 10. These species,
as shown in Fig. 12, can reverse the zeta potential of molybdenite. Ac-
cording to Li and Somasundaran (1991), the pH of precipitation of mag-
nesium 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).
7.3. Depression by other metal cations
Celik and Somasundaran (1986), and Somasundaran et al. (2000)
demonstrated that multivalent ions, such as, Ca2 +, Fe3 +, and Al3 +
56 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
Fig. 12. Zeta potential of molybdenite in the absence and presence of Fe3+, Al3+ and Mg2+
cations (Lopez-Valdivieso, 1980).
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 hydrophobic-
ity of coal, with good correlation between its floatability and the precip-
itation 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 Fig. 16
for Fe3+, Al3+, Cu2+, and Cu+ ions.
It is to be pointed out that molybdenite case is different from other
solids. MoO2− 4 surface 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.
8. Summary
Most of the factors affecting molybdenite floatability depend on
faces and edges surface sites which carry different electrical charges.
Fig. 13. Flotation recoveries of molybdenite as a function of calcium ion concentration at
an ionic strength of 10−2 M KCl (without flotation reagents) (Chander and Fuerstenau,
1972).
Fig. 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).
In this paper – based on molybdenite surface anisotropic properties –
we introduced the concept of various zeta potential-pH curves for mo-
lybdenite faces and edges. Since for all hydrophobic surfaces the iso-
electric 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 nega-
tive in the whole pH range. This explains effect of pH on molybdenite
floatability. AFM reveals that the molybdenite faces are not homoge-
neous and contain craters and nano-size structures. Such surfaces are
then very heterogeneous not only because of the topography but also
Fig. 15. Effect of pH (lime) on the natural flotation (+200 mesh pure molybdenite) in NaCl
solutions (0.6 M) containing different ions (SO2− 2−
4 ; CO3 ; Mg
2+
; and Ca2+ ions), without
any collector and frother (Castro et al., 2012).
 S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58
Fig. 16. Effect of soluble salts on floatability of molybdenite by xanthates (25 mg/L) at
pH 7.5 (Lenkovskaya and Stepanov, 1968; Hoover, 1980).
because of difference in the electrical charge on these surface sites. This
might explain a strong effect of slime coatings, polycations, polysaccha-
rides and flocculants on molybdenite floatability. Likewise, this face het-
erogeneity seems to be an important factor in the interaction of bubbles
and oil droplets on molybdenite faces affecting the floatability of molyb-
denite particles.
It is interesting to add that in the just published paper the zeta po-
tential vs. pH curves for molybdenite faces and edges, back calculated
from the AFM measurements, were provided by Lu et al. (2015).
These experimentally determined values are different from what we es-
timated (Fig. 8). The zeta potential values for the edges given by Lu et al.
(2015) rather resemble our estimated curve for the faces. These discrep-
ancies 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).
Acknowledgments
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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