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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 49
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
1. Introduction hydrophilic surfaces, faces and edges (Johnson et al., 2000; Laskowski,
2012). Molybdenite particles exhibit two types of surfaces: (1) those
Common sulfide mineral collectors are known to adsorb onto mo- that form by the break of the S–S bonds (non-polar faces) and
lybdenite but these reagents are not necessarily effective for molybde- (2) those that are generated by rupture of the strong covalent Mo–S
nite flotation. Flotation of molybdenite is carried out with the use of bonds (polar edges). As a result, the faces are hydrophobic while edges
hydrocarbons (e.g., diesel oil, kerosene, etc.). From this one concludes are hydrophilic. It is then reasonable to assume that crystal faces are re-
that molybdenite must differ from other sulfides in that its surface is al- sponsible for the natural floatability of molybdenite.
ready hydrophobic (Chander and Fuerstenau, 1972). Molybdenite, as all
other inherently hydrophobic minerals, cleaves by rupture of weak re-
2.2. The effect of particle size and morphology on the floatability of
sidual bonds (Gaudin et al., 1957) revealing the surfaces that are hydro-
molybdenite
phobic since they interact with water only via dispersion forces
(Laskowski and Kitchener, 1969). Because of large differences between
Particle size is a very important factor affecting flotation properties
the surface properties of molybdenite and other sulfides, molybdenite
of molybdenite. In porphyry copper–molybdenite ores the flotation
can be recovered from Cu–Mo ores as a by-product with copper at levels
conditions (grinding, reagents, bubble size, etc.) all are optimized with
as low as 0.01% Mo. Approximately half of the world's molybdenum
respect to Cu and not Mo. Fig. 2 shows that the optimum flotation par-
production comes from porphyry Cu–Mo ores (Bulatovic, 2007;
ticle size for molybdenite is around 20 μm, and the size fraction 6.8 μm
Guang-yi et al., 2012).
exhibits the lowest recovery and flotation rate (Castro and Mayta,
One of the most important publications in this area, edited by
1994). However, the optimum particle size for copper sulfide minerals
Sutulov, appeared in 1979 (International Molybdenum Encyclopaedia).
is around 15–100 μm. Therefore, usually it is not economically attractive
This volume also included two reviews on molybdenite flotation
to grind a copper ore to the optimum liberation size of molybdenite.
(Castro, 1979; Shirley, 1979). We feel that considerable advances in un-
The natural floatability of molybdenite is also governed by textural
derstanding of the surface properties and floatability of molybdenite
features (flatness, roundness, relative width, elongation ratio and surface
have recently been made and this calls for a new review.
roughness). Because of the preferential cleavage along the weak S–S
bonds during grinding, platelet shaped fragments exfoliating from larger
2. Crystalline structure and natural floatability of molybdenite particles, are produced (Fig. 4). In the case of flat and elongated particles,
low particle-bubble collision efficiency explains its poor flotation recov-
The crystalline structure of molybdenite (MoS2) was first deter- ery. Hence, the flotation behavior of molybdenite is governed by a com-
mined by Dikinson and Pauling (1923). Molybdenite crystallizes in the bination of: (a) the native floatability (Chander and Fuerstenau, 1972;
hexagonal system as the common polytype 2H and also in the trigonal Chander et al., 1975; Arbiter et al., 1975); and (b) the particle morphol-
system as the 3R polytype (less frequent). Molybdenite (2H) has a hex- ogy (shape and size) (Ametov et al., 2008; Nakhaei and Irannajad, 2014).
agonal layer structure with a complete basal cleavage, showing layers of Molybdenite particles with a high aspect ratio (major axis over minor
trigonal prismatic coordination polyhedra, where each Mo atom is axis) have higher probability of reporting to the concentrate, and coarse
surrounded by a trigonal prism of S atoms (Fig. 1). The sulfur atoms particles with high perimeter to area ratio tend to report to the tailings
form the upper and lower surfaces with the smaller Mo atoms (Triffett and Bradshaw, 2008; Triffett et al., 2008).
sandwiched between these layers. Sulfur–sulfur distances are 2.98 Å Similarly, the shape characteristics of talc particles produced by ball,
within the layers and 3.95 Å between the layers. rod and autogenous mills were investigated by Yekeler et al. (2004)
using Scanning Electron Microscope (SEM). Their results have shown
2.1. Hydrophobic minerals with anisotropic surface properties — that elongation and smoothness helped to increase the hydrophobicity,
molybdenite while roundness and roughness caused a decrease in hydrophobicity
and floatability of talc. The grinding of talc powder decreased crystallin-
A mineral with anisotropic surface properties is characterized by dif- ity due to selective destruction of the (00l) plane and its hydrophobicity
ferent surface properties on different sides of the crystal. This is the case decreases by the grinding effect (Terada and Yonemochi, 2004).
of the sheet structure of inherently hydrophobic minerals, such as mo- For molybdenite particles the faces-to-edges ratio is a function of
lybdenite, talc, graphite, etc. (Chander et al., 1975). In general, minerals particle size, it decreases for fine particles which are therefore less hy-
with anisotropic surface properties do not have to be hydrophobic, as in drophobic than coarse ones (Castro and Correa, 1995; Yang et al.,
the case of clays, which are well recognized to have two types of 2014). Accordingly, small size particles show low floatability (Fig. 3).
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).
common and its occurrence varies depending on the size of the vein
in which it forms. Wider – quartz filled – veins tend to form larger, from well crystallized veins, lack of liberation takes place with dispersed
cleaner crystals of molybdenite while narrow veins result in a coating in quartz veins and veinlets, and losses by sensitivity toward copper de-
of much finer molybdenite on fractured surfaces which can take on a pressant is observed in sooty or smear molybdenite types.
smeared appearance due to in situ movement within these fractures.
The main types of molybdenite in copper porphyry ores are: 2.4. Surface composition of molybdenite and its inherent hydrophobicity
(1) coarse, clean molybdenite with perfect basal cleavage which occurs
in quartz veins, (2) fine-grained scaly molybdenite which appears as Basal planes of molybdenite crystals are formed by rupture of the S–
fine coatings along the joints and fractures of breccia, and (3) amor- S week van der Waals bonds, and are considered hydrophobic due to
phous and dull variety (Sutulov, 1971; Hsu, 1982). Sutulov claimed the surface content of S atoms. According to Triffett et al. (2008), slower
that problems in the recovery of molybdenite arise mainly from the floating molybdenite shows decreasing S content. Therefore, particles
amorphous and finely disseminated molybdenite. According to Shirley reporting to the tailings have a lower concentration of S than those
(1979), molybdenite is commonly lost in copper flotation circuits, as a recovered with concentrates. Surface analysis of molybdenite particles
result of the following problems: (a) lack of liberation; (b) large flakes; by the Time of Flight Laser Ionization Mass Spectroscopy (TOFLIMS)
and (c) oxide coatings. This author observed that large flakes are formed has indeed demonstrated that surface S is depleted on slower floating
particles, while surface oxidation (MoO3) and calcium coating is
increased.
9 nm were observed). These findings are important because they offer angle depends on the method of preparation of the face. For a face
further understanding for the adsorption of some inorganic ions on cleaved under water, they obtained a contact angle of 90°, while for a
faces, such as Ca and Mg ions, and of organic polymers such as dextrin high luster polished face the contact angle was 70°. The surface rough-
and starch, which strongly reduce molybdenite hydrophobicity. They ness and the anisotropic nature of the face then are the main factors
showed that contact angle measurements on crystal faces of molybde- that affect the contact angle values.
nite are performed on rough and anisotropic surfaces composed of Contact angle is also a function of the degree of surface oxidation.
both hydrophobic and hydrophilic areas. Roasting molybdenite decreases contact angle from 80° to 30° depend-
ing on temperature (Chander and Fuerstenau, 1972). Depressing re-
3. Molybdenite wettability agents are able to reduce molybdenite hydrophobicity, e.g., calcium
ions decrease contact angle measured on faces (see Fig. 6).
Contact angle studies performed on molybdenite have shown that Wie and Fuerstenau (1974) also measured the contact angle be-
faces are hydrophobic while edges are hydrophilic. Natural crystals of tween a free iso-octane droplet in water (across water phase) on mo-
molybdenite have been used to obtain a contact angle around 80° for lybdenite surfaces. At pH 4, the contact angle was determined to be
faces (Chander and Fuerstenau, 1972; Kelebek, 1988; Yang et al., about 150°, in alkaline solutions it decreased to 100°, and so these mea-
2014). However, Lopez-Valdivieso et al. (2006) found a contact angle surements turned out to be much more sensitive to pH (to electrical
of 61° at pH 5, which decreases slightly as pH increases (Fig. 6). Fig. 6 charge at solid/liquid interface). In further analysis of these data,
also shows that calcium ions are able to reduce contact angle measured Chander et al. (2007) demonstrated an excellent correlation between
on the crystal faces. Arbiter et al. (1975) have reported that contact 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
Fig. 6. Contact angle on edges and faces of molybdenite particles as a function of pH, in the surfactant. Also plotted is the effect of pH on the oil/water contact angle of molybdenite,
absence and presence of calcium ions (Lopez-Valdivieso et al., 2006). 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
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- depressant activity on molybdenite. However, this depression effect
spond to an increase in xanthate dose, but coarse particles (51.7 μm) flo- was overcome by small additions of fuel oil (Simpson et al., 1983).
tation recovery and rate are significantly enhanced (Castro and Mayta, Chander and Fuerstenau (1974a,b) studied the adsorption of potas-
1994). These results suggest that the effectiveness of xanthate as collec- sium diethyldithiophosphate (KDTP) on the surface of molybdenite as a
tor increases with particle size due to its higher degree of inherent hy- function of pH. They attributed the slight increase in contact angle to the
drophobicity given by the larger faces/edges ratio. physical adsorption of the oxidation product of KDTP, i.e. (DTP)2. The
In the presence of dissolved oxygen semi-conducting minerals (e.g. adsorption of KDTP on the molybdenite surface may proceeds through
sulfides) are able to electro-catalytically oxidize xanthate ions to form three mechanisms: (a) a reaction of ion exchange between the DTP−
non-polar dimmer molecules (e.g. dixanthogen, i.e., a dithiolate), which ions and the HMoO− 2−
4 or MoO4 adsorbed ions; (b) a catalytic oxidation
adsorb onto the faces sites, e.g. for graphite and molybdenite (Afenya, of the collector with formation of (DTP)2; (c) a cooperative adsorption
1982; Allison and Finkelstein, 1971; Allison et al., 1972). Pieces of evi- of DTP− ions favored by (DTP)2. The path (c) proceeds by electrochem-
dence of xanthate adsorption on molybdenite have been reported by ical mechanisms.
Russian researchers, as it was summarized by Castro (1979). However,
no insoluble metal xanthate has been detected on molybdenite. Allison 5.2. Interaction with non-polar oils
and Finkelstein (1971), and Allison et al. (1972) confirmed by a spectro-
photometric technique the formation of dixanthogen and another not- Commonly oily collectors are used to promote molybdenite flotation
identified product on molybdenite with different alkyl xanthates. The (and all other inherently hydrophobic minerals). For primary molybde-
molybdenite rest potential was +0.160 V (for 6.25 × 10−4 M KEX and nite ores a combination of sodium silicate (Na2SiO3) and lime (CaO) is
pH 7) and dixanthogen was the main product identified. Atomic force mi- used at pH 9–11. Sodium silicate (water glass) is employed as disper-
croscopy (AFM) was applied to study in situ the adsorption of potassium sant of the slime coating formed on the mineral particles, and as depres-
ethyl xanthate (KEX) on molybdenite at pH 11. AFM images show a very sant of gangue minerals (Park and Jeon, 2010). Another important factor
sparse adsorption on the basal planes. Adsorbed species are much less on is the use of an emulsifying agent for the non-polar oil collector. It is well
molybdenite compared with chalcopyrite under similar conditions. Then, established that the addition of the emulsifying agent Syntex-L im-
the obtained AFM images show a low adsorption of KEX on the molybde- proved molybdenite flotation at Climax mill, Colorado (Hoover and
nite basal planes, explaining why KEX is not an efficient collector for mo- Malhotra, 1976). Nishkov et al. (1994) studied the use emulsifying
lybdenite (Zhang and Zhang, 2010). Potassium trithiocarbonate (KTTC), a agents for diesel oil in the flotation of El Teniente Cu–Mo ore, reporting
degradation product of potassium ethylxanthate, exhibits a certain 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-
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
nite and the influence of pulp temperature on the dispersibility of diesel
grinding. These are batch flotation tests with 7 g/ton thionocarbamate collector and 5 g/ oil. In flotation pulp temperatures ranging from 10° to 30 °C, the flota-
ton non-polar oil, pH 10.5 (Lopez-Valdivieso, 2004). 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- weight (Beaussart et al., 2012). Ansari and Pawlik (2007a,b) studied
tation recovery of molybdenite is related to the dispersibility of diesel the adsorption and molybdenite depression by lignosulfonate, and con-
oil, i.e., the proportion of high-boiling and low-boiling component in cluded that the high adsorption density of lignosulfonates on molybde-
diesel oil. Therefore, a molybdenum flotation plant should not blindly nite was primarily due to the adsorption of high molecular weight
apply diesel oil instead of kerosene as the collector for molybdenite, fractions. Additionally, other natural polymers such as fulvic and
but should select diesel oil that is suitable for the properties of its ore. humic acids – which are poorly defined anionic polymers with phenolic
Many studies (Crozier, 1979; Smit and Bhasin, 1985; Xia and Peng, and carboxylic groups (products of plant decay) – have also been shown
2007; Wang et al., 2008; Song et al., 1999) have shown that the to depress flotation recovery of molybdenite in acidic solutions
collecting ability of hydrocarbon oils enhance as its carbon chain length (Laskowski and Yu, 1994) similarly to other inherently hydrophobic
increases, which contributes to the enhancement of collecting ability for minerals, such as graphite (Wong and Laskowski, 1984); and coal
coarse molybdenite and intergrowths of molybdenite with gangue. (Pawlik et al., 1997).
However, too long a carbon chain brings down the dispersibility of hy-
drocarbon oil in pulp, causing the adverse effect and recovery decline
6.2. Depression by flocculants
of the valuable mineral. As summarized by Bulatovic (2007) low-
viscosity oils give lower recoveries than the high viscosity oils but at a
Most of the commonly used flocculants depress molybdenite flota-
somewhat higher concentrate grade. Pine oil and alkoxy paraffins give
tion. Therefore, flocculants should not be utilized on middling thick-
better MoS2 recovery than MIBC or polyglycol, and the use of emulsifier
eners in the copper circuits or in the molybdenite plant feed thickener
improves molybdenum recovery significantly.
unless absolutely necessary (Shirley, 1979).
The main function of flocculants used in mineral processing circuits
5.3. Interactions with methyl isobutyl carbinol (MIBC)
is to produce large and strong flocs. It is generally accepted that poly-
mers used as flocculants aggregate suspensions of fine particles by a
Methyl isobutyl carbinol (MIBC) (4-methyl-2-pentanol), a common
bridging mechanism. The bridging is considered to be a consequence
frother, is a partially soluble short-chain aliphatic alcohol commonly
of the adsorption of the segments of the flocculant macromolecules
employed as a week but selective frother in the flotation of Cu–Mo sul-
onto the surfaces of more than one particle. The optimum flocculation
fide ores. For molybdenite MIBC is considered to be an effective frother-
occurs at flocculant dosages corresponding to a particle coverage that
collector. The adsorption of MIBC on molybdenite has been studied by
is significantly less than complete. Incomplete surface coverage ensures
gas chromatography (Veliz and Molina, 1984). It was found that MIBC
that there is sufficient unoccupied surface available on each particle for
is strongly adsorbed on fine molybdenite (6–9 μm), and in pH ranging
the adsorption of flocculant segments during collision of the particles.
from 8 to 12 adsorption decreases as pH increases. Adsorption by hydro-
Low molecular weight polymers are often used as depressant for
phobic interactions was suggested. These results agree with those re-
naturally hydrophobic minerals; South African platinum industry uti-
ported by Castro et al. at pH 11 (1997). Castro and Mayta (1994)
lizes carboxymethyl cellulose, and guar gum, to depress talc
reported that molybdenite recovery is significantly increased by in-
(Steenberg and Harris, 1984).
creasing the dose of MIBC for particle sizes from 6.8 μm to 51.7 μm,
Polymer chains in solution can be irreversibly degraded by breaking
being higher for the 6.8 μm size fraction (the size with poorest flotation
of the polymer chains by shearing forces (shear degradation) (Al
recovery) (Fig. 11).
Hashmi et al., 2013). Then, polymers undergo chain scission and the
On the other hand, it has been found that MIBC is adsorbed on other
overall result is a loss in its flocculation efficiency; this, however, does
inherently hydrophobic minerals promoting their flotation. For exam-
not reduce depressing ability of these polymers (Castro and
ple, Fuerstenau and Pradip (1982) and Miller et al. (1983) have shown
Laskowski, 2013).
that MIBC is adsorbed onto coal. They found that oxidized coal is more
The floatability of molybdenite – similarly to other naturally hydro-
hydrophilic and the adsorption of the non-ionic MIBC molecules is re-
phobic minerals – is strongly depressed by polymers employed as floc-
duced after oxidation. The results indicate that adsorption occurs
culants for example by polyacrylamide flocculants and non-ionic
through hydrophobic interactions between the frother molecules and
flocculants like poly(ethylene oxide) (PEO) (Castro and Laskowski,
the coal surface. The adsorption of MIBC on coal is closely related to
1997, 2013, 2004, 2015). Low molecular-weight shear-degraded poly-
coal floatability and combustible recovery increases with the MIBC
acrylamides also depress molybdenite.
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 7. Depression by hydrolyzable metal cations
adsorbed on low energy surfaces by hydrophobic attractive forces.
This behavior includes plastics, coal, graphite, talc, molybdenite, etc. Molybdenite floatability is highly affected by the presence of hydro-
lyzable metal cations commonly found in process water. Similar effect is
6. Depression of molybdenite reported for talc, which has identical anisotropic surface properties
(Fuerstenau et al., 1988). The natural floatability of talc is depressed
6.1. Depression by polysaccharides and other natural polymers 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
Polysaccharides such as starch and dextrin have been used as molyb- metal cations at the mineral–solution interface depends not only on the
denite depressants for a long time (Hernlund, 1961). The adsorption of ionic charge but also on these ions hydrolysis (James and Healy, 1972c).
dextrin occurs through physical interactions with the molybdenite sur- James and Healy (1972a,b,c) studied the adsorption of various metal
face, possibly due to hydrophobic bonding (Wie and Fuerstenau, 1974). cations as a function of pH on two oxides: SiO2 (low dielectric constant)
Dextrin was found to be a very effective molybdenite flotation depres- and TiO2 (high dielectric constant) as model systems. These authors
sant in the absence of a collector, whereas it does not effectively depress found that a qualitative relationship exists between the pH where an
molybdenite when oil is used as a collector. Recently, substituted dex- abrupt rise in adsorption is observed and the pH of hydrolysis of the
trin has been studied in more detail (Beaussart et al., 2012). The adsorp- metal cations. Hydration shells of the ions constitute a barrier to adsorp-
tion of three dextrins on molybdenite (Wheat dextrin, dextrin TY, tion of highly charged ions on the mineral surface; this makes direct ad-
carboxymethyl (CM) dextrin, and hydroxypropyl (HP) dextrin) were sorption of un-hydrolyzed metal cations very difficult (in acid pH) in
studied through Tapping Mode Atomic Force Microscopy (TMAFM) at spite of the strong electrostatic attraction forces between a cation and
plateau coverage. The isotherms revealed the importance of molecular negatively charged solid surface. Fig. 12 shows the zeta potential of
S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58 55
Fig. 12. Zeta potential of molybdenite in the absence and presence of Fe3+, Al3+ and Mg2+
cations (Lopez-Valdivieso, 1980).
Fig. 13. Flotation recoveries of molybdenite as a function of calcium ion concentration at Fig. 15. Effect of pH (lime) on the natural flotation (+200 mesh pure molybdenite) in NaCl
an ionic strength of 10−2 M KCl (without flotation reagents) (Chander and Fuerstenau, solutions (0.6 M) containing different ions (SO2− 2−
4 ; CO3 ; Mg
2+
; and Ca2+ ions), without
1972). any collector and frother (Castro et al., 2012).
S. Castro et al. / International Journal of Mineral Processing 148 (2016) 48–58 57
Ametov, I., Grano, S.R., Zanin, M., Gredelj, S., Magnuson, R., Bolles, T., Triffett, B., 2008. Cop-
per and molybdenite recovery in plant and batch laboratory cells in porphyry copper
rougher flotation. In: Wang, D.Z., Sun, C.Y., Wang, F.L., Han, L. (Eds.), Proceedings of
XXIV International Mineral Processing Congress. Science Press, Beijing,
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Ansari, A., Pawlik, M., 2007a. Floatability of chalcopyrite and molybdenite in the presence
of lignosulfonates. Part I. Adsorption studies. Miner. Eng. 20, 600–608.
Ansari, A., Pawlik, M., 2007b. Floatability of chalcopyrite and molybdenite in the presence
of lignosulfonates. Part II. Hallimond tube flotation. Miner. Eng. 20, 609–616.
Arbiter, N., Fujii, Y., Hansen, B., Raja, A., 1975. Surface properties of hydrophobic solids. In:
Somasundaran, P., Grieves, R.B. (Eds.), Advances in Interfacial Phenomena of Particu-
late/Solution/Gas Systems; Application to Flotation ResearchAIChE Symp. Series n°
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Castro, S.H., Mayta, E., 1994. A kinetics approach to the effect of particle size on the flota-
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Fig. 16. Effect of soluble salts on floatability of molybdenite by xanthates (25 mg/L) at Castro, S., Stocker, R., Laskowski, J.S., 1997. The effect of hydrophobic agglomerants on the
pH 7.5 (Lenkovskaya and Stepanov, 1968; Hoover, 1980). flotation of fine molybdenite particles. Proceedings 20th IMPC. Aachen vol. 3,
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rides and flocculants on molybdenite floatability. Likewise, this face het- eral Processing — Proceedings of the 1st International Symposium. SME, pp. 29–40.
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and oil droplets on molybdenite faces affecting the floatability of molyb- International Mineral Processing Congress, New Delhi, 2012, pp. 737–752.
Castro, S., Laskowski, J.S., 2013. The effect of flocculants and their degradation products on
denite particles. molybdenite flotation. Proc. Copper 2013 Conference, Santiago-Chile.
It is interesting to add that in the just published paper the zeta po- Castro, S., Uribe, L., Laskowski, J.S., 2014. Depression of inherently hydrophobic minerals
tential vs. pH curves for molybdenite faces and edges, back calculated by hydrolyzable metal cations: molybdenite depression in seawater. Proc. XVII
IMPC 2014, Santiago-Chile, pp. 737–752.
from the AFM measurements, were provided by Lu et al. (2015).
Castro, S., Laskowski, J.S., 2015. Depressing effect of flocculants on molybdenite flotation.
These experimentally determined values are different from what we es- Miner. Eng. 74, 13–19.
timated (Fig. 8). The zeta potential values for the edges given by Lu et al. Chander, S., Fuerstenau, D.W., 1972. On the natural floatability of molybdenite. Trans.
AIME 252, 62–69.
(2015) rather resemble our estimated curve for the faces. These discrep-
Chander, S., Fuerstenau, D.W., 1974a. Electrochemical study of the molybdenite–potassi-
ancies seem to point out that the traditional picture of the molybdenite um diethyldithiophosphate system. Trans. SME 265, 193–197.
face as a homogeneously hydrophobic surface is not necessarily correct Chander, S., Fuerstenau, D.W., 1974b. The effect of potassium diethyldithiophosphate on
(Komiyama et al., 2004; Lopez-Valdivieso et al., 2012). the interfacial properties of molybdenite. Trans. IMM 83, C180–C185.
Chander, S., Wie, J.M., Fuerstenau, D.W., 1975. On the native floatability and surface prop-
erties of naturally hydrophobic solids. In: Somasundaran, P., Grieves, R.B. (Eds.), Ad-
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Acknowledgments
Flotation Research. AIChE Symposium Series, 150 vol. 71, pp. 183–188.
Chander, S., Hogg, R., Fuerstenau, D.W., 2007. Characterization of the wetting and
The authors gratefully acknowledge the Water Research Center for dewetting behavior of powders. Kona 25, 56–75.
Agriculture and Mining (CRHIAM), University of Concepcion; and the Celik, M.S., Somasundaran, P., 1986. The effect of multivalent ions on the flotation of coal.
Sep. Sci. Technol. 21 (4), 393–402.
Chilean Research Council (CONICYT) for financial support through the Dikinson, R.G., Pauling, L., 1923. The crystal structure of molybdenite. J. Am. Chem. Soc. 45,
FONDAP—15130015 grant. 1466–1471.
Crozier, R.D., 1979. Flotation reagent practice in primary and by-product molybdenite re-
covery. Min. Mag. 140, 174–178.
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