Int. J. Miner. Process.

93 (2009) 256–266

Contents lists available at ScienceDirect

International Journal of Mineral Processing
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

A study of mechanisms affecting molybdenite recovery in a bulk copper/
molybdenum flotation circuit
M. Zanin ⁎, I. Ametov, S. Grano, L. Zhou, W. Skinner
Ian Wark Research Institute, University of South Australia (The ARC Special Research Centre for Particle and Material Interfaces), Mawson Lakes Campus, Adelaide, South Australia 5095,
Australia

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

Article history: Molybdenite flotation in the bulk copper/molybdenum flotation circuit at Kennecott Utah Copper was
Received 23 April 2009 studied by means of a combination of plant metallurgical surveys, laboratory flotation tests, mineralogical
Received in revised form 2 October 2009 analysis (QEM-Scan), surface analysis (ToF-SIMS) and contact angle measurements. It was demonstrated
Accepted 3 October 2009
that molybdenite recovery is influenced by flotation feed solids percent and by the mineralogy of the host
rock. Molybdenite recovery was consistently higher at reduced flotation feed solids percent. Furthermore,
Keywords:
the recovery of molybdenite was significantly lower from flotation feeds with high limestone skarn ore
Froth flotation
Molybdenite content. The major factors affecting the flotation recovery of molybdenite from both porphyry and skarn
Sulphide ores copper ores are discussed. It is suggested that the lower flotation recovery of molybdenite compared to the
Ore mineralogy copper sulphide is determined by several factors, including particle morphology, inherent hydrophobicity
and possible formation of slime coatings in the presence of gangue minerals typical of skarn ores.
Implications on plant performance are discussed, and solutions to restore molybdenite recovery presented.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction 1961). The occurrence of large molybdenite crystals in vein controlled
mineralisation as opposed to finely disseminated molybdenite has also
Characteristically, in porphyry copper flotation plants, molybde- been reported (Sutulov, 1975; Podobnik and Shirley, 1982), but no
num exhibits lower recovery than copper, in spite of the apparent clear connection with flotation response has been established. Triffett
natural hydrophobicity of molybdenite (Kelebek, 1988). Furthermore, and Bradshaw (2008) demonstrated that molybdenite particles with
molybdenum recovery displays high variability. While copper high aspect ratio (major axis over minor axis) have higher probability
recovery is usually between 80% and 90%, molybdenum recovery of reporting to the concentrate, and that coarse particles with high
may range between 25% and 85% (Crozier, 1979). Among the copper perimeter to area ratio tend to report to the tailings. It could be noted
sulphide minerals, chalcopyrite usually has higher flotation rate and that aspect ratio itself may not be the critical factor, but it may be a
recovery, but also chalcocite, bornite, digenite and covellite can be proxy for hydrophobicity, as discussed further below.
recovered to values higher than 80% if the relevant electrochemical Ametov et al. (2008) conducted a series of surveys at different
conditions are maintained in the slurry to minimise surface oxidation porphyry copper flotation plants. In the operations investigated, the
(Orwe et al., 1998). Molybdenite recovery, on the contrary, may vary recovery of molybdenite in the rougher/scavengers of the bulk Cu/Mo
significantly from operation to operation, and also within different ore flotation circuit was consistently lower than the recovery of copper
bodies in the same operation. Copper and molybdenum recovery data sulphide, the difference ranging from about 2% to 12% (Ametov et al.,
for a one year period of a typical porphyry copper flotation plant are 2008). Furthermore, a reduction in the flotation feed solids percent
reported in Fig. 1, showing high variability of molybdenum recovery (expressed as solids percent in the slurry by weight) resulted in an
with time. increase in molybdenite recovery, while copper flotation was almost
Extensive research has been carried out in an attempt to link the unaffected (Ametov et al., 2008). The different behaviour of copper
flotation response of molybdenite to the mineral crystal structure, minerals and molybdenite with respect to feed solids percent was
textural features and lithology. The degree of crystallisation is one of explained in terms of flotation hydrodynamics (Ametov et al., 2008).
the factors that have been reported to affect molybdenite flotation
(Hernlund, 1961; Shirley, 1981; Podobnik and Shirley, 1982). Well- 1.1. Mechanisms affecting molybdenite recovery
crystallised molybdenite is considered fast floating, while the almost
amorphous variety is either slow floating or non-floating (Hernlund, The low and highly variable flotation recovery of molybdenum
may be a result of several factors, all related to the properties of the
⁎ Corresponding author. Tel.: +61 8 8302 3263; fax: +61 8 8302 3683. molybdenite (MoS2) mineral. Molybdenite crystal structure consists
E-mail address: massimiliano.zanin@unisa.edu.au (M. Zanin). of hexagonal layers of molybdenum atoms between two layers of

0301-7516/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2009.10.001

having in turn a positive effect on particle- bubble collision efficiency (Ec). the rate at which particles are removed from the slurry by air bubbles can be represented by (Newell and Grano. generated by the breakage of the covalent bonds. in agreement with the findings of Triffett and Bradshaw (2008). due to their peculiar shape factor. 1999). particularly in the case of interacting particles (Schubert. 2008). Zanin et al. 2007).3. Historical recovery data for a typical porphyry copper plant. J. 1. The possible effect of each contributing factor is discussed further below. Hydrodynamic effects (a) molybdenum flotation circuit. (2008) argued that. but only weak van der Waals forces between adjacent S–S dNp = kNp = −Zpb × Ecoll ð1Þ sheets (Lince and Frantz. and it is a purpose of this paper to probe the relative importance of some of these mechanisms. in which Np is the number of particles in the slurry at time t. 2000). have lower probability of collision with bubbles. platelet shaped molybdenite particles may align along streamlines of the suspending liquid and. Miner. Bulk copper/ 1. In effect. (b) particle inherent hydrophobicity. 2008). Zpb the collision frequency. Important hydrodynamic para- meters are bubble diameter. 2). Ametov et al. 2007): sulphur atoms (Fig. attachment (Ea) and stability (Es) efficiencies: Ecoll = Ec × Ea × Es ð2Þ Hydrodynamic conditions have direct influence on both collision frequency and collection efficiency. could be more sensitive to hydrodynamic effects than copper mineral particles. 1982. On the contrary. particles with a high face/edge ratio will have higher probability of being recovered. Furthermore. therefore. very thin particles are potentially produced in grinding. Reducing the feed solids percent reduces the slurry viscosity and increases turbulence. The overall degree of hydrophobicity of molybdenite particles depends on the relative surface exposure of faces (hydrophobic) and edges (hydrophilic). M. Process. 93 (2009) 256–266 257 the particles formed are characterised by strongly hydrophobic and inert faces and hydrophilic and reactive edges. an important factor controlled to a degree by the face/edge ratio (Chander and Fuerstenau. bubble velocity and turbulent energy dissipation (Newell and Grano. flotation rate constant. This could be achieved either by increasing the impeller rotational speed or by reducing the feed solids percent. 2000). molybdenite particles with higher exposure of edges will have lower probability of attachment to air bubbles. Inherent hydrophobicity (b) Due to the cleavage mechanisms of molybdenite. Strong covalent bonds act within S–Mo–S layers. The overall degree of hydrophobicity of molybde- nite particles can also be reduced by the adsorption of metal ions in Fig. Increasing turbulence would increase collision frequency and efficiency. Crystal structure of molybdenite (from Lince and Frantz. In flotation. molybdenite particles. These peculiarities determine the flotation behaviour of molybdenite.. The collection efficiency Ecoll can be described as a product of the collision (Ec). As a result. and therefore increase the rate of particle collection. and Ecoll the collection efficiency. 1. during grinding.2. solution (Raghavan and Hsu. Molybdenite has negative zeta . which is a combination of (a) particle morphology (shape and size) in relation to hydrodynamics (Ametov et al. 1984). (c) particle–particle interactions between molybdenite and gangue minerals (Raghavan and Hsu. k the exfoliating from larger particles.. In flotation. Damping of local energy dissipation occurs in suspensions containing higher volume percent of solids. Hoover. and (d) particle recovery across the froth phase (Dippenaar. platelet shaped fragments. are generally produced. this hypothesis purports that the hydrody- namic diameter is the minimum dimension of the platelets. / Int. This strong anisotropy causes dt preferential cleavage of the molybdenite crystal along the adjacent S–S sheets. 1972. Zanin et al. In an agitated slurry. 1980). 2. as higher volume percent of solids produces higher slurry viscosity. 1984). Fig.

This implies that addition rate of 20 g/t. at a typical induced on the thin film (Hemmings.02% to 0. K_Feldspar KAlSi3O8 38.1. limestone particle–particle interactions with other minerals in the slurry. Plant surveys have been undertaken on Talc Mg3Si4O10(OH)2 0.02 Montmorillonite (Na. and the spatial distribution and orientation of the hydrophilic 2. 93 (2009) 256–266 potential across a wide pH range (Wie and Fuerstenau.0 7.. 2008). 1974). dicresyl- the contact angle. were: oily collector for molybdenite (generic diesel oil was used of the froth phase by film rupture.7 24 0. or striated molybdenite particles in the flotation feed types) have been carried out at the Ian Wark Research Institute. particularly in the rougher/scavengers. in this paper. Froth phase recovery (d) were used for contact angle measurement by the sessile drop method. / Int. In a separate investigation (Zanin et al. 7 0.7 Utah Copperton Concentrator.01 0. flotation feeds (synthetic mineral mixtures and blends of different ore distorted.0 5. composition (modal distribution by QEM-Scan) in Table 2. plant surveys have been undertaken with the presence of Ca2+ ions.. in which molybdenite occurs as a minor phase. the addition of silica to a system of molybdenite plant processing blends of the four main ore types in different particles causes a sharp decrease in molybdenite flotation recovery. due to the breakage of the covalent bonds.4. 2008). Fe)5Si8O22(OH)2 0.0 however. 2008). This feldspar in the quartzite ore sample. Table 1 However. while froth phase issues have Biotite K(Fe. reducing the effect of the collector. including a quartzite ore showing high molybdenum grade The high reactivity of molybdenite edges may also determine and recovery and a more difficult to float. and methylisobutyl-carbinol (MIBC) as frother intermediate to coarse particles having contact angle greater than (15 to 35 g/t). and actinolite.45 9. thus copper ore. form of slime coatings. higher exposure of edges may occur. and it is common to find bent.Mg)3AlSi3O10(F. Zanin et al. For a given particle size.1 8.3. reduce the magnitude. In this paper.5. 1980).04 nite recovery in the collection zone. Typically. significant deformation of particles may occur in tumbling mills (Hoover.5 44 1.9 where major losses of coarse molybdenite occur. Distinct zones of mineralisation and alteration are mined at Kennecott. or even reverse the sign of the zeta potential. adsorption of positively charged ions at the edges may Average head grade of quartzite and limestone skarn ore samples. 2009). Miner.9 flotation tests have been carried out plant slurries. Process.0 0. between negatively charged molybdenite and silica particles.06%. in the skarn ore.08 flotation feeds having different mineralogy. Actinolite Ca2(Mg. reducing its flotation recovery. 7 1.2 In the current study. favouring adhesion on plant slurries and controlled blends of quartzite and skarn ores. Inter-particle interactions with gangue minerals (c) main ore types have been described (Triffett and Bradshaw. Furthermore. Tests on controlled Modal mineral distribution for the major gangue minerals determined by QEM-Scan.3 10. Mo concentrations range from 0. Under these conditions. Reagents transportation of molybdenite particles across the froth phase. The two tions between some of the gangue minerals and molybdenite may ores present distinct gangue minerals: large amounts of quartz and cause slime coatings on the latter.9 600 0.14 58. at a typical addition rate of 22 g/t..1 0. also called froth recovery (Savassi et al.0 on the particle edges may reduce the contact angle and flotability of Skarn 0.6 21 1. In the laboratory flotation tests carried out at the Ian Wark Research and have. . 1984). and laboratory flotation tests have been performed both is possible that the calcium ions act as a ‘bridge’. of some diagnostic tests in which KOH was used. Plagioclase NaxCa(1 − x) (Al. Stability of the froth phase is therefore a factor which should be taken into Quartzite Skarn consideration at plant scale. due to the calcite abundant in the limestone skarn ore sample (shown in Table 2 bridging effect of the adsorbed Ca2+ ions. Single mineral molybdenite samples from WILLYAMA-GEO Dis- coveries were used to produce coarse molybdenite particles which 1. it was shown that froth recovery in the roughers of a porphyry copper flotation plant Table 2 decreases significantly down the bank (from 60% in the first cells to Mineralogical analysis of quartzite and limestone skarn ore samples. andradite. for this reason. as outlined in 2.7 molybdenite particles. Dippenaar (1982) and Hemmings (1981) found a correlation between The reagents used in this study. The pH was adjusted by adding lime. and that froth recovery of molybdenite is Mineral Formula Modal [%] generally lower than froth recovery of the copper sulphide.Si)AlSi2O8 8. Oily collector is typically added in molybdenite 2.258 M. have been shown to adsorb in the [%] [%] [ppm] [%] [%] [%] [%] [%] [%] intermediate to high pH range (Healy.Ca)(Al. Average head grades of the quartzite and mechanism may be relevant in the flotation of an ore with specific skarn ore samples are reported in Table 1. The presence of exposed hydrophilic edges on the bent and distorted particles may The Kennecott Utah Copperton concentrator treats porphyry also prevent spreading of oil droplets on hydrophobic surfaces. and the mineralogical gangue mineralisation and dissolution of ions. investigation was carried out at Kennecott Andradite (Al) Ca3Al2(SiO4)3 0. prepared by dissolving et al. Inherent hydrophobicity and shape may also play a role in the 2. Adsorbed Ca2+ ions Quartzite 0. Ores flotation to enhance the mineral's hydrophobicity.4. 2008). 1997). Cu Fe Mo S SiO2 Al2O3 CaO K2O MgO Calcium ions.0 4.3 2.Mg)6(Si4O10)3(OH)6 − nH2O 4. with the exception 90° are effective film breakers in froth flotation (Dippenaar.2. 1981). Materials and methods edges may determine the probability of attachment of particles to air bubbles on collision. Inter-particle interac. the greater in the laboratory tests)..OH)2 15. 1982). such that four 1. Flat and elongated molybdenite particles may fall into this category. the greater is the destructive compressive stress dithiophosphate (S-8989) collector for copper minerals. in particular. lower recovery across the froth phase (Zanin Institute. This prepared at laboratory scale. synthetic process water was used.8 2.06 been addressed elsewhere (Zanin et al.4 63 13. 20% in the last cells). This possibility is explored as the Skarn ore). J. and ancillary laboratory Calcite CaCO3 1. both in the plant and laboratory size and hydrophobicity of the suspended particles and destabilisation tests. the focus was on identifying factors which affect molybde. It proportions.50 1. in the In the current study. Raghavan and Hsu (1984) showed that. Quartz SiO2 24. talc and effect could be significant at high pH and high alkalinity. low grade. (Triffett and Bradshaw.

e. and flotation tests on both 100% quartzite ore and 50:50 blend of quartzite lip levels) were recorded. the ToF- the KUCC copper circuit. 93 (2009) 256–266 259 Table 3 in a cryogenic container until ToF-SIMS analysis was carried out. Prior to sampling. where copper/molybdenum concentrate is slurry (conditioned rougher feed) was floated without further produced. An impeller speed milling followed by ball milling) and two flotation circuits: a bulk of 1000 rpm and air flowrate of 5 l/min were used in the tests. [%] [%] # [%] During survey 1.3. after each laboratory flotation test performed. Laboratory flotation tests on plant slurries In parallel with the surveys. feed solids percent. using stainless steel rods as processed. The target d80 of the flotation blends were prepared: 100% quartzite. due to the extremely low molybdenum grade.3™. The surface chemistry of the fast (concentrate [ppm] [ppm] from cell 1) and slow (concentrate from cell 11) floating particles was investigated.2. J. homogenised and ground in a 25–30% Cu and 2–4% Mo was produced. All the flotation time of investigation. rougher/scavenger rows. the final concentrate from samples of quartzite and limestone skarn ores provided by Kennecott which. rougher cleaners (2 parallel rows of cells) without regrinding. 2. Ore blend Cu Mo Survey Solids pH The influence of feed solids percent on the recovery of molybdenite type from the two different ore blends was studied.5 and 10.5 0.1 oxygen and frozen in liquid nitrogen. The ore blends were crushed using controlled between 9. the bulk concentrate is separated from the copper minerals. purged with nitrogen to remove 4 27 10. It was not possible to analyse K+ 87 87 molybdenite in the flotation tailings. The regrind circuit product was In diagnostic tests carried out at the Ian Wark Research Institute. 6 and 10 min. by rougher/scavengers of the copper circuit. Methods undertaken on conditioned rougher feed slurries collected in the plant. No samples of slurry for ToF-SIMS analysis were 3 TDS 6980 7010 collected during surveys 3–4.3. Synthetic process water became the focus of investigations.3. Samples from selected surveys were sized by wet/ composition. which ideally contain the non- Mg++ 129 129 floating molybdenite. plant stability was ensured from the control SIMS. it was not possible to pH 7. this part of the circuit varying the grind time for each feed type. conducted on samples generated at laboratory scale. and the pH in the rougher/scavengers was 50:50 quartzite/ skarn ores. additional samples of slurry from the concentrate High quartzite 0. to draw a link between molybdenite surface assayed unsized.06 3 35 10. Zanin et al.3. A bulk concentrate assaying about laboratory jaw and cone crushers.0 High skarn 0. and in-pulp samples were collected from each cell down one of the Flotation tests were carried out as described in 2. varying the water flowrate to the rougher flotation distribution box. SIMS analysis was carried out on the +150 μm particles. over a period of 90 min. and a molybdenite flotation plant. All metallurgical samples were initially and skarn ores. Surveys 1 and 4 were performed at lower solids percent in screening of a molybdenite concentrate from Kennecott (final product the flotation feed. however. Process. [μ S/cm] 6700 8000 different feed ore blends and gangue mineralogy. which under standard Table 4 operating conditions ranged between 30% and 35%. air flows. (Table 3) was used to simulate plant conditions. The rougher concentrate was treated in and size-by-size recoveries were calculated. produced the were used to reproduce plant slurries. and plant data (throughput. The same pH and Four plant surveys were undertaken. the copper circuit consisted of 5 parallel rows of products were assayed on an unsized and size-by-size basis.1. in order to correlate possible differences in surface Na+ 1308 1310 Ca++ 798 798 composition to flotation response. Laboratory flotation tests on coarse molybdenite particles Surveys 1 and 2 were performed with the plant processing a blend The effect of calcium and magnesium ions in solution and gangue with high quartzite ore content.3 0. The copper flotation circuit. out with the plant processing a blend with high limestone skarn ore Coarse molybdenite particles (+150 μm) were obtained by dry content. In each survey.2 compare the surface composition of molybdenite in surveys with Cond.06 1 27 9.1 Samples were placed in plastic vials. 2 35 10. This important aspect of the study was. The scavenger concentrate reported to regrinding (ball milling) along 2.4. four sampling rounds were Similarly to the plant surveys.6 7. The samples were taken from the flotation feed The Copperton concentrator consists of grinding circuits (SAG box where all reagents except frother were added. Therefore.8 of cells 1 and 11 were collected for surface analysis by ToF-SIMS. salts in demineralised water to reproduce the composition of Kennecott process water (Table 3). a statistically significant number of molybdenite particles could SO−− 4 2653 2590 HCO− 189 160 not be analysed. The percent solids. while surveys 3 and 4 were carried minerals on the recovery of molybdenite was studied separately.3. combined with the rougher cleaner concentrate. Data reconciliation and mass balance were performed using the software Bilmat 9. depending on the ore blend laboratory Galigher tumbling mill. upgraded in three scavenger cleaner stages. Grinding was calibrated to a target d80 = 200 μm. M. 75:25 quartzite/skarn and feed was 200 μm. Unsized rougher/scavenger cells. Since Composition of synthetic process water compared with a sample of process water from the focus of the study was recovery of coarse molybdenite. 2. in which timed lip samples reagents scheme were used as in the tests carried out at Kennecott. gangue mineralogy and flotation response .3. The samples were stored frozen . laboratory flotation tests were 2. was adjusted by Feed composition and operating conditions during the plant surveys.5–10) as the plant. in which multiple samples were the coarse particles (+150 μm) from the first concentrate and the last collected from the rougher/scavenger tailings to reduce experimental concentrate were collected by wet screening and analysed by ToF- error. Surface analysis was conducted for the concentrates collected in room. / Int. Laboratory flotation tests on reconstructed feeds with the rougher cleaner tailing. Cl− 1818 1940 i. The tests were conducted using a 5 l Agitair flotation machine 2. Since most of the molybdenite losses occurred in the grinding media. in which molybdenite in collector addition. Three different controlled feed bulk copper/molybdenum concentrate. Miner. while surveys 2 and 3 were carried out at higher solids percent (Table 4). dry sieving and assayed on a size-by-size basis.3. 3. and at the same pH (9. At the Concentrates were collected after 1. as described further below.2. which were Ion Synthetic H2O Process H2O isolated by wet sieving. Plant surveys with forced air supply.

while copper recovery from 85% to 92%. The mineral samples were mounted on to water. In the plant surveys. The 93% recovery at 27% solids) when limestone skarn ore was blended to water pH was adjusted to 10 by adding KOH. Contact angle of molybdenite particles significant increase in molybdenum recovery was obtained by Large molybdenite crystals were obtained from WILLYAMA-GEO reducing the feed solids percent. However. we are investigating surface Surface analysis results on the slurry samples collected during chemistry differences between floating and non(slow)-floating MoS2 survey 1 (in which the flotation feed consisted mainly of quartzite particles. but particularly for the scalpel. J. Considering that. The primary beam current employed in the present study water. 6. being significantly enhanced flotation feed. when solids percent was reduced from 35% to 27%. produced by reverse affected by changes in feed solids percent in the absence of limestone osmosis. Molybdenum recovery. as parallel with the plant surveys are reported in Fig. Copper recovery was marginally described in 2. molybdenum in the feed are superimposed on the recovery curves. A sharp decrease in molybdenite recovery was observed at For both copper and molybdenum. Characterisation techniques Size-by-size analysis of the flotation products was undertaken for surveys 3 and 4 (feed blend with high skarn ore). No significant difference in surface composition between fast 3. bar charts reporting the distribution of copper and and negative ions for surface regions of mineral particles of interest. Δm) of ~ 4000. the +150 μm size fraction contains about 20% of this mode. The ultimate discussed further below. recovery (combined rougher/scavenger flotation) for copper and molybdenum is also reported in Table 5.1. The coarse molybdenite particles were then blended into The laboratory tests (Fig. In the laboratory scale tests. the water advancing and receding reduction in the feed solids percent produced a significant effect on contact angle of face and edge of individual molybdenite particles coarse (+150 μm) molybdenum bearing particles. and the concentration of flotation feed. 3) may be ascribed to changes in hydrodynam- the four plant surveys and the laboratory flotation tests carried out in ics. i.260 M.2. Samples were floated.4. TOF-SIMS spectra were obtained using a PHI TRIFT II System at 30% and 45% solids in the rougher flotation feed. It should be noted that. These concentra- equipped with a gallium liquid metal ion gun (LMIG) in pulsed mode. 3.5 μm and pulse length adjusted to give a mass resolution (m/ particle size fractions. it was possible to partially restore molybdenum copper minerals and molybdenite. and particularly in coarse than 0. 5. In static mode. The recovery of molybdenum was The flotation recoveries of copper and molybdenum in laboratory consistently lower than copper recovery. In standard plant grind. MoS2. Imaging of the sample involved mapping for positive In Fig. An excitation voltage of 25 kV particles to feed solids percent. 3. 93 (2009) 256–266 of the molybdenum plant). in which a 2. Process. the difference increasing at scale tests on blends of quartzite ore and skarn ore are reported in higher feed solids percent and in the presence of limestone skarn ore. the recovery of molybde- ranges typically observed in the plant (8–11 for pH and 0–10− 2 M for num was higher than in the plant across all size ranges. the recovery of this size fraction is same minerals in different streams or under different pulp conditions critical to the overall molybdenite recovery. showing some difference (90% recovery at 35% solids versus carbon prior to final filtration. Results (Fig. Furthermore. two stages of ion exchange and two stages of activated skarn ore.e. Particles were washed in Ensolv (n-propyl skarn ore in the feed blend. since the limestone skarn ore . Samples of quartzite and skarn ore were floated to remove percent. the lowest recovery was achieved increasing concentration of limestone skarn ore in the feed. 4. with the surveys (Fig. on the contrary. the former by diluting with process pulsed electron flood gun. 3a and b). molybdenum recovery was more skarn ore to 85% with 25% skarn ore and 56% with 50% skarn ore in the sensitive to the feed solids percent. 4d) confirmed what was observed in the was 600 pA (DC measurement). was always ions was varied by adding Ca(NO3)2 and Mg(NO3)2.2. Results (concentrate from Cell 1) and slow (concentrate from Cell 11) floating molybdenites was found in this particular case of the 3. Low conductivity water. 2. the analysis is previous tests. type ore. for which recovery were measured by the sessile drop method. Several tens of particles in each processing stream are The area of each bar in the charts is proportional to the relative mass analysed and the data statistically presented in terms of normalised of mineral in the specified particle size range. Fig. Both copper and This is in agreement with the plant surveys and tests carried out on molybdenum recoveries were lower in the presence of limestone plant slurries. increased from 60% to 80% when the feed solids percent was reduced from 35% to 27%. The trend (Fig. The at high solids percent and in the presence of limestone skarn ore ultimate molybdenite recovery decreased from 92% in the absence of (survey 3). showing high sensitivity of the coarse molybdenite confined to the top two monolayers. and no limestone skarn was present) are reported in Fig. Copper flotation was affected to a much lesser extent. It could therefore be concluded that the smaller differences in molybdenite recovery noted between plant and The grade/recovery relationship for copper and molybdenum for laboratory scale (Fig. was used in these experiments. however. Zanin et al.2. tions were achieved by manipulating samples of plant feed collected For insulating samples the surface charge is compensated using a during survey 3 (35% solids). the latter by filtering and re-suspending the solids in process indium foil. 2.15% MoS2 by weight. but molybdenum recovery decreased bromide N 93%) and ethanol to clean the surface from any residual more than copper recovery. Differences in recovery became significant (93% versus 85%) in the presence of limestone skarn ore.4. collected. Miner. Molybdenite crystals were cut and cleaved using a molybdenum recovery across all size ranges. Compared to copper. this conclusion will depend on the feed type. Laboratory flotation tests on reconstructed feeds molybdenum recovery ranged from 75% to 92%. The effect on copper was much less measured at different pH values and Ca2+ concentrations in the pronounced. but with a similar trend with respect to feed collectors and frother added according to the conditioning scheme composition and solids percent. With a reduction in the feed solids collector. at the (to total ion yield) intensity of signals and 95% confidence intervals. higher at low solids percent. to expose fresh crystal edges and faces. Plant Studies and Laboratory Tests on Plant Slurries quartzite ore type. After conditioning. to produce synthetic ore recoveries for both copper and molybdenum compared to the plant containing 0. 4a) revealed increased Discoveries. The feed solids percent is an important was used in un-bunched mode to give a spatial resolution of better driver to molybdenite recovery overall. / Int. may be discerned. In the present case. statistical differences in surface chemistry between the the total molybdenite in the feed.4. a Ca2+ ions). ToF-SIMS Two additional flotation tests were undertaken at laboratory scale. The contact angle was coarse size fractions (+150 μm). 3c and d) showed generally higher the tailings of quartzite and skarn ores. and the flotation tailings were recovery to values characteristic of quartzite ore (from 75% to 85%).1.

8. The ultimate recovery at the completion of flotation is also indicated (dashed lines). K. Miner. The different species of skarn ore was also noted in both fast and slow floating fractions appear in the same proportion on the surface of the two samples. compared to the slow floating sample (Con 4). molybdenite (+150 μm) recovery from quartzite and limestone skarn ores is presented in Fig.3. Apparently. 7. contrary. the cumulative Ore blend Survey Solids Plant recovery Lab recovery type recovery of molybdenite was high. In the fast floating sample slow floating molybdenite (Con 4) collected in the tests with 0% and (Con 1) there are much more exposed molybdenum and sulphur 50% skarn ore in the flotation feed are reported in Fig. Process. J. on the skarn ore. showed very small Significantly higher Mg on the surface of molybdenite in the presence differences in surface chemical composition. 7). Samples of fast (Con 1) and slow (Con 4) floating molybdenite as well as O and OH groups. Ca. there is a . which also showed no surface chemical particles in the quartzite ore which are depressed in the presence of differences on molybdenite. Laboratory flotation tests on coarse molybdenite particles Table 5 Ultimate recovery of copper and molybdenum in plant (after rougher/scavenger The effect of calcium and magnesium ions in solution on coarse flotation) and laboratory. Fe. 7a). molybdenite 2 35 92 88 94 92 recovery from limestone skarn ore was considerably lower (60%) even High skarn 3 35 85 75 90 85 in the absence of calcium and magnesium ions. Furthermore. in the presence of quartzite type ore only. Zanin et al. it is the molybdenite observations at plant scale. (Fig. In the case of quartzite ore. M. and decreased further 4 27 88 85 93 93 to 30% when Ca2+ and Mg2+ ions were added. The addition of calcium and magnesium ions to the pulp did High quartzite 1 27 92 92 95 95 not have an effect on molybdenite flotation. Grade/recovery relationship for copper and molybdenum in the plant surveys (a and b) and in the laboratory tests on plant feed (c and d). samples of fast and slow floating molybdenites showed The ToF-SIMS spectra for the fast floating molybdenite (Con 1) and differences in surface chemistry (Fig. / Int. In contrast. 3. In the presence of 50% skarn ore. contains very little molybdenum (Table 1). were more abundant on the latter sample. within statistical error (Fig. approaching 90% after 8 min of # [%] Cu [%] Mo [%] Cu [%] Mo [%] flotation. 93 (2009) 256–266 261 Fig. 7). This is in agreement with previous 3.

Face contact angle was high (about 100°) and showed that molybdenite in the + 150 μm size fraction mainly independent of solution pH and calcium concentration. fluctuations in the overall recovery of molybdenite in the plant are higher flotation rate. affected the most by changes in feed solids percent. QEM-Scan faces and edges of molybdenite particles have considerably different analysis of the scavenger tailings (Triffett. 9). Higher local turbulent energy dissipation may increase the collision efficiency for From an industrial perspective. Ec. The distribution of copper and molybdenum in the feed is also reported. contact angle on the edges was low (maximum 45°). 3). (1). play significant roles. tion are all contributing factors. Insufficient molybdenite liberation in The effect of pH and calcium ions on the contact angle of the coarse size fractions was also considered in the first instance as a molybdenite was also investigated (Fig. consists of liberated particles. and. However. 2007). and decreased with as outlined in Section 1.1. In contrast. private communication) contact angles. 93 (2009) 256–266 Fig. and therefore and therefore higher collision efficiency. Size-by-size recovery of copper and molybdenum in plant surveys 3 and 4 (after rougher/scavenger flotation) (a and b) and in the laboratory flotation tests on plant feed (c and d). Miner. Zanin et al. Particle size and shape.. Process. The the plant studies was the consistent increase in molybdenite recovery fact that molybdenite recovery in laboratory flotation tests was higher in rougher/scavenger flotation at reduced feed solids percent. / Int.262 M. This confirms that other mechanisms. The coarse (+ 150 μm) size fractions were higher local turbulent energy dissipation (Newell and Grano. morphology and surface composi- ions and gangue minerals of the skarn ore. At laboratory scale. increased pH and calcium ion concentration ([Ca2+] N 4 × 10− 3 M).2. as hypothesised in Section 1. laboratory batch flotation cells have (Ametov et al. 2008). The hydrodynamic behaviour of the flat molybdenite particles in a turbulent environment may explain the increase in molybdenum 4. additional feed solids percent values (30% and 45%) were obtained by manipulating plant feed samples. 4) may also be due hydrodynamic effects. the most important finding from the flat and elongated particles. Discussion recovery observed at reduced solids percent (Fig. Feed blend contained high limestone skarn ore. J. The tests showed that possible cause for the low flotation recovery. This is than in the plant (Fig. according to Eq. synergistic effect between the presence in solution of Ca2+ and Mg2+ particles. in agreement with previous observations for different flotation plants Compared to the plant cells. 4. the recovery of which is . An interesting feature is that it is the coarse and determined to a large extent by the flotation response of the coarse liberated molybdenite that is mainly affected.

N N 23. air 7 l/min. Average with 95% confidence. . Fig. impeller speed 1000 rpm. Agitair 5 l cell. Copper and molybdenum recovery in laboratory flotation tests on reconstructed feeds (blends of quartzite and skarn ores in different ratios). 93 (2009) 256–266 263 Fig. 6. Process. 0% skarn ore = 100% quartzite ore. Miner. 5. Positive (a) and negative (b) ToF-SIMS normalised intensities for + 150 μm molybdenite particles. / Int. Fast floating (Cell 1) and slow floating (Cell 11) molybdenite from plant survey 1 (no skarn ore in the feed). M. Tests at 35% solids (synthetic process water used). J. Zanin et al.

A laboratory flotation and at reduced solids percent. 5) and laboratory (Fig. 7) suggested by contact angle measurements carried out separately on . In any that interactions between molybdenite and some gangue minerals in case. 3d). possibly arising from the intrinsic shape of the particles. Surface forces than from the surface cleaning of slime coatings. while inertial forces hypothesis of slime coatings may hold for some feed types and be less promote detachment.. This was observed at plant scale (Fig. Fast floating (Con 1) and slow floating (Con 4) coarse particles (N 150 μm) in tests with 100% quartzite ore and 50:50 blend of quartzite and skarn ores. Process. The scales. even in high turbulent conditions such as in less likelihood of inter-particle interactions causing slime coatings. ToF. suggesting that the different flotation recoveries of molybde- high surface/bulk ratio of the coarse molybdenite particles may nite at high and low solids percent may be ascribed to hydrodynamic however be beneficial for the stability of particle–bubble aggregates. Zanin et al. 2003).264 M. Diagnostic flotation tests on coarse molybdenite particles hydrophilic components on the slow floating coarse molybdenite in the presence of limestone skarn ore and different levels of calcium particles in the presence of skarn ore (Fig. This could also be a contributing other than hydrodynamics and collision efficiency. it is likely that factors from solution due to oversaturation. Miner. This could be either from and magnesium ions in solution (Fig. others (high quartzite). / Int. Therefore. Average with 95% confidence. 93 (2009) 256–266 Fig. Positive (a) and negative (b) ToF-SIMS normalised intensities for on + 150 μm molybdenite particles. in The high concentration of Ca2+ and SO2− 4 in Kennecott process laboratory flotation tests on plant slurries (Fig. the favour attachment of particles to bubbles. Even a small increase in contact reduction in feed solids percent on molybdenite recovery was high for angle could cause previously non-floatable coarse particles to become some feed blends (high limestone skarn) while it was much lower for floatable and the ultimate recovery is therefore increased. In the absence of skarn the skarn ore lead to molybdenite depression. reduction in slime coatings on the surface of molybdenite particles Another outcome of the plant studies was that the effect of a results in increased contact angle. Es (Pyke et al. J. 3b). A high surface/bulk ratio results in high important for others. and in tests on water (Table 3) may also suggest deposition of calcite and gypsum reconstructed feed blends (Fig. 6). as also molybdenite was apparent at plant (Fig. N N 23. Therefore. no difference in surface composition between fast and slow induced by metal ions adsorbed at the molybdenite edges. 8) corroborate the hypothesis the deposition of fine slimes or adsorption of dissolved ions. but it is not sufficient to justify the different degrees of modification and particle–particle interactions also play a role. molybdenite depression observed in the presence of quartzite and SIMS analysis indicated the presence of elements associated with skarn ores. the effect is strongly ore type dependent. It is surmised that at low pulp density there is stability efficiency. effects. presumably limited by stability efficiency. such as surface factor. The effect could be ore. rather because of a higher surface force/inertial force ratio. 7. 7).

similarly in demineralised water. Inst. Q. 174–178. 1972. andradite. A ‘bridging’ particularly reactive. Bolles. China 24–28 September 2008. On the significance of flotation froth liquid lamella thickness. W. talc and calcite (Table 2). It has been shown that edges have much lower contact angle compared to faces.. Beijing. Fig. This is also in flotation recovery of molybdenite. Metall.. 40. Ca and Fe observed on the formation of slime coatings. J. H.D. at pH 10.W. 9. Extraction of molybdenite from copper flotation products. 1129–1137. Miner. The authors would like to acknowledge the financial support of the sponsors of the AMIRA P260E project and the Australian Research Council (ARC). Copper and molybdenite recovery in plant and batch laboratory cells in porphyry copper rougher flotation: Proceedings of XXIV International Mineral Processing Congress... Particularly low molybde- num recovery was observed in the presence of limestone skarn ore. Metall. agreement with the findings of Raghavan and Hsu (1984) on In terms of strategies to increase molybdenite recovery at plant molybdenite/silica mineral systems. R. R. The destabilisation of froth by solids. Mag. Liang. Min. I. Yao. Grano. Healy. Metall. Flotation reagent practice in primary and by-product molybdenite recovery. W. Sch. M. Trans. Zanin... in particular at high pH (pH N 10) and high alkaline conditions ([Ca2+] N 10− 2 M). and flotation. Dippenaar. Inst. and adsorption of Ca2+ and/or Mg2+ may have effect of calcium and magnesium adsorbed on the surface of the combined effect of reducing the overall hydrophobicity of molybdenite and some fine gangue particles in the slurry is possible molybdenite particles and “bridging” for particle–particle interactions and may lead to the formation of slime coatings. Recovery of coarse molybdenite particles (+ 150 μm) in flotation tests on When limestone skarn ore was blended to the feed in laboratory synthetic feeds. Z. Long. Trans. pp. rheology and reduced potentially responsible for the high Mg. edges). Symp. 1961. As a general rule. Fig. S. after conditioning at different pH values and Ca2+ and discussion for molybdenite. Magnuson. (Eds. 93 (2009) 256–266 265 5.W.F.. Am. Chander.J. Int.15% MoS2 by weight). A. The mechanism of film rupture. The recovery of molybdenum in the rougher/scavengers of the bulk Cu/Mo flotation circuit at Kennecott Utah Copper is highly variable. Process. R. On the natural flotability of molybdenite.D. 1982. Min... in the presence and absence of Ca2+ and Mg2+ ions. I.. after surface cleaning. Engrs. Inst. This is the subject for future investigation. 7). J.. Cheng. Triffett.. Min. 9. pp.C. 177–196. M. Complex Sulphide Ores. Fuerstenau. Hemmings. Higher concentrations of Ca. (Ed.. B.W. This benefit may be a result which are much more abundant in the limestone skarn ore are: of a combination of hydrodynamic effects (higher local turbulent actinolite. S.. 1984. London. highly reactive.). 62–69. S. D. Process. 56. 9). surface chemistry. / Int. IMM. it was found that operating the rougher/scavenger flotation rows at a lower feed solids percent (27% against 35%) ensures higher and more stable molybdenite recovery.). 43–56. Support from the Management at Kennecott Utah Copper and site personnel is also gratefully acknowledged.. M. Molybdenite particles from the final concentrate. Fe.. Hernlund. 2008). T. In: Jones. Crozier. . as in typical flotation environment. Conclusions The experimental results confirm that the flotation of molybdenite from porphyry copper ores is more sensitive to the operating environment than that of the copper sulphide minerals.. 1981. Preferential cleavage along the weakly bound S–S layers may impart to the molybdenite particles singular hydrodynamic behaviour (low collision efficiency due to the flat and elongated particle shape). Minerals solution which gave immediate benefits. In: Zuo.. 1979. It also appears that preventing slimes surface of molybdenite when floated in the presence of limestone from adsorbing on molybdenite particles during flotation may benefit skarn ore (Fig. References Ametov. This conclusion would be consistent with the fact molybdenite recovery. Tests were flotation tests. operating the rougher/scavengers at low solid percent was a causing molybdenite depression in the presence of skarn ore.L. all of them related to the peculiar properties of molybdenite. These minerals are energy dissipation and collision efficiency). 2008.. Ser. 140. Mg and K were measured on the slow floating molybdenite particles compared to the fast floating. Pulp chemistry. T. Miner. Min. 100–112. Several factors have been identified which could affect molybde- nite flotation. and always lower than the recovery of copper. Water chemistry effects in the flotation of sulphide ores — a review in proximity of face and edges. and anisotropy in hydrophobicity (hydrophobic faces and hydrophilic. thus reducing the with the negatively charged gangue minerals. volume 1. were blended with ground quartzite and skarn ore (0. 8. 1–14. S. that the presence of the above mentioned minerals in the flotation feed has been correlated to periods of low molybdenite recovery Acknowledgements (Triffett et al. to what was observed in the plant. Gredelj. C. concentrations. Contact angle measured by means of the sessile drop method. which have been correlated to the faces and edges (Fig.R. J. 1980. C 90..R. Contact angle (advancing) of coarse molybdenite particles (+150 μm) measured Hoover. Min. — Australas. Slime coatings are possibly scale. The edges of molybdenite particles are presence of some gangue minerals typical of the skarn ore.E. Zanin et al. Sect. C96–C102. 252. molybdenite recovery decreased significantly. M. Colo.

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