You are on page 1of 9

Minerals Engineering 22 (2009) 386–394

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

The critical importance of the grinding environment on fine particle recovery in flotation
Stephen Grano
Ian Wark Research Institute, The ARC Special Research Centre for Particle and Material Interfaces, University of South Australia, Mawson Lakes, Adelaide, SA 5095, Australia

a r t i c l e

i n f o

a b s t r a c t
This paper examines published and new experimental evidence on the effect of the grinding environment on fine (À10 lm) value mineral recovery in flotation. Reasons for increases in fine value mineral recovery from ores with fully electrochemically inert grinding media are discussed in relation to reduced surface contamination by iron hydroxide emanating from the grinding media. The application of stirred milling technology, which allows the use of fully inert grinding media, to primary grinding applications may lead to increased fine value mineral recovery in flotation rougher applications. It is suggested that the effect of the grinding media, which is important for fine particles and progressively becomes more important as the grind size becomes finer, is principally due to the abrasion mechanism of the minerals with the grinding media in the production of fine particles. Opportunities for research and industry application are discussed. Ó 2008 Published by Elsevier Ltd.

Article history: Received 10 April 2008 Accepted 28 October 2008 Available online 20 December 2008 Keywords: Grinding environment Grinding media Fine particle flotation

1. Introduction The importance of the grinding environment on the flotation behaviour of sulphide minerals and ores has been known for many years (Rey and Formanek, 1960). However, it is not commonly appreciated that the grinding environment may play a key role in controlling fine value mineral floatability, as well as selectivity against sulphide gangue mineral components. More recently, the operating benefits of grinding with fully inert ceramic media at plant scale has been described as (i) increased recovery of fine value mineral particles, (ii) improved selectivity against sulphide gangue mineral components, and (iii) reduced collector consumption, amongst other benefits (Pease et al., 2006a). Another author has stated that ‘‘the flotation recovery of liberated valuable minerals in the 0–10 lm fraction”, ‘‘would be affected detrimentally to a greater extent than the intermediate fraction by the presence of the iron hydroxides” derived from mild steel grinding media (Johnson, 2006). The development of stirred milling technology, utilising fully inert grinding media, effectively avoids contamination of mineral surfaces from grinding media sources (Pease et al., 2006b). This paper discusses the collective evidence of these benefits, with a specific focus on fine value mineral recovery, from both the published literature and in a specific experimental study. Attention will turn firstly to a brief review of the published literature in this field. During grinding a number of chemical mechanisms may operate:

E-mail address: stephen.grano@unisa.edu.au 0892-6875/$ - see front matter Ó 2008 Published by Elsevier Ltd. doi:10.1016/j.mineng.2008.10.008

(a) Eh effect – The reducing environment when grinding with reactive steel media decreases the Eh and dissolved oxygen of the slurry immediately after grinding (Grano et al., 1990). Since thiol collector adsorption is strongly Eh dependent this may reduce floatability if an aeration stage is not provided before flotation. In the publications and experimental study discussed further below, the effect of Eh is considered, and efforts undertaken to minimise the effect of Eh through its control after grinding and before collector conditioning. (b) Iron hydroxide coatings on surfaces – Even with aeration and restoration in the Eh after grinding there may be continuing depression of value mineral floatability due to the presence of iron hydroxide generated from oxidation of electrochemically reactive steel media (Grano et al., 1990). As discussed further below, this is the main contributing factor to reduced fine particle floatability after grinding with electrochemically reactive steel media types. (c) Oxygen reduction – This can occur on some sulphide minerals and promotes the formation of metal hydroxides. (d) Precipitation from solution – During the process of size reduction in milling, there is an increase in surface area and often an increase in pulp temperature, factors which may promote precipitation from saturated solutions. An example is the surface precipitation of gypsum from calcium sulphate saturated solution during secondary grinding in the lead/zinc concentrator of Mount Isa Mines Limited (Cullinan, 1999). This has implications for the water composition which is used in the milling process.

3. grind size d80 = 130 lm. 0 1 10 100 1000 Particle Size / Microns Fig. 1990). 1990). 6% Pb and 9% Zn. Differences in the amount of iron hydroxide generated in the two mills gave different pyrite and chalcopyrite flotation responses with respect to cyanide addition due to complexation of the iron with cyanide (Grano et al...S. instead. Importantly. 1990). 1999). This work showed that there was increased chalcopyrite recovery at the same conditioning and flotation Eh values. Evidently.. 2. 1999).. 1994). 1994). Sodium ethyl xanthate collector 80 g/t addition. 3. In a separate study on a copper ore at plant scale.2% Cu (adapted from Grano et al. pH 7. increased sphalerite recovery in intermediate size fractions.8–8. this may lead to increased collector additions and lower selectivity against sphalerite with mild steel media (Pease et al. .. (1990). and hydrophobisation. but this increase was greater after grinding with high chromium alloy steel media (Cullinan et al.2. 2a).3.. In this particular study. 1999) (Fig. 2006b). grinding with high chromium alloy steel media increased fine (À5 lm) galena maximum recovery compared with grinding with high carbon steel (mild steel) media which is more electrochemically active (Cullinan et al. grind size 64% À74 lm. 3. as the conditioning and flotation Eh was controlled to the same values. and in a mild steel media and mill at a grind Eh of À220 mV.. pH 8. reducing the separation efficiency of galena against sphalerite (Cullinan et al. In the study by Grano et al. grinding in 100 100 80 Ceramic Media Recovery / %v 80 Recovery / % 60 40 Mild Steel Media 60 40 Autogenous 20 Conventional 20 0 -500 -400 -300 -200 -100 0 100 200 300 400 500 Eh /mV Fig. this allowed the effect of the grinding environment to be evaluated independently of the conditioning and flotation Eh (Grano et al.1 1 10 100 Particle Size / Microns Fig. 3).. 2006). for the case of grinding in a ceramic mill and with ceramic media (Grano et al. pH 8.2–8. grind size d80 = 90 lm. allowing laboratory flotation testing (Grano et al. increasing collector additions above 80 g/t did not increase fine galena maximum recovery but. The Eh was controlled to different values after grinding by the addition of oxidants/ reductants. for both grinding environments. 2b). samples of the mill products were screened to remove coarse particles. The flotation rate constant dependency on particle size followed the expected pattern with the flotation rate constant decreasing for particle sizes from 30 to 3 lm (Fig. 1994) (Fig. with electrochemically reactive steel media showing greater levels of oxidation with high ionic strength water.. The maximum recovery and flotation rate constant were calculated assuming a single floatable species in the laboratory batch cell (adapted from Cullinan et al. Sodium isobutyl xanthate collector 40 g/t addition. 1999). Chalcopyrite recovery from Mount Isa copper ore as a function of conditioning and flotation Eh after grinding in a ceramic media and mill at a grind Eh of 325 mV. In a study on a lead/zinc ore at laboratory scale. There was an increase in the flotation rate constant for ultra-fine galena particles less than 3 lm. emanating from the high carbon steel media (Cullinan et al.. the surfaces of the fine galena particles after grinding with high carbon steel media were less conducive to collector adsorption 100 80 60 40 20 0 (a) Maximum Recovery High Carbon Steel High Chromium Steel (b) Rate Constant Rate Constant /Min-1 3 2 1 0 0. 1... 2. Galvanic coupling and oxygen reduction may also be influenced by the conductivity of the water used in milling. In a plant context. and after grinding in two different chemical environments (Fig.1–8. Grano / Minerals Engineering 22 (2009) 386–394 387 Maximum Recovery/ % (e) Galvanic coupling – Galvanic coupling of the media with sulphide minerals can greatly accelerate oxidation of the media and oxygen reduction on the sulphide minerals (Huang and Grano. 2006a). The increased maximum recovery of fine galena was associated with reduced surface contamination by iron hydroxide. For each mill type.6% Cu (adapted from Grano et al. 1994). Chalcopyrite recovery from Mount Isa copper ore as a function of particle size after grinding in a fully autogenous mill and a conventional mill using mild steel media.. flotation of a chalcopyrite ore was conducted as a function of conditioning and flotation Eh. (a) Maximum recovery and (b) flotation rate constant of galena from Mount Isa lead/zinc ore as a function of galena particle size after grinding with high carbon steel and high chromium (26%) alloy steel. 1999). Attention will turn now to the published evidence of how fine particle floatability may be affected by the grinding environment. This bears out the difficulty generally found of separating fine particles of value minerals (À10 lm) with low floatability from other sulphide minerals in intermediate size fractions (20–40 lm) (Johnson. grinding in a fully autogenous plant mill gave higher fine (À8 lm) chalcopyrite recovery than grinding in a conventional plant ball mill which used mild steel media (Grano et al. over the Eh range of 0–400 mV. Sodium isobutyl xanthate collector 80 g/t addition. Most importantly. 1).

Sodium isobutyl xanthate (SIBX) collector was then added and conditioned for a further 3 min with continuing aeration. After charge correction. and after grinding in a stirred laboratory mill with ceramic media. In the case of ceramic media. The estimated mean energy dissipation was less than 1 W kgÀ1 of pulp.. and dry screening to 150 lm (Johnson.. 2% Al2O3. Arsenopyrite recovery as a function of particle size at pH 7 after grinding in the Magotteaux MillÒ with mild steel. carbonate. All surfaces were then etched to approximately 25 nm using an accelerated Ar+ beam at 4 kV. After grinding and transfer to the flotation cell an aeration stage was applied for 5 min to increase the Eh in both cases to 230–250 mV (SHE). No reagents were added to the grinding mills.6 eV due to the presence of graphitic carbon and unavoidable hydrocarbon contamination. Sodium isopropyl xanthate collector 800 g/t addition. grind size d50 = 17 lm (adapted from Huang and Grano. precycloning to obtain nominally À4 lm on chalcopyrite. 15%. Due to the dolomite present in the ore. The flotation data on an unsized basis is presented as cumulative grade and recovery of copper and pyrite at these flotation times.. The highest fine (À10 lm) arsenopyrite recovery was obtained for the case of grinding with ceramic media (Fig. The grinding time was adjusted to achieve d80 = 110 lm for both grinding environments which was 15 min in the case of mild steel media and 140 min in the case of ceramic media. Single mineral arsenopyrite. 4. 1994).388 S. Iron in pyrite occurs as a shoulder to the above peak at approximately 707 eV. hydroxide and sulphate). 2004) and in a laboratory stirred bead mill using ceramic media (Huang and Grano. In this current paper. or in a closed fully ceramic tumbling ball mill (21 Â 19 cm £) with ceramic media (1–2 cm £) at 60% solids by weight. Grinding in the mild steel ball mill with mild steel media is referred to as mild steel media in the text and diagrams below. 2. silica. the chalcopyrite is 90% liberated (Johnson.0 and 8. The powdered nature of the samples dictates that some proportion of the surface will not be etched due to shadowing. The recovery of the individual minerals is displayed as a function of the geometric mean particle size in the figures. The presence of iron(III) as ferric hydroxide/oxide or in chalcopyrite was indicated by a charge corrected Fe 2p3/2 peak at approximately 710 eV. the fully inert environment of the autogenous mill resulted in higher fine chalcopyrite recovery due to less iron hydroxide present in the system (Grano et al. and tailings were sized using a combination of wet screening at 38 lm. 21% and 30% chromium alloy steel media.2 (±0. The first concentrate. 4). One kilogram of the crushed ore (À1. 4% CaO and 5% MgO). Grinding in the ceramic ball mill with ceramic media is referred to as ceramic media in the text and diagrams below. avoiding effects related to Eh. and was in this range under the conditions studied. pH 7. Surface analysis using X-ray photoelectron spectroscopy (XPS) is employed to quantify iron hydroxide surface atomic concentration. the flotation recovery of single mineral arsenopyrite was studied after grinding in the Magotteaux MillÒ (Greet et al. 2006b). cyclosizing with recovery of the 4–8 lm fraction. pyrite (12.5. The revolution speed was 40 rpm for each grinding mill..1). the increased arsenopyrite recovery noted was principally accounted by the decreased surface contamination from iron hydroxide rather than any intrinsic benefits of the stirred milling action (Huang and Grano. The pH was not intentionally controlled during grinding or in flotation. At a grind d80 of 110 lm. The sauter mean bubble diameter in the collection zone of the flotation cell was 0. Experimental The copper ore was obtained from Mount Isa Mines. The important feature here is to use large diameter and sufficiently competent media to allow size reduction of relatively coarse particles at plant scale (Gao et al. This will serve to further the evidence showing how fine particles may be affected by the grinding environment and. 2. and non-sulphide gangue principally as quartz (61% SiO2. XPS measurements on the aerated mill discharge samples (prior to collector addition) were carried out with a Perkin Elmer PHI 560 spectrometer using Al Ka X-ray source.0 min cumulative flotation times.6%) as chalcopyrite. A C1s component also occurred at approximately 288–290 eV corresponding to carbonate from the dolomite contained in the ore. and concentrates were collected at 0. and grinding in a stirred mill. advances in stirred milling technology have lead to the possibility of grinding main stream feeds using fully inert grinding media (Pease et al. This point needs further examination.8 mm. The superficial gas rate in flotation was 0. Methyl isobutyl carbinol as frother was added just prior to the commencement of flotation at an addition of 10 g/t for all tests. 2006b). Mount Isa. the combined second and third concentrates. 2006a). Only atomic concentrations of the major chemical species are reported. more specifically. evaluated for a range of different media types displaying different electrochemical activity (Huang and Grano. The presence of sulphur as either sulphide (161–163 eV) or as sulphate ($168 eV) was indicated by S2p peaks and allowed partitioning of these sulphur types. Batch flotation was carried out in a 3 dm3 cell. The initial surfaces were first examined in survey mode to identify all elements present and then the various elemental regions scanned for chemical bonding information. 2006). the grinding media. a broad high intensity O1s emission near 532 eV indicated the presence of several different oxygen containing species (i. the pH was buffered to approximately 8. a peak occurred at approximately 284. Grano / Minerals Engineering 22 (2009) 386–394 100 75 Mild Steel 50 15% Cr 21% Cr 25 30% Cr Ceramic 0 0 10 20 30 40 50 Particle Size / Microns Fig. 2006b). 1987). 2006a)..e. Arsenopyrite floatability decreased with an increasing amount of iron hydroxide in the mill discharge and the degree of galvanic interaction of the arsenopyrite with grinding media. Surface species were calculated assuming stoichiometric Maximum Recovery/ % . In another example. Reasons why fine particles of the value mineral are more adversely affected by iron hydroxide emanating from grinding media sources are discussed further below. 2000). In general.7 mm) was ground in either a closed steel lined tumbling ball mill (15 Â 20 cm £) with mild steel media (1–2 cm £). The presence of copper(I) in chalcopyrite was indicated by a Cu 2p3/2 peak near 932 eV. The ore contained copper (3. large diameter ceramic media is used in a tumbling mill to demonstrate the importance of fully electrochemically inert grinding media on the flotation recovery of fine chalcopyrite and its selectivity against pyrite from a chalcopyrite containing ore. Determining the ratios of these peaks allowed portioning of these carbon types. Recently. operating at 800 rpm.2 cm sÀ1.5%). assuming that all copper was present in chalcopyrite and iron not resident in chalcopyrite was contained in pyrite.

17 Ceramic Media 17-22 22-38 38-45 45-55 55-75 75-100 +105 Particle Size Range / Microns Fig. SiO2. Grano / Minerals Engineering 22 (2009) 386–394 À species of C. Chalcopyrite distribution as a function of particle size range in the mill product for both grinding environments. There was close agreement in the total oxygen occurring in these calculated species and the total atomic concentration of oxygen. 5. These subtle differences in the particle size distribution produced with the different grind environments 20 % inSize Range 15 10 5 0. and hence differences in breakage rates between the minerals. CO2 (with for example Ca. Al2O3. there were small differences in the distribution of chalcopyrite between the ceramic and mild steel media (Fig.5 0 Mild Steel Media 5-7 7-9 9. particularly quartz. and hence low stress intensities. the overall distribution of chalcopyrite was significantly finer in the case of grinding with ceramic media (d80 $ 45 lm) than with mild steel grinding (d80 $ 70 lm). It is likely that differences in the size distribution of chalcopyrite reflect differences in impact and stress intensity between the two grinding mills. For both grinding environments. 5).S. (2006) has shown that at low stirrer speeds. 3 2À SO4 (with for example Ca. a greater difference in breakage rate was apparent for the softer chalcopyrite relative to the other minerals. 6. 5). FeS2 and Fe(OH)3 as the major surface species. This may represent an opportunity to improve the energy efficiency of liberation of softer value minerals by reducing the contribution of impact breakage and exploiting differences in breakage rates between minerals at low stress intensity. chalcopyrite presented as a finer distribution than pyrite. Due to the low specific gravity of the ceramic media (SG $ 3) compared with the mild steel media (SG $ 9). which in turn was finer than non-sulphide gangue (not shown here) reflecting differences in the hardness of the predominant minerals. There was less chalcopyrite contained in the 38–105 lm size fraction. Mg). Parry et al. However. Differences in grind product d80 were less marked for pyrite (ceramic media d80 $ 75 lm. Fe). the stress intensity and contribution from impact breakage would be much lower for the ceramic media. Cu2S. Copper grade as a function of copper recovery (a) and pyrite recovery as a function of copper recovery (b) for various collector additions and for the two grinding environments. Particle and mineral size distribution in the mill products While the same grind product d80 (110 lm) on an all mineral basis (solids) was achieved for both grinding environments. Results 3. In the current situation. 389 3. mild steel media d80 $ 80 lm) and for nonsulphide gangue (d80 $ 105 lm for both grinding environments).1. . 30 25 Ceramic Media Cu Grade / % 20 15 10 5 0 Mild Steel Media (a) Copper Grade / Recovery Ceramic Media SIBX=50 g/t SIBX=80 g/t SIBX=120 g/t Mild Steel Media Pyrite Recovery / % 60 50 40 30 20 10 0 60 (b) Pyrite Selectivity SIBX=50 g/t SIBX=80 g/t SIBX=120 g/t 65 70 75 80 85 90 95 100 Chalcopyrite Recovery/% Fig. with commensurately more chalcopyrite distributed uniformly throughout the size fractions below 38 lm in the case of ceramic media (Fig. while prolonged grinding times were required to achieve the same particle d80 in the case of the ceramic media due to low absolute breakage rates. the breakage rate of soft minerals were higher than those for hard minerals.

Etch Grind type Atomic concentration (%) of major species Saturated hydrocarbon Without etch With 25 nm etch Mild steel Ceramic Mild steel Ceramic 10 16 4. Chalcopyrite recovery on a size-by-size basis The key contribution to increased recovery of chalcopyrite for the case of ceramic media is increased recovery of fine chalcopyrite. In contrast. 2008).5 min). 3. the large difference in copper recovery between the grinding environments on an unsized basis noted in Fig. 6). Methods to discriminate iron hydroxide precipitates from media and mineral sources are presently being pursued (Julianto. decreased the surface concentration of iron hydroxide and commensurately increased the surface atomic concentration of copper sulphide. 6 was due to the large difference in fine copper recovery.5 min) and long (8.5 Sulphate 7. high collector additions does not increase coarse (105 lm) copper recovery. increases in the surface exposure of copper sulphide after grinding with ceramic media may be interpreted to be a result of lower surface coverage of the iron hydroxide.5 5. the low recovery of this size fraction dominates losses in the case of mild steel media. Flotation separation on an unsized basis It is clear that grinding with ceramic media produced a vastly superior copper grade-recovery relationship (Fig. Table 1 Eh and pH values in the mill discharge. 6b). The increased presence of iron hydroxides species on the particle surfaces after grinding with mild steel media was confirmed by XPS analysis (Table 2). prior to collector conditioning.2 1. Aeration after grinding increased the Eh values in the case of grinding with mild steel media to a similar value to that of ceramic media.1 Eh (mV) 230 À220 Table 2 Atomic concentrations (%) of major species determined by XPS of mill discharge samples for the two grind environments.1 0.. 5). This partially contributed to the lower selectivity of copper against pyrite for the mild steel media at the same collector addition.8 30 16 . As over 20% of the chalcopyrite in the feed is in size fractions below 10 lm (Fig.6 Alumina 7. 2002). grinding with ceramic media shows much higher fine copper recovery which accounts for the large difference in copper recovery between the two grind environments. A minor contributing factor was a higher flotation rate of pyrite recovery. In a plant context. In any case.1 0. As in the case of the mild steel media. High collector addition (120 g/t) does not increase fine copper recovery at all in the case of grinding with mild steel media. FeðOHÞ3 þ eÀ ! FeðOHÞ2 þ OHÀ FeðOHÞ2 þ 2eÀ ! Fe þ OHÀ E0 ¼ À0:56 V ð 1Þ ð 2Þ E0 ¼ À0:87 V as a result of the preferential oxidation of the mild steel media to form ferric and ferrous hydroxides. less than 10 lm (Fig.2. the small amount of chalcopyrite contained in the very coarsest size fraction (105 lm) after grinding with ceramic media is probably contained in low grade composites with silica which display very low hydrophobicity. Grano / Minerals Engineering 22 (2009) 386–394 necessitated that recovery be assessed on a particle size basis as discussed further below.4. as previously noted on an unsized basis (Fig. The reduction in Eh is a result of the redox reactions such as Differences in flotation recovery of fine chalcopyrite can not be accounted by differences in Eh during the collector adsorption stage in these experiments. The main contributing factor was the higher flotation rate and ultimate recovery of chalcopyrite in the case of ceramic media. The over layer of iron hydroxide evidently occurred to a degree on most of the minerals suggesting its unselective adsorption during grinding with mild steel media. Hence. 3. 3.5 5 Carbonate 20. for the two grind environments.5 5.5 16 Silica 25.5 42 Copper sulphide 0.2 Iron hydroxide 21. This would need confirmation using quantitative mineralogical analysis.3 11. grinding with mild steel media reduces the Eh by 450 mV (Table 1). It is surmised that while the difference in breakage rate between chalcopyrite and the non-sulphide gangue minerals was greatest in the case of the ceramic media.5 Iron sulphide 0 0. Measurements of EDTA extractable iron confirmed high concentrations of iron hydroxide present in the pulps produced after grinding with mild steel media (395 mg/l) compared with ceramic media (45 mg/l). adding high collector additions mainly serves to lower the copper grade-recovery relationship due to increased pyrite recovery.. a small amount of chalcopyrite was contained within predominantly non-sulphide gangue (silica) particles in the coarsest size fraction.4 0. 2006b). 6a). It is speculated that most of the copper is contained in predominantly liberated chalcopyrite particles for size fractions below 105 lm and for both grind environments. The pH of the pulp was also slightly decreased after grinding with mild steel media. but does increase coarse copper recovery marginally at short (0. for the mild steel media when compared with ceramic media at the same collector addition. 2003b). silica and alumina (Table 2).6 7.9 37. For the ceramic media. Grinding with ceramic media.1 20 9.3 8. 7). Pulp and surface chemistry When compared to ceramic media. The dissolve oxygen in the pulp after grinding with mild steel media was less than 0.5 1. and that high collector additions did not increase fine copper recovery at all. high collector additions does not increase fine copper recovery at short and long flotation times. attempts to increase copper recovery by adding more collector would increase pyrite recovery without necessarily increasing copper recovery appreciably (Pease et al.. Indeed. The effect was greatest after etching to 25 nm suggesting that the iron hydroxide occurred mainly as an over layer on other minerals. than grinding with mild steel media. A possible explanation for the increased pyrite recovery with the mild steel medium may be related to copper activation of pyrite which is enhanced at reducing Eh values during grinding (Peng et al.6 12. a size fraction which displayed lower recovery than for mild steel media.2 0.5 12. with and without 25 nm etching. is the fact that adding very high collector additions (120 g/t) did not restore copper recovery appreciably for the case of mild steel media.3. before the aeration stage.5 30.1 mg dmÀ3. Of greater significance. consistent with increased consumption of hydroxyl ions to form precipitates with ferric and ferrous hydroxide (Peng et al. Grind type Ceramic Mild steel pH 8.0 min) flotation times.390 S. However. as indicated by the higher recovery at short flotation times (first data point at 0. and selectivity against pyrite (Fig.

Chalcopyrite flotation rate constant as a function of size Differences in chalcopyrite recovery as function of particle size were reflected in the distributed constant (assuming a single floatable and a non-floatable component) (Fig. It is also worthwhile pointing out that the very high flotation rate constants achieved for size fractions over the range of 0– 105 lm in the case of ceramic media are characteristic of a hydrophobic surface with an advancing contact angle in the range of 70– 80° across these size fractions (Muganda. only flotation rate constant data at this collector addition is shown. Fine particles. except through recovery by the entrainment mechanism. a pronounced non-floatable fraction of chalcopyrite is observed (Fig. the attachment efficiency approaches unity for fine particles less than 10 lm (Dai et al. It is clear that in the case of mild steel media. Distributed flotation rate constant of chalcopyrite as a function of particle size at 50 g/t SIBX collector addition and for the two grinding environments. approx- Chalcopyrite 6 Rate Constant / min-1 5 4 3 2 1 0 1 10 100 1000 Ceramic Media Mild Steel Media Particle Size / Microns Fig. 2008). the data for which is shown in Fig. In the case of the mild steel media. 8.0 min SIBX=50 g/t SIBX=80 g/t SIBX=120 g/t Particle Size / Microns Fig. The maximum attainable contact angle for isobutyl xanthate is approximately 80° (Sutherland and Wark. 2007).5.5 min 0 80 Ceramic Media SIBX=50 g/t SIBX=80 g/t SIBX=120 g/t Mild Steel Media Recovery / % 60 40 20 0 1 10 100 1000 (b) Tf=8. require a critical advancing contact angle ($63°) be exceeded to allow their attachment to bubbles (Gontijio et al. and recovery to high values (>95%) would be possible given normal cell residence times and hydrodynamics (Grano et al. but will not increase fine copper recovery. Chalcopyrite recovery as a function of particle size for flotation times (Tf) of 0. As the optimum separation was achieved at 50 g/t of SIBX. At these high contact angles. The fraction of floatable component. 7b. Increasing the flotation time will have the effect of increasing pyrite recovery in intermediate size fractions. suggesting that the flotation rate. Grano / Minerals Engineering 22 (2009) 386–394 391 Chalcopyrite 100 80 Recovery / % 60 40 20 (a) Tf=0.. . which is very high... It is impossible to recover the non-floatable fraction of fine chalcopyrite in the case of grinding with mild steel media by simply increasing flotation time. 1999). In a plant context. at infinite flotation time. is controlled through bubble-particle collision frequency and efficiency.5 min (a) and 8. 2007).0 min (b) for various collector additions and for the two grinding environments. was effectively the same as the ultimate recovery at 8 min of flotation time. as discussed further below. and with very high collector additions. which can not be recovered at very long flotation times. the flotation rate of the fine hydrophobic chalcopyrite would be high. 3. less than 5 lm. 8). 1955). 7b).S. 7.

9). Grano / Minerals Engineering 22 (2009) 386–394 imately 40% of the fine chalcopyrite does not exceed this critical contact angle and therefore appears in a non-floatable component which reports to the flotation tailing. It could be surmised that the fine chalcopyrite is affected to a greater extent than the other size fractions. and not coarse. 2006b). the optimum separation of chalcopyrite from pyrite on an unsized basis (Fig. 2003b). due to the mechanism of generation of fine particles in abrasion with the grinding media and other minerals.. pyrite flotation is very sensitive to oxygen content during grinding due to its inadvertent metal ion activation (Huang and Grano. 2004). 1994). Particularly. when compared with ceramic media at the same collector addition (Fig. Time of flight secondary ion mass spectrometry showed a higher concentration of iron hydroxide on fine galena particles and much less on coarse galena particles (Peng et al.. 2003a). for both grind environments.. Further improvements to selectivity may be possible by controlling other aspects of the grinding environment apart from the media type. 2006a). The high floatability of pyrite in the intermediate size fractions at high collector addition. 3. a high contact angle value on the fine particles is possible giving rise to high maximum recovery and flotation rate constant. but does increase recovery of gangue sulphide minerals in intermediate size fractions. The exact mechanism/s are still unclear. 2003a). which would be apparent in the rougher concentrate. galena particles during grinding has been presented elsewhere (Peng et al..5 min (a) and 8. an effective pyrite depressant in this system (Grano et al. would make its separation in subsequent cleaning stages difficult without taking specific steps to actively depress pyrite by some means. when regrinding with reactive steel media (Pease et al. In the case of grinding with ceramic media. In any case.. increasing collector addition to increase fine chalcopyrite recovery only serves to increase pyrite recovery in intermediate size fractions.5 min Recovery / % 80 60 40 20 0 Ceramic Media SIBX=50 g/t SIBX=120 g/t (b) Tf=8. Pyrite recovery as a function of particle size for flotation times (Tf) of 0.0 min (b) for various collector additions and for the two grinding environments.6. Pyrite recovery on a size-by-size basis The main contribution to the increased flotation rate and ultimate recovery of pyrite in the case of mild steel media was from increased recovery of pyrite in intermediate size fractions (15– 55 lm).. Future advances in stirred milling technology may allow pulp chemical control of these types of mills also. 9. lower collector additions could be expected for the case of ceramic grinding media as high copper recovery is achieved at low collector additions (Pease et al.. Adding high collector additions does not increase fine chalcopyrite recovery. and methods to characterise the surfaces of fine particles exclusively of other size fractions in real ore slurries still need development (Kinal. In a plant context. 6b) occurs for grinding with ceramic media at the lowest collector addition. 4. Discussion It is apparent that the surfaces of the minerals become contaminated with iron hydroxide emanating from their contact with the grinding media in the case of grinding with reactive mild steel media. It should be noted that the usual practice for this ore is to add sodium cyanide. Recently. 2006c). Other studies have shown that the collectorless and collector-induced flotation of chalcopyrite (size range 38–75 lm) is reduced by the presence of small concentrations of ferric hydroxide over the pH range of 6–8 (Grano et al. Pyrite 100 (a) Tf=0. a specialised laboratory grinding mill has been developed which allows the pulp chemistry during grinding to be more conveniently controlled to optimise selectivity and to allow closer correlation of the laboratory to plant grinding chemistry (Greet et al.392 S. A possible explanation may also be related to the higher levels of oxidation of the fine sulphide particles enhancing adsorption of iron hydroxide through a range of mechanisms (Peng et al. . This observation concurs with those at plant scale which show that adding more collector generally does not increase fine value mineral recovery.. Importantly. 2008). 2006c).0 min Recovery / % 80 60 40 20 0 1 10 100 1000 Mild Steel Media SIBX=50 g/t SIBX=120 g/t Particle Size / Microns Fig. This concurs with previous studies on the chalcopyrite-pyrite mineral system that have shown that grinding under reducing conditions promotes pyrite activation by copper (Peng et al. but increases pyrite recovery in intermediate size fractions. Only collector additions of 50–120 g/t of SIBX are shown for clarity. Attention will now turn to the mechanism for the depression of chalcopyrite by iron hydroxide. 2003a). such as pH and the dissolved oxygen content during grinding as has been shown for a complex copper–lead–zinc ore (Huang and Grano.. Evidence for the association of iron hydroxide derived from reactive mild steel media with fine.

. rather than balls used in this current study.. less than 10 lm. 1997b). narrower particle size distributions and improved surface properties of the mineral particles remain a target for research. Generally. It is expected that the relative benefits of grinding with electrochemically inert media will increase with decreasing target grind size due to the increasing contribution of fine particles less than 10 lm (Ye. the increase in fine chalcopyrite recovery with lime addition to mills (Orwe et al. In other cases. during grinding with ceramic media may mitigate against undue mineral oxidation during grinding.3 MW IsaMill using MT1 ceramic media (Pease et al..b). 2004).g. 2004). Controlling the pulp chemical environment. In the study of Goncalves et al. The pH of the grind needs also to be considered in the pulp chemical matching of the laboratory to the plant (Greet et al. 2006b)... Even for the floating fraction. to an extent. 2006a). for example. This highlights the importance of examining flotation behaviour as a function of particle size at least. specifically the pulp oxygen content. (2003) speculated that the reason for this was related to oxidation of the predominantly bornite mineral during prolonged grinding in the oxidising environment of the ceramic mill and media (Eh + 200 mV). Reduction in the adsorption of thiol collectors onto chalcopyrite is the principal mechanism responsible.. Grano et al. it has been observed that the Eh value of a ball discharge increases as the grind pH increases with lime or soda ash addition (e. 2006b). Grano / Minerals Engineering 22 (2009) 386–394 393 1997a.. Pease et al. then the reduced flotation rate and maximum recovery of fine chalcopyrite after grinding with reactive steel media can be easily explained. the floatability of fine particles of chalcopyrite may be more greatly affected.. The Magotteaux MillÒ allows the pulp oxygen content and pH during grinding to be continuously controlled independently of the grinding media type (Greet et al. the flotation rate of the fine particles is reduced when grinding with mild steel media due to the decreased contact angle on these particles. This may explain. As an example.. Conclusions Experimental evidence of the effect of the grinding environment on fine (À10 lm) value mineral recovery in flotation was presented. 5. Clearly. It is also worthwhile pointing out that the magnitude of the benefits of grinding with electrochemically inert grinding media will depend upon the prevailing pulp chemical environment (pH. 2006c). bubble attachment can no longer take place and the fine particles report to the tailings as a non-floating component. In a recent study on a complex copper–lead–zinc sulphide ore. 2008).. In the case of fine chalcopyrite particles. 1997c) suggesting that media oxidation reactions are inhibited at high pH... particularly for the case of hydrophilic surface coatings which may be present on minerals prior to grinding. 2006. The ‘‘consumption” of xanthate collector by grinding media oxidation products has been suggested as a possible mechanism to account for decreased sulphide mineral recovery with reactive steel grinding media (Rey and Formanek. with high affinity sites for thiol adsorption on chalcopyrite obscured by the presence of ferric hydroxide (Grano et al. It is well established that bornite may oxidise more rapidly than chalcopyrite (Fullston et al. are contributing factors. The Magotteaux MillÒ (Greet et al. 2001). Recent developments in large scale stirred milling technology using competent ceramic media will allow their application to relatively coarser particle applications (Anyimadu et al. in a laboratory study on Solobo copper ore. 2004) has been specially developed to allow the pulp chemical environment to be manipulated and was used in the study by Huang and Grano (2006c). it is not possible to operate at elevated pH such as in the flotation of pyrite and arsenopyrite for gold recovery. (2003) found that grinding in a ceramic mill with ceramic media did not yield the same flotation results as that produced by grinding in a mill with stainless steel rods. it has been found that enhanced selectivity of chalcopyrite against gangue sulphide minerals was achieved by using both high chromium grinding media and low oxygen content during grinding (Huang and Grano. are required to reduce the contact angle of the chalcopyrite to less than the critical contact angle required for fine particle attachment to bubbles (Gontijio et al. In terms of other pulp chemical parameters. Quantifying contributions to increased rougher recovery from improved liberation. With attritioning. Goncalves et al. of the order of 20%.b). ore mineralogy and target particle size. The above discussion demonstrates the importance of considering also the chemical environment generally in the evaluation of grinding media. and gangue slime coatings which seems to be particularly important in molybdenite flotation. 2007). Goncalves et al. 1997). Hence. Reasons for increases in fine value mineral recovery from ores with fully electrochemically inert grinding media are discussed in relation to reduced surface contamination by iron . media type. Experimental evidence has shown that the flotation recovery of intermediate size galena (25–38 lm). Eh). 2007). At a critical coverage of iron hydroxide. In the case of ceramic media. Only relatively small surface coverage’s of hydrophilic iron hydroxide. Further development of stirred milling technology to allow continuous control of the pulp chemical environment in grinding is also warranted. in a separate study on arsenopyrite flotation (Huang and Grano.. surface oxidation products may be removed from the particle surfaces. It is now possible to grind a rougher tailing from 150 lm to 55 lm in a 3. with low surface area. is severely depressed by iron hydroxide at only 8% of an equivalent monolayer (Bandini et al. further work is required to differentiate these mechanisms. If fine particles of chalcopyrite have indeed higher coverage’s of iron hydroxide. However. oxidation products of the minerals at the surface. a more likely explanation is related to the continuing presence of the iron hydroxide layer and the reduced area on the particle surface which can be rendered hydrophobic through collector adsorption. these require a higher critical contact angle to affect their attachment to bubbles when compared with intermediate sized particles (Gontijio et al. (2003). However. differences in the target grind d80 and the use of rods in the study by Goncalves et al.. Attention will now turn to whether the benefits of grinding with fully inert media is only a result of decreased contamination by iron hydroxide. Grinding technology which minimises the production of fine particles will also assist with improving recovery and selectivity (Pease et al. (2003) the amount of fines (À10 lm) in the laboratory mill product was relatively low at 10% compared with the currently reported study which was 20%. the grind pH is also critical. it seems possible that even at high pH there is still surface contamination by grinding media through other mechanisms which requires further examination. 1960). or if there is an intrinsic benefit also in the attrition mechanism of size reduction which may be more important with the ceramic media in the current study. However. 1999). the effective contact angle on the chalcopyrite surfaces is reduced by the continuing presence of hydrophilic iron hydroxide overlayers which do not interact with thiol collectors at neutral to alkaline pH values. the increased arsenopyrite recovery noted was principally accounted by decreased surface contamination from iron hydroxide (Huang and Grano. Thus while intermediate sized particles may have some coverage of iron hydroxide. 2006a). 2006a. This has been addressed.S. and grinding in a stirred bead mill. Another important aspect in the evaluation of the impact of the grinding media is the particle size distribution after milling. Examples include iron hydroxide from grinding media contamination derived from previous grinding stages in plants..

K. Metall. University of South Australia..A.. J.J. 1999. Young. Fornasiero. 2006.D. Cullinan. J. Zeta potential study of the oxidation of copper sulfide minerals.. 1999. 1990.. Publ. Gao. Klein. Inst. Bandini. S. 666–674. C. Smart. M.Sc.. V. their production and separation.. In: Proc. D.. IsaMill media competency and its effect on milling performance... Mineral. Part II: effect of grinding on flotation. pp. 1999.C. J..R.A. pp. Huang. D.W. Characterising the surface phases on fine particles less than 10 lm in heterogenous mixtures. C. T. is principally due to the abrasion mechanism of the minerals with the media in the production of the fine particles. University of South Australia. Chile.. Grano. D. 1960. 38th Annual Meeting of the Canadian Mineral Processors. Inst. Muganda.R. 1987. Julianto. 2008. Thesis. Thesis. Grano... Correlating particle contact angle to flotation rate in a well defined turbulent environment. Optimising grinding and regrinding chemistry. Minerals Engineering 10 (1). 891–896.. W.. pp.. Grano. 27–45. The experimental work described in this paper was conducted in the early 1990s in a project with Mount Isa Mines Ltd. Recent developments and future needs. 5th Int. J.. The influence of electrochemical environment on the flotation behaviour of Mount Isa Mines copper and lead/ zinc ores..E. Parry.. J.. The effect of grinding conditions on fine galena flotation and its separation from pyrite. Particle-bubble attachment in mineral flotation. 1213–1216. D. Rule. Galvanic interaction between grinding media and arsenopyrite and its effect on flotation... pp. 1997c.. Ralston. Peng. Cullinan. 87–101. Journal of Colloid and Interface Science 217 (1). Young. G.. Australasian Institute of Mining and Metallurgy Inc. A model study of copper rougher recovery optimisation at PT Freeport Indonesia. Grano / Minerals Engineering 22 (2009) 386–394 XPS and dissolution study. D. particularly in the presence of oxidised lead minerals. G.F.. Johnson. W. D. A. Grano. Mineral and Metallurgical Processing 18 (2). J. Afr.. Ralston.. D. 351– 388. S. R. Wong. In: III Latin-American Congress on Froth Flotation (University of Concepcion Publ. Minerals Engineering 12.C. M. Grano S. Rule.. C. 487–497. J.. J.. Sutherland. 231–249.. Ralston. Ph. Metall Publ. 2006. Electrochemistry in Mineral and Metal Processing VII 2.. Bradshaw.W. J. M. Ralston. 696–705.. University of South Australia.. V. M. Peres.. S.D... L.R. Fornasiero.D... Improving the flotation response of fine galena. 2000. Surface modifications in the chalcopyrite – sulphite ion system. Ralston. (Eds. S. London. Australia. Young. Mular. Minerals Engineering 14 (5). Designing flotation circuits for high fines recovery. P.. 2007.C. Fullston. B. The South African Institute of Mining and Metallurgy. Ralston.W. Acknowledgments The author gratefully acknowledges financial support and permission to publish from Xstrata Copper. S.. 2003b. Curry. S. Galena flotation.W. Control of grinding conditions in the flotation of chalcopyrite and its separation from pyrite. Ph..... 2006a. 2006b. Z. Investigating fine galena recovery problems in the lead circuit of Mount Isa Mines lead/zinc concentrator. D. International Journal of Mineral Processing 69... Distinguishing and quantifying the relative contributions of oxidized iron from grinding media and mineral sources. Fornasiero. University of South Australia. Dithiophosphate collector adsorption study. Grano... Surface modifications in the chalcopyrite – sulphite ion system. 2008. J.W.L. Lauder. Ralston. 2006. Y. It is suggested that the effect of the grinding media. which is important for fine particles and progressively becomes more important for finer grind sizes. Collectorless flotation. C.D. 1994. C. C. Chalcocite oxidation and its influence on fine copper recovery at the Ok Tedi concentrator. Johnson. In: Lorenzen.D. 182–197.. S. Grano S. 2002. Minerals Engineering 17 (7–8). Minerals Engineering 16 (11). Greet.W. The development of ultra-fine grinding at Anglo Platinum.. (Aust. A. Andrade. Peng. Akroyd.K. Towards prediction of oxidation during grinding 1.. J. Skinner. pp. Grano. Barnes.L...W. Grano. Minerals Engineering 19 (6–8). Some factors affecting the selectivity in the differential flotation of lead – zinc ores. B. Grano.R. V. International Journal of Mineral Processing 78. Colloidal iron oxide slime coatings and galena particle flotation. Min. Paper 16. 2006c. 2006a. N. 1999. 17–39. Y. International Journal of Mineral Processing 30. International Journal of Mineral Processing 50 (1–2). 1997b. J. Cronin. Ralston. Liberated 0–10 lm particles from sulphide ores. S.. J. N. 117–120. Part I: grinding media effects. Metall. 2008. .F. The Magotteaux MillÒ: investigating the effect of grinding media on pulp chemistry and flotation performance. I..C. I.. Orwe. 2006b. Cnossen. Grano. 69–97. Turkey (pp. Colloids and Surfaces A: Physicochemical and Engineering Aspects 146 (1–3). S. Principles of Flotation. M. XXIII International Mineral Processing Congress. Y. Steinier. The author would like to express gratitude to Bill Johnson for his guidance in this and other projects. N.. 739–747.. In: International Platinum Conference ‘‘Platinum Surges Ahead”. though this mechanism needs to be substantiated through further experimental studies. 2003. Skinner. Ph. G.. D. Ninth Mill Operators Conference. Thesis. Rey. 9–20. Transforming flow sheet design with inert grinding media – the IsaMill. Concepcion. International Journal of Mineral Processing 50 (1–2). Canadian Journal of Chemical Engineering 85. Improving the flotation behavior of a sulfide ore by controlling electrochemical interactions during grinding.M.. Melbourne (pp. University of South Australia. Part I. Harbort. S. 343–353. In: Fifth Mill Operators Conference. 98). Grano. Kinal. Sollaart. 85– 96. K. N. PNG.D. M... Prestidge. Aust. Fornasiero. Thesis. Papua New Guinea.. Prestidge. The effect of grinding conditions on the flotation of a sulphide copper ore. M.R. Formanek. Istanbul..R. The effect of autogenous and ball mill grinding on the chemical environment and flotation of the copper ore of Mount Isa Mines Limited.). L.R.. 2007. 1997a.R. Curry..).R. Small. 70–76. Dai. V. Prestidge.. 493–498. The limits of fine and coarse particle flotation. Comparison of ultra-fine grinding technologies. Ralston.. 177–184). D.. D.. XXII International Mineral Processing Congress.. Gontijio.... Ralston. Publ. C. electrochemical society transactions. Inst... Lin. 1997. X. S.. Johnson. Johnson.C.F.. Quantifying galvanic interaction during grinding. II. Grano. Ph. S. Ye. Ralston. 2001. Fornasiero...R.. W.... 25–38. G. S. Madang.. Grano. Skinner. Johnson.. Ralston.. 178–213. H. 2003a.).L.394 S. 655–669.L. D. Minerals Engineering 15. 143–149. Huang. pp. Sth. D.. C. Greet. J. References Anyimadu.R. 2008. Peng. Thesis. In: Proc. pp. Grano. 1–26. Galvanic interaction between grinding media and arsenopyrite and its effect on flotation. Goncalves. Pease.. 1955. Min. hydroxide emanating from the grinding media. 113–121. P.L.. 2004.St.. Minerals Engineering 19. 831–840. J.. Knopjes. J... Ralston.E. Huang. G..R. P. Min. K. M. J. An appreciation of chalcopyrite metallurgy in the copper concentrator.. Mount Isa Mines Technical Report.. Fornasiero.. Pease.. S. International Journal of Mineral Processing 78... Wark. J. N. Control of the solution interaction of metabisulphite and ethyl xanthate in the flotation of the Hilton ore of Mount Isa Mines Limited.. Process Congr.