Minerals Engineering 22 (2009) 386394

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

The critical importance of the grinding environment on ne particle recovery in otation

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 ne (10 lm) value mineral recovery in otation. Reasons for increases in ne 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 ne value mineral recovery in otation rougher applications. It is suggested that the effect of the grinding media, which is important for ne particles and progressively becomes more important as the grind size becomes ner, is principally due to the abrasion mechanism of the minerals with the grinding media in the production of ne particles. Opportunities for research and industry application are discussed. 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 otation

1. Introduction The importance of the grinding environment on the otation 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 ne value mineral oatability, as well as selectivity against sulphide gangue mineral components. More recently, the operating benets of grinding with fully inert ceramic media at plant scale has been described as (i) increased recovery of ne value mineral particles, (ii) improved selectivity against sulphide gangue mineral components, and (iii) reduced collector consumption, amongst other benets (Pease et al., 2006a). Another author has stated that the otation recovery of liberated valuable minerals in the 010 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 benets, with a specic focus on ne value mineral recovery, from both the published literature and in a specic experimental study. Attention will turn rstly to a brief review of the published literature in this eld. During grinding a number of chemical mechanisms may operate:

E-mail address: stephen.grano@unisa.edu.au 0892-6875/$ - see front matter 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 oatability if an aeration stage is not provided before otation. 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 oatability 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 ne particle oatability 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.

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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). Galvanic coupling and oxygen reduction may also be inuenced by the conductivity of the water used in milling, with electrochemically reactive steel media showing greater levels of oxidation with high ionic strength water. In the study by Grano et al. (1990), otation of a chalcopyrite ore was conducted as a function of conditioning and otation Eh, and after grinding in two different chemical environments (Fig. 1). This work showed that there was increased chalcopyrite recovery at the same conditioning and otation Eh values, over the Eh range of 0400 mV, for the case of grinding in a ceramic mill and with ceramic media (Grano et al., 1990). In this particular study, as the conditioning and otation Eh was controlled to the same values, this allowed the effect of the grinding environment to be evaluated independently of the conditioning and otation Eh (Grano et al., 1990). Attention will turn now to the published evidence of how ne particle oatability may be affected by the grinding environment. In a study on a lead/zinc ore at laboratory scale, grinding with high chromium alloy steel media increased ne (5 lm) galena maximum recovery compared with grinding with high carbon steel (mild steel) media which is more electrochemically active (Cullinan et al., 1999) (Fig. 2a). The increased maximum recovery of ne galena was associated with reduced surface contamination by iron hydroxide, emanating from the high carbon steel media (Cullinan et al., 1999). The otation rate constant dependency on particle size followed the expected pattern with the otation rate constant decreasing for particle sizes from 30 to 3 lm (Fig. 2b). There was an increase in the otation rate constant for ultra-ne galena particles less than 3 lm, for both grinding environments, but this increase was greater after grinding with high chromium alloy steel media (Cullinan et al., 1999). Importantly, increasing collector additions above 80 g/t did not increase ne galena maximum recovery but, instead, increased sphalerite recovery in intermediate size fractions, reducing the separation efciency of galena against sphalerite (Cullinan et al., 1999). This bears out the difculty generally found of separating ne particles of value minerals (10 lm) with low oatability from other sulphide minerals in intermediate size fractions (2040 lm) (Johnson, 2006). Evidently, the surfaces of the ne 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

0 0.1 1 10 100

Particle Size / Microns

Fig. 2. (a) Maximum recovery and (b) otation 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. Sodium ethyl xanthate collector 80 g/t addition; pH 7.88.2; grind size d80 = 90 lm, 6% Pb and 9% Zn. The maximum recovery and otation rate constant were calculated assuming a single oatable species in the laboratory batch cell (adapted from Cullinan et al., 1999).

and hydrophobisation. In a plant context, this may lead to increased collector additions and lower selectivity against sphalerite with mild steel media (Pease et al., 2006b). In a separate study on a copper ore at plant scale, grinding in a fully autogenous plant mill gave higher ne (8 lm) chalcopyrite recovery than grinding in a conventional plant ball mill which used mild steel media (Grano et al., 1994) (Fig. 3). For each mill type, samples of the mill products were screened to remove coarse particles, allowing laboratory otation testing (Grano et al., 1994). Differences in the amount of iron hydroxide generated in the two mills gave different pyrite and chalcopyrite otation responses with respect to cyanide addition due to complexation of the iron with cyanide (Grano et al., 1994). Most importantly, 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

100

200 300

400 500

Eh /mV
Fig. 1. Chalcopyrite recovery from Mount Isa copper ore as a function of conditioning and otation Eh after grinding in a ceramic media and mill at a grind Eh of 325 mV, and in a mild steel media and mill at a grind Eh of 220 mV. The Eh was controlled to different values after grinding by the addition of oxidants/ reductants. Sodium isobutyl xanthate collector 40 g/t addition; pH 8.18.3; grind size 64% 74 lm, 2.6% Cu (adapted from Grano et al., 1990).

0 1 10 100 1000

Particle Size / Microns

Fig. 3. 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. Sodium isobutyl xanthate collector 80 g/t addition; pH 8.28.3; grind size d80 = 130 lm, 3.2% Cu (adapted from Grano et al., 1994).

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100

75 Mild Steel 50 15% Cr 21% Cr 25 30% Cr Ceramic 0 0 10 20 30 40 50

Particle Size / Microns

Fig. 4. Arsenopyrite recovery as a function of particle size at pH 7 after grinding in the Magotteaux Mill with mild steel, 15%, 21% and 30% chromium alloy steel media, and after grinding in a stirred laboratory mill with ceramic media. Single mineral arsenopyrite. Sodium isopropyl xanthate collector 800 g/t addition; pH 7, grind size d50 = 17 lm (adapted from Huang and Grano, 2006b).

the fully inert environment of the autogenous mill resulted in higher ne chalcopyrite recovery due to less iron hydroxide present in the system (Grano et al., 1994). Reasons why ne particles of the value mineral are more adversely affected by iron hydroxide emanating from grinding media sources are discussed further below. In another example, the otation recovery of single mineral arsenopyrite was studied after grinding in the Magotteaux Mill (Greet et al., 2004) and in a laboratory stirred bead mill using ceramic media (Huang and Grano, 2006b). The highest ne (10 lm) arsenopyrite recovery was obtained for the case of grinding with ceramic media (Fig. 4). Arsenopyrite oatability decreased with an increasing amount of iron hydroxide in the mill discharge and the degree of galvanic interaction of the arsenopyrite with grinding media, evaluated for a range of different media types displaying different electrochemical activity (Huang and Grano, 2006a). In the case of ceramic media, and grinding in a stirred mill, the increased arsenopyrite recovery noted was principally accounted by the decreased surface contamination from iron hydroxide rather than any intrinsic benets of the stirred milling action (Huang and Grano, 2006b). This point needs further examination. Recently, advances in stirred milling technology have lead to the possibility of grinding main stream feeds using fully inert grinding media (Pease et al., 2006a). The important feature here is to use large diameter and sufciently competent media to allow size reduction of relatively coarse particles at plant scale (Gao et al., 2000). In this current paper, large diameter ceramic media is used in a tumbling mill to demonstrate the importance of fully electrochemically inert grinding media on the otation recovery of ne chalcopyrite and its selectivity against pyrite from a chalcopyrite containing ore. This will serve to further the evidence showing how ne particles may be affected by the grinding environment and, more specically, the grinding media. Surface analysis using X-ray photoelectron spectroscopy (XPS) is employed to quantify iron hydroxide surface atomic concentration. 2. Experimental The copper ore was obtained from Mount Isa Mines, Mount Isa. The ore contained copper (3.6%) as chalcopyrite, pyrite (12.5%), and non-sulphide gangue principally as quartz (61% SiO2, 2% Al2O3, 4% CaO and 5% MgO). At a grind d80 of 110 lm, the chalcopyrite is 90% liberated (Johnson, 1987).

One kilogram of the crushed ore (1.7 mm) was ground in either a closed steel lined tumbling ball mill (15 20 cm ) with mild steel media (12 cm ), or in a closed fully ceramic tumbling ball mill (21 19 cm ) with ceramic media (12 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. Grinding in the ceramic ball mill with ceramic media is referred to as ceramic media in the text and diagrams below. No reagents were added to the grinding mills. 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. The revolution speed was 40 rpm for each grinding mill. The pH was not intentionally controlled during grinding or in otation. Due to the dolomite present in the ore, the pH was buffered to approximately 8.2 (0.1), and was in this range under the conditions studied. After grinding and transfer to the otation cell an aeration stage was applied for 5 min to increase the Eh in both cases to 230250 mV (SHE), avoiding effects related to Eh. Sodium isobutyl xanthate (SIBX) collector was then added and conditioned for a further 3 min with continuing aeration. Methyl isobutyl carbinol as frother was added just prior to the commencement of otation at an addition of 10 g/t for all tests. Batch otation was carried out in a 3 dm3 cell, operating at 800 rpm, and concentrates were collected at 0.5, 2.0 and 8.0 min cumulative otation times. The otation data on an unsized basis is presented as cumulative grade and recovery of copper and pyrite at these otation times, assuming that all copper was present in chalcopyrite and iron not resident in chalcopyrite was contained in pyrite. The rst concentrate, the combined second and third concentrates, and tailings were sized using a combination of wet screening at 38 lm, precycloning to obtain nominally 4 lm on chalcopyrite, cyclosizing with recovery of the 48 lm fraction, and dry screening to 150 lm (Johnson, 2006). The recovery of the individual minerals is displayed as a function of the geometric mean particle size in the gures. The supercial gas rate in otation was 0.2 cm s1. The estimated mean energy dissipation was less than 1 W kg1 of pulp. The sauter mean bubble diameter in the collection zone of the otation cell was 0.8 mm. 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. The initial surfaces were rst examined in survey mode to identify all elements present and then the various elemental regions scanned for chemical bonding information. All surfaces were then etched to approximately 25 nm using an accelerated Ar+ beam at 4 kV. The powdered nature of the samples dictates that some proportion of the surface will not be etched due to shadowing. Only atomic concentrations of the major chemical species are reported. After charge correction, a peak occurred at approximately 284.6 eV due to the presence of graphitic carbon and unavoidable hydrocarbon contamination. A C1s component also occurred at approximately 288290 eV corresponding to carbonate from the dolomite contained in the ore. Determining the ratios of these peaks allowed portioning of these carbon types. In general, a broad high intensity O1s emission near 532 eV indicated the presence of several different oxygen containing species (i.e., carbonate, silica, hydroxide and sulphate). The presence of sulphur as either sulphide (161163 eV) or as sulphate (168 eV) was indicated by S2p peaks and allowed partitioning of these sulphur types. 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. Iron in pyrite occurs as a shoulder to the above peak at approximately 707 eV. The presence of copper(I) in chalcopyrite was indicated by a Cu 2p3/2 peak near 932 eV. Surface species were calculated assuming stoichiometric

Maximum Recovery/ %

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species of C; CO2 (with for example Ca, Mg); Al2O3; SiO2; Cu2S; 3 2 SO4 (with for example Ca, Fe), FeS2 and Fe(OH)3 as the major surface species. There was close agreement in the total oxygen occurring in these calculated species and the total atomic concentration of oxygen.

389

3. Results 3.1. 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, there were small differences in the distribution of chalcopyrite between the ceramic and mild steel media (Fig. 5). For both grinding environments, chalcopyrite presented as a ner distribution than pyrite, which in turn was ner than non-sulphide gangue (not shown here) reecting differences in the hardness of the predominant minerals. However, the overall distribution of chalcopyrite was signicantly ner in the case of grinding with ceramic media (d80  45 lm) than with mild steel grinding (d80  70 lm). Differences in grind product d80 were less marked for pyrite (ceramic media d80  75 lm; mild steel media d80  80 lm) and for nonsulphide gangue (d80  105 lm for both grinding environments).

There was less chalcopyrite contained in the 38105 lm size fraction, with commensurately more chalcopyrite distributed uniformly throughout the size fractions below 38 lm in the case of ceramic media (Fig. 5). It is likely that differences in the size distribution of chalcopyrite reect differences in impact and stress intensity between the two grinding mills, and hence differences in breakage rates between the minerals. Due to the low specic gravity of the ceramic media (SG  3) compared with the mild steel media (SG  9), the stress intensity and contribution from impact breakage would be much lower for the ceramic media. Parry et al. (2006) has shown that at low stirrer speeds, and hence low stress intensities, the breakage rate of soft minerals were higher than those for hard minerals. In the current situation, 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, a greater difference in breakage rate was apparent for the softer chalcopyrite relative to the other minerals, particularly quartz. This may represent an opportunity to improve the energy efciency 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. These subtle differences in the particle size distribution produced with the different grind environments

20

% inSize Range

15 10 5 0- 5 0

Mild Steel Media

5-7 7-9 9- 17

Ceramic Media
17-22 22-38 38-45 45-55 55-75 75-100 +105

Particle Size Range / Microns

Fig. 5. Chalcopyrite distribution as a function of particle size range in the mill product for both grinding environments.

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. 6. 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.

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necessitated that recovery be assessed on a particle size basis as discussed further below. 3.2. Flotation separation on an unsized basis It is clear that grinding with ceramic media produced a vastly superior copper grade-recovery relationship (Fig. 6a), and selectivity against pyrite (Fig. 6b), than grinding with mild steel media. The main contributing factor was the higher otation rate and ultimate recovery of chalcopyrite in the case of ceramic media. A minor contributing factor was a higher otation rate of pyrite recovery, as indicated by the higher recovery at short otation times (rst data point at 0.5 min), for the mild steel media when compared with ceramic media at the same collector addition. This partially contributed to the lower selectivity of copper against pyrite for the mild steel media at the same collector addition. 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., 2003b). Of greater signicance, 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. Indeed, adding high collector additions mainly serves to lower the copper grade-recovery relationship due to increased pyrite recovery. In a plant context, attempts to increase copper recovery by adding more collector would increase pyrite recovery without necessarily increasing copper recovery appreciably (Pease et al., 2006b). 3.3. Pulp and surface chemistry When compared to ceramic media, grinding with mild steel media reduces the Eh by 450 mV (Table 1). The reduction in Eh is a result of the redox reactions such as

Differences in otation recovery of ne chalcopyrite can not be accounted by differences in Eh during the collector adsorption stage in these experiments. Grinding with ceramic media, decreased the surface concentration of iron hydroxide and commensurately increased the surface atomic concentration of copper sulphide, silica and alumina (Table 2). The effect was greatest after etching to 25 nm suggesting that the iron hydroxide occurred mainly as an over layer on other minerals. Hence, 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. 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. Measurements of EDTA extractable iron conrmed 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). Methods to discriminate iron hydroxide precipitates from media and mineral sources are presently being pursued (Julianto, 2008). 3.4. 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 ne chalcopyrite, less than 10 lm (Fig. 7). As over 20% of the chalcopyrite in the feed is in size fractions below 10 lm (Fig. 5), the low recovery of this size fraction dominates losses in the case of mild steel media. High collector addition (120 g/t) does not increase ne copper recovery at all in the case of grinding with mild steel media, but does increase coarse copper recovery marginally at short (0.5 min) and long (8.0 min) otation times. In contrast, grinding with ceramic media shows much higher ne copper recovery which accounts for the large difference in copper recovery between the two grind environments, as previously noted on an unsized basis (Fig. 6). As in the case of the mild steel media, high collector additions does not increase ne copper recovery at short and long otation times. For the ceramic media, high collector additions does not increase coarse (105 lm) copper recovery, a size fraction which displayed lower recovery than for mild steel media. 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. However, 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. This would need conrmation using quantitative mineralogical analysis. 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, a small amount of chalcopyrite was contained within predominantly non-sulphide gangue (silica) particles in the coarsest size fraction. In any case, the large difference in copper recovery between the grinding environments on an unsized basis noted in Fig. 6 was due to the large difference in ne copper recovery, and that high collector additions did not increase ne copper recovery at all.

FeOH3 e ! FeOH2 OH FeOH2 2e ! Fe OH

E0 0:56 V

1 2

E0 0:87 V

as a result of the preferential oxidation of the mild steel media to form ferric and ferrous hydroxides. The increased presence of iron hydroxides species on the particle surfaces after grinding with mild steel media was conrmed by XPS analysis (Table 2). The dissolve oxygen in the pulp after grinding with mild steel media was less than 0.1 mg dm3. The pH of the pulp was also slightly decreased after grinding with mild steel media, consistent with increased consumption of hydroxyl ions to form precipitates with ferric and ferrous hydroxide (Peng et al., 2002). 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, prior to collector conditioning.
Table 1 Eh and pH values in the mill discharge, before the aeration stage, for the two grind environments. Grind type Ceramic Mild steel pH 8.3 8.1 Eh (mV) 230 220

Table 2 Atomic concentrations (%) of major species determined by XPS of mill discharge samples for the two grind environments, with and without 25 nm etching. Etch Grind type Atomic concentration (%) of major species Saturated hydrocarbon Without etch With 25 nm etch Mild steel Ceramic Mild steel Ceramic 10 16 4.5 5 Carbonate 20.1 20 9.6 7.6 Alumina 7.5 12.3 11.5 16 Silica 25.5 30.9 37.5 42 Copper sulphide 0.2 0.4 0.2 1.5 Sulphate 7.5 5.5 1.5 5.5 Iron sulphide 0 0.1 0.1 0.2 Iron hydroxide 21.6 12.8 30 16

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Chalcopyrite 100 80

Recovery / %

60 40 20 (a) Tf=0.5 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=8.0 min

SIBX=50 g/t SIBX=80 g/t SIBX=120 g/t

Particle Size / Microns

Fig. 7. Chalcopyrite recovery as a function of particle size for otation times (Tf) of 0.5 min (a) and 8.0 min (b) for various collector additions and for the two grinding environments.

3.5. Chalcopyrite otation rate constant as a function of size Differences in chalcopyrite recovery as function of particle size were reected in the distributed constant (assuming a single oatable and a non-oatable component) (Fig. 8). As the optimum separation was achieved at 50 g/t of SIBX, only otation rate constant data at this collector addition is shown. The fraction of oatable component, at innite otation time, was effectively the same as the ultimate recovery at 8 min of otation time, the data for which is shown in Fig. 7b. It is impossible to recover the non-oatable fraction of ne chalcopyrite in the case of grinding with mild steel media by simply increasing otation time, except through recovery by the entrainment mechanism. Increasing the otation time will have the effect of increasing pyrite recovery in intermediate size fractions, but will not increase ne copper recovery, as discussed further below. It is also worthwhile pointing out that the very high otation 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, 2008). The maximum attainable contact angle for isobutyl xanthate is approximately 80 (Sutherland and Wark, 1955). At these high contact angles, the attachment efciency approaches unity for ne particles less than 10 lm (Dai et al., 1999), suggesting that the otation rate, which is very high, is controlled through bubble-particle collision frequency and efciency. In a plant context, the otation rate of the ne hydrophobic chalcopyrite would be high, and recovery to high values (>95%) would be possible given normal cell residence times and hydrodynamics (Grano et al., 2007). In the case of the mild steel media, a pronounced non-oatable fraction of chalcopyrite is observed (Fig. 7b), which can not be recovered at very long otation times, and with very high collector additions. Fine particles, less than 5 lm, require a critical advancing contact angle (63) be exceeded to allow their attachment to bubbles (Gontijio et al., 2007). It is clear that in the case of mild steel media, 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. 8. Distributed otation rate constant of chalcopyrite as a function of particle size at 50 g/t SIBX collector addition and for the two grinding environments.

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imately 40% of the ne chalcopyrite does not exceed this critical contact angle and therefore appears in a non-oatable component which reports to the otation tailing. In the case of grinding with ceramic media, a high contact angle value on the ne particles is possible giving rise to high maximum recovery and otation rate constant. 3.6. Pyrite recovery on a size-by-size basis The main contribution to the increased otation 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), when compared with ceramic media at the same collector addition (Fig. 9). 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., 2003b). In any case, increasing collector addition to increase ne chalcopyrite recovery only serves to increase pyrite recovery in intermediate size fractions, for both grind environments. The high oatability of pyrite in the intermediate size fractions at high collector addition, which would be apparent in the rougher concentrate, would make its separation in subsequent cleaning stages difcult without taking specic steps to actively depress pyrite by some means. This observation concurs with those at plant scale which show that adding more collector generally does not increase ne value mineral recovery, but does increase recovery of gangue sulphide minerals in intermediate size fractions, when regrinding with reactive steel media (Pease et al., 2006a). Importantly, the optimum separation of chalcopyrite from pyrite on an unsized basis (Fig. 6b) occurs for grinding with ceramic media at the lowest collector addition. Adding high collector additions does not increase ne chalcopyrite recovery, but increases pyrite recovery in intermediate size fractions. In a plant context, 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., 2006b). It should be noted that the usual practice for this ore is to add sodium cyanide, an effective pyrite depressant in this system (Grano et al., 1994). Further improvements to selectivity may be possible by controlling other aspects

of the grinding environment apart from the media type, such as pH and the dissolved oxygen content during grinding as has been shown for a complex copperleadzinc ore (Huang and Grano, 2006c). Particularly, pyrite otation is very sensitive to oxygen content during grinding due to its inadvertent metal ion activation (Huang and Grano, 2006c). Recently, 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., 2004). Future advances in stirred milling technology may allow pulp chemical control of these types of mills also. 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 could be surmised that the ne chalcopyrite is affected to a greater extent than the other size fractions, due to the mechanism of generation of ne particles in abrasion with the grinding media and other minerals. Evidence for the association of iron hydroxide derived from reactive mild steel media with ne, and not coarse, galena particles during grinding has been presented elsewhere (Peng et al., 2003a). Time of ight secondary ion mass spectrometry showed a higher concentration of iron hydroxide on ne galena particles and much less on coarse galena particles (Peng et al., 2003a). A possible explanation may also be related to the higher levels of oxidation of the ne sulphide particles enhancing adsorption of iron hydroxide through a range of mechanisms (Peng et al., 2003a). The exact mechanism/s are still unclear, and methods to characterise the surfaces of ne particles exclusively of other size fractions in real ore slurries still need development (Kinal, 2008). Attention will now turn to the mechanism for the depression of chalcopyrite by iron hydroxide. Other studies have shown that the collectorless and collector-induced otation of chalcopyrite (size range 3875 lm) is reduced by the presence of small concentrations of ferric hydroxide over the pH range of 68 (Grano et al.,

Pyrite
100

(a) Tf=0.5 min

Recovery / %

80 60 40 20 0
Ceramic Media

SIBX=50 g/t SIBX=120 g/t

(b) Tf=8.0 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. 9. Pyrite recovery as a function of particle size for otation times (Tf) of 0.5 min (a) and 8.0 min (b) for various collector additions and for the two grinding environments. Only collector additions of 50120 g/t of SIBX are shown for clarity.

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1997a,b). Reduction in the adsorption of thiol collectors onto chalcopyrite is the principal mechanism responsible, with high afnity sites for thiol adsorption on chalcopyrite obscured by the presence of ferric hydroxide (Grano et al., 1997b). Hence, 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 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, 1960). However, 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. Only relatively small surface coverages of hydrophilic iron hydroxide, of the order of 20%, are required to reduce the contact angle of the chalcopyrite to less than the critical contact angle required for ne particle attachment to bubbles (Gontijio et al., 2007). Experimental evidence has shown that the otation recovery of intermediate size galena (2538 lm), with low surface area, is severely depressed by iron hydroxide at only 8% of an equivalent monolayer (Bandini et al., 2001). In the case of ne chalcopyrite particles, less than 10 lm, these require a higher critical contact angle to affect their attachment to bubbles when compared with intermediate sized particles (Gontijio et al., 2007). Thus while intermediate sized particles may have some coverage of iron hydroxide, the oatability of ne particles of chalcopyrite may be more greatly affected. At a critical coverage of iron hydroxide, bubble attachment can no longer take place and the ne particles report to the tailings as a non-oating component. Even for the oating fraction, the otation rate of the ne particles is reduced when grinding with mild steel media due to the decreased contact angle on these particles. If ne particles of chalcopyrite have indeed higher coverages of iron hydroxide, then the reduced otation rate and maximum recovery of ne chalcopyrite after grinding with reactive steel media can be easily explained. Attention will now turn to whether the benets of grinding with fully inert media is only a result of decreased contamination by iron hydroxide, or if there is an intrinsic benet also in the attrition mechanism of size reduction which may be more important with the ceramic media in the current study. With attritioning, surface oxidation products may be removed from the particle surfaces. This has been addressed, to an extent, in a separate study on arsenopyrite otation (Huang and Grano, 2006b). In the case of ceramic media, and grinding in a stirred bead mill, the increased arsenopyrite recovery noted was principally accounted by decreased surface contamination from iron hydroxide (Huang and Grano, 2006b). However, further work is required to differentiate these mechanisms, particularly for the case of hydrophilic surface coatings which may be present on minerals prior to grinding. Examples include iron hydroxide from grinding media contamination derived from previous grinding stages in plants, oxidation products of the minerals at the surface, and gangue slime coatings which seems to be particularly important in molybdenite otation. It is also worthwhile pointing out that the magnitude of the benets of grinding with electrochemically inert grinding media will depend upon the prevailing pulp chemical environment (pH, Eh), media type, ore mineralogy and target particle size. As an example, in a laboratory study on Solobo copper ore, Goncalves et al. (2003) found that grinding in a ceramic mill with ceramic media did not yield the same otation results as that produced by grinding in a mill with stainless steel rods. Goncalves et al. (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). It is well established that bornite may oxidise more rapidly than chalcopyrite (Fullston et al., 1999). Controlling the pulp chemical environment, specically the pulp oxygen content, during grinding with ceramic media may mitigate against undue mineral oxidation during grinding. In a recent study on a complex copperleadzinc sulphide ore, 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, 2006c). The above discussion demonstrates the importance of considering also the chemical environment generally in the evaluation of grinding media. The Magotteaux Mill (Greet et al., 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). The Magotteaux Mill allows the pulp oxygen content and pH during grinding to be continuously controlled independently of the grinding media type (Greet et al., 2004). Further development of stirred milling technology to allow continuous control of the pulp chemical environment in grinding is also warranted. In terms of other pulp chemical parameters, the grind pH is also critical. Generally, 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.g., Grano et al., 1997c) suggesting that media oxidation reactions are inhibited at high pH. This may explain, for example, the increase in ne chalcopyrite recovery with lime addition to mills (Orwe et al., 1997). The pH of the grind needs also to be considered in the pulp chemical matching of the laboratory to the plant (Greet et al., 2004). However, it seems possible that even at high pH there is still surface contamination by grinding media through other mechanisms which requires further examination. In other cases, it is not possible to operate at elevated pH such as in the otation of pyrite and arsenopyrite for gold recovery. Another important aspect in the evaluation of the impact of the grinding media is the particle size distribution after milling. In the study of Goncalves et al. (2003) the amount of nes (10 lm) in the laboratory mill product was relatively low at 10% compared with the currently reported study which was 20%. Clearly, differences in the target grind d80 and the use of rods in the study by Goncalves et al. (2003), rather than balls used in this current study, are contributing factors. This highlights the importance of examining otation behaviour as a function of particle size at least. It is expected that the relative benets of grinding with electrochemically inert media will increase with decreasing target grind size due to the increasing contribution of ne particles less than 10 lm (Ye, 2008). Grinding technology which minimises the production of ne particles will also assist with improving recovery and selectivity (Pease et al., 2006a). Recent developments in large scale stirred milling technology using competent ceramic media will allow their application to relatively coarser particle applications (Anyimadu et al., 2006; Pease et al., 2006a,b). It is now possible to grind a rougher tailing from 150 lm to 55 lm in a 3.3 MW IsaMill using MT1 ceramic media (Pease et al., 2006a). Quantifying contributions to increased rougher recovery from improved liberation, narrower particle size distributions and improved surface properties of the mineral particles remain a target for research.

5. Conclusions Experimental evidence of the effect of the grinding environment on ne (10 lm) value mineral recovery in otation was presented. Reasons for increases in ne value mineral recovery from ores with fully electrochemically inert grinding media are discussed in relation to reduced surface contamination by iron

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S. Grano / Minerals Engineering 22 (2009) 386394 XPS and dissolution study. International Journal of Mineral Processing 50 (12), 126. Grano, S.R., Johnson, N.W., Ralston, J., 1997c. Control of the solution interaction of metabisulphite and ethyl xanthate in the otation of the Hilton ore of Mount Isa Mines Limited, Australia. Minerals Engineering 10 (1), 1739. Grano, S.R., Akroyd, T., Mular, M., 2007. A model study of copper rougher recovery optimisation at PT Freeport Indonesia. In: Proc. Ninth Mill Operators Conference. Aust. Inst. Min. Metall Publ., pp. 2538. Greet, C.J., Small, G.L., Steinier, P., Grano, S.R., 2004. The Magotteaux Mill: investigating the effect of grinding media on pulp chemistry and otation performance. Minerals Engineering 17 (78), 891896. Huang, G., Grano, S., 2006a. Galvanic interaction between grinding media and arsenopyrite and its effect on otation, Part I. Quantifying galvanic interaction during grinding. International Journal of Mineral Processing 78, 182197. Huang, G., Grano, S., 2006b. Galvanic interaction between grinding media and arsenopyrite and its effect on otation, Part II: effect of grinding on otation. International Journal of Mineral Processing 78, 178213. Huang, G., Grano, S., 2006c. Improving the otation behavior of a sulde ore by controlling electrochemical interactions during grinding, electrochemical society transactions. Electrochemistry in Mineral and Metal Processing VII 2, 920. Johnson, N.W., 1987. An appreciation of chalcopyrite metallurgy in the copper concentrator, Mount Isa Mines Technical Report. Johnson, N.W., 2006. Liberated 010 lm particles from sulphide ores, their production and separation. Recent developments and future needs. Minerals Engineering 19 (68), 666674. Julianto, J., 2008. Distinguishing and quantifying the relative contributions of oxidized iron from grinding media and mineral sources, M.Sc. Thesis, University of South Australia. Kinal, J., 2008. Characterising the surface phases on ne particles less than 10 lm in heterogenous mixtures, Ph.D. Thesis, University of South Australia. Muganda, S., 2008. Correlating particle contact angle to otation rate in a well dened turbulent environment, Ph.D. Thesis, University of South Australia. Orwe, D., Grano S.R., Lauder, D.W., 1997. Chalcocite oxidation and its inuence on ne copper recovery at the Ok Tedi concentrator, Papua New Guinea. In: Fifth Mill Operators Conference, Madang, PNG, (Aust. Inst. Min. Metall. Publ.), pp. 85 96. Parry, J., Klein, B., Lin, D., 2006. Comparison of ultra-ne grinding technologies. XXIII International Mineral Processing Congress, Istanbul, Turkey (pp. 177184). Pease, J.D., Curry, D.C., Barnes, K.E., Young, M.F., Rule, C., 2006a. Transforming ow sheet design with inert grinding media the IsaMill, Paper 16, 38th Annual Meeting of the Canadian Mineral Processors, pp. 231249. Pease, J.D., Curry, D.C., Young, M.F., 2006b. Designing otation circuits for high nes recovery. Minerals Engineering 19, 831840. Peng, Y., Grano, S.R., Fornasiero, D., Ralston, J., 2002. Towards prediction of oxidation during grinding 1. Galena otation. Minerals Engineering 15, 493498. Peng, Y., Grano, S.R., Fornasiero, D., Ralston, J., 2003a. In: Lorenzen, L., Bradshaw, D. (Eds.), The effect of grinding conditions on ne galena otation and its separation from pyrite. XXII International Mineral Processing Congress., Sth. Afr. Inst. Min. Metall. Publ., pp. 696705. Peng, Y., Grano, S.R., Fornasiero, D., Ralston, J., 2003b. Control of grinding conditions in the otation of chalcopyrite and its separation from pyrite. International Journal of Mineral Processing 69, 87101. Rey, M., Formanek, V., 1960. Some factors affecting the selectivity in the differential otation of lead zinc ores, particularly in the presence of oxidised lead minerals. In: Proc. 5th Int. Mineral. Process Congr, London, pp. 343353. Sutherland, K.L., Wark, I.W., 1955. Principles of Flotation. Australasian Institute of Mining and Metallurgy Inc., Melbourne (pp. 98). Ye, X., 2008. Optimising grinding and regrinding chemistry, Ph.D. Thesis, University of South Australia.

hydroxide emanating from the grinding media. It is suggested that the effect of the grinding media, which is important for ne particles and progressively becomes more important for ner grind sizes, is principally due to the abrasion mechanism of the minerals with the media in the production of the ne particles, though this mechanism needs to be substantiated through further experimental studies. Acknowledgments The author gratefully acknowledges nancial support and permission to publish from Xstrata Copper. The experimental work described in this paper was conducted in the early 1990s in a project with Mount Isa Mines Ltd. The author would like to express gratitude to Bill Johnson for his guidance in this and other projects. References
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