Minerals Engineering 126 (2018) 24–27

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Minerals Engineering
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Short communication

Effect of using different grinding media on the flotation of a base metal T

sulphide ore
⁎
K.C. Corina, , Z.G. Songa,b, J.G. Wiesea, C.T. O'Connora
a
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town, Cape Town, South Africa
b
State Key Laboratory of Mineral Processing, Beijing General Research Institute of Mining and Metallurgy, Beijing, China

A R T I C LE I N FO A B S T R A C T

Keywords: In the present investigation flotation was used as a diagnostic to understand the effects of changes to the media
Milling media during the grinding stage. A Base Metal Sulphide (BMS) ore was ground under media of different shapes and
Flotation compositions to determine the effect of different rod/ball material on the flotation performance of the ore. The
Base metal sulphides observations from flotation for different media are discussed in terms of water recovery, solid recovery and
PGMs
valuable mineral recovery. The chemical parameters; pH, redox potential (Eh) and dissolved oxygen (DO) levels
were measured. For a given grind (D80 = 75 μm), media shape had no effect on flotation performance of a BMS
ore. Different grinding media had significant effects on slurry chemical properties and flotation performance.
Mild steel rods (RMMS) produced the highest solids recovery, nickel and pyrrhotite (Po) recovery, with the
highest ethylenediaminetetraacetic acid (EDTA) extractable iron and the lowest DO level. Chrome steel balls and
stainless steel rods produced the lowest metal recovery, EDTA extractable iron and the highest DO level. Ferric
ions were seen to depress talc.

1. Introduction improve the flotation of sulphides compared to mild or forged steel

The main purpose of crushing and grinding of ores in mineral pro-
cessing is to prepare the ore particles for downstream processing. One
of the most important such downstream processes is flotation and hence
in many respects flotation performance represents an excellent diag-
nostic of the efficiency of the comminution process. Among many of the
different variables involved in the comminution of ores, the shape and
composition of milling media can have a significant impact on the
nature of the particles produced. Specifically the use of mild or stainless
steel or inert/ceramic media can influence the surfaces of the particles.
Wet or dry milling has also been shown to significantly affect the flo-
tation of ores and this has also been found to be mineral specific
(Chapman et al., 2011). The use of mild or forged steel media can result
in the generation of oxyhydroxide species in the pulp. The gaseous at-
mosphere used in the grinding, such as having a relatively inert low
dissolved oxygen (DO) concentration, can affect the chemical nature of
the particle surfaces. Changing the chemical conditions, such as pH, or
adding flotation reagents, such as collectors, into the mill may also
affect the ultimate floatability of the particles. Previous studies have
investigated the use of balls or rods made from mild steel, ceramic,
stainless steel or chrome steel to investigate the effects of different
media on flotation. Stainless steel or chrome media have been found to
media (Rey and Formanek, 1960; Peng et al., 2003a, 2003b; Huang and
Grano, 2006; Bruckard, 2011). Miettunen et al. (2012), in a study of a
low sulphur containing platinum group mineral (PGM) ore found that
forged media grinding in a CO2 atmosphere led to the highest Pt and Pd
grades and recoveries whereas the high chrome grinding media gave
lower flotation recoveries. Studies carried out using autogenous
grinding have indicated that sulphide minerals produced in the non-
reducing, low iron grinding environment of the autogenous mill ex-
hibited enhanced flotation properties compared with conventional
grinding (Bruckard, 2011). Khonthu (2012) found that stirred milling
improved the flotation performance of the fine fraction of a PGM ore.
Chapman et al. (2011) found that dry milling improved the flotation
performance of a base metal sulphide but produced the opposite effect
when applied to a PGM ore thus emphasizing the importance of using at
least two quite different ore types when carrying out such investigations
since the results obtained may be ore specific. Conventional milling
methods make use of either steel rods or balls as media and the use of
these media types may result in the production of particles with dif-
ferent characteristics due to different breakage mechanisms. While the
shape of the mill product is considered a valuable characteristic, this
was not within the scope of this study.
In the present investigation, the effect of using rods or balls of

⁎
Corresponding author.
E-mail address: Kirsten.Corin@uct.ac.za (K.C. Corin).

https://doi.org/10.1016/j.mineng.2018.06.019
Received 5 December 2017; Received in revised form 20 June 2018; Accepted 21 June 2018
Available online 28 June 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
K.C. Corin et al.
different composition during milling in a tumbling mill on the flotation
behaviour of a base metal sulphide (BMS) has been investigated. In this
study, apart from investigating the effect of media shape and compo-
sition on flotation behaviour, the effect on factors such as the chemical
properties (pH, Eh and DO) of the mill product were also determined.
2. Experimental procedures
2.1. Milling procedures
The ore samples were received from a Cu-Ni base metal operation
located in South Africa containing approximately 5% total sulphide (Cu
0.36 wt%, Ni 0.67 wt%, S 5.67 wt%) and 7% talc. 3 kg representative
samples were used for each test. Grinding was performed in the absence
of reagents at 67% solids. The media used were, respectively, stainless
steel rods (RMSS), mild steel rods (RMMS), 21% chrome steel balls
(BMCS) and forged steel balls (BMFS). The particle size distributions of
the feed and product after grinding were determined using wet sieving.
The grinding time was determined to obtain a product with a d80 of
75 µm. Vickers Hardness Test ASTM C1237 were conducted by an ex-
ternal laboratory. Talc samples obtained from Wards were chopped into
small chunks before being pulverized to +38–75 μm.
2.2. Batch flotation tests
Batch flotation tests were performed at 30% solids, in an 8 L la-
boratory bottom driven batch flotation cell. The impeller speed was set
at 1200 rpm and the air flow rate was maintained at 7 L/min
throughout the test. 50 g/t sodium isobutyl xanthate (SIBX) was used as
a collector and 20 g/t DOW 200 as a frother. Two feed samples were
taken before and a tails sample after each flotation test. Four con-
centrates were collected by scraping the froth into a collecting pan at
15 s intervals for 2, 4, 6 and 8 min, with a total flotation time of 20 min.
The batch flotation tests of talc were performed in a flotation cell with a
capacity of 500 ml with the impeller speed set at 200 rpm, and air flow
rate at 1 L/min, using 50 g talc. One feed, all concentrate and tailings
samples were analyzed for copper and nickel using a Bruker S4 Explorer
XRF Spectrophotometer. A Leco S632 sulphur analyzer was used to
determine the total sulphur content of the samples. A sulphur balance
calculation enabled the pyrrhotite (FeS) content to be determined
(Corin et al., 2011). pH, Eh and DO values were measured inside the
flotation cell using a 556 Multi-Probe System. The measurements were
made after the ore had been transferred to the flotation cell, the pulp
conditioned for 5 min and before any reagents were added. All tests
were performed in duplicate. Assuming the stoichiometries for chal-
copyrite and pentlandite to be CuFeS2 and (FeNi)S respectively, the
recoveries of total copper and total nickel can be used to estimate the
recoveries of chalcopyrite and pentlandite respectively. The recovery of
pyrrhotite can be estimated by balance from the copper, nickel and
sulphur values determined.
2.3. EDTA extraction method
The second feed sample underwent EDTA extraction for iron.
(Rumball and Richmond, 1996) The 25 ml aliquot was injected into a
400 ml beaker containing 250 ml of a 3% (w/v) solution of EDTA, pH
modified to 7.5 with sodium hydroxide (NaOH). This EDTA / slurry
solution was stirred for 5 min before being filtered; the filtrate was
submitted for analysis by Atomic Absorption Spectroscopy (AAS).
3. Results and discussion
3.1. Effect of different milling conditions on the chemical condition of the
flotation pulp
Table 1 presents data describing the chemical condition of the mill
25
Minerals Engineering 126 (2018) 24–27
product prior to flotation. The pH is the natural pH of the ore and
hardly changed during the grinding stage. As expected, in general, as
the DO concentrations increased the Eh of the pulp also increased. A
number of oxidation-reduction reactions would be occurring in the mill.
The mild steel media would undergo oxidation (Eq. (1)
Fex(s) → Fe(1−x) (s) + Fe2+ (aq) + 2e (1)
The corresponding reaction is the reduction of oxygen in the pulp
according to Eqn. (2) which results in a decrease in the DO con-
centration.
1/2 O2 + H2O + 2e → 2OH− (2)
Moreover chalcopyrite is anodic relative to pyrite and pyrrhotite
and hence will undergo oxidation thus also providing electrons for the
reduction of the oxygen. The very low DO levels and Eh values observed
in the case of using mild steel for the BMS is expected as this reactive
media may have enhanced the inter-mineral galvanic interactions and
promoted the reduction of the pulp oxygen. Table 1 also illustrates well
that DO concentrations are useful indicators of the chemical condition
in the mill since, irrespective of the pH levels, the Eh is relatively
strongly related to the DO concentrations.
3.2. Flotation results for the BMS ore
Chalcopyrite is seldom a strong indicator of a change in conditions
since it is so readily floatable and as can be seen there is little difference
between chalcopyrite recoveries for the different milling conditions,
Table 1. On the other hand there is a very significant increase in the
recovery of pentlandite when mild or forged steel media are used. In-
terestingly this is also accompanied by a significant increase in grade
indicating that this effect is not merely a result of an increase in mass
pull. There is also an increase in recovery and grade in the case of
pyrrhotite when mild or forged steel media are used.
Table 1 also shows the amounts of EDTA extractable Fe, Cu and Ni.
Of special interest is the amount of Fe. As can be seen the mild and, to a
lesser extent, forged steel media resulted not surprisingly in the highest
concentrations of Fe ions. As shown in Table 1 these conditions also
resulted in significant increases in the recoveries and grades of pen-
tlandite and to a lesser extent of pyrrhotite. The concentrations of EDTA
extractable Cu and Ni were very low.
These results indicated a strong correlation between the amount of
EDTA extractable Fe ions present in the pulp and the recoveries of
pentlandite and pyrrhotite. In order to investigate this further, tests
were carried out to investigate whether the addition of ferrous or ferric
ions could result in a similar outcome. In the first instance the presence
of these ions on the solids and water recoveries was investigated. It was
decided to use chloride salts of iron since this would ensure that the
effect of just the Fe ions would be investigated. For both divalent and
trivalent Fe under the pH conditions found in this study, the dominant
species would be iron hydroxides (Rao and Leja, 2004). The base case
used was the result obtained when the ore was milled with chrome steel
balls (BMCS) since this had resulted in the lowest Fe concentration viz.
0.57 mg/g and the effect of Fe ions would be minimal. The DO con-
centrations in the case of the rod mill mild steel (RMMS) was the lowest
and for BMCS was the highest (cf. Table 1).
As can be seen in Fig. 1(a) the addition of Fe ions (using FeCl2 or
FeCl3) significantly increased the solids and water recovery. However,
the flotation results had indicated an increase in grades and hence this
increase in mass pull was selective towards the recovery of pentlandite
and particularly pyrrhotite, thus diluting the grade of chalcopyrite.
Fig. 1(b), (c) and (d) show the grade-recovery results obtained using the
same conditions as those used in Fig. 1(a). As can be seen there was a
significant increase in both grades and recoveries of pentlandite and
pyrrhotite after the addition of Fe ions relative to the results obtained in
the case of BMCS.
K.C. Corin et al. Minerals Engineering 126 (2018) 24–27

Table 1
(a) Chemical conditions after milling, (b) Grades and recoveries (%) obtained, (c) Amounts of EDTA extracted Fe, Cu and Ni of different grinding products.
Media type Chemical conditions after milling (a) Grades and recoveries of the valuable components (b) EDTA extracted ions, mg/g (c)

*
Cu Ni Po

pH Eh (mV) (vs SHE) DO (ppm) Rec Grade Rec Grade Rec Grade Cu Ni Fe

RMSS 9.45 85.7 4.8 75 2.2 18 1.50 10 7.01 0.03 0.09 0.57
BMCS 9.60 88.9 5.3 74 2.01 19 1.45 8.5 6.2 0.02 0.06 0.57
RMMS 9.96 31.9 0.6 80 1.75 43 3.01 14 10.2 0.01 0.03 5.09
BMFS 9.80 105.0 2.6 77 1.7 34 2.04 10 8.2 0.01 0.02 0.93

* Determined by elemental balance of S.

The increase in the grade of pentlandite and pyrrhotite remains

difficult to explain. Since a significant component of the gangue was
talc (7.22%) and given that talc is naturally floatable it was possible
that the Fe ions were having a depressing effect on the talc. Fig. 2 shows
the results obtained for the recovery of talc in the presence of a frother
as well as in the presence of a frother and Fe3+ ions. Clearly the Fe ions
resulted in a decrease in talc recovery and this may explain the increase
in grade even though the solids recovery was greater.

4. Conclusions

Different grinding media had significant effects on the slurry

chemistry and flotation performance of the BMS ore. The more re-
ductive media is more readily oxidized consuming more O2, lowering
the DO and producing more EDTA extractable iron. Mild steel rods
(RMMS) produced the highest solids, Ni and Po recovery, with the
highest EDTA extractable Fe and the lowest DO. Chrome steel balls and
stainless steel rods produced the lowest metal recovery, lowest EDTA
Fig. 2. Effect of FeCl3 on solids and water recovery of talc.
extractable Fe and the highest DO. Verification tests using chrome steel

Fig. 1. (a) Solids-water recoveries (b) Cu grade-recovery (c) Ni grade-recovery (d) Pyrrhotite grade-recovery.

26
K.C. Corin et al.
balls (BMCS) introducing Fe ions and purging with N2 to obtain the Fe
contents and DO level conditions of mild steel rods (RMMS) products
indicated that the flotation performance of RMMS grinding products
was more likely as a result of the higher levels of iron in the pulp.
Unique to this study are the results of talc batch flotation which proved
the hypothesis that the major effect of RMMS mild steel rods in the
grinding of a BMS ore, compared to chrome steel balls (BMCS) and
stainless steel rods (RMSS), would be that the former would result in a
significantly higher iron contents which would reduce the hydro-
phobicity of talc and decrease the frother consumption of the talc sur-
face, hence restore the frother function and improve the froth stability,
solid recovery and sulphide minerals recovery.
Acknowledgements
The authors wish to thank the UCT-ARG Post-Doctoral Fellowship
for funding.
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