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Flotation characteristics of a complex copper ore: a comparison between wet and

dry grinding

Conference Paper · September 2012

DOI: 10.13140/2.1.4695.6485

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 Paper No.220

FLOTATION CHARACTERISTICS OF A
COMPLEX COPPER ORE: A COMPARISON
BETWEEN WET AND DRY GRINDING
Saeed Farrokhpay1, 2,* and Hamid Reza Manouchehri1, 3

ABSTRACT
It is known that the grinding condition has a major effect on the beneficiation characteristics of the
minerals in subsequent processing, in particular, flotation. In the flotation process, particles surface
and their condition can significantly influence collector adsorption and flotation performance. For
example, particle shape and its surface roughness occurred during grinding may influence flotation
characteristics of a specific ore. In fact, adsorption of different cationic and anionic species on mineral
surfaces can be varied depending on the selected comminution procedure. The flotation performance
of sulphide minerals can be detrimentally affected by the surface oxidation. The amount of surface
oxidation may reduce the hydrophobicity of the mineral and makes adsorption of collectors less
selective. Improved liberation may generally result in improved flotation recovery. However, this may
result in finer grinding and slimes, and consequently, reduce the overall flotation recovery.
This paper discusses the effect of wet and dry grinding on copper flotation of a complex Cu-Pb-Zn ore.
Industrially, wet grinding is preferred due to its higher energy efficiency and owing to downstream
processing requirements. In this study, series of flotation tests were conducted,and surface analysis
(XPS and ToFSIMS) were performed after wet or dry grinding at two different P 80 values. Mineralogical
study was also conducted to investigate the liberation of valuable minerals after grinding. A higher
copper flotation recovery was found for wet grinding. However, the copper recovery was increased by
further grinding in both conditions (wet and dry). The results showed a higher collector adsorption on
copper mineral surfaces after wet grinding. The surface analysis also revealed that the ore is slightly
more oxidized after dry grinding probably due to higher temperature during dry grinding.
Keywords: sulphide ore, flotation, wet grinding, dry grinding, copper recovery

INTRODUCTION
In ore preparation for flotation, various grinding procedures are industrially applied. These methods may affect the
flotation performance due to variation in liberation, particle size and size distribution, or surface characteristics of
the ore sample. For valuable mineral liberation, it has been shown that the particle composition distribution of a
given size fraction after grinding is constant (for that mineral), regardless of the grinding method or the overall size
distribution (Palm et al, 2010). However, it has also been shown that grinding environment and media may play a
significant role in both flotation recovery and selectivity. For example, ceramic mill can produce an oxidizing
environment, allowing sphalerite activation by copper ions, while steel media produces a reducing environment
and prevents this action (Wei and Sandenbergh, 2007).
Industrially, wet grinding is often preferred because most subsequent processes such as flotation and leaching
are performed wet. However, in areas where water is scarce or where a dry process is followed after
comminution, dry grinding may be preferred. It should be noted that wet grinding requires less power per ton of
material ground than dry grinding. Wet grinding also does not require elaborate dust control equipment.

1. Ian Wark Research Institute, University of South Australia, Mawson Lakes SA 5095, Australia.
2. Currently: JKMRC, The University of Queensland, 40 Isles Road, Indooroopilly, Qld 4068, Australia. Email: s.farrokhpay@uq.edu.au.
3. Sandvik SRP AB, SE-233 81, Svedala, Sweden. Email: hamid.manouchehri@sandvik.com.

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01370
 FARROKHPAY AND MANOUCHEHRI

The effect of grinding mode on the efficiency of mineral separation (for pyrite and non-pyritic minerals from coal)
has been investigated (Liu et al, 1993). It has reported that for <600 micron feed, grinding mode had no effect on
the efficiency of separation of either pyrite or non-pyritic minerals. However, for <75 micron feed, a higher
selectivity is achieved after wet grinding. That was attributed to the dry state aggregation of coal with mineral
matter (Liu et al, 1993). A similar trend has been also observed for other mineral systems (Balaz, 2000).
Seke (2005) has observed that the grinding environment (wet or dry) can influence the pulp potential and
subsequently, the surface properties of the mineral. The recovery of sphalerite is higher when it is ground in a dry
environment. Palm et al (2010) have also presented results of their study of the flotation of sphalerite which had
been subjected to wet or dry grinding before flotation. They have reported that dry grinding produces a greater
amount of fines, probably due to the more abrasive environment compared to the wet grinding, but this does not
reduce the recoveries as one may expect. Dry grinding also causes a significant increase in the amount of
sphalerite in the <10 micron size fraction. Dry grinding was accompanied by a significant coating from a
passivating layer of ions, but it did not inhibit xanthate adsorption or the ultimate flotation recovery (Palm et al,
2010).
The effect of dry and wet grinding on the flotation of complex sulphide ore from Merensky Reef in South Africa
has been also investigated (Feng and Aldrich, 2000). In that research, scanning electron and atomic force
microscopy investigations showed that the dry ground samples have relatively rough particle surfaces with a high
concentration of microstructural defects, while the wet ground samples have smoother and cleaner surfaces.
Therefore, the activated particle surfaces after dry grinding can accelerate the dissolution of the particles, as well
as the adsorption of reagents onto the particle surfaces (Feng and Aldrich, 2000).
Palm et al (2010) indicated that in flotation tests, dry ground samples produce the highest grades and recoveries.
This is similar to that obtained by Seke (2005) who observed a greater recovery of sphalerite after dry grinding.
Surface coverage of certain ions namely Al+Si+Ca+Mg can lead in passivation layers on the surface of the
mineral. It is possible that dry grinding produce high energy sites on the ore particles due to increased
temperatures and friction (during grinding). When the sample is repulped, these high energy sites may have a
higher attraction for the Al+Si+Ca+Mg ions which are still present as ions at the operating pH. During wet
grinding, iron oxide and hydroxides are produced and these ions may occupy the high energy sites, and therefore
decrease the amount of sites available for the Al+Si+Ca+Mg ions.
There are also limitations for dry grinding. Firstly, it generates heat which may result in more surface oxidation
(and consequent lower flotation performance). It is also limited for feed material with low moisture content. The
agglomeration of particles during dry grinding may also be problematic as discussed above. However, it may be
possible that some or all advantages of wet grinding to be obtained from dry grinding if the mill is operated at the
right condition with right parameters (Sachweh and Gerl, 2008).
The purpose of this study is to investigate the effect of wet and dry grinding on copper flotation of a complex Cu-
Pb-Zn ore.

EXPERIMENTAL PROCEDURE
Materials
3
The ore used in the current study was a massive sulphide ore with a density of 4.3 g/cm and a typical head
elemental assay of 0.5% copper, 1.4% lead and 8.5% zinc. The mineralogy is dominated by pyrite (about 80%).
The other gangue mineral assemblage is minor, comprising of calcite, dolomite, quartz and other silicates. The
copper occurs as chalcopyrite, lead as galena, and zinc as sphalerite.

Grinding & Flotation

The ore sample was crushed (to <2 mm), riffled in 1 kg bags and kept frozen to avoid surface oxidation. The
crushed ore samples were then ground for a pre-determined time in wet and/or dry condition to obtain P80 of 45
and 25 micron. Flotation tests were carried out using a 1 L Denver flotation cell. The impeller speed during
3
flotation tests was 1000 rpm and the air flow rate was 5 dm /min. The superficial gas velocity (Jg) was 0.8 cm/s. In
all flotation experiments, the froth was removed from the cell using a hand scraper and concentrates were

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01371
FLOTATION CHARACTERISTICS OF A COMPLEX COPPER ORE: A COMPARISON BETWEEN WET AND DRY GRINDING

collected at 2, 4 and 8 minutes of flotation. After collection, the concentrates were filtered, dried and assayed in a
standard manner. The flotation tests were undertaken using 100 g/t potassium amyl xanthate (PAX) as the copper
collector and 2000 g/t meta bisulphite (MBS) as the pyrite depressants. The conditioning stages were comprising
MBS addition, lime conditioning to obtain pH 10.0, and collector conditioning. Methyl isobutyl carbinol (MIBC) was
used to maintain a stable froth. The pulp volume was maintained at a constant value by the addition of water; the
pulp pH was controlled during flotation and adjusted if needed. All recalculated head assays for these samples
were crosschecked to determine both the reproducibility of the sampling technique and the consistency of the ore
feed being used. To ascertain reproducibility, each test was performed in triplicate. Samples were taken after
grinding or after collector addition for surface analysis (kept frozen in liquid nitrogen) and mineralogy.

Surface Analysis
X-ray photo spectroscopy (XPS) analysis was performed using a Kratos Axis-Ultra photoelectron spectrometer
with a monochromatic AlKα X-ray source. The atomic concentration for each element was determined from
survey spectra peak areas and their respective sensitivity factors. Fitting of individual, high resolution spectra,
were used to determine the chemical species of elements. Samples were washed (with a pH 10.0 aqueous
solution) to remove suspended colloid particles and were introduced immediately in the fore vacuum of the XPS
spectrometer as slurry. XPS normally analyses the first 20-50 Å of a surface and provides chemical information,
both quantitatively and qualitatively, for elements. It also gives useful information regarding the
oxidation/alteration of sulphides. XPS analysis was conducted on the samples after grinding in wet or dry
conditions.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed on the samples after collector
addition using a PHI TRIFT II spectrometer. ToF-SIMS analysis can identify the species present on the surface of
the ore samples. The grains were analyzed and imaged for Ca, Mg, Al, Si, Na, Fe, Cu, and CH 3 during positive
ion analysis, and O, OH, S, F, Cl, SO,SO2, C2H, CH, as well as xanthate, during negative ion analysis. The
intensities obtained were normalized for the elements of interest and presented as a relative percent normalized
yield.

RESULTS AND DISCUSSION

Ore size distribution after grinding
Figures1 and 2 show the particle size distribution for P80 of 45 and 25 micron, respectively (for both dry and wet
grinding). It can be seen that in the case of P80 of 45 micron, the size distribution is slightly different in dry versus
wet grinding. A smooth distribution for wet grinding is observed while a slightly bi-model distribution can be seen
for dry grinding. Therefore, while the P80 value for both grinding conditions is almost similar, the size distribution is
slightly different, i.e. more coarse particles present after dry grinding. These coarse particles may affect the
recovery of copper flotation. When considering the size distribution for P 80 of 25 micron, a similar trend can be
observed for both wet and dry grinding. Moreover, no extra fine fraction is observed after dry grinding (for both P 80
of 25 and 45 micron) which is not in agreement with the results reported for sphalerite grinding by Palm et al
(2010).

Figure 1. The particle size distribution for P80 of 45 micron for both wet (a) and dry (b) grinding.

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01372
 FARROKHPAY AND MANOUCHEHRI

Figure 2. Particle size distribution for P80 of 25 micron for both wet (a) and dry (b) grinding.

Flotation
Table 1 shows the flotation grade and recovery for copper, zinc and lead for both P 80 of 45 and 25 micron, after
wet and dry grinding. It can be confirmed that copper recovery is considerably lower for dry grinding versus wet
grinding for both P80 of 45 and 25 micron. The copper recovery is about 77% for P80 of 45 micron in wet grinding,
but it decreases to about 71% in dry grinding. This may be due to the different size distribution obtained after dry
and wet grinding. As discussed above, more coarse particles are present after dry grinding. However, the copper
recovery for dry grinding increases to about 77% when the P 80 reduces to 25 micron (longer grinding time). The
copper recovery considerably increases to about 86% in wet grinding for P 80 of 25 micron which is not unusual as
one may expect better liberation of copper bearing minerals in coarse composites after regrinding (Farrokhpay et
al, 2010). It should be highlighted that grinding is the highest energy consuming stage in mineral processing
which accounts for up to 50% of a concentrator’s energy consumption (Wills and Napier-Munn, 2008). Therefore,
one should consider the higher energy consumption when choosing lower P 80 values (finer grinding).The lower
copper recovery for dry versus wet grinding can be also correlated to either more surface oxidation after dry
grinding, or higher collector adsorption after wet grinding, or both. This hypothesis will be examined by surface
analysis using XPS and Tof-SIMS in the next section. Table 1 also shows the time needed for wet or dry grinding
to obtain both 45 and 25 micron P80. It can be seen that the time needed in dry grinding is at least 50% more than
that of wet condition (for both P80 sizes).
It is worth mentioning that the grade of copper concentrates is similar for all tested conditions
(Table 1) which is not in agreement with what have been recently reported (Palm et al, 2010). Table 1 also shows
that, whether it is wet or dry grinding condition, lead recovery is more or less unchanged. However, for P80 of 45
micron, zinc recovery considerably decreases in dry grinding.

Table 1. Flotation results.

P80 (micron) 45 25
Grinding condition wet dry wet dry
Grinding time (minutes) 16 25 25 37
Cu recovery (%) 77.1 72.5 84.1 77.6
Cu grade (%) 2.0 1.8 1.9 1.8
Zn recovery (%) 57.1 32.8 39.8 36.1
Zn grade (%) 23.0 13.1 14.0 10.6
Pb recovery (%) 54.7 59.7 60.2 58.3
Pb grade (%) 4.0 4.1 3.5 3.6

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01373
FLOTATION CHARACTERISTICS OF A COMPLEX COPPER ORE: A COMPARISON BETWEEN WET AND DRY GRINDING

Surface analysis
XPS
XPS characterization analysis of the ore samples after both wet and dry grinding, for P 80 of 45 and 25 micron, are
presented in Table 2.These results indicate that lead, zinc and iron are present in both oxidized (probably oxy-
+ 2+
hydroxides) and un-oxidized (sulphide) forms. Surface copper is present mainly as Cu , with some Cu when the
P80 reduces to 25 micron (for both wet and dry grinding). Table 2 also shows relatively little SO x species for
sulphur; while the amount of S and Poly-S (which is beneficial for flotation) is higher after wet grinding, for both
P80 values. The amount of oxidized surface lead, zinc or iron is more or less similar in all conditions suggesting
that more surface oxidation is not happening in dry grinding as one may expect.

Table 2. XPS results.

P80 (micron) 45 25
Grinding condition wet dry wet dry
O 51.9 54.2 57.1 55.3
Zn 5.2 5.1 3.9 5.0
Zn-S 4.5 4.4 2.9 4.4
Zn-Ox 0.7 0.7 1.0 0.6
Cu 1.5 1.5 1.2 1.4
+
Cu 1.5 1.5 0.8 0.9
2+
Cu - - 0.4 0.5
Fe 5.2 5.4 3.4 4.5
Fe-S 3.0 3.1 1.2 2.1
Fe-Ox 2.2 2.3 2.2 2.4
Pb 1.4 1.5 1.2 1.3
Pb-S 0.3 0.3 0.2 0.4
Pb-Ox 1.1 1.2 1.0 0.9
S 19.5 17.2 18.0 15.8
S-Pb/Zn 4.7 4.5 2.9 3.6
S-Fe/Cu 10.5 7.7 8.1 7.6
Poly-S 3.1 4.1 6.3 3.6
SO4 1.2 0.9 0.7 0.9
Si 7.5 8.0 8.0 8.3

Tof-SIMS
ToF-SIMS analysis was performed to investigate the surface composition of the ore particles at different grinding
conditions, as described. Figure 3 and 4 report the spectra of the positive and negative species, respectively, as
identified on the surface of the ore particles after dry and wet grinding for different P80 values. A higher exposed
copper and iron is observed on the ore samples after wet grinding than dry grinding for both P 80 values. Figure 5
also highlights the presence of xanthate component on the ore surface (at higher magnification). Clearly, higher
collector adsorption is observed after wet grinding.

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01374
 FARROKHPAY AND MANOUCHEHRI

Figure 3. The Tof-SIMS spectra of the positive species as identified on the surface of the ore particles after dry
and wet grinding for different P80 values.

Figure 4. The Tof-SIMS spectra of the negative species as identified on the surface of the ore particles after dry
and wet grinding for different P80 values.

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01375
FLOTATION CHARACTERISTICS OF A COMPLEX COPPER ORE: A COMPARISON BETWEEN WET AND DRY GRINDING

Figure 5. The Tof-SIMS spectra of xanthate (PAX) fragments at higher magnification to show the presence of
xanthate component on the ore surface.

Mineralogy
Table 3 represents the chalcopyrite liberation data for both P80 of 25 and 45 micron, after wet and dry grinding. It
can be seen that the amount of the liberated chalcopyrite particles is 63% for P 80 of 45 micron at wet grinding;
however, it is only 53% when the ore is ground in dry condition (similar P 80 of 45 micron). Therefore, one may
expect lower copper flotation after dry grinding, as observed in this study. The amount of liberated copper bearing
particles is considerably more for finer feed, i.e., P80 25 micron, at wet grinding mode that results in a higher
copper flotation recovery.

Table 3. P80 liberation data from QEMSCAN

P80 45 25
Grinding condition Wet Dry Wet Dry
Liberated (%) 63 53 88 83
Composite (%) 37 47 12 17

CONCLUSIONS
In this study, the effect of wet and dry grinding on the flotation of a complex Cu-Pb-Zn ore was investigated.
Flotation results indicated a higher copper recovery after wet grinding of the ore for two different tested P 80 values.
However, the copper recovery was increased by further grinding in both conditions (wet and dry). Surface
analysis (using XPS and Tof-SIMS) and mineralogical studies (using QEMSCAN) were conducted after wet or dry
grinding at two different P80 values to define the reasons for the higher recovery in wet grinding. The surface
analysis results showed a higher recovery for copper after wet grinding corresponds to a higher collector

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01376
 FARROKHPAY AND MANOUCHEHRI

adsorption on the copper mineral surfaces. Furthermore, it was revealed that the ore is slightly more oxidized
after dry grinding probably due to the higher temperature occurs during dry grinding which results in reduction in
collector adsorption and therefore the recovery of value minerals.

REFERENCES
Balaz, P, 2000. Extractive Metallurgy of Activated Minerals (Elsevier: Amsterdam).

Farrokhpay, S, Manouchehri, H R and Grano, S, 2010. Effect of feed classification by hydrocycloning on copper
recovery in flotation, Canadian Metallurgical Quarterly, 49(2): pp 107-112.

Feng, D and Aldrich, C, 2000. A comparison of the flotation of ore from the Merensky Reef after wet and dry
grinding, International Journal of Mineral Processing, 60(2): pp 115-129.

Liu, D, Vasudevan, T V, Somasundaran, P and Harris, C C, 1993. Effect of wet versus dry grinding on rejection of
pyrite and non-pyritic minerals from Pittsburgh No. 8 Coal by flotation, International Journal of Coal
Preparation and Utilization, 13(1-2): pp 63-72.

Palm, N A, Shackleton, N J, Malysiak, V and O’Connor, C T, 2010. The effect of using different comminution
procedures on the flotation of sphalerite, Minerals Engineering, 23: pp 1053-1057.

Sachweh, J and Gerl, S, 2008. Tower Mill- new approaches to improve dry milling operations, in Proceedings of
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the 24 International Minerals Processing Congress, pp 427-435 (China Scientific Book Service Co. Ltd:
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Seke, M D, 2005. The optimization of the selective flotation of galena and sphalerite at Rosh Pinah Mine. PhD
thesis, University of Pretoria, Pretoria, South Africa.

Wei, Y and Sandenbergh, R F, 2007. Effects of grinding environment on the flotation of Rosh Pinah complex
Pb/Zn ore, Minerals Engineering, 20: pp 264-272.

Wills, B A and Napier-Munn, T J, 2008. Wills' Mineral Processing Technology (Elsevier: Oxford).

XXVI INTERNATIONAL MINERAL PROCESSING CONGRESS(IMPC) 2012 PROCEEDINGS / NEW DELHI, INDIA / 24 - 28 SEPTEMBER 2012 01377

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