Minerals Engineering 53 (2013) 108–112

Contents lists available at ScienceDirect

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

Copper–molybdenum ores flotation in sea water: Floatability and

frothability
O. Ramos a, S. Castro a,⇑, J.S. Laskowski b
a
Department of Metallurgical Engineering, University of Concepción, Concepción, Chile
b
N.B. Keevil Institute of Mining Engineering, University of British Columbia, Vancouver, Canada

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

Article history: Laboratory rougher flotation tests were conducted with two samples of Cu–Mo ores in fresh water and in
Received 19 February 2013 sea water as a function of pH. In both cases Cu recoveries were slightly lower in sea water than in fresh
Accepted 10 July 2013 water for a wide range of pH (pH 7–12). Flotation of molybdenite was however strongly depressed in sea
Available online 15 August 2013
water at pH higher than 9.5. Frothers were characterized by measuring froth thickness in a modified lab-
oratory flotation cell as a function of pH, salinity, frother type, and solids content (%). It was found that for
Keywords: all tested frothers, foamability in two-phase systems was better in sea water than in fresh water. How-
Cu–Mo sulfide ores
ever, froth layer thickness measurement showed that frothability also depends on solids content and
Cu–Mo ores flotation
Sea water
increases with increasing pulp density. At high solids content (35%) the frothability depended strongly
Sea water flotation on pH. At pH of 9 it was similar for fresh water and sea water, however, once the pH is raised further
Froth stability frothability increases sharply when the tests are carried out in fresh water, but this was not observed
Foam stability in sea water. The froth in sea water is drier than in fresh water, and this probably also depends on solids
content.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Cu and Mo recoveries are lower when Cu–Mo sulfide ores are
floated in sea water (Castro et al., 2012b). The high salinity of sea
water seems to be the main responsible factor. Also frothability
of flotation pulps is affected by the presence of inorganic electrolytes
and this raises the question whether sea water requires different
flotation conditions, or whether new criteria for selection of froth-
ing agents are needed (Castro et al., 2012a). In this paper relation-
ships between Cu and Mo recovery and pulp frothability in rougher
flotation both in fresh water and sea water are considered.
Mineral flotation requires formation of a froth layer that is to
some extent stable. Frothing agents prevent bubble coalescence
and reduce bubble size. It is known that foams are stabilized not
only by surface-active compounds (e.g. frothers) but also by sur-
face-inactive compounds (e.g. inorganic ions) (Quinn et al., 2007;
Castro et al., 2010). Foamability of frothing agents in distilled water
does not necessarily predict froth stability under flotation condi-
tions. Lekki and Laskowski (1975) have shown that frothers do
not have to be strongly surface active agents. For example, they re-
ported that di-acetone alcohol, a commercial flotation frother
which was used by the copper industry in Poland, was not a surface
active agent but it was performing very well as a frothing agent.
⇑ Corresponding author. Tel.: +56 41 2204956; fax: +56 41 2243418.
E-mail address: scastro@udec.cl (S. Castro).
While there was no foam when foamability tests were carried
out in the presence of this agent in distilled water, the three-phase
froth was sufficiently stable. The same phenomenon has been re-
ported for pine oil. While there was no foam when the foamability
was tested with pine oil, both in fresh water and in sea water, the
presence of hydrophobic particles was found to strongly stabilize
the pine oil froth (Castro et al., 2012a).
The reverse criterion is also valid, i.e., strong foaming agents do
not necessarily produce the most stable froths. Melo and Laskow-
ski (2007) reported for DF-1012 that while the foams generated
with the use of this frother were the most stable and carried most
water, the froth studied in the presence of hydrophobic bituminous
coal particles was remarkably less voluminous when this frother
was utilized. The same phenomenon was observed by Kuan and
Finch (2010) who studied the effect of hydrophobic talc particles
on the properties of foams in the presence of a polyglycol frother.
Frothing agents are employed in flotation to facilitate air disper-
sion into fine bubbles and to stabilize froth. Froth stability depends
on the frother type and concentration, but also is a function of
other variables, such as particle size, hydrophobicity, solids per
cent, pH, and airflow rate. For example, as reported by Tao et al.
(2000), coal particles can stabilize or destabilize the froth. This de-
pends both on the size of these particles as well as on their concen-
tration. The 100 mesh size fraction (150 lm) destabilized froth
at lower concentrations but stabilized it at higher concentrations,
while micronized coal particles showed froth-breaking power. In

0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.07.009
 O. Ramos et al. / Minerals Engineering 53 (2013) 108–112 109

this work the variables affecting froth stability are extended to Table 1
electrolyte concentration, particularly to sea water. Average analysis for both Cu–Mo ores samples (Sample A and B).

Dynamic froth stability – which has been further explored in Sample Cu (%) Mo (%) Fe (%) Moisture (%) Specific gravity (g/cm3)
this paper - has been the subject of several investigations. Barbian A 0.56 0.017 5.76 2.60 2.60
et al. (2003) reported that the equilibrium height and the dynamic B 0.43 0.008 6.26 1.31 2.60
stability factor1 increase when airflow rate and frother concentra-
tion increase. Aktas et al. (2008) reported that the dynamic froth sta- 2.2. Methods
bility strongly depends on particle size, showing that finer particles
increased froth height. 2.2.1. Flotation tests
To study the effect of frothing agents, solids content, pH and These tests were carried out in a 3 L Agitair LA-500 laboratory
type of water (sea water or fresh water) particle size, hydrophobic- mechanically agitated flotation cell, at 900 rpm and airflow rate
ity (type and dosage of collectors), airflow rate, impeller speed, etc., of 10 L/min.
were maintained constant. While the primary objectives were to
study frothing phenomena with different frothing agents, pH and
2.2.2. Experimental conditions
pulp densities, the relationship between frothing and Cu and Mo
Sample A: feed particle size P80 = 210 lm (29% +100 Tyler mesh);
recovery has also been looked into.
conditioning time = 5 min, and rougher flotation time = 7 min.
Sample B: feed particle size P80 = 150 lm (20% +100 Tyler mesh);
conditioning time = 5 min, and rougher flotation of time = 10 min.
2. Experimental material and methods
2.2.3. Froth layer thickness measurements
In this work rougher flotation tests were conducted with two These measurements were carried out in the same but modified
copper ores at laboratory flotation scale under standard industrial flotation cell without discharge of concentrate, as was described
conditions, and Cu and Mo recoveries were calculated as a function elsewhere (Castro et al., 2012a).
of pH with sea water and tap water. Subsequently, frothing exper-
iments were conducted with the same copper ores and flotation
3. Results
conditions, modifying the flotation cell and applying a digital pho-
tographical method coupled to image analysis. Froth layer thick-
3.1. Rougher flotation tests
ness and mass of water transferred to the froth volume were
measured as a function of pH and solids content, with sea water
Figs. 1 and 2 show flotation results obtained with two different
and fresh water.
chalcopyritic Cu–Mo ore samples floated in fresh water and sea
water. Molybdenite flotation in sea water was depressed in alka-
line solutions when pH was higher than 9.0–9.5. At the same time,
2.1. Materials
Cu recovery was only slightly reduced and was not significantly
affected by pH. As was previously discussed (Castro et al.,
2.1.1. Samples tested
2012a,b; Laskowski and Castro, 2012) in sea water, that is, in
Two chalcopyritic Cu–Mo ore samples were tested, which were around 0.6 solution of NaCl containing around 1,300 ppm Mg2+
obtained from two different Chilean copper mines. The chemical
ions, magnesium hydroxy-complexes ðMgðOHÞþ ðaqÞ Þ and colloidal
assay for both samples is given in Table 1. magnesium hydroxide precipitate (Mg(OH)2(s)). The molybdenite
depression seems to result from the adsorption of such Mg species
on the surface of molybdenite particles.
2.1.2. Flotation reagents
Sample A: The following flotation reagents were used. Collec- 3.2. Frothing measurements
tors: Matcol TC-123 (22 g/ton) (isopropyl ethyl thionocarbamate)
(Mathiesen); Sascol-95 (11 g/ton) (n-butanol and pentanol iso- As Figs. 3 and 5 demonstrate (Sample A and B), at pH > 9 the
mers) (Hitech Chemicals); Diesel (10 g/ton). Frother: Matfroth- froth layer thickness measurements under rougher flotation
355 (10 g/ton) (blend of polyglycols-alkyl alcohols).
Sample B: The following flotation reagents were used. Cytec’s
100
collectors: Aero MX-7017 (26 g/ton) and Aero MX-945 (21 g/ton)
(modified thionocarbamates). Frother: MIBC (21 g/ton). 90

80

70
2.1.3. Frothing gents
Recovery, %

Methyl isobutyl carbinol (MIBC), DF-250, and Matfroth-355 60

were commercial products provided by Cytec-Chile, Moly-Cop 50
Chile S.A., and Mathiesen S.A.C., respectively.
40
A local sample of sea water (with a salinity of 3.35%) from near
%Rec. Cu (Fresh water)
Concepción City was employed. Fresh water was local tap water, 30
%Rec Mo (Fresh water)
and pH in flotation and frothing tests was adjusted with the use 20 %Rec. Cu (Sea water)
of lime. %Rec Mo (Sea water)
10

1 0
The dynamic stability factor represents the lifetime of a bubble in the froth, and is
7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
defined as the ratio of the total volume of froth at equilibrium to the volumetric gas
rate introduced into the system (Bikerman, 1973). The dynamic stability factor (R) is pH
V
expressed as R ¼ Qf ¼ Hmax
Q
A
where Vf is the foam volume, Q is the gas volumetric
flowrate and Hmax and A are the total foam height and the cross-sectional area of the Fig. 1. Cu and Mo rougher flotation recovery at laboratory scale in fresh water and
vessel. sea water as a function of pH (35% solids content, Sample A).
110 O. Ramos et al. / Minerals Engineering 53 (2013) 108–112

100 7
90
6

Froth layer thickness, cm

80
70 5
Recovery, %

60
4
50
3
40
%Rec. Cu (Fresh water)
30 2
%Rec Mo (Fresh water)
20 %Rec. Cu (Sea water)
%Rec Mo (Sea water) 1 Sea water
10 Fresh water

0 0
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
pH pH

Fig. 2. Cu and Mo rougher flotation recovery at laboratory scale in fresh water and Fig. 5. Froth layer thickness under rougher flotation conditions at laboratory scale
sea water as a function of pH (34% solids content, Sample B). as a function of pH, for fresh water and sea water (34% solids content, Sample B)
(Castro et al., 2012a).

9
1800 9
8 Froth layer thickness (Fresh water)
8
Froth layer thickness,cm

1600

Froth layer thickness, cm

Froth layer thickness (Sea water)
Weight of water (Fresh water)
Weight of water (Sea water) 7
7 1400
Mass of water, g

6
1200 5
6
1000 4
5 3
800
2
4 Sea water 600
Fresh water 1

400 0
3
8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
pH
pH
Fig. 6. Mass of water transferred to the rougher concentrate as a function of pH for
Fig. 3. Froth layer thickness under rougher flotation conditions at laboratory scale
fresh water and sea water; and a comparison with the froth layer thickness in fresh
as a function of pH, for fresh water and sea water (35% solids content, Sample A)
water and sea water as a function of pH (34% solids content, Sample B).
(Castro et al., 2012a).

8
1600 10
Froth thickness (Fresh water) 7
Froth thickness (Sea water) 9
Froth layer thickness, cm
Froth layer thickness, cm

1400 Mass of water (Fresh water)

Mass of water (Sea water) 8 6
Mass of water, g

7
1200
5
6
1000 5 4
4
800 3
3
2 2 Fresh water
600 Sea water
1 1
400 0
8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 0
0 5 10 15 20 25 30 35 40
pH
Solids content,%
Fig. 4. Mass of water transferred to the rougher concentrate as a function of pH for
fresh water and sea water; and a comparison with the froth layer thickness in fresh Fig. 7. Froth layer thickness as a function of solids content (%) for the frother
water and sea water as a function of pH (35% solids content, Sample A). Matfroth-355 in sea water (pH 9.5) and fresh water (pH 10.5) (Sample A).

conditions, are clearly lower when measured in sea water than in

fresh water. Also the amount of water transferred to the froth is low, but the frothability in sea water is similar to that in fresh
lower in sea water (Figs. 4 and 6). All these measurements were water. In fresh water a strong effect of pH is observed and the froth
carried out at 34–35% pulp densities. At pH < 9 frothability is layer thickness increases up to a maximum at around pH of 10.5.
 O. Ramos et al. / Minerals Engineering 53 (2013) 108–112 111

9 8

8 7

Froth layer thickness, cm

Froth layer thickness, cm

7
6
6
5
5
4
4
3
3
2
2 Fresh water
Fresh water
Sea water 1
1 Sea water

0 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Solids content,% Solids content, %

Fig. 8. Froth layer thickness as a function of solids content (%) for the frother DF- Fig. 11. Froth layer thickness as a function of solids content (%) for the frother MIBC
250 in sea water (pH 9.5) and fresh water (pH 10.5) (Sample A). in sea water (pH 9.0) and fresh water (pH 10.5) (Sample B).

8 Figs. 7–9 show the effect of solids content (ore Sample A) on the
froth layer thickness in rougher flotation experiments. These tests
7
were carried out with three frothers: Matfroth-355, DF-250 and
Froth layer thickness, cm

6 MIBC. Similar tests but with the ore Sample B are shown in
Fig. 10 (with DF-250) and Fig. 11 (with MIBC).
5 Results for Sample A, in absence of solid particles, show that the
foamability in sea water is higher than in fresh water, particularly
4
for polyglycol frothers. If pulp density is slightly increased, the
3 foam collapse is observed with DF-250 and Matfroth-355. This
phenomenon characterizes the foam-to-froth transition in sea
2 water. However, at higher pulp densities froth is stabilized as sol-
Fresh water ids content increases. The froth layer thickness profile shown in
1 Sea water Figs. 3 and 5 corresponds to 34% and 35% solids content, where
0 the frothability of pulps in sea water is lower than in fresh water.
0 5 10 15 20 25 30 35 40 However, at more diluted pulp densities (below 25–30%) this
Solids content,% behavior reverses and the frothability in sea water is similar or
higher than in fresh water, particularly with DF-250 and Mat-
Fig. 9. Froth layer thickness as a function of solids content (%) for the frother MIBC froth-355 (polyglycol type frothers). This behavior is of great inter-
in sea water (pH 9.5) and fresh water (pH 10.5) (Sample A).
est and it extends our results to the frothing phenomena in cleaner
and scavenger circuits, which are usually operated at lower solids
content. A similar trend was observed with Sample B, as shown in
12
Figs. 10 and 11.

10
Froth layer thickness, cm

4. Discussion
8
As Figs. 1 and 2 demonstrate flotation of molybdenite is clearly
depressed in sea water when pH is higher than 9.5. In the first
6
stage of processing Cu–Mo ores, in which Cu–Mo bulk concentrate
is produced, commonly lime is used to depress pyrite, and it has
4 been well established that any excess of calcium depresses flota-
tion of molybdenite. In this system hydrolyzing ions play a very
2 Fresh water
important role. When flotation is carried out in sea water the use
Sea water
of lime results in precipitation of magnesium hydroxide which is
0 much less soluble than calcium hydroxide. This has been shown
0 5 10 15 20 25 30 35 40 to be the main reason for poor flotation of molybdenite in sea
Solids content, % water in alkaline environment (Castro et al., 2012b). NaCl concen-
tration in sea water is about 0.6 M but it is not the high ionic
Fig. 10. Froth layer thickness as a function of solids content (%) for the frother DF- strength of sea water but the presence of secondary ions (such as
250 in sea water (pH 9.0) and fresh water (pH 10.5) (Sample B).
Mg2+ and Ca2+) that depresses flotation when pH is raised above
9.5 (Laskowski and Castro, 2012).
If profiles of Cu and Mo recovery (Figs. 1 and 2) are compared Other important factor to be considered is the charge of bub-
with the froth layer thickness (Figs. 3 and 5) as a function of pH bles, particularly when cationic hydroxy-complexes are formed
no relationship is observed. It is likely that pH 10.5, usually em- in the system. Chin and Somasundaran (1991) have shown that
ployed in rougher flotation circuits operating with process water, magnesium hydroxy-complexes and magnesium hydroxide are
is selected because of the higher frothability at this pH. characterized by a very high affinity towards the liquid/gas inter-
112 O. Ramos et al. / Minerals Engineering 53 (2013) 108–112
face. Their adsorption makes bubbles positively charged. This has
been entirely confirmed by Han et al. (2004). Eigeles and Volova
(1968) results leave no doubt that any precipitates accumulating
on the surface of bubbles affect very strongly the flotation process.
As Figs. 4 and 6 shows when pH of sea water is raised above 9.5
both frothability in the rougher flotation and the mass of water
carried out by the froth are affected. These indices are higher in
fresh water in which there is no precipitating colloidal magnesium
hydroxide and the ionic strength is lower.
Frothability is different from foamability as it is also affected
by the presence of solid particles. In this paper we did not inves-
tigate pure minerals, two samples of Cu–Mo ores were used in
our tests. Such samples contain only limited amounts of valuable
components (Cu sulfides and molybdenite), some other hydro-
phobic particles (e.g. pyrite), but the majority of the particles
are hydrophilic gangues. These tests then show how mostly
hydrophilic particles affect frothability. As Figs. 7–11 indicate, in
general, frothability increases with increasing solids content. Such
gangue particles are present in the froth mainly by an entrain-
ment mechanism. When magnesium hydroxy-complexes and col-
loidal magnesium hydroxide are present in bulk solution, bubbles
are positively charged by adsorption of these magnesium species.
This system is then likely to be very different from other flotation
systems. Tao et al. (2000) reported that (hydrophobic) coal parti-
cles can stabilize or destabilize the froth. This depended both on
the size of these particles as well as on their concentration, for in-
stance, the 100 mesh size fraction destabilized froth at lower
concentrations but stabilized it at higher concentrations. In the
case of copper ores (mostly hydrophilic particles) these phenom-
ena are different and the effect of sea water (at alkaline pH range)
becomes clearly visible only at high solids content (above 30%).
These conditions have been further studied and the results are gi-
ven in Figs. 3 and 5. As these figures demonstrate, at high solids
content (35% Sample A, Fig. 3 and 34% solids content, Sample B,
Fig. 5) only around pH 9 the frothability in fresh water and sea
water are similar. In fresh water frothability increases steeply
with pH (up to about pH 10.5), but there is no such an increase
when the tests are carried out in sea water. Apparently in envi-
ronment of 0.6 M NaCl solution containing Mg2+ (1,300 ppm)
and Ca2+ (400 ppm) when magnesium precipitates as hydroxide
there are some other counteracting phenomena that depress
frothability. Since frothability in fresh water increases with pH
these counteracting phenomena must increase too making the
frothability in sea water insensitive to pH.
5. Conclusions
Several conclusions are evident from the discussed data:
– The most important variable in the flotation of Cu–Mo ores in
sea water is pH.
– For chalcopyritic ores Cu recovery is slightly lower in sea water
than in fresh water under similar conditions over the pH range
from 7 to 12.
– Mo recovery in sea water is strongly depressed at pH higher
than 9.5, the conditions under which magnesium hydroxide
start precipitating in sea water.
– Foamability of flotation frothers is higher in sea water than in
fresh water, but it changes in the presence of solid particles.
However the frothability increase with solids content is negligi-
ble over the solids concentration range up to 20%.
– At higher solids per cent (>30%) more voluminous froth is gen-
erated in fresh water than in sea water.
– At high solids content (30–35%), frothability in fresh water is a
strong function of pH; frothability in sea water under these con-
ditions is clearly depressed when compared with frothablity in
fresh water and does not depend on pH much.
Acknowledgements
Funding for this project was provided by the CORFO-INNOVA
CHILE (Project 08CM01-18), with industrial sponsorship from:
Antofagasta Minerals, (Esperanza project); BHP Billiton, (Minera
Escondida Ltd.); Anglo American Chile (Mantos Blancos); and Teck
(Carmen de Andacollo), through AMIRA-AUSTRALIA operating Re-
search Grant P968.
References
Aktas, Z., Cilliers, J.J., Banford, A.W., 2008. Dynamic froth stability: particle size,
airflow rate and conditioning time effects. Int. J. Miner. Process. 87, 65–71.
Barbian, N., Ventura-Medina, E., Cilliers, J.J., 2003. Dynamic froth stability in froth
flotation. Miner. Eng. 16, 1111–1116.
Bikerman, J., 1973. Foams. Applied Physics and Engineering, vol. 10. Springer-
Verlag, Berlin.
Castro, S., Venegas, I., Landero, A. and Laskowski, J.S., 2010. Frothing in sea water
flotation systems. In: Proc. 25th Int. Mineral Processing Congress, IMPC-2010,
Brisbane, pp. 4039–4047.
Castro, S., Ramos, O., Cancino, J.P. and Laskowski, J.S., 2012a. Frothing in the
flotation of copper sulfide ores in sea water. In: Proc. International Symposium
on Water in Mineral Processing. The 2012 SME Annual Meeting, Seattle, USA,
pp. 211–223.
Castro, S., P. Rioseco, Laskowski, J.S., 2012b. Depression of molybdenite in sea water.
In: Proc. 26th Int. Mineral Processing Congress, IMPC-2012, New Delhi-India,
pp. 737–752.
Chin, I., Somasundaran, P., 1991. Reversal of bubble charge in multivalent inorganic
salts – effect of magnesium. J. Colloid. Interface Sci. 146, 215–218.
Eigeles, M.A., Volova M.L., 1968. Activation of air bubbles by the insoluble products
of reactions in flotation. In: Proc. 8th Int. Mineral Processing Congress,
Leningrad, vol. 2, pp. 353–364.
Han, M.Y., Ahn, H.J., Shin, M.S., Kim, E.R., 2004. The effect of divalent metal ions on
the zeta potential of bubbles. Water Sci. Technol. 50 (8), 49–56.
Kuan, S.H., Finch, J.A., 2010. Impact of talc on pulp and froth properties in F150 and
1-pentanol frother systems. Miner. Eng. 23, 1003–1009.
Laskowski, J.S., Castro S., 2012. Hydrolyzing ions in flotation circuits: sea water
flotation. In: Proc. 13th International Mineral Processing Symposium, IMPS
2012, Bodrum–Turkey, pp. 219–227.
Lekki, J., Laskowski, J.S., 1975. A new concept of frothing in flotation systems and
general classification of flotation frothers. In: Proc. 11th Int. Mineral Processing
Congress, Cagliari, pp. 427–448.
Melo, F., Laskowski, J.S., 2007. Effect of frothers and solid particles on the rate of
water transfer to froth. Int. J. Min. Proc. 84, 33–40.
Quinn, J.J., Kracht, W., Gomez, C.O., Gagnon, C., Finch, J.A., 2007. Comparing the
effect of salts and frothers (MIBC) on gas dispersion and froth properties. Miner.
Eng. 20, 1296–1302.
Tao, D., Luttrell, G.H., Yoon, R.-H., 2000. A parametric study of froth stability and its
effect on column flotation of fine particles. Int. J. Miner. Process. 59, 25–43.