Minerals Engineering 109 (2017) 10–13

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Minerals Engineering

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Short communication

The impact of seawater with calcium and magnesium removal for the flotation of
copper-molybdenum sulphide ores
a,⇑ a c a,b b
Ricardo I. Jeldres , María P. Arancibia-Bravo , Arturo Reyes , Claudia E. Aguirre , Lorena Cortes , Luis A.
a
Cisternas
aDept. of Chemical Engineering and Mineral Process, Universidad de Antofagasta, Antofagasta, Chile
b Csiro-Chile International Center of Excellence, 2827 Apoquindo Street, 12th floor, Las Condes, Santiago, Chile
c Centro de Investigación Científico Tecnológico para la Minería (CICITEM), Antofagasta, Chile

article info abstract

Article history: The use of seawater in the flotation of copper-molybdenum sulphide ores is becoming increasingly important. However, the
Received 7 October 2016 Revised complex chemistry by the presence of calcium and magnesium hydroxyl-complexes interferes with the recovery of
19 December 2016 Accepted 4 molybdenite. This study analyzes the impact of pre-treated seawater with calcium and magnesium removal on the floatability
February 2017 Available online 1
of copper-molybdenum sulphide ores. The pretreatment was carried out by a mixture of Na 2CO3 and CaO, which promotes the
March 2017
precipitation of calcium and magnesium ions. Three different conditions were compared, (i) flotation in seawater at pH 11.5;
(ii) flotation in pretreated seawater with calcium and magnesium removal at pH 11.5; and (iii) flota-tion in seawater at natural
Keywords: pH, i.e. pH 7.6. While the copper recovery was similar in all cases, the recov-ery of molybdenum at high alkaline condition
Calcium and magnesium removal was notably increased when seawater harness was reduced. On the other hand, a high pyrite depression was reached because
Copper-molybdenum sulphide ores
Seawater flotation the oxidizing atmosphere at pH 11.5 allows Fe(OH)3 formation.

2017 Elsevier Ltd. All rights reserved.

1. Introduction associated increased gas hold-up in flotation systems (Quinn et al., 2007).

Regarding the increased scarcity of water that mining compa-nies are
facing, the use of seawater in flotation processes is becom-ing increasingly
important (Cisternas and Moreno, 2014), and its efficient use has become one
of the challenges for the Chilean min-ing industry (Cisternas and Gálvez,
2014). The presence of a high saline environment caused by seawater
inevitably brought about some adversities, including lower efficiency in
flotation stages. However, it has been demonstrated that salinity is not
detrimental by itself on flotation operations, but rather it is beneficial for the
recovery of some minerals. Lucay et al. (2015) showed that floata-bility of
molybdenite is significantly improved in concentrated NaCl solutions due to
ions reduce the electrostatic repulsion between bubbles and the anionic edges
of molybdenite. Besides, Troncoso et al. (2014) showed that the contact angle
of some min-erals might increase with the electrolyte concentration and ions
valence. Another positive effect of saline environment is that inter-facial air-
liquid films may be stabilised by the presence of certain inorganic salts,
owing to inhibition of bubble coalescence and the
However, Laskowski and Castro (2012) showed that at high pH (pH > 10),
the flotation of molybdenite is very sensitive to magne-sium hydroxyl-
complexes and colloidal magnesium hydroxide. It could be explained because
+
MgOH (aq) absorbs onto molybdenite surface and then the precipitation of
colloidal Mg(OH)2(s) may form a hydrophilic coating that reduces its
floatability.
Additionally, calcium also has negative impacts on flotation. This might
2+
be explained by: gypsum precipitation from calcium ions (Ca ) and sulphate
2
ions (SO4 ) on the faces of particles; the contact angle of particles decreases
when calcium ions are adsorbed onto the edges and micro-edges of
molybdenite; the adsorption of calcium ions on molybdenite and quartz may
cause heterocoagulation; and the precipitation of calcium hydroxide at pH >
10 seems to counteract xanthate adsorption, decreasing the mineral
hydrophobicity (Lucay et al., 2015; Dávila-Pulido et al., 2015). Thus, it is
expected that molybdenite recovery is sensitive to the presence of lime (CaO)
which in the flotation of Cu-Mo sul-phide ores is commonly used to depress
pyrite where the best range has been observed between pH 10–12.

⇑ Corresponding author.
Poor floatability of molybdenite due to calcium and
E-mail address: jeldresresearch@gmail.com (R.I. Jeldres). magnesium compound and the increased lime consumption
http://dx.doi.org/10.1016/j.mineng.2017.02.003 0892-6875/ have been claimed
2017 Elsevier Ltd. All rights reserved.
 R.I. Jeldres et al. / Minerals Engineering 109 (2017) 10–13 11

as the biggest challenges in Cu-Mo sulphide ores flotation in sea-water 2.3. Flotation procedure
(Castro, 2012) and new methods are required to reach high recoveries of both
copper and molybdenum with an appropriated separation of gangue iron Ores were ground in a ceramic mill for 11.9 min getting a P 80 < 170 lm
sulphides. For a complete review of the use of seawater in flotation see
particle size. The ground samples were transferred into a batch cell and made
Jeldres et al. (2016) and for a resume of main papers see Supplementary
up to a volume of 2750 ml for each test, giving a 30 wt% flotation pulp
material. In this sense, the aim of this study is to analyze the flotation of Cu-
density. All reagents were added 5 min before flotation and mixed at a
Mo sulphide minerals in seawater with calcium and magnesium removal.
constant rate. Flotation gas was air at a flow rate of 8 L/min. The froth was
Seawater pretreatment is carried out by a mixture of CaO and Na 2-CO3, scraped every 10 s during the test. Adsorption atomic spectroscopy
which promotes Ca and Mg ions precipitation. The main chemical reactions determined the composition of the flotation concentrates.
that occur in seawater include the speciation of CO 2, speciation of Mg and
Ca, and salts precipitation, which are included in Supplementary material.

3. Results and discussion

3.1. Ca and Mg removal

2. Methodology
2.1. Materials
Seawater from the coast of Antofagasta (Chile) was used (its composition
in Ramos, 2013). The copper-molybdenum sulphide ores were acquired from
local mining, where a chemical analysis indicated that the elemental
composition was: Cu: 0.55%, Mo: 0.010%, Fe: 4.26%. Oxiquim S.A. (a
chemical industry in Antofa-gasta) provided the reagents, as follow Oxi-2650
(primary xanthate collector, 45 gpt), Oxi-41 (secondary dithiophosphate
collector, 22 gpt), and Oxi-92 (frother, 30 gpt).
2.2. Seawater pretreatment: Ca and Mg removal
The seawater pretreatment consists of Ca and Mg ions removal, promoted
by the Na2CO3 and CaO addition. For this work, 0.05 M of each reagent was
used giving a global concentration of 0.1 M. The reagents were poured into
seawater and then mixed for 30 min at room temperature. Vacuum filtration
separated Mg and Ca ions precipitates and then the filtered seawater was used
for the flota-tion tests. The Ca and Mg concentration was measured by induc-
tively coupled plasma mass spectrometry (ICP-MS).
The experiments were carried out by adding two reagents: CaO and
Na2CO3. Results are shown in Fig. 1, which correspond to the average of
duplicate experiments. Also, the standard deviation is incorporated.
Lime (CaO) is a promoter of magnesium precipitation since its
concentration in seawater was reduced from 1280 ppm to 10 ppm after
applying 0.1 M of CaO, but as it was expected, cal-cium concentration was
vastly increased (Fig. 1a). The precipita-tion of magnesium happens because
lime is an alkalinizing reagent that leads to the formation of calcium and
magnesium hydroxides as indicated among possible salt precipitation
reactions in Appendix. On the other hand, sodium carbonate (Na2CO3) is use-
ful to precipitate calcium, but the reduction of magnesium is con-servative
(Fig. 1b). This shows that calcium carbonate is more liable to the precipitation
than magnesium carbonate. Fig. 1c illus-trates the effect of adding CaO-
Na2CO3 mixtures at different pro-portions on the removed amount of calcium
and magnesium from seawater. For the subsequent flotation testing, it was
chosen a combination of both reagents (50–50%), giving a global concen-
tration of 0.1 M. Consequently, it avoids the excess of calcium and
magnesium, where their final concentrations were 176 ppm and 190 ppm
respectively.
concentration [ppm]

Ca, 3000 1400 Ca

Mg 2500 Ca 1200 Mg
conc 2000 Mg 1000
entra 800
1500
tion
600
[ppm]
1000 400
500 200 b)
Mg

0
Ca,

0
0,00 0,02 0,04 0,06 0,08 0,10 0,00 0,02 0,04 0,06 0,08 0,10

CaO [M]
Na2CO3 [M]
[ppm]

1600 Ca in pretreated seawater

1400
concentration

Mg in pretreated seawater
400

1200 Ca in seawater
1000 Mg in seawater

800
600
Mg

200 c)
Ca,

0
0,0 0,2 0,4 0,6 0,8 1,0

%CaO

Fig. 1. Impact of different alkalizing reagents addition on the calcium and magnesium concentration in treated seawater: (a) impact of CaO; (b) impact of Na 2CO3; (c) impact
of CaO/Na2CO3 ratio (global concentration: 0.05 M).
12 R.I. Jeldres et al. / Minerals Engineering 109 (2017) 10–13

100 100
a) b)
80 80

Mo recovery (%)
Cu
recov 60 60

ery 40 40
(%)
20 20

0 0

0 2 4 6 8 10 12 0 2 4 6 8 10 12
Time (min) Time (min)
100
c) Test 1: Seawater at pH 11.5
(%)

80
Test 2: Pretreated seawater at pH 11.5
20
Test 3: Seawater at pH 7.6
Ferecovery

60
40

0
0 2 4 6 8 10 12
Time (min)

Fig. 2. Impact of seawater condition on the cumulative mineral recovery: (a) copper, (b) molybdenum, (c) iron.

3.2. Flotation in seawater 4. Conclusions

Fig. 2a shows cumulative copper recovery versus time. After 12 min, the
maximum recoveries are similar in all cases, but some differences were found
in the flotation kinetics. Fig. 2b shows that Mo recovery, reached by test 2,
was 73.1% which is much higher than test 1 (12.7%). The main reason is that
Ca and Mg were mostly removed from seawater reducing the formation of
hydroxyl-complexes, sulphates, and carbonates (Fig. 1). As it was previously
mentioned, at high pH these complexes added to molybdenite sur-face
decreased its floatability. Besides, pH was incremented by using NaOH
instead of lime avoiding the addition of extra calcium to the suspension.
Moreover, pretreated seawater still contains 176 ppm of Ca and 190 ppm of
Mg. This amount eventually could be diminished by using different CaO-
Na2CO3 proportions.
Fig. 2c shows the pH importance on pyrite depression. For test 3,
performed in seawater at pH 7.6, the lowest Fe depression was obtained
(recovery: 34.5%), whereas the highest was reached in seawater at pH 11.5
(test1, 7.3%). It is due to the oxidizing atmo-sphere at the high alkaline
condition. The intermediate amount was achieved with pretreated seawater at
high alkaline condition (test 2, 22.9%).
Promising results have been found by using seawater in flota-tion without
desalination due to the high Mo recovery and pyrite depression, which can be
obtained just removing Ca and Mg ions by a mixture of Na 2CO3 and CaO.
Moreover, these results eventu-ally might be optimized through improving Ca
and Mg removal by testing combinations of CaO-Na2CO3 at different
proportions and also NaOH could be incorporated in the pretreatment. How-
ever, there is no consensus on this matter since there are some reports in
which the results are apparently contradictory. For example, Hirajima et al.
(2016) found that both MgCl2 and CaCl2 reduced the floatability of
molybdenite and chalcopyrite at pH > 9. Nagaraj and Farinato (2014) showed
similar detrimental effects of MgCl2 on the floatability of molybdenite, but
CaCl2 was reported to have no significant effect. Probably, the differences
could be explained by the selected reagents, and that behaviour might be a
function of the ore used in the tests.
Rougher flotation of Cu-Mo sulphide ores was carried out in three
separate environments: (i) test 1: flotation in seawater at high alkaline
condition (pH 11.5); (ii) test 2: flotation in pretreated seawater at pH 11.5; and
(iii) test 3: flotation in seawater at natural pH. The main conclusions are
mentioned below:
High copper and molybdenum recoveries can be achieved at the high
alkaline condition when the seawater hardness is reduced.
A high pyrite depression can be reached at pH 11.5 using pre-treated
seawater. This is due to the oxidizing atmosphere at the high alkaline
condition.
Acknowledgements
Authors thank INNOVA CORFO Projects Csiro Chile 10CEII-9007.
Appendix A. Supplementary maerial
Further information about the research on seawater flotation and
modelling of the data provided in this manuscript are included in the
supplementary material. Supplementary data associated with this article can
be found, in the online version, at http://
dx.doi.org/10.1016/j.mineng.2017.02.003.
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