Effects of Metallic Ions on the Flotation of Spodumene and Beryl

Abstract: Effects of multivalent metallic cations, such as Ca 2+ and Fe3+, on the flotation of
spodumene and beryl were studied. The results show that Fe3+ and Ca2+ exhibit efficient
activation on the flotation of spodumene and beryl. The activation of Fe3+ happens quite well
within a pH range of 6–9 while the concentration of Fe3+ is 35 mg/L. Efficient activation of Ca
2+ takes place over at a pH over 11.6 at a concentration of 140 mg/L. The zeta potential of beryl
and spodumene shifts slightly to positive values when activated by Ca2+, but markedly by Fe3+.
New stretching frequencies of 1594.24 cm–1 and 1587.13 cm–1 have been found in the FTIR
spectra of the two minerals after their interaction with Fe3+ and the collector. These new
stretching frequencies are the asymmetric stretching frequencies of COO– (carboxyl anion), so
thecollector may be chemically absorbed on the surface of Fe 3+-activated beryl and
spodumene.

1. Introduction

Spodumene is a silicate with a single-chain structure where Li-O bonds are weaker than Al-O
bonds. Consequently, the number of broken Li-O bonds and exposed Li + are dominant on the
broken planes of spodumene. The large ionic radius and the small ion charges of Li+ lead to
weak adsorption of anionic collectors. Beryl is a ring-chain structured silicate and the main
broken bonds are Al-O and Be-O on the broken planes of beryl, so there are many Al3+ and
Be2+ on the surface of beryl. These metallic surface sites are favorable for the adsorption of
anionic collectors on the surface of beryl [1–5].

In a study,investigations of surface chemistry have been carried out for the oleate–spodumene
system. The adsorption interaction of oleate on spodumene turns out to be the chemisorption
that involves the chemical reaction between the carboxylate group of oleate and the cationic
Al sites on the surface of spodumene. The surface aluminum sites at the {110} cleavage plane
of spodumene are largely preferred compared with those at other crystal planes for
chemisorption of the carboxylic group in oleate collectors[6].

The flotation separation of beryl from spodumene was affected by the presence of Ca2+ and
Fe3+ in the flotation pulp, thus NaOH, Na2CO3 and Na2S were used as regulators to complete
the flotation separation of beryl from spodumene. The speciesof CO3 2– show a stronger
depression on spodumene than on beryl while using Ca 2+ as activator and after the activation
of Fe3+, Na2S shows a stronger depression on spodumene [7]. The zeta potentials of spodumene
and beryl have also been changed markedly by the addition of Fe3+ instead of the addition of
Ca 2+ [8]. The adsorption properties of calcium ions on clay particle surfaces (such as kaolin and
montmorillonite) in coal slurry were studied. Experimental results show that the hydroxy
complex, Ca(OH)2 precipitation and ion electrostatic adsorption are the three possible
adsorption forms of calcium ions on sample surfaces[9]. In this study, investigations on the
floatability of spodumene and beryl will be carried out both in the absence and presence of Fe3+
and Ca2+. The reaction mechanisms will be studied as well.
2. Experimental

2.1. Materials and reagents

Pure mineral samples of spodumene and beryl were supplied by the XingJiang
Keketuohai Rare Metal Mine. The chemical compositions of spodumene and beryl are
presented in Table 1. Three mineral samples were hand-picked and ground by a
porcelain mill with an agate ball and screened to － 0.12+0.038 mm. A dilute
hydrochloric solution of a 0.3% concentration was used to remove the impurities on the
surface of the samples. The samples were washed using distilled water until it reached
the natural pH.

FeCl3·6H2O and CaCl2 with analytical grade were used as activators. NaOH and HCl were
used to control the pulp pH. A mixture of collectors, which contained 75% oleic acid and
25% dodecyl amine, was adopted as the collector in the micro-flotation tests.

2.2. Micro-flotation tests

Micro-flotation tests were performed on a laboratory flotation machine with 30 mL

cellat 1 600 rpm. Distilled water and pure mineral samples of 5 g were used in each test.
The pulp was stirred for 1 min with a pH regulator, 1 min with an activator and 2 min
with the collector. The flotation time was 3 min. The flotation products were filtrated,
dried and weighed for the recovery calculation.

2.3. Zeta potential measurements

Zeta potentials were measured by using a Brookhaven Zeta plus zeta meter (USA). The
mineral samples were ground to 0–5 µm in an agate mortar. The suspensions with 0.05%
concentration (mass fraction) were dispersed in a beaker for 15 min and then the pH
values of the suspensions were measured. The average values of three measurements
were adopted as the measurement results of zeta potential .

2.4. FTIR spectroscopy

A single beam Fourier Transform Infrared (FTIR750) spectrophotometer, called Nicolet,

was used to study the mechanism of reagents and minerals. The samples were ground
to －2 µm and mixed with a suitable concentration of FeCl3 and the collector and air-
dried at a room temperature of 22 ℃.
 3. Results and Discussion
3.1. Micro-flotation of minerals
Fig. 1 shows the dependence of mineral recovery as a function of pH with a collector
concentration at 200 mg/L. It is seen that the flotation of beryl and spodumene reach
maximum values at a pH of 3.5 and 2.8, respectively. It is also noted from Table 1 that
the content of Fe2O3 in both minerals is about 0.5%– 0.6%. This flotation peak of both
minerals is possibly related to the electrostatic adsorption of dodecyl amine and the
interaction of oleic acid and ferric impurities [6].The flotation of these two minerals
reduces to a very low level within a pH range of 6–10.

Fig. 1 Recovery of minerals as a function of pH with a 200 mg/L collector

Spodumene and beryl samples were strongly stirred for 8 min in a solution of 200 mg/L NaOH.
The pulp was allowed to settle for 5 min and the upper liquid was removed. The flotation of
the settlement products with the collector concentration of 160 mg/L was then carried out.
The results are shown in Fig. 2.

Fig. 2 Recovery of minerals as a function of pH with a 160 mg/L collector after alkaline leaching
The results in Fig. 2 reveal that the floatability of spodumene and beryl have been improved in
the alkaline pH region after alkaline leaching, even though the dosage of the collector had been
cut by 40 mg/L. These results indicate that the aluminum sites were brought to the surface by
alkaline leaching. The adsorption of oleic acid was enhanced [3,6] . Since the surface metallic
sites, such as Al, Be and Fe, benefit the flotation of spodumene and beryl [1–5,7–8] , Ca2+ and
Fe3+ were used in the flotation of spodumene and beryl. The results are presented in Fig. 3. It
is noteworthy that Fe3+ and Ca2+ show different activation effects on the flotation of
spodumene and beryl. Fe3+ provides the optimal activation between pH of 6 and 9 (see Fig. 3c).
However, the most efficient activation of Ca2+ occurs when the pH is over 11.6 (as shown in Fig.
3a). It is well know that the key species of Fe3+ is the solid phase of Fe(OH)3 between pH 6 and
9 and the main species of Ca2+ are the CaOH+ , the aqueous and the solid phase of Ca(OH)2
when the pH is over 11.6 [9]. From Fig. 3b and d, it is clear that Fe3+ and Ca2+ show adequate
activation on beryl at concentrations of about 7.5 mg/L and 60 mg/L, respectively. The optimal
activation concentration of Fe3+ for spodumene is about 35 mg/L, but Ca 2+ appears to activate
the spodumene adequately while its concentration is 140 mg/L.

a) As a function of PH with 140 mg/L CaCl2 and a 200 mg/L collector

b) As a function of CaCl2 concentration with a 200 mg/L collector at 11.6 ph
c) As a function of ph with 40 mg/L FeCl3.6h2o and a 200mg/L collector
d) As a function of FeCl3. 6H2O concentration with a 200 mg/L collector at 7.5Ph

3.2 Effects of washing on the flotation

Washing tests have been carried out to investigate the change of floatability of both
minerals while they were activated by Fe3+ and Ca2+. After the activation by Fe3+ or
Ca2+, the pulp was allowed to settle for 1 min and the upper liquid was decanted,
after which distilled water was added and stirred for 1 min. The pulp was also allowed
to settle for 1 min and the up per liquid was decanted. This procedure is called
‘washing once’. ‘Washing twice’ and ‘washing thrice’ were done by analogy.
FeCl3·6H2O was used at a concentration of 35 mg/L at a pH of 7.5, while CaCl2 was
used with a concentration of 140 mg/L at a pH of 11.6. Flotation of the settlements
was then carried out with the addition of a 200 mg/L collector. The results are
presented in Fig. 4.
 Fig. 4 Effect of washing on the flotation of beryl and spodumene

It can be observed that the floatability of the two minerals decreases rapidly after washing when
the minerals were activated by Ca2+. The flotation recovery of beryl and spodumene falls to a
non-activated level after washing thrice. In contrast, the floatability of the two minerals was not
markedly affected after the washing while the minerals were activated by Fe3+. These results
show that the activation of Fe3+ for the two minerals is more lasting than that of Ca 2+. Maybe
the carbon dioxide in the air will precipitate Ca2+, but this should not be the key factor under
our test conditions because carbon dioxide is rare in the air. As mentioned above, the effective
species of Fe3+ is the solid phase of Fe(OH)3 and the key species of

Ca2+ are CaOH+ , the aqueous and solid phases of Ca(OH)2 under the tests conditions. The first
hydroxyl complexes of metal ions, such as CaOH+ , suggest that they interact with silicate
minerals through the bonding with one oxygen atom, but hydroxides of metal ions, such as
Fe(OH)3, will interact with silicates in the form of bonding with two oxygen atoms, so the
adsorption of the metal ion hydroxides, such as Fe(OH)3, is firmer than that of the first hydroxyl
complexes, such as CaOH+ [10]. It is to be noted that the Ksp of Ca(OH)2 and Fe(OH)3 are about
1×10–5.19 and 1×10–38.8 , respectively, so the Ca(OH)2 is expected to dissolve much more
readily than that of Fe(OH)3 [10].

3.3 Zeta potential measurement

The zeta potential of minerals as a function of pH in distilled water is presented in Fig. 5. This
figure clearly shows that the surface charge on beryl and spodumene reverses its sign at a pH of
2.76 and 2.68, respectively. The surface charges of the two minerals are negative in the pH range
of 3 to 12. These results are in agreement with other studies [11–13] .

From Fig. 5, it can also be seen that the zeta potential of the two minerals shifts slightly to
positive values when they are activated by 140 mg/L CaCl2. However, the zeta potential of the
two minerals dramatically shifts to positive values when they are activated by 35 mg/L
FeCl3·6H2O. The sign of zeta potential of both minerals reversed at a pH of 6.8 for spodumene
and at pH 8.6 for beryl. It is interesting to note that these two pH values correspond to the PZC
of Fe(OH)3 [10].
 Fig. 5 Zeta potential of beryl and spodumene as a function of pH

In the presence of Fe3+ and the collector, the zeta potential of beryl was also measured and this
result is also presented in Fig. 5. It can be seen that the zeta potential of beryl has been changed
slightly in the presence of the collector without the addition of Fe3+. This may be due to small
exposed surface metal sites, such as Al and Be, which has been discussed earlier. On the other
hand, the zeta potential of beryl has been changed greatly with the same collector after the
activation of Fe3+. This indicates that the interaction between collector and minerals may be
the chemical adsorption through the species of Fe3+ adsorbed on the surface of the minerals.

3.4. FTIR spectroscopy

The infrared spectra of spodumene and beryl under different conditions are presented in Fig. 6a
and b.

(a) Spodumene
(b) Beryl
 Fig. 6 Infrared spectra of spodumene and beryl samples

The infrared spectra of the two minerals which interacted with the collector are different
from those of natural minerals. The new bands of 2 934.78 cm –1 and 2 860.87 cm–1 for
spodumene, 2 928.18 cm–1 and 2 850.92 cm–1 for beryl can be found in their infrared
spectra. The peaks are, respectively, the CH2 and CH3 stretching frequencies.

Peaks of 2 928.99 cm–1 and 2 843.48 cm –1 for spodumene, 2 927.27 cm –1 and 2 858.42
cm –1 for beryl can also be observed in the infrared spectra of the two minerals after they
interacted with Fe3+ and the collector. They are also CH2 and CH3 stretching frequencies.
At the same time, there are new bands at 1 594.24 cm –1 for spodumene and 1 587.13 cm
–1 for beryl in their infrared spectra. These two bands are the asymmetric stretching
frequencies of －COO– . These indicate that the collector may be chemically absorbed on
Fe3+-activated spodumene and beryl.

4. Conclusions

1) The floatability of spodumene and beryl is very poor while using the collector mixture at a
neutral and alkaline pH. But the floatability of the two minerals improved under the same pH
range after alkaline leaching.

2) Fe3+ and Ca 2+ show a good activation on the flotation of spodumene and beryl. The best
activation of Fe3+ appears in a pH range of 6–9, while the most efficient activation of Ca2+
occurs in the region of pH ＞11.6. Fe3+ shows adequate activation on both minerals at a low
concentration of about 35 mg/L, but Ca2+ cannot activate the minerals adequately until its
concentration is high enough at about 140 mg/L.

3) The zeta potential of beryl and spodumene shifts slightly to positive values when they are
activated by Ca2+ and markedly so by Fe3+. The floatability of the two minerals decreased
rapidly after washing while the minerals were activated by Ca 2+, but in the case of Fe3+, the
floatability of the two minerals has not been markedly affected by washing. This indicates that
the activation of Fe3+ is more lasting than that of Ca2+ for both minerals.

4) New stretching frequencies of 1 594.24 cm –1 for spodumene and 1 587.13 cm –1 for beryl
were found to be the asymmetric stretching frequencies of －COO– , which means that we can
presume that the collector mixture may be chemically absorbed on the Fe3+ activated beryl
and spodumene.