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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.

Three mineral samples were hand-picked and ground by a porcelain mill with an agate ball and screened to - 0. FeCl3·6H2O and CaCl2 with analytical grade were used as activators.3.4. Experimental 2. Materials and reagents Pure mineral samples of spodumene and beryl were supplied by the XingJiang Keketuohai Rare Metal Mine. Zeta potential measurements Zeta potentials were measured by using a Brookhaven Zeta plus zeta meter (USA).3% concentration was used to remove the impurities on the surface of the samples. The mineral samples were ground to 0–5 µm in an agate mortar. . which contained 75% oleic acid and 25% dodecyl amine. FTIR spectroscopy A single beam Fourier Transform Infrared (FTIR750) spectrophotometer. Micro-flotation tests Micro-flotation tests were performed on a laboratory flotation machine with 30 mL cellat 1 600 rpm. dried and weighed for the recovery calculation.2. 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 ℃. 2. 1 min with an activator and 2 min with the collector. The pulp was stirred for 1 min with a pH regulator. The average values of three measurements were adopted as the measurement results of zeta potential . The suspensions with 0. The flotation time was 3 min. NaOH and HCl were used to control the pulp pH. was used to study the mechanism of reagents and minerals. was adopted as the collector in the micro-flotation tests. Distilled water and pure mineral samples of 5 g were used in each test. 2. A mixture of collectors. A dilute hydrochloric solution of a 0.05% concentration (mass fraction) were dispersed in a beaker for 15 min and then the pH values of the suspensions were measured. called Nicolet.12+0.2. 2. The chemical compositions of spodumene and beryl are presented in Table 1.038 mm.1. The samples were washed using distilled water until it reached the natural pH. The flotation products were filtrated.

8. Fig. The pulp was allowed to settle for 5 min and the upper liquid was removed. 3.6%.The flotation of these two minerals reduces to a very low level within a pH range of 6–10. It is seen that the flotation of beryl and spodumene reach maximum values at a pH of 3. Results and Discussion 3. 2.5%– 0. Micro-flotation of minerals Fig. Fig.1. 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]. 1 shows the dependence of mineral recovery as a function of pH with a collector concentration at 200 mg/L. 2 Recovery of minerals as a function of pH with a 160 mg/L collector after alkaline leaching . 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 results are shown in Fig. respectively.5 and 2. It is also noted from Table 1 that the content of Fe2O3 in both minerals is about 0. The flotation of the settlement products with the collector concentration of 160 mg/L was then carried out.

even though the dosage of the collector had been cut by 40 mg/L. Be and Fe. such as Al.6. The pulp was also allowed to settle for 1 min and the up per liquid was decanted. The optimal activation concentration of Fe3+ for spodumene is about 35 mg/L. benefit the flotation of spodumene and beryl [1–5. while CaCl2 was used with a concentration of 140 mg/L at a pH of 11.6 [9]. 3. It is noteworthy that Fe3+ and Ca2+ show different activation effects on the flotation of spodumene and beryl. but Ca 2+ appears to activate the spodumene adequately while its concentration is 140 mg/L. Fe3+ provides the optimal activation between pH of 6 and 9 (see Fig. 3b and d. respectively. the most efficient activation of Ca2+ occurs when the pH is over 11. The results are presented in Fig. From Fig. 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 pulp was allowed to settle for 1 min and the upper liquid was decanted.5. ‘Washing twice’ and ‘washing thrice’ were done by analogy.The results in Fig. This procedure is called ‘washing once’. the aqueous and the solid phase of Ca(OH)2 when the pH is over 11. After the activation by Fe3+ or Ca2+. . 3c).7–8] . Ca2+ and Fe3+ were used in the flotation of spodumene and beryl.6 (as shown in Fig.5 mg/L and 60 mg/L. However.6] . Flotation of the settlements was then carried out with the addition of a 200 mg/L collector. 3a). it is clear that Fe3+ and Ca2+ show adequate activation on beryl at concentrations of about 7. These results indicate that the aluminum sites were brought to the surface by alkaline leaching. 4. Since the surface metallic sites. 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. after which distilled water was added and stirred for 1 min. The results are presented in Fig. The adsorption of oleic acid was enhanced [3.6 ph c) As a function of ph with 40 mg/L FeCl3.5Ph 3.6h2o and a 200mg/L collector d) As a function of FeCl3. 6H2O concentration with a 200 mg/L collector at 7. FeCl3·6H2O was used at a concentration of 35 mg/L at a pH of 7. 2 reveal that the floatability of spodumene and beryl have been improved in the alkaline pH region after alkaline leaching.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+.

It is interesting to note that these two pH values correspond to the PZC of Fe(OH)3 [10]. so the Ca(OH)2 is expected to dissolve much more readily than that of Fe(OH)3 [10]. the floatability of the two minerals was not markedly affected after the washing while the minerals were activated by Fe3+. 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. the aqueous and solid phases of Ca(OH)2 under the tests conditions. such as CaOH+ . the zeta potential of the two minerals dramatically shifts to positive values when they are activated by 35 mg/L FeCl3·6H2O. respectively. The flotation recovery of beryl and spodumene falls to a non-activated level after washing thrice. Fig. but this should not be the key factor under our test conditions because carbon dioxide is rare in the air. . 3. These results show that the activation of Fe3+ for the two minerals is more lasting than that of Ca 2+. These results are in agreement with other studies [11–13] . The surface charges of the two minerals are negative in the pH range of 3 to 12. As mentioned above. 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+. However. The first hydroxyl complexes of metal ions.19 and 1×10–38. 5. will interact with silicates in the form of bonding with two oxygen atoms. such as Fe(OH)3.3 Zeta potential measurement The zeta potential of minerals as a function of pH in distilled water is presented in Fig. such as Fe(OH)3. such as CaOH+ [10]. Maybe the carbon dioxide in the air will precipitate Ca2+. is firmer than that of the first hydroxyl complexes. In contrast.8 . the effective species of Fe3+ is the solid phase of Fe(OH)3 and the key species of Ca2+ are CaOH+ . respectively. 5.68.8 for spodumene and at pH 8. so the adsorption of the metal ion hydroxides. From Fig. but hydroxides of metal ions. The sign of zeta potential of both minerals reversed at a pH of 6.6 for beryl. suggest that they interact with silicate minerals through the bonding with one oxygen atom.76 and 2. It is to be noted that the Ksp of Ca(OH)2 and Fe(OH)3 are about 1×10–5. This figure clearly shows that the surface charge on beryl and spodumene reverses its sign at a pH of 2.

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.4. This may be due to small exposed surface metal sites. On the other hand. 5. Fig. 3. which has been discussed earlier. 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 has been changed greatly with the same collector after the activation of Fe3+. FTIR spectroscopy The infrared spectra of spodumene and beryl under different conditions are presented in Fig. 6a and b. (a) Spodumene (b) Beryl . such as Al and Be. 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+. the zeta potential of beryl was also measured and this result is also presented in Fig.

92 cm–1 for beryl can be found in their infrared spectra.13 cm –1 for beryl in their infrared spectra. .78 cm –1 and 2 860. The new bands of 2 934.18 cm–1 and 2 850. The best activation of Fe3+ appears in a pH range of 6–9.6. 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.24 cm –1 for spodumene and 1 587. Conclusions 1) The floatability of spodumene and beryl is very poor while using the collector mixture at a neutral and alkaline pH. the floatability of the two minerals has not been markedly affected by washing.13 cm –1 for beryl were found to be the asymmetric stretching frequencies of -COO– . Peaks of 2 928. 2) Fe3+ and Ca 2+ show a good activation on the flotation of spodumene and beryl. but Ca2+ cannot activate the minerals adequately until its concentration is high enough at about 140 mg/L. 4) New stretching frequencies of 1 594.27 cm –1 and 2 858. Fig. 2 927. They are also CH2 and CH3 stretching frequencies. 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 CH2 and CH3 stretching frequencies. This indicates that the activation of Fe3+ is more lasting than that of Ca2+ for both minerals. there are new bands at 1 594. 4.24 cm –1 for spodumene and 1 587. The peaks are.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. The floatability of the two minerals decreased rapidly after washing while the minerals were activated by Ca 2+. These two bands are the asymmetric stretching frequencies of -COO– .48 cm –1 for spodumene.87 cm–1 for spodumene. 2 928. But the floatability of the two minerals improved under the same pH range after alkaline leaching.99 cm–1 and 2 843. but in the case of Fe3+. These indicate that the collector may be chemically absorbed on Fe3+-activated spodumene and beryl. respectively. which means that we can presume that the collector mixture may be chemically absorbed on the Fe3+ activated beryl and spodumene. while the most efficient activation of Ca2+ occurs in the region of pH >11. At the same time. Fe3+ shows adequate activation on both minerals at a low concentration of about 35 mg/L.