Mar.

2007

Journal of China University of Mining & Technology

Vol.17

No.1

J China Univ Mining & Technol 2007, 17(1): 00350039

Effects of Metallic Ions on the Flotation of Spodumene and Beryl

WANG Yu-hua, YU Fu-shun
School of Resources Processing and Bioengineering, Central South University, Changsha, Hunan 410083, China Abstract: Effects of multivalent metallic cations, such as Ca2+ 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 69 while the concentration of Fe3+ is 35 mg/L. Efficient activation of Ca2+ 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 cm1 and 1587.13 cm1 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 Fe3+-activated beryl and spodumene. Key words: spodumene; beryl; metallic ions; activation; flotation CLC number: TD 923

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 [15]. In a study,investigations of surface chemistry have been carried out for the oleatespodumene 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 Ca2+ 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 Ca2+ [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
2.1

Experimental
Materials and reagents

Pure mineral samples of spodumene and beryl were supplied by the XingJiang Keketuohai Rare

Received 16 August 2006; accepted 05 October 2006 Project 2005CB623701 supported by the National Key Basic Research & Development Program (973) of China Corresponding author. Tel: +86-731-8830545; E-mail address: wangyh@mail.csu.edu.cn

36

Journal of China University of Mining & Technology

Vol.17

No.1

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.
Table 1
Minerals Spodumeme Beryl

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 610.

Chemical compositions of pure minerals (%)

BeO 0.028 12.143 Li2O 7.81 0.10 SiO2 62.74 65.25 Al2O3 25.99 17.17 Fe2O3 0.54 0.63 CaO 0.36 0.37

FeCl36H2O 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

Fig. 1

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

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

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.

Zeta potentials were measured by using a Brookhaven Zeta plus zeta meter (USA). The mineral samples were ground to 05 m 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

Fig. 2

Recovery of minerals as a function of pH with a 160 mg/L collector after alkaline leaching

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 m and mixed with a suitable concentration of FeCl3 and the collector and air-dried at a room temperature of 22 .

3
3.1

Results and Discussion

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

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[15,78], 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

WANG Yu-hua et al

Effects of Metallic Ions on the Flotation of Spodumene and Beryl

37

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 Ca2+ appears to activate the spodumene adequately while its concentration is 140 mg/L.

Fig. 3

Recovery of minerals under different conditions

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. FeCl36H2O 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.

(a) Beryl

(b) Spodumene

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 Ca2+. 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

38

Journal of China University of Mining & Technology

Vol.17

No.1

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 1105.19 and 11038.8 , 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 [1113]. 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 FeCl36H2O. 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) Bery1

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 cm1

and 2 860.87 cm1 for spodumene, 2 928.18 cm1 and 2 850.92 cm1 for beryl can be found in their infrared spectra. The peaks are, respectively, the CH2 and CH3

WANG Yu-hua et al

Effects of Metallic Ions on the Flotation of Spodumene and Beryl

39

stretching frequencies. Peaks of 2 928.99 cm1 and 2 843.48 cm1 for spodumene, 2 927.27 cm1 and 2 858.42 cm1 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 cm1 for spodumene and 1 587.13 cm1 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 Ca2+ show a good activation on the flotation of spodumene and beryl. The best activation

of Fe3+ appears in a pH range of 69, 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 Ca2+, 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 cm1 for spodumene and 1 587.13 cm1 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.

References
[1] [2] Sun C Y, Yin W Z. Principle of Silicate Minerals Flotation. Beijing: Science Press, 2001. (In Chinese) Jia M X, Sun C Y. Flotation and surface characteristics of some silicate minerals and its crystal chemistry analysis. Conservation and Utilization of Mineral Resources, 2001, 5: 2529. (In Chinese) [3] Sun C Y, Jia M X. Flotability of some silicate minerals with sodium oleate as collector. Nonferrous Metals, 2001, 53(4): 5761. (In Chinese) [4] Yin W Z, Sun C Y. The analysis of silicates surface character by the X-ray photoelectron energy spectrum. Journal of North East University, 2002, 23(2): 156159. (In Chinese) [5] Jia M X, Sun C Y. Study on adsorption behavior of metal ions. Mining & Metallurgy, 2001, 10(3): 2530. (In Chinese) [6] Kwang S M, Fuerstenau D W. Surface crystal chemistry in selective flotation of spodumene (LiAl[SiO3]2) from other aluminosilicates. Int. J. Miner. Process, 2003, 72: 1124. [7] Li Y K. Studies on the mechanism of regulators on the flotation separation between spodumene and beryl. Metallic Ore Dressing Abroad, 1991, (78): 8996. (In Chinese) [8] Li Y K, Zhang Z H, Sun J, et al. Study on the regularity and the mechanism of activation of Ca2+, Fe3+ in flotation of beryl and spodumene. Rare Metals, 1982, 1(2): 3141. (In Chinese) [9] Zhang M Q, Liu J T, Li X B. Adsorption properties and mechanism of calcium ions on clay particle surface in coal slurry. Journal of China University of Mining & Technology, 2004, 33(5): 548551. (In Chinese) [10] Wang D Z, Hu Y H. Solution Chemistry of Flotation. Hunan: Hunan Science and Technology Press, 1988. (In Chinese) [11] Torem M L, Peres A E, Damian R A. On the mechanisms of beryl flotation in the presence of some metallic cations. Minerals Engineering, 1992, 5(1012): 12951304. [12] Fuerstenau D W, Pradip. Zeta potentials in the flotation of oxide and silicate minerals, Advances in Colloid and Interface Science, 2005, 114115: 926.