International Journal of Mineral Processing 100 (2011) 179183

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International Journal of Mineral Processing

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

Comparative studies of reverse cationic/anionic otation of Vale iron ore

X. Ma a,, M. Marques b, C. Gontijo b
a b

CSIRO Process Science and Engineering, Box 312, Clayton, Victoria, 3168, Australia Vale S.A., 1122 Paraiba Street, Belo Horizonte, M.G., 30, 130-141, Brazil

a r t i c l e

i n f o

a b s t r a c t
The comparative studies of reverse cationic/anionic otation routes were conducted using Vale iron ore in batch scale otation tests. The effect of slimes on the performance of the two otation routes was also studied. After desliming, the overall Fe recovery in reverse anionic otation is signicantly higher than reverse cationic otation at the same concentrate grade. For ultrane particles (b 10 m), the metal loss in reverse cationic otation is over 92% due to the entrainment of hematite ultrane particles. However, in reverse anionic otation, metal loss is as low as 42% in the particle size range of 5 to 10 m, while rejecting almost all the quartz ultrane particles at the same time. In the coarse particle size range (N 210 m), the performance of reverse cationic otation is slightly better than reverse anionic otation, with more quartz coarse particles rejected. The major advantage of reverse anionic otation over reverse cationic otation was found to be its excellent capability to selectively separate ultrane particles of quartz and hematite. 2011 Elsevier B.V. All rights reserved.

Article history: Received 9 March 2011 Received in revised form 4 July 2011 Accepted 10 July 2011 Available online 20 July 2011 Keywords: Iron ore Reverse cationic otation Reverse anionic otation Desliming

1. Introduction Reverse cationic otation is currently the most widely used otation route in the iron ore industry. The metal loss at the de-sliming stage, which is essential in reverse cationic otation, and the high cost of amine collectors are the common issues/problems of reverse cationic otation. Reverse anionic otation rejects quartz by rst activating it with the use of lime, and then oating it using fatty acids as collectors. The advantages of reverse anionic otation, in comparison to reverse cationic otation, include its relatively lower sensitivity to the presence of slimes and lower reagent cost because fatty acids are the main components of the waste from the paper industry (Wasson et al., 1963). Houot (1983) claimed that the tolerance of slimes in reverse anionic otation is so high that desliming prior to otation is not essential. In recent years, reverse anionic otation has been successfully applied in China's major iron ore area, Anshan (Shen and Huang, 2005; Zhang et al., 2006). The reverse anionic otation was conducted without desliming, which appears to support the claim by Houot (1983). Since the investigation of reverse anionic otation by U.S. Bureau of Mines (Wasson et al., 1963), a variety of new ether amine collectors have been developed for iron ore otation. McGlothin and O'Brien (1983) reported that an ether monoamine derived from isononyl alcohol provides improved otation performance in

comparison to traditional ether amine collectors, especially for iron ores of ne particle size. However, a comparative study of the effectiveness of reverse anionic otation and reverse cationic otation using isononyl ether amines has not been conducted. In this work, the otation performance of reverse anionic otation and reverse cationic otation using isononyl ether amines was closely compared. The tolerance of the two otation routes to slimes was also studied. 2. Experimental 2.1. Materials The Vale iron ore samples used in this work include the feed and underow of a cyclone. The samples were characterized with XRF (X-ray uorescence) and the content of the major components is shown in Table 1. X-ray diffraction (XRD) analysis of the samples found that in both samples iron mainly occurs in the form of hematite, with impurities including quartz, kaolinite, talc and muscovite. Particle size analysis was conducted using standard laboratory wet and dry screening methods. Subsieve sizing was performed using a modied CSIRO cyclosizing technique (Kelsall et al., 1974). Cumulative percent passing size distributions of the two samples are presented in Fig. 1. The d80 of the cyclone feed and underow was found to be 109 m and 129 m, respectively. Sodium oleate was obtained from Sigma. Isononyl ether amines (EDA C and EDA 3C) were provided by Clariant. Fresh solutions of these reagents were prepared each day as a 1% solution. Corn starch was obtained from Wintersun, USA. Starch was gelatinized using sodium hydroxide at room temperature to a 2% solution. Calcium

Corresponding author. Tel.: + 61 3 95458731; fax: + 61 3 95628919. E-mail address: mark.ma@csiro.au (X. Ma). 0301-7516/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.minpro.2011.07.001

180 Table 1 Chemical analysis of Vale iron ore samples. Vale iron ore sample Cyclone feed Cyclone underow Component (%) Fe 40.36 39.60 SiO2 39.01 41.40 CaO 0.025 0.025

X. Ma et al. / International Journal of Mineral Processing 100 (2011) 179183

100

Mn3O4 0.649 0.364

Al2O3 1.390 0.641

TiO2 0.092 0.089

P 0.015 0.009

MgO 0.178 0.141

Cumulative recovery (%)

80

Fe (Oleate) Fe (Oleate)
SiO (Oleate) SiO22oleate

60

Fe (EDA C) Fe (EDA C) SiO (EDA C) SiO22(EDA C )

oxide and sodium hydroxide are ACS-certied chemicals from Ajax Finechem.

40

Fe (EDA 3C ) Fe (EDA 3C) SiO22(EDA 3C ) SiO (EDA 3C)

20

2.2. Methods Flotation tests were conducted in a 3L laboratory Denver cell using 2.5 kg iron ore. For both conditioning and otation, the impeller speed was 1200 rpm. Before otation, the pulps were rst conditioned with starch for 3 min and then conditioned with a collector for 3 min. The reverse cationic otation tests were conducted at pH 10.5 and the reverse anionic otation tests were performed at pH 11.5. Individual timed concentrates were collected during the oats. Melbourne tap water was used in all the test work. The otation products and tailings were dried in an oven at 60 C and analyzed using XRF.

10

15

20

Flotation time (min)

Fig. 2. Cumulative recovery of quartz and iron as a function of otation time using sodium oleate, EDA C and EDA 3C as collectors. 1000 g/t starch was used as a depressant of hematite.

3. Results and discussion The cumulative recovery of quartz and iron as a function of otation time in reverse cationic/anionic otation is shown in Fig. 2. Obviously, the otation of quartz in reverse cationic otation is signicantly faster than that in reverse anionic otation. In reverse anionic otation, even after prolonged otation time, a small portion of quartz remains unoated. The extent to which concentration occurs can be gaged by calculating the size-by-size recoveries of elements. The recovery-size curves in Fig. 3 illustrate that, for ultrane particles (b10 m), Fe recovery to the concentrates is extremely low in reverse cationic otation, ranging from 3 to 7%, probably due to the entrainment of hematite ultrane particles to the froth products. However, in reverse anionic otation, the recovery of hematite ultrane particles is signicantly higher, with almost all the quartz ultrane particles rejected. The recovery of hematite in the particle size range of 5 to 10 m is 58%, and decreases to 15% for ner particles.

In contrast, in the coarse particle size range (N210 m), reverse cationic otation performs better than reverse anionic otation, with more coarse quartz particles rejected. The unoated coarse particles of quartz in reverse anionic otation shown in Fig. 3 correspond to the small portion of quartz unoated even after prolonged otation time in Fig. 2. The grade-recovery curves for the otation tests using sodium oleate, EDA C and EDA 3C as collectors are presented in Fig. 4. At the same concentrate grade, the recovery of iron was found to decrease in the order oleate N EDA C N EDA 3C. The selectivity of quartzhematite separation using these collectors follows the same order (Fig. 5). As Fig. 3 shows, the unoated quartz in reverse anionic otation increases sharply at particle size coarser than 210 m. Therefore, the sharp decrease in the curve for oleate above 66% Fe (Fig. 4) is due to the difculty to remove the quartz particles coarser than 210 m in reverse anionic otation. According to Iwasaki (1983) and Nummela and Iwasaki (1986), the efciency of quartz otation decreases at particle size coarse than 75 m, for both cationic and anionic otation. A visual analysis of the results reported by Vieira and Peres (2007) reveals that, at

100 100
Before desliming

Weight percent passing (%)

After desliming

80

Recovery (%)

Fe reverse Fe - (Reverse

60

anionic flotation) Fe reverse Fe - (Reverse cationic flotation)

10

40

20

SiO reverse SiO22-(Reverse anionic flotation) anionic flotation SiO - reverse SiO22(Reverse cationic flotation) cationic flotation

1 1 10 100 1000

0 1 10 100 1000

Particle size (m)

Fig. 1. Cumulative percent passing size distributions of the sample before and after desliming.

Average particle size (m)

Fig. 3. Size-by-size recoveries of individual components for reverse cationic otation and reverse anionic otation of deslimed samples.

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100 95

Table 2 Effect of starch dosage on reverse cationic otation (without desliming prior to otation). Starch dosage (g/t) The grade and recovery of Fe and SiO2 in concentrates (%) Fe 1000 Grade Recovery Grade Recovery Grade Recovery 45.19 38.85 66.11 54.81 67.86 50.35 SiO2 34.52 28.98 5.18 4.4 2.64 1.99

Fe recovery (%)

90 85
Oleate

1250 1500

80
EDA C

75 70 35 40

EDA 3C

45

50

55

60

65

70

Fe grade (%)
Fig. 4. Fe recovery as a function of Fe grade for the otation tests on deslimed samples, using sodium oleate, EDA C and EDA 3C as collectors.

pH 10 using 60 g/t ether monoamine as a collector, the otation recovery of quartz particles from 74 to + 38 m is close to 100%, and decreases to ~ 50% for quartz particles from 150 to + 74 m. The otation of quartz basically ceases for quartz particles from 297 to + 150 m. The results in this work demonstrate that in the coarse particle size range, isononyl ether amine performs better than oleate, with more quartz coarse particles oated. The presence of slimes was found to cause signicant detrimental effects in both otation routes. The 10 micron fraction of the sample without desliming (cyclone feed) appears to be alumina rich, containing 33.93% Fe, 25.36% SiO2 and 12.86% Al2O3. Starch is the universal depressant of iron oxides in iron ore otation (Araujo et al., 2005; Ma, 2008), which also serves as a occulant of ultrane particles (Iwasaki et al., 1980; Iwasaki, 1989, 1990). Without desliming prior to otation, the consumption of starch was found to increase signicantly. In reverse cationic otation, the optimum starch dosage used on deslimed samples, i.e. 1000 g/t starch, was found insufcient to depress hematite. When starch dosage increases from 1000 g/t to 1500 g/t, the concentrate grade increases from 45.19% Fe to 67.86% Fe. The recovery of iron also improves signicantly, but remains below 60% (Table 2). In reverse anionic otation, a similar trend was

1.0
No Selectivity

Fraction of SiO2 unfloated

Oleate EDA C EDA 3C

observed, but the consumption of starch is even higher than that in reverse cationic otation (Table 3). At 1000 g/t starch, the grades of the concentrate and the feed are practically the same, which indicates no separation between hematite and quartz. When the starch dosage increases from 1000 to 2000 g/t, some depression of hematite was observed and the selectivity of reverse anionic otation was improved signicantly. For economic reasons, the starch dosage used in this work was controlled at 2000 g/t. The otation performance of reverse anionic otation and reverse cationic otation is compared in Figs. 6 and 7. The grade-recovery curves in Fig. 6 demonstrate that, at the same concentrate grade, the recovery of iron in reverse anionic otation is approximately 18% higher than that in reverse cationic otation. However, as the reverse anionic otation test proceeds, hematite starts to oat and reports to froth, indicating insufcient depression of the iron mineral. The SiO2/ Fe selectivity plots for reverse cationic otation and reverse anionic otation in Fig. 7 also clearly demonstrate higher selectivity in reverse anionic otation. The higher concentrate grade obtained in reverse cationic otation of the sample without de-sliming seems to be related to the entrainment of ultrane particles. As demonstrated on the deslimed sample, the entrainment of ultrane particles to froth in reverse cationic otation is signicantly higher than that in reverse anionic otation (Fig. 3). In reverse cationic otation without desliming, the slimes were observed to report to the froth in the rst few minutes leaving the rest of the otation process little affected by the slimes. Although Houot (1983) reported that desliming prior to otation is not essential in reverse anionic otation, because of its relatively high tolerance to slimes, it has not been validated with experimental evidence so far. The successful application of reverse anionic otation without desliming prior to otation in China's iron ore industry appears to support Houot's claim. However, a detailed study of China's practice found that the otation feed is processed using more than one stage of magnetic separation, which could be regarded as a selective desliming method. In the literature, the importance of electrostatic interactions between mineral particles for otation involving ultrane particles is widely recognized (Meech, 1981; Pindred and Meech, 1984;

0.1
Table 3 Effect of starch dosage on reverse anionic otation (without desliming prior to otation). Starch dosage (g/t) 1000 The grade and recovery of Fe and SiO2 in concentrates (%) Fe SiO2 40.97 96.55 36.24 52.99 18.55 23.65

0.0 0.0

0.1

1.0
1500 2000

Fraction of Fe unfloated
Fig. 5. SiO2/Fe selectivity plots for the otation tests on deslimed samples, using sodium oleate, EDA C and EDA 3C as collectors.

Grade Recovery Grade Recovery Grade Recovery

40.06 97.63 44.45 61.60 55.79 72.36

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X. Ma et al. / International Journal of Mineral Processing 100 (2011) 179183

100

90

Fe recovery (%)

80

70

otation. This could reduce the selectivity of starch adsorption, as discussed above, and contributes to the lower selectivity of reverse cationic otation in the presence of ultrane particles (Figs. 5, 7). After the addition of lime to otation pulp, the surface charged of quartz is reversed from negative to positive to accommodate the adsorption of fatty acids. The addition of lime may cause coagulation of quartz particles. However, at this stage, starch molecules already chemically adsorb on hematite surfaces and hence the coagulation caused by lime cannot interfere with the selective adsorption of starch in reverse anionic otation. 4. Conclusions
Reverse anionic flotaiton Reverse cationic flotaiton

60

50 35 40 45 50 55 60 65 70

Fe grade (%)
Fig. 6. Fe recovery as a function of Fe grade for reverse anionic otation and reverse cationic otation without desliming.

Cristoveanu and Meech, 1985). A generally accepted detrimental effect of slimes in iron ore otation is the heterocoagulation of ultrane quartz particles with coarser hematite particles and the heterocoagulation of ultrane hematite particles with coarser quartz particles (Fuerstenau et al., 1958; Usui, 1972). Because amine collectors adsorb on both quartz and hematite surfaces, the selective adsorption of starch on hematite plays a key role in the selective separation of quartzhematite (Ma, 2011). Such heterocoagulation masks the surface properties of the coarser particles and signicantly reduces the selective adsorption of starch. Reverse anionic otation is conducted at a higher pH value (pH 1112), in comparison to reverse cationic otation (pH 1010.5). Since the PZC of pure hematite is around pH 9 (Penners and Koopal, 1987; Hesleiner et al., 1991), the surface charge of hematite in reverse cationic otation (pH 1010.5) would be relatively low. Before adding starch to otation pulp, the repulsive electrostatic forces between the negatively charged quartz and hematite particles in reverse anionic otation are supposed to be stronger than that in reverse cationic otation. Consequently, the heterocoagulation of ultrane quartz/hematite particles to coarser hematite/quartz particles can be expected to be more signicant in reverse cationic

Superior performance of reverse anionic otation was achieved for ultrane particles (b10 m). In contrast, no selective separation of such ne particles was made in reverse cationic otation, even with the use of isononyl ether amines that perform better than traditional ether amines for nely ground iron ores. For coarse particles (N210 m), however, reverse cationic otation performs better than reverse anionic otation, with more coarse quartz particles rejected. Although reverse anionic otation works better for ultrane particles, desliming prior to otation was still found essential when the amount of slimes is high enough. The presence of high amount of slimes substantially increases reagent consumption in both otation routes and the detrimental effect of slimes cannot be fully corrected by adding more reagents. The iron ore otation practice in China without desliming probably benets from the use of magnetic separation before otation, which could be regarded as a selective desliming method. Acknowledgment The authors wish to thank Vale for providing nancial support and permitting the publication of this work. The authors also wish to thank Ms C. Edwards and Ms L. Malishev for sample preparation as well as the staff of CSIRO Materials Characterisation. The authors' gratitude is extended to Dr R. Holmes, Mr D. McCallum, Mr K. Davey and Ms L. Smith for their help at various stages of this work. Reference
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1.0
No Selectivity Reverse anionic flotation

Fraction of SiO2 unfloated

Reverse cationic flotation

0.1

0.0 0.0

0.1

1.0

Fraction of Fe unfloated
Fig. 7. SiO2/Fe selectivity plot for reverse anionic otation and reverse cationic otation without desliming.

X. Ma et al. / International Journal of Mineral Processing 100 (2011) 179183 Pindred, A., Meech, J.A., 1984. Interparticular phenomena in the otation of hematite nes. Int. J. Miner. Process. 12, 193212. Shen, H., Huang, X., 2005. A review of the development in iron ore processing from 2000 to 2004. Min. Met. Eng. 25, 2630 (In Chinese). Usui, S., 1972. Heterocoagulation. In: Danielli, J.F., Rosenberg, M.D., Cadenhead, D.A. (Eds.), Progress in Surface and Membrane Science, Volume 5. Academic Press, New York, pp. 223266.

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