Minerals Engineering xxx (2012) xxxxxx

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore
Boris Albijanic a,b,, Dee J. Bradshaw b,, Anh V. Nguyen a
a b

School of Chemical Engineering, The University of Queensland, Brisbane, QLD 4072, Australia Julius Kruttschnitt Mineral Research Centre, The University of Queensland, Brisbane, QLD 4068, Australia

a r t i c l e

i n f o

a b s t r a c t
Flotation occurs as a result of bubbleparticle attachment. This is controlled by the particle surface properties which are created by surface liberation of valuable minerals and collector adsorption within the chemical environment. This paper examines the contribution of both collector dosage and liberation of valuable minerals to bubbleparticle attachment time measurements. In order to evaluate particles of different liberation, the bubbleparticle attachment time measurements were conducted with a sized fraction of concentrates and tails obtained by otation of a copper sulde ore (Northparkes Mine, Australia) in a mechanically agitated batch otation cell. Quantitative mineral liberation analysis was performed to analyze all concentrates and tails. The results indicated that for particles with high Cu grade, a small increase of collector dosage resulted in a dramatic reduction of attachment time with no further increase on subsequent addition of collector. However, for particles with moderate Cu grade, the effect of collector addition on attachment time was reduced much less because valuable minerals were mainly moderately and poorly liberated. For particles with low Cu grade, collector addition made no difference. All these results conrmed that there is a highly non-linear correlation between mineral liberation, Cu grade, collector dosage and attachment time. Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved.

Article history: Available online xxxx Keywords: Froth otation Attachment time Mineral liberation analysis Collector dosage Copper sulde ore

1. Introduction Flotation is the widely used physicochemical technique to beneciate ores by separating particles with different surface properties using air bubbles. The controlling mechanism for successful otation is bubbleparticle attachment. The factors affecting bubbleparticle attachment mechanism have been traditionally determined by contact angle measurements (Leja, 1982; Nguyen and Schulze, 2004). However, it has been proven that these measurements cannot always be used to predict the otation response of pure minerals obtained using Hallimond tube (Ye and Miller, 1988; Ye et al., 1989; Yoon and Yordan, 1991; Su et al., 2006). An alternative measure for predicting the susceptibility of a mineral to oat is bubbleparticle attachment time which represents the time required for attachment of particles to an air bubble when they are in close proximity (Ye and Miller, 1988; Ye et al., 1989; Yoon and Yordan, 1991; Albijanic et al., 2010).

Corresponding authors. Present address: Western Australia School of Mines, Curtin University, Kalgoorlie, WA 6433, Australia (B. Albijanic). Tel.: +61 89088 6117; fax: +61 73365 5832 (B. Albijanic), tel.: +61 7 3365 5832 (D.J. Bradshaw). E-mail addresses: boris.albijanic@curtin.edu.au (B. Albijanic), d.bradshaw@uq. edu.au (D.J. Bradshaw).

Bubbleparticle attachment time is commonly determined with a device originally developed by Glembotsky (1953). By using this device, a strong correlation was found between bubbleparticle attachment time and otation performance, e.g., the highest otation recovery occurs at the shortest attachment time (Ye and Miller, 1988; Ye et al., 1989; Yoon and Yordan, 1991; Gu et al., 2003). The principle of attachment time measurements is based on keeping a captive bubble in contact with a bed of mineral particles for a series of controlled times, from which the attachment time is determined at a pre-selected percentage (e.g. 50%) of bubbleparticle attachment. It should be noted that other methods can be also used to estimate attachment time such as the wetting lm stability measurements (Letocart et al., 1999), direct observation of bubbleparticle attachment interactions as well as using models to back-calculate attachment time from experimental otation data (Danoucaras et al., 2010). Numerous researchers have proved that attachment time is sensitive enough to show changes in both surface chemistry and physical properties of particles, and these ndings were summarized by Albijanic et al. (2010). For example, there is an optimum collector dosage, pH and ionic strength at which the attachment time is the shortest and the otation recovery is the highest (Yoon and Yordan, 1991; Gu et al., 2003). All these studies have been performed using pure minerals. However, there is limited data for bubbleparticle attachment time of real ore particles. For example,

0892-6875/$ - see front matter Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.mineng.2012.06.007

Please cite this article in press as: Albijanic, B., et al. The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore. Miner. Eng. (2012), http://dx.doi.org/10.1016/j.mineng.2012.06.007

B. Albijanic et al. / Minerals Engineering xxx (2012) xxxxxx

Albijanic et al. (2011) have recently determined attachment time for real ore particles and have found that at xed chemical conditions the higher the Cu grade in otation products the shorter the attachment time. However, the literature does not provide the data for attachment time of real ore particles as a function of collector dosage. For that reason, the main objective in this work is to investigate the contribution of collector dosage and the liberation of valuable copper minerals on attachment time measurements, and thus establish the relationship between attachment time, collector dosage and the mineralogy of a copper sulde ore. 2. Materials and methods 2.1. Sample preparation by otation In order to evaluate the performance of samples of different grade and liberation, batch otation experiments were performed using low grade copper sulde ore (1% Cu) obtained from Northparkes mine, New South Wales, Australia. The particle size distribution of the feed was reduced to P80 of 90 lm by wet milling at 60% solids in a laboratory rod mill. The ground sample was transferred to a 5 L bottom driven batch otation cell, and the required amount of tap water was added to the system ($25% solid ratio). The measured pH of the otation pulp was between 8.2 and 8.8. Brisbane tap water was used in the otation experiments. The impeller speed was set at 800 rpm. 14 mg/L of the Interfroth 6880 alcohol based frother (Chemical & Mining Services Pty Ltd., Australia) was added to the otation pulp. After 2 min of conditioning, 15 L/min of air was introduced through diffusers placed at the bottom of the otation cell, and the otation took place. An automatic scraper was used to collect the froth into two launders every 8 s. The concentrates were collected after 0.5 min, 4 min and 10 min. Then, the concentrates and tails were wet screened to obtain the sample (106 53 lm). It is well known that attachment time is sensitive to particle size (Ye et al., 1989; Yoon and Yordan, 1991; Gu et al., 2003; Albijanic et al., 2011). Our various 106 53 lm samples could have to some extent different particle size distributions, but it was not possible to use narrower fractions due to the experimental constraints. Namely, the amount of collected fraction (106 53 lm) for bubbleparticle attachment time measurements was less than 1 g. It should be also noted that this size fraction is considered in the range of optimum oatability (Muganda et al., 2012) and was considered appropriate for bubbleparticle attachment time measurements. 2.2. Mineral assays A Mineral Liberation Analyzer (MLA) was employed to determine the modal mineralogy and liberation of the sized samples of (106 53 lm) concentrates and tails. The analysis using the MLA is given elsewhere in detail (Gu, 2003; Fandrich et al., 2007). It is important to note that MLA measures cross sectional area fraction. For that reason, Leigh et al. (1993) developed the model to calculate the standard deviation of 2D liberation measurements:

100 Bornite 80
40.4 % Cu

Chalcopyrite Pyrite

Mineral grade (%)

60
22.2 % Cu

40
12.3 % Cu

20 0 Con-1 Con-2 Con-3

0.2 % Cu 0.2 % Cu

Tails

Fig. 1. Sulde mineral grade of the 106 53 lm fraction in concentrates and tails.

concentrates the cross-sectional and surface-area fractions are likely to be very similar, while those for tails are likely to differ. The modal mineralogy of sulde minerals in otation products (concentrates collected after 0.5 min (Con-1), 4 min (Con-2) and 10 min (Con-3)) and tails obtained by mineral liberation analysis is given in Fig. 1. As seen in Fig. 1, the valuable minerals in the otation products are bornite and chalcopyrite. The weight percentage of these minerals decreased from 46.7% bornite and 31% chalcopyrite (Con-1) to 12.5% bornite and 12.4% chalcopyrite (Con-3). In other words, Cu grade decreased from 40.4% Cu (Con-1) to 12.3% Cu (Con-3). Flotation products also contain about 2% of pyrite which is gangue sulde mineral. The tails is mainly composed of non-sulde minerals such as silicates and oxides. In addition, the particle liberation data for copper sulde minerals were grouped into three classes: highly liberated (10075% of the mineral of interest), moderately liberated (7525% of the mineral of interest) and poorly liberated valuable particles (<25% of the mineral of interest) as shown in Fig. 2. As seen in Fig. 2, the amount of liberation decreased as the concentrate number increases. The highly liberated particles were recovered in Con-1 and Con-2 better than the moderately and poorly liberated particles. However, in the case of Con-3, the most dominant are the moderately liberated particles. For tails, the poorly liberated particles are the predominant fraction.

2.3. Bubbleparticle attachment time measurements The bubbleparticle attachment time measurements were performed with the Induction Timer (University of Alberta, Canada) (Gu et al., 2003) as shown in Fig. 3. Before conducting attachment time measurements, different dosages of the sodium isobutyl xanthate (C5H9NaOS2) collector (Senmin Pty Ltd., South Africa) were added to the supernatant solution obtained after otation. It should be noted that apart from the sodium isobutyl xanthate, other collectors, used in otation of copper sulde minerals, can be also applied. The pH of solution was the same as the pH during otation experiments. The sample with the prepared solution was transferred to a small cell under the bubble holder. A bubble of about 1.5 mm in diameter was generated using a microsyringe, and then the distance between the bubble and the particle bed was adjusted using the three-dimensional micro-translation stage. Next, the bubble was kept in contact with the bed of particles for the controlled contact time from 10 ms to 3000 ms. Then the attachment of particles to the bubble was visually observed through the lens and CCD camera linked to a monitor. Ten measurements were performed at different areas of the particle bed and the observations were recorded. And, the contact time at which attachment efciency represents 100% is chosen as an attachment time (Albijanic et al., 2011).

ry 1:12y y2

s 1 1 N0 N1

where y is the liberation at composition C; N0 is number of particles with composition lower than C and N1 is number of particles with composition higher than C. The number of particles for one 2D areal section was about 10,600. The standard deviation was lower than 0.02 in the case of concentrates. However, in the case of tails, the maximal standard deviation was 0.34. This shows that in

Please cite this article in press as: Albijanic, B., et al. The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore. Miner. Eng. (2012), http://dx.doi.org/10.1016/j.mineng.2012.06.007

B. Albijanic et al. / Minerals Engineering xxx (2012) xxxxxx

27.1% 41.5% 81% 14.9% 4.09% 22.7% 23.8%

61.2%

7.43% 49.2% 35.8% 31.4%

Con-1

Con-2

Con-3

Tails
moderately and j poorly liberated

Fig. 2. The distribution of liberation classes of copper sulde minerals in 106 53 lm fractions of concentrates and tails as h highly, particles.

Driver head Attached particles Capillary Bubble SiBX solution Lens Light

PC CCD camera Micro-translation stage

Particle bed

Bubble

Attached particles on bubble surface

Particle bed

Step 1

Step 2

Step 3

Fig. 3. A schematic illustration of bubbleparticle attachment time experiments.

3. Results and discussion 3.1. Bubbleparticle attachment time measurements The bubbleparticle attachment time measurements as a function of the sodium isobutyl xanthate (SiBX) dosage were conducted for 106 53 lm fraction obtained from the otation concentrates collected after 30 s (Con-1), 4 min (Con-2) and 10 min (Con-3), and for the tails. Fig. 4 shows the typical results for attachment efciency (expressed as a number of successful attachments in 10 observations) as a function of contact time. In this study, the attachment time was dened as the contact time at 100% attachment efciency. It should be noted that there is a critical contact time above which attachment efciency increases rapidly with increasing contact time which is in agreement with our previous work (Albijanic et al., 2011). The reason for this is probably because above the critical contact time there is more time for drainage of wetting lm between a bubble and a particle, improving signicantly the bubbleparticle attaching force.

The attachment time methodology is quite reproducible for the attachment time less than 3000 ms. However, this methodology is unreliable for very long attachment time due to the extrapolation of experimental data with the lines being indications of trends (the attachment time for tails was 65,000 25,000 ms). Table 1 shows the results for the attachment time. At constant collector dosage, attachment time of otation products increased with the increase of otation time. The reason for this is due to the decrease of valuable liberated particles in otation products. Because tails was mainly composed of non-valuable minerals, attachment time of tails was higher than that of otation products. This is in good agreement with our previous results (Albijanic et al., 2011). 3.2. Correlation between bubbleparticle attachment time, Cu grade, Cu liberation and collector dosage The bubbleparticle attachment time measurements were plotted against SiBX dosage for various Cu grade and Cu liberation, as

Please cite this article in press as: Albijanic, B., et al. The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore. Miner. Eng. (2012), http://dx.doi.org/10.1016/j.mineng.2012.06.007

B. Albijanic et al. / Minerals Engineering xxx (2012) xxxxxx

100

1000000

Attachment efficiency (%)

80

100000

Attachment time (ms)

10000

60

1000

40

20

Con-1 Con-2 Con-3 Tail

100

10
100000

0 1 10 100 1000 10000

SiBX (M) 0 10-6 10-5 10-4 10-3

0 5 10 15 20 25 30 35 40 45

Contact time (ms)

Fig. 4. Attachment efciency for the concentrates and tails as a function of contact time obtained in the presence of 105 M SiBX the lines being indications of trends.

Cu (%)

Table 1 Attachment time of otation products and tails in the presence of 105 M SiBX determined at 100% attachment. Products Con-1 Con-2 Con-3 Tails Attachment time (ms) 15 15 3000 65,000 25,000

Tails

Con-3

Con-2

Con-1

Fig. 6. Attachment time vs Cu grade for concentrates and tails.

1000000

100000

10000

1000

100

10

10-6

10-5

10-4

10-3

SiBX (M)
Fig. 5. Attachment time vs SiBX dosage for concentrates and tails (h Con-1; s Con2; D Con-3; r tails).

shown in Fig. 5. It is noted that in Fig. 5, Cu liberation was shown instead of liberation of chalcopyrite and bornite, because these two minerals are hydrophobic in the presence of collector (Ackerman et al., 1989). Fig. 5 showed that when the Cu grade was between 22.2% and 40.4%, the increase of SiBX dosage resulted in decreasing attachment time over 100-fold from 2000 ms (107 M SiBX) to 16 ms (103 M SiBX). In this case, copper minerals were mainly highly liberated. However, at 12.3% Cu grade, attachment time decreased

10-fold with increasing of SiBX dosage. The reason for this is not only due to the moderate Cu grade but also because 41.5% and 22.7% of particles containing copper sulde minerals were moderately liberated and poorly liberated, respectively. In the case of tails, Cu grade is 0.2% only and therefore the increase of SiBX dosage did not affect attachment time. These results support the practical observation that it is the moderate grade composite particles that benet from increased collector concentration but that poorly liberated particles or low grade streams are not affected. It is important to note that both the number of particles containing copper as well as the liberation of copper sulde minerals in each particle would have inuenced attachment time. These effects have not been decoupled in this work and this is worth investigating further. The attachment time data can also be plotted as a function of Cu grade at various SiBX dosages (see Fig. 6). As seen in Fig. 6, at SiBX dosage equal to 107 M, the increase of Cu grade resulted in a slight reduction of attachment time. However, at SiBX dosage higher or equal to 106 M, the increase of Cu grade had a dramatic effect on attachment time, reducing attachment time up to 2500-fold. It should be noted that the increase of SiBX dosage enhanced the surface coverage of SIBX molecules on the valuable minerals, and thus improved hydrophobicity of these minerals. However, quantitative determination of the surface coverage was beyond the scope of this study. These results clearly demonstrated that at constant collector dosage the lower the copper grade the higher the attachment time. This is in agreement with the results obtained by Danoucaras et al. (2010) who calculated attachment time in the otation cell for galena size liberation classes using Vianna (2004) measurements and applying fundamental models for particle collection by bubbles. It should be noted that Danoucaras et al. (2010) calculated that attachment time decreased from about 100 ms (the fraction of galena particles was 5%) to about 50 ms (liberated galena particles). The experimental results showed that in the presence of collector, attachment time for particles at high Cu grade (22.240.4%) was between 10 ms and 40 ms which is close to the value calculated by Danoucaras et al. (2010). On the other hand, for particles at low Cu grade, the measured

Please cite this article in press as: Albijanic, B., et al. The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore. Miner. Eng. (2012), http://dx.doi.org/10.1016/j.mineng.2012.06.007

Attachment time (ms)

B. Albijanic et al. / Minerals Engineering xxx (2012) xxxxxx

attachment time was much higher (100-fold) than the calculated attachment time obtained by Danoucaras et al. (2010). Indeed, although the trends are consistent, particles recovered in the rst concentrates are faster oating and correlate to shorter attachment times, it is not clear how well the measured attachment time matches to real attachment times in otation because attachment time measurements have been performed in a quiescent environment with static particles and thus attachment time method cannot completely simulate the contact between a bubble and a particle in a otation cell. Fig. 6 shows that in the absence of collector, the difference in attachment times between the concentrates was lower and in the approximate ratio to the times of collection in the otation cell. This represents the differences in natural oatability of the particles with different grades and the associated effects on attachment time which is consistent with the data of Danoucaras et al. (2010). Apart from the degree of liberation, in this study, it was found that attachment time of composite particles decreased with the increase of collector dosage which means that higher dosage of collector is needed to improve recovery of composite particles in the otation cell. Similarly, Vianna (2004) demonstrated that the rate of otation of minerals and ore particles increased with the increase of collector dosage. As regards the effect of frother on bubbleparticle attachment time, in the literature differing observations have been reported (Lekki and Laskowski, 1971; Drelich et al., 1997). For the system investigated in our study the effect of frother on attachment time was beyond the scope of our work, and has not been assessed; however, it would be an interesting topic for future studies. The correlation among attachment time, liberation of copper sulde minerals, Cu grade and collector dosage can be used as a tool to estimate collector dosage and Cu grade in concentrates and tails. This correlation is highly non-linear and is difcult to predict. However, attachment time measurements give important insights into bubbleparticle attachment mechanism of Cu sulde minerals found in Nothparkes ore. The similar correlation among attachment time, the grade of valuable metal, liberation of valuable minerals and collector dosage may exist for other otation systems since the majority of valuable minerals are recovered by bubble particle attachment mechanism. 4. Conclusion The attachment time and the MLA method were used to study the contribution of liberation and grade of valuable minerals and collector dosage to attachment time. In this study, a copper sulde ore (Northparkes Mine, Australia) was employed. The attachment time measurements performed for the concentrates and tails indicated that the attachment time is dependent on liberation of valuable minerals, grade of valuable metal and collector dosage. The attachment time of otation products collected after 30 s and 4 min decreased dramatically with the increase of collector dosage. The attachment time of the otation product collected after 10 min was less reduced with the increase of collector dosage due to the less Cu grade and less liberation of Cu minerals. Under constant

collector dosage, the attachment time of otation products decreased with the increase of Cu grade. Correlation among attachment time, Cu grade, liberation of copper minerals and collector dosage is highly non-linear and difcult to predict. Nevertheless, these results clearly showed that attachment time measurements give important insights into bubbleparticle attachment mechanism. Acknowledgement Financial support from the AMIRA International P9O Project and the member companies is gratefully acknowledged. References
Ackerman, P.K., Harris, G.H., Klimpel, R.R., Aplan, F.F., 1989. Evaluation of otation collectors for copper suldes and pyrite, III. Effect of xanthate chain length and branching. International Journal of Mineral Processing 21 (12), 141156. Albijanic, B., Ozdemir, O., Nguyen, A.V., Bradshaw, D., 2010. A review of induction and attachment times of wetting thin lms between air bubbles and particles and its relevance in the separation of particles by otation. Advances in Colloid and Interface Science 159 (1), 121. Albijanic, B., Amini, E., Wightman, E., Ozdemir, O., Nguyen, A.V., Bradshaw, D.J., 2011. A relationship between the bubble particle attachment time and the mineralogy of a copper sulde ore. Minerals Engineering 24, 13351339. Danoucaras, A., Vianna, S. and Nguyen, A.V., 2010. A modelling approach using a back-calculated induction time to predict recoveries in otation. XXV International Mineral Processing Congress, pp. 18271836. Drelich, J., Miller, J.D., Li, J.S., Wan, R.Y., 1997. Bubble attachment time measurements at a chalcopyrite surface using a high-speed video system. XX International Mineral Processing Congress, pp. 5364. Fandrich, R., Gu, Y., Burrows, D., Moeller, K., 2007. Modern SEM-based mineral liberation analysis. International Journal of Mineral Processing 84 (14), 310 320. Glembotsky, V.A., 1953. The time of attachment of air bubbles to mineral particles in otation and its measurement. Izv. Akad. Nauk SSSR (OTN) No. 11, pp. 1524 1531 (in Russian) Gu, Y., 2003. Automated scanning electron microscope based mineral liberation analysis. Journal of Minerals and Materials Characterization and Engineering 2, 3341. Gu, G., Xu, Z., Nandakumar, K., Masliyah, J., 2003. Effects of physical environment on induction time of air-bitumen attachment. International Journal of Mineral Processing 69 (14), 235250. Leigh, G.M., Sutherland, D.N., Gottlieb, P., 1993. Condence-limits for liberation measurements. Minerals Engineering 6 (2), 155161. Leja, J., 1982. Surface Chemistry of Froth Flotation. Plenum Press, New York, 758p. Lekki, J., Laskowski, J., 1971. Dynamic effect of frother-collector joint action in otation. Institute of Mining and Metallurgy, Transaction Section C 80, 174 180. Letocart, P., Radoev, B., Schulze, H.J., Tsekov, R., 1999. Experiments on surface waves in thin wetting lms. Colloids and Surfaces A: Physicochemical and Engineering Aspects 149 (13), 151159. Muganda, S., Zanin, M., Grano, S.R., 2012. Benchmarking the otation performance of ores. Minerals Engineering 26, 7079. Nguyen, A.V., Schulze, H.J., 2004. Colloidal Science of Flotation. Marcel Dekker, New York, p. 840. Su, L., Xu, Z., Masliyah, J., 2006. Role of oily bubbles in enhancing bitumen otation. Minerals Engineering 19 (68), 641650. Vianna, S., 2004. The effect of particle size, collector coverage and liberation on the oatability of galena particles in an ore. PhD thesis. The University of Queensland <http://library.uq.edu.au/record=b2191204>. Ye, Y., Khandrika, S.M., Miller, J.D., 1989. Induction-time measurements at a particle bed. International Journal of Mineral Processing 25 (34), 221240. Ye, Y., Miller, J.D., 1988. Bubble/particle contact time in the analysis of coal otation. Coal Preparations (Gordon & Breach) 5 (34), 147166. Yoon, R.-H., Yordan, J.L., 1991. Induction time measurements for the quartz-amine otation system. Journal of Colloid and Interface Science 141 (2), 374383.

Please cite this article in press as: Albijanic, B., et al. The relationships between the bubbleparticle attachment time, collector dosage and the mineralogy of a copper sulde ore. Miner. Eng. (2012), http://dx.doi.org/10.1016/j.mineng.2012.06.007