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International Journal of Mineral Processing 124 (2013) 814

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Effect of frothers on bubble coalescence and foaming in electrolyte solutions and seawater
S. Castro a,, C. Miranda a, P. Toledo b, J.S. Laskowski c
a b c

Department of Metallurgical Engineering, University of Concepcion, Concepcin, Chile Department of Chemical Engineering, University of Concepcion, Concepcin, Chile Department on Mining Engineering, The University of British Columbia, Vancouver, Canada

a r t i c l e

i n f o

a b s t r a c t
Inhibition of bubble coalescence is of fundamental importance in a otation process because it determines the size of bubbles and foam stability. For this work commercial frothers have been selected, MIBC, DF-250, DF-400 and DF-1012; and NaCl as inorganic electrolyte. Surface tension measurements used to characterize the tested frothers revealed that these frothers have quite different properties. Polypropylene glycols are much more surface active than MIBC. The differences between these two are further augmented in concentrated NaCl electrolyte solutions. The concept of the surface tension switch point (s.t.s.p.) is introduced to characterize the effect of electrolyte concentration on frother properties. The s.t.s.p. values for MIBC and DF-250 were determined to be around 120 ppm and 1.2 ppm, respectively. The effect of MIBC and DF-250 frothers on bubble coalescence was not very different, although ner bubbles were generated in the presence of MIBC than of DF-250 in seawater. Only dynamics foamability measurements (DFI) conrmed the differences, the foams produced in the presence of DF-250 were much more stable, also in electrolyte solutions. This fact conrms the importance of dynamic effects in foam formation and stabilization. 2013 Elsevier B.V. All rights reserved.

Article history: Received 5 October 2011 Received in revised form 11 July 2013 Accepted 13 July 2013 Available online 20 July 2013 Keywords: Bubble coalescence Foaming Frothers Critical coalescence concentration Seawater otation

1. Introduction The sizes of bubbles, which are determined by bubble coalescence, play a very important role in the otation process. Flotation frothers weakly surface active compounds are employed to facilitate air dispersion into ne bubbles and to stabilize the froth. Bubble coalescence is a particularly complex phenomenon especially when it takes place in saline water or seawater, since both surface active compound (frother) and surface-inactive compound (inorganic salt) are able to stabilize bubbles against coalescence and thus reduce bubble size. The mechanism of bubble coalescence in solutions of frothers has been extensively studied. The coalescence of bubbles can be completely prevented at frother concentration exceeding a particular concentration, referred to as critical coalescence concentration (CCC) (Cho and Laskowski, 2002; Laskowski et al., 2003; Grau et al., 2005; Grau and Laskowski, 2006). Inorganic electrolytes also inhibit bubble coalescence (Laskowski et al., 2003) and increase gas holdup in otation systems (Quinn et al., 2007; Kracht and Finch, 2010). Smaller bubbles rise at lower velocities and thus gas residence time increases.

Corresponding author. E-mail address: scastro@udec.cl (S. Castro). 0301-7516/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.minpro.2013.07.002

Most of common inorganic electrolytes show positive coalescence inhibition, some salts do not affect it suggesting that specic-ion effects and ionwater interactions play a role (Marrucci and Nicodemo, 1967; Zieminski and Whittemore, 1971; Lessard and Zieminski, 1971; Keitel and Onken, 1982; Craig et al., 1993a,b; Weissenborn and Pugh, 1995 and 1996; Deschenes et al., 1998; Craig, 2004). In a number of applications, e.g., froth otation in brines and in seawater, frothers are used in concentrated electrolyte solutions. Flotation of potash ores is carried out in a NaClKCl saturated brine, which is a solution of 67 mol of NaClKCl/L. The surface tension measurements carried out with MIBC under such conditions (Laskowski et al., 2003) revealed an interesting relationship between surface tension, MIBC concentration and electrolyte concentration. This relationship is shown in Fig. 1 as we decided to explore it further in this work. As it is seen, the three experimental surface tension isotherms intersect at one MIBC concentration and it seems that this intersection point could be used to depict the effect of ionic strength of the solution on the surface properties of tested frothers. The aim of the present work is to study bubble coalescence in the presence of common otation frothers in electrolyte solutions and in seawater. A better understanding of the mechanism of bubble coalescence in otation cells, when seawater or saline water is used, is needed if seawater otation is to be commercialized. The bubble coalescence in this work is studied using bubble size measuring technique and dynamic foamability tests.

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S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814 9

90

Surface Tension (mN/m)

80

70

101 cm height and 4.5 cm inner diameter, with the pore size range being from 40 to 100 m; and 500 mL of solution was used in each experiment. The equations used to express the DFI as a function of gas ow rate and frother concentration are: rt V : Q 1

60

50
Saturated Brine 50% Brine Water

where, rt V Q
100 1000 10000

40

is the retention time is the total gas volume in the system (solution + foam) is the volumetric gas ow rate. Then, the dynamic foamability index (DFI) is calculated from:

30 1

10

Concentration (ppm)
Fig. 1. The effect of MIBC and electrolyte concentration on surface tension of aqueous solutions (Laskowski et al., 2003). Saturated brine stands for NaClKCl saturated brine of 67 mol/L.

DFI

  rt : C C 0

2. Experimental 2.1. Materials MIBC (methyl isobutyl carbinol) was provided by Cytec-Chile, and the polyglycol frothers DF-200, DF-250, DF-400 and DF-1012 were commercial products obtained from Moly-Cop Chile S.A. Sodium chloride used in this study was of reagent grade (Merck). A local sample of seawater from Concepcion city (Bellavista-Tome) with a salinity of 33.5 was employed. 2.2. Apparatus 2.2.1. Surface tension measurements KSV Sigma 700 tensiometer, with a Pt Du Noy ring, was used in the surface tension measurements. Bi-distilled water was used for preparation of solutions. The Wilhelmy plate method was used in a few cases to cross-check results. No differences were found. Low frother concentration solutions were prepared by successive dilution of a 5 ppm frother solution. All the measurements were carried out at ambient temperature and resulting pH. 2.2.2. Bubble size measurements The bubble size analyzer (BSA) developed by the Cape Town University (UCT) was employed. This comprises a glass capillary and two pairs of photo-transistor-LED detectors. Bubbles are drawn up through the capillary tube under vacuum and collected in a modied burette. The suction rate is controlled by a peristaltic pump. The bubbles are transformed into cylinders inside of the glass capillary, and their velocities and length measured using the optical detectors. The total volume of gas collected in the burette is utilized in order to estimate the absolute size of the bubbles. A detailed description of the instrument has been published by Randall et al. (1989). The size of bubbles was measured in a 4.5 cm inner diameter column (the same column was employed in the DFI measurements) in which nitrogen gas was bubbled through the sinter glass frit either in water or in electrolyte solutions and the bubbles could freely collide with each other. The gas ow rate was 275 cm3/min. 2.2.3. Dynamic foamability index The DFI method (Malysa et al., 1981; Czarnecki et al., 1982) requires determination of gas retention time in a column (in which gas is bubbled through sintered disc) as a function of gas ow rate and frother concentration. What is measured is the total height of the solution plus the foam phase. These tests were carried out in a glass column of

Finally, it can be graphically determined from the slope of the initial part of the rt vs. C curve. 3. Results and discussion 3.1. Surface tension of frothers in aqueous NaCl solutions As Fig. 1 demonstrates, for MIBC aqueous solutions there is a characteristic concentration point, which splits the whole range into two concentration ranges. This is conrmed in Fig. 2. At MIBC concentration of about 120 ppm there is a critical point. Over the MIBC concentration range exceeding this point (we will call it the surface tension switch point, s.t.s.p.) the surface tension of the MIBC solutions containing NaCl is lower than the surface tension of MIBC aqueous solutions. This agrees very well with Fig. 1. The same results re-plotted in Fig. 3 as a function of NaCl concentration clearly indicate that up to about 120 ppm of MIBC curves are dominated by the surface-inactive compound (NaCl). Only at the MIBC concentrations higher than the s.t.s.p., the plot starts resembling the situation in which a surface-active compound is present in the system. This behavior is contrasted with another commercial frother, DF-250. As Fig. 4 demonstrates, the surface tension switch point for DF-250 is situated around DF-250 concentration of 1.2 ppm. This is very different from MIBC for which s.t.s.p. is around 120 ppm. The results when re-plotted (Fig. 5) reveal quite a different relationship between DF-250, NaCl concentration, and surface tension from

80

Surface tension (mN/m)

in water NaCl 0.1M NaCl 0.5 M NaCl 1 M NaCl 3 M

60

40

20 10

100

1000

MIBC Concentration (ppm)

Fig. 2. Effect of MIBC concentration on surface tension of aqueous solutions in the presence of NaCl (Castro et al., 2012a).

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10 S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814

80

Surface tension (mN/m)

70

60

50

0 ppm 10 ppm 15 ppm 30 ppm 50 ppm 100 ppm 130 ppm 150 ppm 200 ppm 400 ppm 810 ppm

40

30 0.0

0.5

1.0

1.5

2.0

2.5

3.0

NaCl concentration (M)

Fig. 3. Effect of NaCl concentration on surface tension of aqueous solutions in the presence of MIBC.

those shown in Fig. 3. Only at extremely low concentrations of DF-250 the situation is dominated by a surface-inactive compound (NaCl). Thus, in this case in almost whole range the properties of the system are determined by the frother. As these results show the two selected frothers are characterized by the properties which are quite different, especially in electrolyte solutions. Since MIBC is not very surface-active, below its s.t.s.p. any increase in ionic strength leads to a domination of the effect of surfaceinactive compound. This is very different for a much more surface active DF-250 which presence in electrolyte solutions is not masked by the effect of surface-inactive compound. 3.2. Effect of frothers on bubble coalescence Fig. 6 shows the bubble size versus frother concentration curves of MIBC and DF-250 (and two additional polyglycol frothers) illustrating the bubble coalescence phenomena in distilled water, and the critical coalescence concentration. The results demonstrate that DF-250 frother is more effective in preventing bubble coalescence than MIBC. This behavior is in agreement with their surface activity. 3.3. Effect of inorganic electrolytes on bubble coalescence Inorganic salts (NaCl) inhibit bubble coalescence as is shown in Fig. 7. However, the shape of the curves was somehow different from those obtained with frothers, where the CCC is usually determined by

the graphical interpretation as an intersection of two straight lines. In the case of NaCl and other electrolytes, three straight lines can be drawn through the experimental points. The concept of the critical coalescence concentration, originally dened to evaluate surface-active agents, was extended in this work to inorganic electrolytes. The values of CCC for electrolytes are considerably higher (around two orders of magnitude higher) than those for frothers (see Figs. 6, 7 and Table 1). Effect of the frothers (MIBC and DF-250) and NaCl, on bubble size is showed in Figs. 8, 9 and 10. It is clear that the primary bubbles generated in NaCl (electrolyte) are ner than in frother solutions. If it is assumed that the size of bubbles generated by a sparging mechanism in a otation cell is identical to the size of bubbles at c N CCC (Grau and Laskowski, 2006), then it must be observed that the sizes of such primary bubbles are different in salt solutions. 3.4. Bubble coalescence in mixed frotherelectrolyte systems Fig. 8 shows the effect of MIBC concentration on bubble coalescence at varying sodium chloride concentrations. The rst top curve shows the effect of MIBC on bubble size at increasing MIBC concentrations in distilled water. Then, the same effect is shown at 0.54, 2.0, and 5.0 M NaCl. At low concentrations of MIBC (up to 10 ppm), in NaCl solutions
90

75

Surface tension (mN/m)

70 65 60 55 50

water NaCl 0.1M NaCl 0.5M NaCl 1M NaCl 3M NaCl 4M seawater

Surface tension, (mN/m)

80

80

70

60

50

40

30 45 40 0 1 2 3 4 5 6 7 8 9 10
100 ppm

NaCl concentration, (M)

NaCl 5 ppm 200 ppm 2 ppm 10 ppm 400 ppm 3 ppm 50 ppm 800 ppm

DF-250 concentration (ppm)

Fig. 4. Effect of DF-250 concentration on surface tension of NaCl aqueous solutions (Castro et al., 2012a).

Fig. 5. Surface tension as a function of NaCl concentration for various DF-250 concentrations.

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S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814 11

Sauter mean bubble diameter, (mm)

1.8
CCC DF-1012

Table 1 The critical coalescence concentration (CCC) for NaCl and frothers.
MIBC DF-250 DF-400 DF-1012

1.6 1.4

CCC DF-400 CCC DF-250 CCC MIBC

Compound NaCl MIBC DF-250 DF-400 DF-1012

CCC, mmol/L 778.0 0.08904 0.04165 0.02154 0.01580

CCC, ppm 45,466 8.9 10.95 8.52 6.28

1.2 1.0 0.8 0.6 0.00

0.01580

0.05
0.04165 0.02154

0.10
0.08904

0.15

0.20

0.25

0.30

Concentration, (mmol/L)

Fig. 6. Sauter bubble diameter as a function of the concentration of the frothers (MIBC, DF-250, DF-400 and DF-1012) in distilled water, with graphical determination of the critical coalescence concentration.

NaCl concentration on DFI of MIBC and DF-250 frothers. While the surface tension measurements of MIBC and DF-250 solutions revealed a very large difference between these two frothers, the bubble coalescence measurements in which the bubble size was monitored did not reveal signicant differences. It is therefore interesting to observe that the foamability tests exhibit very signicant differences between the two tested frothers. 4. Discussion As concluded by Traube (1926), the surface-active substances are displaced from their aqueous solutions by surface-inactive substances, and this additionally decreases surface tension of water. Our Figs. 1, 2 and 4 are clearly in agreement with this concept. With increasing concentration of frother surface tension of the solution decreases, but as shown in Figs. 2 and 4 frother ability to decrease surface tension is augmented in electrolyte solutions. Fig. 15 shows a schematic representation of the s.t.s.p. concept. Since the slope of the curve when surface tension is plotted versus frother concentration changes with electrolyte concentration the two curves shown in Fig. 15 intersect at a given frother concentration. This concentration is the surface tension switch point. The change of the slope of the curve surface tension = f(c) indicates that a relatively weakly surface active compound changes into a stronger surface active compound at increased electrolyte concentration. This effect is very likely different in different electrolytes. Our bubble size measurements took place in a column in which bubbles were generated by passing nitrogen under pressure through a glass frit. Since a stream of bubbles is generated in such a device the bubbles collide with each other and their size is preserved only if they do not coalesce. As Fig. 6 indicates only at frother concentrations exceeding the CCC values the bubbles do not coalesce and all have uniform size. Our foamability tests were carried out in the same column which was used for bubble size measurements. The foam starts to form when the number of bubbles arriving at the liquid/gas interface exceeds the number of rupturing bubbles. However, this coalescence process now takes place in the foam and the properties and stability of the liquid lms separating
1.6

the bubble size slightly tends to increase, but then it is stabilized and decreases again. However, the bubble size in NaCl solutions, for all concentrations of MIBC, was smaller than in distilled water. Hence, these results imply that the size of the primary bubbles generated by a sparging mechanism depends on electrolyte concentration (decreases with increasing electrolyte concentration). The results obtained with DF-250 (Figs. 9 and 10) are similar. 3.5. Behavior of frothers in seawater Seawater contains around 0.550.60 M NaCl, and some secondary ions, such as, magnesium, calcium, sulfate, etc. Seawater, similar to inorganic electrolytes, is by itself able to prevent bubble coalescence. However, the effect of frothers on bubble coalescence was more pronounced in seawater than in pure electrolyte solutions. These results suggest that secondary ions play a signicant role. The blend of frothers and seawater clearly stabilizes bubbles against coalescence (see Figs. 1113) (Castro et al., 2010). Comparison of Figs. 11 and 12 seems to indicate that the bubbles generated in seawater in the presence of MIBC are ner than those generated in the presence of DF-250 (see Figs. 12 and 13). 3.6. Foamability in mixed frotherelectrolyte systems In this paper we also used the dynamic foamability index (DFI) as a method of characterizing bubble coalescence. Fig. 14 shows the effect of
1.6

Sauter mean bubble diameter, (mm)

Sauter mean bubble diameter, (mm)

1.4

1.4

0.00 M NaCl 0.54 M NaCl (seawater) 2M NaCl 5M NaCl

1.2

1.2

1.0

1.0
CCC for NaCl

0.8

0.8

0.6

0.6

0.4 0.4 0 1
0.7780

0 2 3 4 5

20

40

60

80

100

MIBC concentration, (ppm)

Fig. 8. Sauter bubble diameter as a function of MIBC concentration, for 0; 0.54; 2; and 5 M NaCl solutions.

NaCl concentration, (M)

Fig. 7. Sauter bubble diameter as a function of the concentration of NaCl solutions.

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12 S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814

Sauter mean bubble diameter, (mm)

Sauter mean bubble diameter, (mm)

1.6
Distilled water (DF-250)

1.4

1.4

0.6M NaCl (DF-250)

1.2

1.2

without MIBC 2 ppm 4 ppm 6 ppm 8 ppm 10 ppm 15 ppm 30 ppm 50 ppm 100 ppm Seawater salinity: 3.35%

1.0

1.0

0.8

0.8

0.6 0 10 20 30 40 50 60 70 80 90 100

DF-250 Concentration, (ppm)

Fig. 9. Sauter bubble diameter as a function of the concentration of DF-250, for 0 and 0.6 M NaCl concentrations.

10

20

30

40

50

60

70

80

90

100

Seawater %, (v/v)
Fig. 11. Sauter bubble diameter as a function of dilution of seawater (%), at different MIBC concentrations (Castro et al., 2010).

bubbles in the foam are now very different from the lms separating bubbles between colliding bubbles in an aqueous solution. The experimental results indicate that while the bubble coalescence characterized by bubble size measurements was not very sensitive to a type of frother, the results of the foamability tests turned out to be very different. In comparison with MIBC, the foamability is obviously better when DF-250 frother is utilized, especially at high salt concentrations. This conrms the importance of dynamic effects in foam formation (Malysa, 1992; Malysa and Lunknheimer, 2008) and possibly different types of the stabilizing forces which operate under studied conditions. While the bubble size measurements did not show any signicant differences between the two studied frothers, these measurements turned out to be sensitive to electrolyte composition. As Figs. 8, 9 and 10 demonstrate the size of the bubbles start increasing when frother (either MIBC or DF-250) is added to the solution. However, as Fig. 13 shows, when frothers are added to seawater the size of the bubbles decreases. Since seawater contains not only NaCl but also calcium, magnesium and other ions, this effect implies a different inuence of the inorganic ions on the surface activity of the tested frothers. As the results published a few years ago show (Grau and Laskowski, 2006) the frothers affect not only bubble coalescence but also bubble breaking process. These results (Figs. 713) indicate that the size of primary bubbles, the bubbles generated by a sparging device, is clearly affected by electrolytes. For example, this size decreases with seawater concentration suggesting that the bubble generating process in electrolyte solutions is more efcient.
0.84

Surface elasticity forces are induced and operate only under dynamic conditions. It is a self-healing capacity of the lm against external disturbances. The elasticity effects are possible only if a layer with different properties is formed at the interface, the layer in which there is a gradient of concentration. In the case of a surface-active agent this is very easy to visualize: such molecules accumulate at the liquid/gas interface (adsorption) and the gradient of concentrations at the interface is clearly established. The movement or any other dynamic disturbance that affects this gradient will immediately initiate the action of the self-healing forces. These are Marangoni dynamic elasticity effects. In the case of aqueous solutions of inorganic electrolytes the concentration of ions is lower in the surface layer than in the bulk (increasing surface tension), and the concentration gradient within this surface layer is also established. The elasticity effects should then also be possible. But it is also known, that in the presence of electrolytes the foam becomes drier, the bubbles carry less water with them and it was reported that the foaming is reduced under such conditions (Iskra and Laskowski, 1969). Our measurements indicate that this happens only at very high electrolyte concentrations; in the case of MIBC for NaCl concentration higher than 1 M, and of DF-250 for NaCl concentration higher than 2 M. The surface tension measurements indicate that the accumulation of the frother at the interface (adsorption) increases with increasing electrolyte concentration. This initially improves foaming. The adsorbed frother bonds some water molecules by hydrogen bonding but, apparently, the amount of such water in a bubble hydration shell is reduced

Sauter mean bubble diameter, (mm)

Sauter mean bubble diameter, (mm)

1.4

0.82

1.2

0.80

without DF-250 2 ppm 4 ppm 6 ppm 8 ppm 10 ppm 15 ppm 30 ppm 50 ppm 100 ppm Seawater salinity: 3.35%

0.78
06M NaCl (MIBC) 06M NaCl (DF-250)

1.0

0.76

0.8

0.74 0 10 20 0 10 20 30 40 50 60 70 80 90 100

Concentration, (ppm)
Fig. 10. Sauter bubble diameter as a function of the concentration of MIBC and DF-250 in 0.6 M NaCl concentration.

Seawater %, (v/v)
Fig. 12. Sauter bubble diameter as a function of dilution of seawater (%), at different DF-250 concentrations (Castro et al., 2010).

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S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814 13

0.78

Sauter mean bubble diameter, (mm)

0.76

MIBC (seawater) DF-250 (seawater) DF-400 (seawater) DF-1012 (seawater) Seawater salinity: 3.35%

0.74

0.72

0.70

0.68

0.66 0 20 40 60 80 100

Concentration, (ppm)
Fig. 13. Sauter bubble diameter as a function of frother concentration, for MIBC, DF-250, DF-400, and DF-1012, in seawater. Fig. 15. Schematic representation of the surface tension switch point (s.t.s.p.) concept.

at higher electrolyte concentrations. This seems to be explaining the observed reduced foaming when electrolyte concentration is very high. As Tan et al. (2004) demonstrated, the maximum in foaming when it is plotted vs. frother concentration also results from limited solubility of the frother and appearance of undissolved droplets at high concentrations. Since frother solubility is likely dependent on electrolyte concentration, this phenomenon may also play a role in concentrated electrolyte solutions. According to the most recent paper by Tan et al. (2009) a key parameter is the surface dilational viscosity which determines the Marangoni effect and retards water drainage then resulting in wetter foams and increased water recovery.

3.5x106 3.0x106 2.5x106 2.0x10

6

DF-250 (Distilled water) DF-250 (Seawater)

(a)

1.5x106 106 5.0x105 40x103 30x103 20x103 10x103 0 -10x103 -20x103

MIBC (Distilled water) MIBC (Seawater)

(b)

Samples of commercial frothers were utilized in this project. Nominal chemical formulas of the tested frothers can be written as: CH3CH(CH3)CH2CH(OH)CH3 for MIBC and CH3(OC3H6)nOH of DFseries of polyglycol frothers. While n = 3 in DF-200 frother, n = 4 in DF-250 and n = 6.3 in DF-1012. It must be borne in mind, however, that these are nominal formulas. In one of our papers (Melo and Laskowski, 2006) we measured surface tension for the suite of frothers which also included MIBC, DF-200 and DF-1012. While DF-200 is slightly more surface active than MIBC, DF-1012 was much more surface active. The surface tension vs. concentration curve for DF-1012 is very similar to the curves obtained in this project for DF-250 (Fig. 4). However, if elasticity forces are responsible for the stabilization of a dynamic system such as foam column then the stability of the foam is rather determined by the nonequilibrium adsorption parameters (Wantke et al., 1994). The dynamic surface tension measurements (Comley et al., 2002) showed very large differences between DF-200 and MIBC; while dynamic surface tensions for DF-200 practically did not depend on bubble life time this turned out to be very different for MIBC. This agrees well with Grau and Laskowski's data (2006) for DF-200. Grau and Laskowski also showed that while the dynamic surface tensions for DF-250 and DF-1012 frothers were similar these dynamic effects were very much larger than for DF-200. More complete analysis will require new dynamic surface tension measurements for the tested frothers as the composition of the samples of commercial frothers may differ; the tests should also include experiments at varying electrolyte concentrations. Finally, these results are relevant to otation practice in highly concentrated saline solutions and in seawater. Inorganic electrolyte is able to reduce bubble size in a similar way to frothing agents, explaining why in the salt otation process of natural hydrophobic minerals the addition of a frother is not necessary (Klassen and Mokrousov, 1963; Castro and Laskowski, 2011). When a collector is necessary to confer hydrophobicity to mineral particles, the froth stability is a function of bubble size, but other parameter needs also to be considered, such as, solid content, particle size, degree of hydrophobicity, water's salinity, pH, etc. (Castro et al., 2012b).

Dynamic Foamability Index, (s x L/mol)

5. Conclusions Two frothers (MIBC and DF-250), selected for the studies on bubble coalescence in otation systems, were shown to exhibit different surface activities as characterized by surface tension measurements.

NaCl concentration, (M)

Fig. 14. Effect of NaCl concentration, and also seawater, on the dynamic foamability index of DF-250 and MIBC.

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14 S. Castro et al. / International Journal of Mineral Processing 124 (2013) 814 Castro, S., Ramos, O., Cancino, J.P., Laskowski, J.S., 2012b. Frothing in the otation of copper sulphide ores in sea water. In: Drelich, J. (Ed.), Proc. 1st International Symposium. Water in Mineral Processing. SME, pp. 211223. Cho, Y.S., Laskowski, J.S., 2002. Effect of otation frothers on bubble size and foam stability. Int. J. Miner. Process. 64, 6980. Comley, B.A., Harris, P.J., Bradshaw, D.J., Harris, M.C., 2002. Frother characterization using dynamic surface tension measurements. Int. J. Miner. Process. 64, 81100. Craig, V.S.J., 2004. Bubble coalescence and specic-ion effects. Curr. Opin. Colloid Interface Sci. 9, 178184. Craig, V.S.J., Ninham, B.W., Pashley, R.M., 1993a. Effect of electrolytes on bubble coalescence. Nature (London, United Kingdom) 364 (6435), 317319. Craig, V.S.J., Ninham, B.W., Pashley, R.M., 1993b. The effect of electrolytes on bubble coalescence in water. J. Phys. Chem. 97 (39), 1019210197. Czarnecki, J., Malysa, K., Pomianowski, A., 1982. Dynamic frothability index. J. Colloid Interface Sci. 86, 570572. Deschenes, L.A., Barrett, J., Muller, L.J., Fourkas, J.T., Mohanty, U., 1998. Inhibition of bubble coalescence in aqueous solutions. 1. Electrolytes. J. Phys. Chem. B 102, 51155119. Grau, R.A., Laskowski, J.S., 2006. Role of frothers in bubble generation and coalescence in a mechanical otation cell. Can. J. Chem. Eng. 84, 170182. Grau, R.A., Laskowski, J.S., Heiskanen, K., 2005. Effect of frothers on bubble size. Int. J. Miner. Process. 76, 225233. Iskra, J., Laskowski, J.S., 1969. Quoted after J.S. Laskowski, frothers and frothing, frothing in otation II. In: Laskowski, J.S., Woodburn, E.T. (Eds.), Gordon and Breach, 1997, pp. 150. Keitel, G., Onken, U., 1982. Inhibition of bubble coalescence by solutes in air/water dispersions. Chem. Eng. Sci. 37, 16351638. Klassen, V.I., Mokrousov, V.A., 1963. An Introduction to the Theory of Flotation. Butterworths, London. Kracht, W., Finch, J.A., 2010. Effect of frother on initial bubble shape and velocity. Int. J. Miner. Process. 94, 115120. Laskowski, J.S., Cho, Y.S., Ding, K., 2003. Effect of frothers on bubble size and foam stability in potash ore otation systems. Can. J. Chem. Eng. 81, 6369. Lessard, R.R., Zieminski, S.A., 1971. Bubble coalescence and gas transfer in aqueous electrolytic solutions. Ind. Eng. Chem. Fundam. 10 (2), 260269. Malysa, K., 1992. Wet foams: formation, properties and mechanism of stability. Adv. Colloid Interf. Sci. 40, 3783. Malysa, K., Lunkenheimer, K., 2008. Foams under dynamic conditions. Curr. Opin. Colloid Interface Sci. 13, 150162. Malysa, K., Lunkenheimer, K., Miller, R., Hartenstein, C., 1981. Surface elasticity and frothability of n-octanol and n-ostanoic acid solutions. Colloids Surf. 3, 329338. Marrucci, G., Nicodemo, L., 1967. Coalescence of gas bubbles in aqueous solutions of inorganic electrolytes. Chem. Eng. Sci. 22, 12571265. Melo, F., Laskowski, J.S., 2006. Fundamental properties of otation frothers and their effect on otation. Miner. Eng. 19, 766773. Quinn, J.J., Kracht, W., Gomez, C.O., Gagnon, C., Finch, J.A., 2007. Comparing the effect of salts and frother (MIBC) on gas dispersion and froth properties. Miner. Eng. 20, 12961302. Randall, E.W., Goodall, C.M., Fairlamb, P.M., Dold, P.L., O'Connor, C.T., 1989. A method for measuring the sizes of bubbles in two- and three-phase systems. J. Phys. Sect. E: Sci. Instrum. 22, 827833. Tan, S.N., Fornasiero, D., Sedev, R., Ralston, J., 2004. The interfacial conformation of polypropylene glycols and foam behaviour. Colloids Surf. A 250, 307325. Tan, S.N., Jiang, A., Liau, J.J., Grano, S.R., Horn, R.G., 2009. The surface dilational viscosity of propylene glycol solutions and its inuence on water ow and foam behaviour. Int. J. Miner. Process. 93, 194203. Traube, J., 1926. Attraction intensity or attraction pressure. In: Alexander, J. (Ed.), Colloid Chemistry. Chemical Catalog Co., vol. 1, pp. 640646. Wantke, K., Malysa, K., Lunkenheimer, 1994. A relation between dynamic foam stability and surface elasticity. Colloids Surf. A 82, 183191. Weissenborn, P.K., Pugh, R.J., 1995. Surface tension and bubble coalescence phenomena of aqueous solutions of electrolytes. Langmuir 11, 14221426. Weissenborn, P.K., Pugh, R.J., 1996. Surface tension of aqueous solutions of electrolytes: relationship with ion hydration, oxygen solubility, and bubble coalescence. J. Colloid Interface Sci. 184, 550563. Zieminski, S.A., Whittemore, R.C., 1971. Behavior of gas bubbles in aqueous electrolyte solutions. Chem. Eng. Sci. 26, 509520.

These differences were further augmented in aqueous solutions at a high ionic strength. The concept of the surface tension switch point (s.t.s.p.) was introduced as the frother concentration at which the surface tension of frother aqueous solutions containing NaCl is lower than the surface tension of the frother in distilled water. It is suggested that the s.t.s.p. values may characterize the effect of salt concentration on frother properties. The s.t.s.p. values for MIBC and DF-250 were determined as 120 ppm for MIBC and 1.2 ppm for DF-250. The bubble coalescence was studied through the measurements of bubble size and foamability. The bubble size measurements revealed that inorganic salts similar to frothers, are able to prevent bubble coalescence, but at a concentration several orders of magnitude greater. If electrolytes are compared with frothers, the ner bubbles are generated in electrolyte solutions than in the presence of frothers. In the bubble size measurements carried out in NaCl solutions, the addition of MIBC or DF-250 does not decrease the size of bubbles beyond the values observed in the electrolyte solution alone. This is very different from seawater. In seawater with the addition of frother the bubble generation/coalescence produces ner bubbles. In this system, MIBC seems to be more efcient in preventing bubble coalescence if compared with a polyglycol type frother. While characterization of bubble coalescence in NaCl solutions through bubble size measurements turned out not to be very sensitive to differences between two tested frothers, the dynamic foamability tests showed much higher foamability of the DF-250 solutions in comparison with MIBC. These differences were especially visible at high electrolyte concentrations (and in seawater). The differences observed when different experimental techniques are utilized indicate that bubble stability against coalescence strongly depends on the dynamic nature of the tests which are selected for such studies. Acknowledgements Funding for this project was provided by the CORFO-INNOVA CHILE (Project 08CM01-18), with industrial sponsorship from: Antofagasta Minerals, (Esperanza); BHP Billiton, (Minera Escondida Ltd.); Anglo American Chile (Mantos Blancos); and Teck (Carmen de Andacollo), through AMIRA-AUSTRALIA operating Research Grant P968. References
Castro, S., Laskowski, J.S., 2011. Froth otation in saline water. KONA Powder Part. J. 29, 414. Castro, S., Venegas, I., Landero, A., Laskowski, J.S., 2010. Frothing in seawater otation systems. Proc. XXV Int. Mineral Processing Congress. CURRAN ASSOCIATES INC., pp. 40394047 (Brisbane). Castro, S., Toledo, P., Laskowski, J.S., 2012a. Foaming properties of otation frothers at high electrolyte concentrations. In: Drelich, J. (Ed.), Proc. 1st International Symposium. Water in Mineral Processing. SME, pp. 5160.