ADVANCES IN FLOTATION OF MINERALS FINES

Fabiano Capponi, Elves Matiolo, Denise G. Nunes, Jorge Rubio*

Departamento de Engenharia de Minas-Laboratrio de Tecnologia Mineral e Ambiental-Universidade Federal do Rio Grande do Sul, Av. Osvaldo Aranha 99/512, 90035-190, Porto Alegre, RS, Brazil; jrubio@vortex.ufrgs.br; http://www.lapes.ufrgs.br/Laboratorios/ltm/ltm.html

Carlos Perez Guerrero Codelco-Divisin Chuquicamata, Chuquicamata-Chile Gabriel Berkowitz IM2-Instituto de Innovacin en Mineria y Metalurgia S.A. Filial Codelco. Av. Del Parque 4980, Ciudad Empresarial, Huechuraba-Santiago-Chile.

ABSTRACT This paper describes some advances in flotation research in fines (F, 38-13 m) and ultrafines (UF, < 13 m) mineral recovery by two different techniques, at laboratory scale. Extender flotation and flotation with multi-bubbles (bubbles with a wide size distribution) of copper sulphide fines (ore feed of about 1 % Cu) were compared with a standardised mill laboratory procedure. Comparative evaluation was made through concentrate grade and recovery (size by size results included), true (bubbles-particles attachment only) flotation recoveries and process kinetics. Both techniques yielded higher metallurgical efficiencies than the mill standard but better results were obtained with the extender flotation, with emulsified diesel oil (90 gt-1). Concentrate recoveries were of the order of 85-90 % (84 % in standard conditions), 14-17 % Cu grade (15 % Cu in the standard) and 3.5-4.5 min-1 for the Klimpel rate constant (3 min-1 in the standard). Size by size and true flotation results proved that metallurgical and kinetic gains, obtained with the two techniques, might be attributed to fines and ultrafines enhancement. Data obtained are discussed in terms of physical and physico-chemical parameters related to aggregation and capture (of particles by bubbles) phenomena and the practical potential of these techniques are envisaged. Keywords: Fines, flotation, techniques, copper ores INTRODUCTION
The problem (very old) of processing by flotation, the fine (F, 38-13 m) and ultrafines (UF, < 13 m) mineral particles continues to be one of the major technical challenges in the area of mineral processing (Trahar, 1981, Sivamohan, 1990, Collins and Read, 1971). Some agreement exists in that the problem is caused by the intrinsic properties of these particles: small mass, high interfacial free energy. Thus, main flotation drawbacks are related to the low probability of bubble-particle collision and adhesion, mechanical entrainment and entrapment, "slime coating", higher flotation reagent adsorption, formation of dense froths and low process kinetics. Many different processes for solving their poor flotation recovery have been proposed over the last three decades but, unfortunately, most of them have not found practical applications yet (Bulatovic and Wyslouil, 2000, Subrahmanyan and Fossberg,,1990, Song and Valdivieso, 1998, Rubio and Hoberg, 1993, Warren, 1992, Mehrotra et al., 1983). A good example is the case of selective flocculation with polyelectrolytes that despite more than 30 years of extensive studies still remain a "promising" process (Kitchener, 1978, Rubio and Kitchener, 1977, Sivamohan, 1990, Mathur et al., 2000).

* = Corresponding author

However, some practical alternatives to alleviate problems with the fines are currently under way:

Reduction of the F-UF generation in the mill; Optimisation of the capture stage; Selective aggregation of the F-UF; Recovery of the F-UF in tailings plants

The alternatives for reducing the generation of F-UF are possible by controlling and optimising crushing, grinding and re-grinding stages, classifying the flotation feed into F-UF and Coarse circuits and by introducing Unit and/or Rougher-flash operations to yield high grade, final concentrates and reducing mass to an eventual regrinding. Regarding the optimisation of the capture (collection) stage, all existing models are addressed to the need for a wide bubble size distribution (100m-2 mm) to obtain a better flotation size-by-size, Yoon, 1999, Yoon 2000, Franzidis and Manlapig, 1999. However, conventional cells do not provide sufficient bubbles in the range < 600 m. Upcoming flotation devices, namely Jet (Jameson) flotation cell and the Microcel column claim that a substantial amount of bubbles < 600 m are generated and consequently they are more suitable for fines recovery (Mohanty and Honaker, 1999, Jameson and Manlapig, 1991, Yoon and Luttrell, 1994, Yoon et al., 1992). Yet, the problem of recovering the fines and specially the ultrafines (<13 m) by flotation still continues. Aggregation of particles, with the use of reagents (surfactants, polymers and oils), to solve the problems of fineness has been attempted by many ways (Kitchener, 1978, Song, et al., 1999). Aggregation by surfactants conducted under strong agitation led to the method known as "shear flocculation" technique (Warren, 1992) whereby separation by settling was possible. Conversely, the separation of the formed aggregates using bubbles was named floc-flotation (Song and Valdivieso, 1998, Warren, 1992). Again, none of these techniques appear to be used industrially. The use of selective flocculation requires process high selectivity. Unfortunately, this is the main limiting factor because most flocculants are not truly "specific" polymers and usually adsorb unselectively onto the surfaces of either gangue or middling particles, flocculating them together with the mineral values. All ideas tested to solve these drawbacks have not succeeded (Rubio and Kitchener, 1977, Rubio and Marabini, 1987, Matur et al., 2000). Nonpolar oils have been also used to aggregate (agglomeration, in this case) fine particles at varying oil /solids ratio. The higher the oil concentration, the bigger are the agglomerates. These units are separated either using air bubbles (low oil /solids ratio) or by gravity when agglomerate sizes are bigger (high oil dosages). The latter is known as oil-agglomeration process or spherical agglomeration (Mehrotra et al., 1983, Laskowski, 1992). Should the amount of oil is increased further to levels exceeding in a few times the voids volume; a three-phase system is formed (solid, water and the oil phase). Hydrophobic particles are transferred to the oil phase from the aqueous phase leading to a liquid-liquid extraction Laskowski, 1992). However, there is a situation, not much explored, whereby the oil, if emulsified, interact firstly (as droplets) with the hydrophobic mineral surfaces, then spreads it out as an oil layer. This leads to an optimised flotation, known as extender flotation, which appears to combine an enhanced hydrophobicity with some degree of particle aggregation (Laskowski and Dai, 1993, Laskowski and Wang, 1997). The aim of this work is to compare, at laboratory scale, standardised flotation copper sulphides mill tests with flotation techniques based on oil extender using emulsified oils and flotation with a mixture of bubbles (fines and coarse). Comparisons were measured through the separation parameters; grade, recovery and flotation rate constants included size-by-size results to assess the flotation behaviour of the F and UF fractions. This work constitutes a part of a big project, which is being continued, now at pilot plant scale. EXPERIMENTAL Materials Ore. Copper porphyry samples, containing about 1/3 of the mass and about 37 % of the total copper content in the fines and ultrafines fractions were used throughout this work. Table l and Figure 1 show feed size-to-size mass and copper distribution (total, 0.94 % Cu). Samples were dried, weighed and quartered in aliquots to yield about 38 % solids by weight in the cell.

Table 1. Averaged size-by-size mass and copper distribution in sample Size, m > 295 295-212 212-150 150-75 75-40 40-15 15-5 <5 Mass distribution by size Weight, % Cumulative % 17.66 17.6 30.61 12.9 40.64 10.0 51.46 10.6 67.51 16.05 79.64 12.13 87.62 7.98 100 12.38 % Cu 0.47 0.65 0.81 1.17 1.31 1.39 1.25 0.67 % Cu Cumulative % 0,08 0,17 0,25 0,38 0,59 0,75 0,85 0,94

120 100 Weight, %. 80 Weight, % Copper %

1 0.8 0.6 Copper, %.

60 0.4 40 20 0
> 295 295-212 212-150 150-75 75-40 40-15 15-5 <5

0.2 0 Size, m
Figure 1. Copper and mass size distribution in sample.

Reagents. Common collectors and frothers mixtures for copper sulphides were used. Lime, as pH regulator to pH 10.5 was added at the conditioning stage together with SF-113 (sodium isopropyl xanthate) at 30 gt-1 concentrations. The frother (20 gt-1) was a mixture of DF - 250 (a propylene glycol), MIBC (Methyl isobutyl carbinol) and pine oil. Diesel and Kerosene were the extender oils studied and corresponded to commercial chemicals commonly used in the vehicles industry. The Diesel oil, which yielded the best results, has a density of 0.831 gcm-1, a 38.82 API grade and a viscosity of 4.5 cp (mPa.s). Methods Conventional, "standardised" (mill) kinetic flotation tests were conducted in a 3L laboratory Denver D12 cell. Conditioning of the feed (38 % solids content, pH 10.5), at 1000 rpm (no turbulence), was conducted in the cell, during 3 min to allow collector and frother adsorption. Data (quadruplicates) were obtained from concentrates taken at 1, 3, 5, 7 and 9 min flotation using a mechanical scrapper and keeping constant the pulp volume. Samples (concentrates and tailings) were then filtered, dried, weighed and analysed for copper by atomic absorption. Extender flotation tests. In this case, kerosene or diesel-in-water emulsions were prepared in a high free rotational speed stirrer (Turrax, with up to 23.000 rpm), during 10 min. The extender oils were used as an extra reagent added after the collector and frother addition during the conventional conditioning. Oil concentrations were 30, 60, 90 and 120 mgl-1. Oils were added to water at the desired pH 10.5, and the oil to water volume ratio was kept at 1:99. Under favourable emulsification conditions, the oil could be entirely

dispersed into the aqueous phase (otherwise, part of the oil stuck to the wall of the container). After the emulsion additions, the flotation procedure proceeded similarly to the standard mill flotation test. Flotation with multibubbles. Here, bubbles sizing about (50-200 m) generated by drawing air through an aspiration nozzle into water were discharged, at different times and volumes (see Table 2 below), in the cell along with the bubbles produced in the actual cell (0.7-2 mm). Bubbles size distributions were measured using a new technique (Rodrigues and Rubio, 2003) and full data are not shown in this work.
Table 2. Experimental conditions in the flotation with injected bubbles. SB = injected small bubbles. T = flotation times.

Tests SB 1 SB 2

T=0 400 200

Injected volume, ml T = 3 min T = 5 min 100 100 50 50

T = 7.5 min 100 50

All concentrates were analysed by the content of Cu and the process efficiency was measured by evaluating separation parameter recovery, true recovery (Warren 1985), grade and constant rate. All results obtained are average of at least three different experiments. Finally, to assess the performance of flotation in the F and UF fractions, size by size copper recoveries were measured in the fractions: > 40 m; 40-15 m; 15-5 m and < 5 m. This was possible using micro-sieves from Retsch model USG.

RESULTS AND DISCUSSION Standard Flotation Tests

Figures 2 and 3 show kinetic flotation results yielding recoveries up to 84-85 % Cu with rate constants (Klimpel model) of the order of 3 min-1. Recovery-grade curves are presented in Figure 4 showing concentrate grades up to 15-15.5 % Cu. All results presented very low standard deviation (< 1 %) making all data obtained very reliable.
100 80 Copper Recovery % 60 40 20 0 0 2 4 6 8 10 Flotation Time, min

STD Average STD 1 STD 2 STD 3 STD 4

Figure 2. Flotation kinetic curves of a copper sulphide ore: Mill Standard (STD).

STD Average

STD 3

STD 3

STD 2

STD 1 2.0 2.3 2.5

-1

2.8

3.0

3.3

3.5

k, min (Klimpel)
Figure 3. Standard (STD) flotation rate constants of a copper sulphide ore.

16

Copper Grade, %

15 STD Average 14 STD 1 STD 2 13 STD 3 STD 4 12 55 60 65 70 75 80 85 90

Copper Recovery, %
Figure 4. Standard (STD) flotation of a copper sulphide ore: Grade-recovery curves.

Extender flotation studies

Figures 5 and 6 show comparative values between the mill standard test and those with diesel oil-in water emulsions. Best results were obtained with the extender diesel oil (90 mgL-1) and not with kerosene at any concentration.

100 80 Copper Recovery, % 60 40 20 0 0 2 4 6 8 10 Flotation Time, min

Figure 5. Flotation kinetic of a copper sulphide ore: Comparative curves for Standard (STD) and Extender flotation with Diesel oil (different concentrations).

STD Average Extender 30 ppm Extender 90 ppm Extender 120 ppm

Extender D 120 ppm

Extender D 90 ppm

Extender D 30 ppm

STD average 0.0 0.5 1.0 1.5

-1

2.0

2.5

3.0

3.5

4.0

k,min (Klimpel)
Figure 6. Flotation kinetic of a copper sulphide ore: Comparative rate constants for Standard (STD) and Extender flotation with emulsified diesel oil (different concentrations).

It is believed that during oil extender, enhanced hydrophobisation and aggregation of the fines themselves or with coarser particles (carrier) takes place. This may explain, results obtained, higher recoveries and concentrates grades and improved process kinetics. Figure 7 illustrates that hydrophobic aggregation occurs after the spreading of the oil at the collector-coated particles (fines and ultrafines). The capture of either hydrophobic enhanced particles or aggregates is highly improved in this oil extender technique (Figure 7 a, b). This aggregation hypothesis has been proved by monitoring the aggregate formation in a microscope and by measuring true flotation recovery values (recovery through bubbles only). More, the effect only occurs with oils having aromatics content, below about 40 % but with naphtenic fractions, and comprising chain lengths of from about 17- about twenty-two carbon atoms. These extender oils had to be highly emulsified and included diesel and ESSO 2600 brand (results not shown here). Yet, the effect was not found with kerosene, light oil without naphtenic groups and low aromatics content. Smitt and Basin (1985),

reported similar results for molybdenite and Laskowski and co-workers, for flotation recovery of coarse potash fractions (Laskowski and Dai, 1993, Laskowski and Wang, 1997).

OIL F-UF F-UF B F-UF

OIL
F-UF F-UF F-UF F-UF F-UF F-UF F-UF F-UF B

Oil extender (a)

Oil extender (b)

Figure 7. Aggregation phenomena in oil extender flotation of copper sulphide fine (F) and ultrafine (UF) particles

Flotation with enhanced bubbles size distribution

Fines particle capture (magnitude and kinetic) enhances in the presence of small bubbles leading to higher recoveries and flotation rate constants (Figures 8 and 9). Results obtained appear to prove most of the reported models pointing out the enhanced capture of particles by bubbles, the main drawback in fine flotation, Yoon, (1999, 2000), Franzidis and Manlapig (1999). The usual, conventional flotation cells do not generate bubbles smaller than 600 m, thus floating preferentially (exclusively) the coarse particles. In this work, by widening the bubble size distribution in the cell, through the injection of small bubbles, the bubble surface flux and the fines capture highly increase (Hieskanen, 2000). Similarly, the generation of fine bubbles, in a cavitation tube, and in columns has improved the flotation of mineral fines and it is expected that this fine bubbling approach will be utilised for the design of future flotation devices (Solari and Gochin, 1992, Zhou et al., 1994, 1995 and 1997).
100 80 Copper Recovery, % 60 40 20 0 0 2 4 6 8 10 Flotation Time, min

STD Average SB 1 SB 2

Figure 8. Flotation kinetic of a copper sulphide ore: Comparative curves for Standard (STD) and with injection of small bubbles (SB): For SB1 and SB2, see Table 2.

STD Average

SB 2

SB 1

2.0

2.5

3.0
-1

3.5

4.0

4.5

k, min , (Klimpel)

Figure 9. Flotation of a copper sulphide ore: Comparative rate constants for Standard (STD) and flotation with injection of small bubbles (SB): Conditions for SB1 and SB2, see Table 2.

Best metallurgical results obtained in this work are attributed to fines and ultrafines enhancement because of the following reasons: 1. The quality of the laboratory data to evaluate accurately the flotation performance, especially in the size by size tests; 2. The technical optimisation of the finer fractions is clearly reflected in the true flotation recovery values (Figure 10). Should the F and UF were not floated, no true flotation values (through particles-bubbles attachment only) higher than the mill flotation standard would have been obtained.

SB 1

Extender 90 ppm

STD Average

58

60

62

64

66

68

70

True Copper Recovery, %

Figure 10. Flotation of a copper sulphide ore: Comparative true flotation values for Standard (STD), Extender (diesel) flotation and with injection of small bubbles (SB): Conditions for SB1 and SB2, see Table 2.

3. Metallurgical results in the fines and ultrafines fractions. Figures 11 and 12 show size-by-size copper recoveries results, after classification of produced concentrates and tailings using micro-sieves. Results clearly show that flotation of the F and UF fractions is highly improved with injection of small bubbles (SB)

and with the addition of an extender collector. Figure 11 shows that copper recoveries, after 9-min flotation, were higher in all F and UF fractions using multibubbles or emulsified Diesel oil. Moreover, similar behaviour occurred at the very first minute (Figure 12) showing, as expected, an improvement in process kinetics.

> 40 Size fraction, m

15 - 40

5 - 15
Extender D90 ppm SB 1

-5 60 70 80 Cu recovery, %

STD Average

90

100

Figure 11. Comparative size-by-size copper recoveries in concentrates (9 min).

> 40 Size fraction, m

15 - 40

5 - 15 SB 1 Extender D90 ppm -5 STD Average 20 40 60 Cu recovery, % 80 100

Figure 12. Comparative size-by-size copper recoveries in concentrates (1 min).

It is believed that the techniques presented here will establish shortly a new basis for the flotation enhancement of the F and UF, aimed at solving a very old problem. This work is being continued, now at pilot plant scale, and results will be published en the near future.

CONCLUSIONS
Results found in this work showed that extender flotation with emulsified diesel oil (> 90 gt-1) and conventional flotation plus injected small bubbles (50-200 m), yielded higher metallurgical efficiencies than the mill standard for copper sulphide fines. Concentrate recoveries increased in about 2-4 %, 3-5 % in true flotation recoveries and between 20-30 % in flotation rate. Size by size, kinetics and true flotation results proved that metallurgical gains might be attributed to fines (F, 38-13 m) and ultrafines (UF, <

13 m) flotation enhancement. All data are explained in terms of physical aggregation and hydrophobicity factors that improve the capture of fine and ultrafines particles by bubbles. It is believed that these results represent actual advances in the improvement of fine particle flotation.

ACKNOWLEDGEMENTS
The authors are thankful to all Institutions supporting research in Brazil and Chile.

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