Colloids and Surfaces A 598 (2020) 124810

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Colloids and Surfaces A

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

Combined microflotation of glass beads T

a,b, c, a
N.N. Rulyov *, L.O. Filippov *, O.V. Kravchenko
a
Institute of Biocolloid Chemistry, National Academy of Sciences of Ukraine, Kyiv, Ukraine
b
PV “TURBOFLOTSERVICE”, Kyiv, Ukraine
c
Université de Lorraine, CNRS, GeoRessources, F54000 Nancy, France

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: It is well established that application of microbubbles in combination with coarser ones ensures a significant increase in
Combined microflotation the flotation efficiency of very fine (< 20 μm) and very coarse (> 100 μm) particles. The objective of this study is to
Air-in-water micro dispersion determine the impact of microbubbles on the flotation efficiency of medium-sized particles (50−80 μm). In tests runs
Glass beads we used glass beads (ballotini) of various size grades in the range:50; 50−63; 63−71; 71−80 μm as flotation objects.
Microbubbles
We used CTAB as both a collector and a frother at the dosage of 0.06 mg per 1 g of ballotini. Prior to starting flotation
by coarse bubbles, a dosage of microbubbles less than 60 μm in size in the form of a concentrated (66 vol. %) mi-
crobubbles dispersion in CTAB solution of (0.2 g L−1) produced by the MBGen-0.012 generator was fed into a flotation
cell. The best flotation performance is observed for the fraction of 63−71 μm, whereas the flotation rate constants for
all fractions are directly proportional to the volume dosage of microbubbles, when it does not exceed 0.2 mL g−1. The
size of microbubbles significantly affects the flotation effectiveness and depends on the concentration of the collector/
frother used for their production. The main mechanism of flotation performance enhancement through microbubbles
application, involves formation of coarse aggregates comprising large number of microbubbles and particles, which
provides for a significant increase in the capture efficiency of aggregates by coarse bubbles.

1. Introduction this technology is the feedstock comminution needed to separate a

valuable mineral from gangue. This size reduction process leads to
Flotation is one of the most efficient methods of ore and coal ben- sufficiently wide particle size distribution ranging from several micro-
eficiation. An essential precondition for a successful implementation of meters to several hundred micrometers. The flotation process involves

⁎
Corresponding authors.
E-mail addresses: nrulyov@gmail.com (N.N. Rulyov), lev.filippov@univ-lorraine.fr (L.O. Filippov).

https://doi.org/10.1016/j.colsurfa.2020.124810
Received 25 January 2020; Received in revised form 14 March 2020; Accepted 1 April 2020
Available online 11 April 2020
0927-7757/ © 2020 Elsevier B.V. All rights reserved.
N.N. Rulyov, et al. Colloids and Surfaces A 598 (2020) 124810

several sub-processes consisting in the interaction between particles indicate that the bulk ballotini (93.8 wt. %) comprise particles in the
and bubbles. The flotation rate constant and therefore the recovery is range of 50−71 μm.
the results of the efficiency of the consecutive sub-processes such as Flotation tests were run on tap water using a laboratory pneumatic-
particle-bubble collision (Ec), attachment (Ea) and stability of bubble mechanical flotation cell Mekhanobr-FM1M having a cell volume of 3 L
particle aggregates (Es = 1-Ed) [1,2]. The separation of particles of a and the cross section dimensions of 120 × 100 mm. The air flowrate
valuable component from gangue minerals is achieved through appli- was 1 L/min, and the rotor speed (diameter 60 mm) was 1000 rpm. The
cation of special reagents, which in the flotation process ensure selec- air was supplied by a controlled capacity peristaltic pump.
tive attachment of particles of the mineral (or gangue), to the surface of In all test runs, we used ballotini suspension in tap water; the sus-
rising bubbles. It is well known that the flotation rate significantly pension volume amounted to 3 L, with ballotini content of 0.1 kg.
depends on the collision efficiency of particles by a rising bubble Ec , Cetyltrimethylammonium bromide (CTAB, C19H42BrN), produced by
which in its turn depends on the ratio between the sizes of particle dp AppliChem GmbH (FRG) company was used both as a collector and a
and the bubble Db [3–5]. The practice shows [6] that very fine particles frother; its dosage in all experiments was 0.06 mg per 1.0 g of ballotini. It
(below 20 μm) and quite large ones (above 100 μm) float significantly is worth to note that the collector used impacts not only the particle hy-
worse compared to medium sized particles (in the range 50−80 μm). In drophobicity but also the froth structure when the concenraion is varied in
the first case, this phenomenon is due to the fact that in the first ap- the experiments. Thus, overall flotaion results obtained include the effect
proximation the value of Ec , is proportional to the square of the ratio of froth sability too. Microbubbles were produced by MBGen-0.012 unit, a
dp/ Db [7,8], which suggests that when, for example, the particle size generator of air-in-water microdispersion, made by Turboflotservice
decreases by two fold, floatability falls 4 fold. In the case of coarse company (see Fig. 2). Microbubbles in the form of concentrated (66 vol.
particles, the critical factor that reduces the efficiency of their capture %) microdispersion of air in CTAB solution (0.2 g L−1) were fed from the
by a large bubble can be attributed to the high energy of their collision generator outlet into the flotation cell through a narrow PVC tube. The
[9], and also to the high probability of particles detachment from a generator had the following capacity characteristics: for CTAB solution
bubble surface under the impact of turbulent pulsations of the hydro- 1.9 mL s−1, for microbubbles production up to 3.48 mL s−1. Then these
dynamic field inside a flotation cell [10,11]. When a coarse particle parameters, and the time for feeding the microbubbles dispersion into a
collides with a large rapidly rising bubble, a sufficiently thick liquid flotation cell were used to calculate a volume dose of microbubbles per
film forms between them, but the collision time is too short to reduce unit weight of ballotini and to define CTAB consumption in a flotation cell
the film thickness to a level when a thin film rupture appears, allowing required to ensure that a total dose is equal to 0.06 mg g−1.
a particle to attach to a bubble surface under the effect of surface forces. 1, 2-metering peristaltic pumps respectively for air and frother so-
As a result, a particle bounces back from a bubble surface under the lution; 3–push button for air and frother solution metering pumps; 4-
influence of the capillary forces acting from the side of a bubble surface, push button for disperser; 5 – disperser drive; 6 – instrument carry
deformed by a particle impact. Calculations presented by Rulev et al. handle; 7– disperser head; 8 – pipe for air-in-water microdispersion
[9] show that for a coarse particle to get attached to a large fast rising discharge; 9 - pipe for feeding air-in-water mix into disperser head.
bubble, a particle has to perform several consecutive jumps in order to During the test runs ballotini suspension was placed in a flotation
dissipate the excessive kinetic collision energy. cell, then a required amount of CTAB was introduced into the cell with
One potential solution of the challenge of fine particles flotation in- following mixing at a rotor speed of 1000 rpm but no air was supplied.
volves the application of a technique, now termed as the combined mi- After that, for a certain set pre-defined time, MBGen-0.012 generator fed
croflotation, when alongside with coarse air bubbles flotation also em- an air-in-water micro-dispersion into the flotation cell, and after that the
ploys relatively small amounts of microbubbles. As far back as the middle atmospheric air was supplied. Froth samples were collected in batches:
of the last century, it was found [12] that the introduction into pulp even 2 × 0.5 min and 2 × 1 min. Upon the completion of the flotation test,
relatively small amounts of microbubbles below 50 μm in size sig- collected froth samples were filtered, dried and weighed. Numerical re-
nificantly accelerates flotation recovery of fine particles (below 20 μm) sults shown graphically actually present the data averaged over three
by relatively coarse bubbles (1−2 mm) produced in a flotation cell. measurement runs. The relative measurement error comprises 2.5–3.4 %.
Recently published papers [13–16] theoretically and experimentally A laboratory unit, schematically shown in Fig. 3, was used to collect
substantiate the findings as in this case, microbubbles act as flotation the data on the dispersity of microbubbles produced by the MBGen-
carriers collecting on their surface fine particles, and then large bubbles 0.012 generator. This unit allows to get micrographs of bubbles coming
float these aggregates, as it is shown in Fig. 1a. The recent research directly out of MBGen-0.012 generator into to the CTAB solution. In
[17–19] have also demonstrated that the use of micro- and nanobubbles measurement runs, a peristaltic pump sucked in the microbubbles dis-
in combination with coarse bubbles boosts the flotation performance of persion into a photographic cell. The photos were taken once the pump
coarse particles, larger than 100 μm. The studies show that when on the and the generator were switched off (and respectively the flow
particles surface there are some well-settled micro- or nanobubbles, it is stopped). The procedure was repeated several times, and then the sta-
quite likely that colliding with a coarse bubble, a particle gets attached to tistical processing of obtained images was performed. To estimate ac-
a bubble due to the coalescence of small and coarse bubbles, as it is tual dimensions of bubbles, we used a calibrated tungsten filament of
shown in Fig. 1b. Thus, in the flotation of coarse particles by large 35 μm of diameter placed inside the photographic cell.
bubbles, microbubbles act rather as collectors than flotation carriers. The laboratory set schematically shown in Fig. 4 was used for ob-
Based on the above, we can assume that application of micro- and taining visual information on aggregates consisting of microbubbles
nanobubbles in combination with coarse bubbles can significantly in- and ballotini particles, which were formed in a flotation cell upon the
tensify the flotation not only of fine and coarse particles, but also of introduction of microbubbles into a cell. At the start of the measure-
medium-sized ones. The objective of this study was to establish the ments, ballotini suspension (10 g L−1) in a CTAB solution (5 mg L−1)
effect of microbubbles on the kinetics of pneumatic-mechanical flota- was placed in a one-liter beaker. When mixing started, MBGen-
tion of medium-sized particles simulated by glass beads (ballotini) of 0.012 generator was feeding microbubbles dispersion into the beaker
various size fractions. for 2–3 s, after that the photos of the mixture were taken in the mode
described above.
2. Experimental
3. Results and discussion
A suspension of glass beads (ballotini) produced by SWARCO-
Vestglas served as a flotation object. Table 1 shows the chemical Fig. 5 shows a typical micrograph of bubbles produced by MBGen-
composition and the size distribution of flotation objects. The data 0.012 generator. Statistical processing of micrographs of this type

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N.N. Rulyov, et al. Colloids and Surfaces A 598 (2020) 124810

Fig. 1. Graphics explaining the role of microbubbles in the combined microflotation of fine (a) and coarse (b) particles. The arrow shows a rebound of a coarse
particle from a coarse bubble in the absence of a microbubble between them at the collision.

Table 1 application should increase. This is proven by the data on kinetics of

Chemical composition and size distribution of ballotini particles. ballotini recovery (71−80 μm) shown in Fig. 7, obtained for various
Chemical composition Size distribution
concentrations of CTAB solution fed into the microbubbles generator.
From Fig. 6 it follows that the increase in CTAB concentration and,
Chemical component Content wt. % Particle size μm Content wt. % hence, the decrease of microbubbles size leads to enhanced of both the
flotation rate and the ultimate recovery.
SiO2 > 65.0 +80 0.59
Fig. 8 shows the flotation kinetics of the initial ballotini suspension
Al2O3 0.5−2.0 71−80 2.86
Fe2O3 < 0.15 63−71 69.02 at various dosage of CTAB in the absence of microbubbles, which de-
MgO > 2.5 50−63 24.76 monstrates that at a dosage of 0.05 mg g−1 in 3 min almost 90 % re-
CaO > 8.0 40−50 0.55 covery is achieved.
Na2O > 14.0 33−40 1.05
Based on the data shown in Figs. 6–8, in the major test runs on the
Other 2.0 −33 1.17
combined microflotation we selected and further maintained following
CTAB concentrations: 2 mg L−1 in the flotation cell; and 0.2 g L-1 in the
solution used for microbubbles generation.
For studying the effects of microbubbles on the flotation kinetics of
various particles size, the ballotini sieved into specific size fractions, in
microns: < 50; 50−63; 63−71; 71−80, which were analyzed sepa-
rately. Fig. 9 shows the recovery kinetic curves for different fractions in
the absence of microbubbles and at a dosage of microbubbles of
0.23 mL g−1, which demonstrate that for every fraction we can observe
not only a significant increase in flotation rate, but also increased ul-
timate recovery.
Fig. 10 shows the dependence of flotation rate constants at the in-
itial flotation time on the dosage of microbubbles for various fractions.
The dependencies were calculated based on experimental data related
to the recovery kinetics by the method of fitting the first-order reaction
equation using the technique of least squares for the time interval
0−1 min. The obtained results show that for all fractions, the flotation
rate constant is directly proportional to the microbubbles dosage in the
range 0−0.20 mL g−1. It is an interesting observation that similar re-
sults were obtained in the case of combined microflotation of finely
dispersed quartz (−21 μm) [13], which were later theoretically sub-
Fig. 2. Air-in-water microdispersion generator «MBGen-0.012». stantiated in [15].
Thus, for small microbubbles dosage f for the flotation rate constant
the following expression is valid
allowed calculating the integral functions of bubbles size distribution.
For illustrative purposes, Fig. 6 shows the distribution functions of K (f ) = K 0 + bf
bubbles received in the CTAB solution of the concentration of 0.1 and
0.2 g L−1 respectively. These findings demonstrated that at CTAB so- where K 0 is the flotation rate constant at zero dosage of microbubbles, b
lution concentration of 0.2 g L−1, 80 % of bubbles have size below is the proportionality coefficient.
33 μm and 50 % - below 17 μm. When CTAB concentration decreases by Fig. 11 shows dependencies of flotation rate constants on the
two fold, these values increase respectively to 52 and 25 μm. average particle size in fractions at different microbubbles dosage,
Obviously, when microbubbles get finer, the effectiveness of their which demonstrate that the maximum floatability is observed for

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N.N. Rulyov, et al. Colloids and Surfaces A 598 (2020) 124810

Fig. 3. Laboratory set layout for micrographing of bubbles produced by MBGen-0.012 generator.

particles in 63−71 μm fraction and the minimum floatability - for parameter b and the ratio K 0,1/ K 0 , that indicate that the largest relative
particles size in the fraction < 50 μm. For comparison, Table 2 presents increase in the flotation rate constant is observed for the smallest
the values of flotation rate constants at a zero dosage of microbubbles (< 50 μm) and largest (71−80 μm) fractions. At the same time, the
K 0 , at a dosage 0.11 mL g−1 (K 0,1), as well as the values of the largest value of the parameter b corresponds to the fraction

Fig. 4. Laboratory set layout for micrographing aggregates formed by ballotini and air microbubbles produced by MBGen-0.012 generator.

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Fig. 7. Kinetics of ballotini (size fraction 71-80 μm) recovery for a micro-
bubbles dosage of 0.23 mL per gram of ballotini and various concentrations of
CTAB solution fed into the microbubbles generator. Total CTAB concentration
in flotation cell – 2 mg/L.

Fig. 5. Micrograph of bubbles produced by MBGen-0.012 generator in CTAB

solution of 0.2 g L-1.

Fig. 8. Recovery kinetics of the initial ballotini suspension (−90 μm) at dif-
ferent CTAB dosage in the absence of microbubbles.

Fig. 6. Cumulative size distribution functions of bubbles produced by MBGen-

0.012 generator in CTAB solution 0.1 and 0.2 g L−1.

(63−71 μm), which has the highest floatability. The case that for
medium-sized particles b parameter is significantly higher compared to
that for coarse and fine particles can be attributed to the fact, that, “b”
parameter refers to the flotation rate increase at low microbubbles
dosage approaching zero. As coarse bubbles already nicely float
medium-sized particles, even small amounts of microbubbles suffi-
ciently enhance their flotation rate. In terms of fine and coarse particles,
the enhancement in their flotation rate requires significant amounts of
microbubbles. Hence, at higher microbubbles dosages the relative in-
crease in their flotation rates is considerably greater compared to that
for medium-sized particles.
These observations provided evidence that after microbubbles are Fig. 9. Recovery kinetic of various ballotini size fractions without microbubbles
application (solid lines) and at a microbubbles dosage of 0.23 mL/g (dashed lines).
fed into a flotation cell but before the start of air supply in the form of
CTAB content in the solution fed into the microbubbles generator is 0.2 g L−1.
coarse bubbles, formation of aggregates occur which comprise ballotini
particles and microbubbles, and the aggregate size increases with the
increase of the microbubbles dosage. Thus, for example, at a micro- significantly enhanced the flotation rate. As an illustration, Fig. 12
bubbles dosage of around 0.5 mL g−1, the aggregate size was 3−5 mm, shows an aggregates micrograph taken by a unit schematically shown in
and naturally, after the supply of coarse bubbles into a flotation cell this Fig. 4; this photo clearly shows that each aggregate comprises several

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N.N. Rulyov, et al. Colloids and Surfaces A 598 (2020) 124810

Fig. 10. Dependence of the flotation rate constant on the dosage of micro-
bubbles at the initial moment of flotation.

Fig. 12. Micrograph of flotation aggregates: light beads present ballotini, dark
ones – microbubbles.

large, they are floated comparatively well by coarse bubbles, as it

generally shown in Fig. 13.
As the increased microbubbles dosage induces both aggregates
growth in size and their better buoyancy, we can project that for suf-
ficiently large dosage of microbubbles, it may be possible to exclude the
use of coarse bubbles, as it is suggested by the principles of turbulent
microflotation presented in [20–22]. However, in this case the micro-
bubbles dosage should be significantly higher than 1 mL/g, which is
required to ensure fast formation of aggregates, and their sufficient size,
to provide for efficient separation of aggregates from the pulp and their
transfer into the concentrate.

4. Conclusions
Fig. 11. Dependence of flotation rate constant on the mean size of particles in a
fraction at various microbubbles doses. The above research findings suggest the following conclusions:

1 In flotation of medium-sized particles (50−80 μm) the application

Table 2
of microbubbles in combination with coarse bubbles provides for a
Ratio of flotation rate constants in the absence of microbubbles (K 0 ) and at the
significant increase in the flotation rate and the ultimate recovery.
dosage of microbubbles 0.11 mL g−1 (K 0,1).
2 The flotation rate constant is directly proportional to the volume
Size fraction, μm K 0 min−1 K 0,1 min−1 K 0,1/K 0 b g mL−1 min−1 dosage of microbubbles, when this dosage does not exceed 0.2 mL
g−1.
< 50 0.3 0.72 2.40 3.82
50−63 0.67 1.25 1.86 5.27 3 The size of microbubbles significantly influences the effectiveness of
63−71 1.07 1.67 1.56 5.45 their application and depends on the concentration of a collector/
71−80 0.42 0.96 2.28 4.91 frother used for their generation.
4 The principle mode of microbubbles action, which enhances the
flotation efficiency, involves the formation of large aggregates
microbubbles and multiple ballotini particles. In this test the ballotini formed by a large number of microbubbles and particles that en-
content was decreased roughly by three folds compared to its content in sures the significant increase in the efficiency of aggregates capture
flotation test runs in order to ensure better visual clarity of separate by coarse bubbles. Obviously, in an actual flotation system the ef-
hetero aggregates. fects of microbubbles, particle hydrophobiciy and froth stability
Hence, we have every reason to argue that in the flotation of could not be de-coupled when the collector used acts also as a
medium-sized particles, microbubbles act rather as flocculants than as frother.
flotation carriers or collectors. And since these aggregates are fairly

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Fig. 13. Model of combined microflotation of ballotini, where microbubbles act as a flocculant: (а) – formation of ballotini/microbubbles aggregates; (b) – flotation
of aggregates by coarse bubbles.

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