Mineral Processing and Extractive Metallurgy Review

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Recovery of fine and ultrafine mineral particles by

electroflotation – A review

Bogale Tadesse, Boris Albijanic, Fidele Makuei & Richard Browner

To cite this article: Bogale Tadesse, Boris Albijanic, Fidele Makuei & Richard Browner (2018):
Recovery of fine and ultrafine mineral particles by electroflotation – A review, Mineral Processing
and Extractive Metallurgy Review, DOI: 10.1080/08827508.2018.1497627

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
https://doi.org/10.1080/08827508.2018.1497627

Recovery of fine and ultrafine mineral particles by electroflotation – A review

Bogale Tadesse, Boris Albijanic, Fidele Makuei, and Richard Browner
Department of Mining Engineering and Metallurgical Engineering, Western Australian School of Mines, Curtin University, Kalgoorlie, Australia

ABSTRACT KEYWORDS
Fine and ultrafine particles are successfully recovered by flotation when fine bubbles are present. Ultrafine particles;
Electroflotation is a technique in which fine bubbles are generated by the electrolysis of water. This electroflotation; electrolytic
article reviews the experimental studies into mineral recovery by electroflotation and the potential bubbles
application of electrolytic bubbles in the recovery of fine and ultrafine mineral particles. The literature
reveals that electroflotation resulted in better recoveries of ultrafine particles (e.g. dolomite, magnesite,
and pyrite) as compared with dispersed-air flotation because electrolytic bubbles are smaller in size and
are more active than those generated during dispersed-air flotation.

1. Introduction bubbles with a mean diameter from 17 to 105 μm based on

Flotation method involves the introduction of air bubbles into
ore slurries in which the target particles selectively attach to
air bubbles and rise to the surface, overflowing the flotation
cell into the flotation launder. This method works well for
particles of a limited size range, beyond which its efficiency
reduces substantially. More precisely, particles finer than
approximately 10 μm are in general not effectively and selec-
tively separated by traditional froth flotation because they
tend to follow liquid streamlines around bubble due to their
low inertia, reducing the probability of collision between
particles and bubbles (Zhou et al. 1997; Dai et al. 1998). A
number of factors such as contact angle, surface roughness,
hydrophobicity, zeta potential, reagent type and pH are
known to affect flotation performance because of their impact
on the adsorption of collectors on mineral particles. However,
in the case of ultrafine particles, due to their higher specific
surface area and higher surface energy, the adsorption of
collectors becomes non-specific. That is, fine and ultrafine
particles behave differently from coarse particles during flota-
tion. The challenges encountered during flotation of fine and
ultrafine particles by mechanical cells are well documented
(Gaudin et al. 1931, 1942; Flint and Howarth 1971; Trahar
and Warren 1976; Fuerstenau 1980; Yoon and Luttrell 1989;
Miettinen et al. 2010). Thus, fine and ultrafine particle separa-
tion by flotation is now considered as a major challenge in
mineral recovery and extensive research is necessary to
improve flotation performance (Ahmadi et al., 2014).
Given that the probability of collection of fine particles
increases with decreasing bubble size (Dai et al. 2000), various
techniques have been developed for the generation of fine
bubbles for flotation separation. In electroflotation, bubbles
are generated through the electrolytic breakdown of water
which leads to the formation of fine hydrogen and oxygen
the conditions of electrolysis (Han et al. 2002; Jiménez et al.
2010). The technique is particularly attractive because bubbles
sizes can be controlled by varying the current density, pulp
pH, and electrode materials.
The application of flotation for the recovery of valuable
minerals originated from Broken Hill, Australia in 1904
(Elmore 1905). Some reports suggest that the technique of
electroflotation originated mainly in the USSR for the treat-
ment of waste water and the clarification of grape liquor
(Matis and Peleka 2010). Commercial applications of elec-
troflotation are reported in silk and meat industries, oil
refining, leather industries and steel plants mostly in the
former USSR and a few in Germany, Japan, and the UK
(Bhaskar Raju and Khangaonkar 1984a; Matis and Gallios
1986). Other small scale studies include the electroflotation
of pyrite (Kyrdos et al., 1994), chalcopyrite (Bhaskar Raju
and Khangaonkar 1982), sphalerite (Llerena et al. 1996),
dolomite and magnesite (Matis et al. 1993), and silica
(Sarkar et al. 2011), removal of heavy and toxic metals
from wastewater (Zouboulis and Matis 1989, 2012; Il’in
et al. 2014; Oliveira et al., 2015), and the separation of oil
and low-density suspended solids from various wastewaters
(Alexandrova et al. 1994; Kubritskaya et al. 2000; Chen
2004; Kyzas and Matis 2016).
The focus of this work is on the physics governing the
generation of electrolytic bubbles and the potential applica-
tion of electrolytic bubbles to recovery fine particles by elec-
troflotation. The modeling of electroflotation process will also
be reviewed.
The article is organized as follows. The mechanisms of
bubble formation in electroflotation will be briefly reviewed
in the next section. This is followed by an overview of factors
affecting bubble size during electroflotation. Advantages and

CONTACT Bogale Tadesse Bogale.tadesse@curtin.edu.au Department of Mining Engineering and Metallurgical Engineering, Western Australian School of
Mines, Curtin University, Egan St, Kalgoorlie, WA 6430, Australia
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gmpr.
© 2018 Taylor & Francis Group, LLC
2 B. TADESSE ET AL.
disadvantages of the use of electroflotation in fine and ultra-
fine particle recovery will be described in Section 4. The
modeling of electroflotation process will be reviewed in the
last section.
Before reviewing electroflotation, it is important to highlight
that the classification of particles into coarse, fine, and ultrafine.
A particle size classification for gravity separation has been
proposed elsewhere (Sivamohan and Forssberg 1985).
However, in this article in relation to electroflotation, coarse
particles range in size from 38 to 250 µm, fine particles are those
in the range between 10 and 38 µm while ultrafine particles are
those in the range between 1 and 10 µm in diameter.
2. Mechanisms of Bubble Formation in
Electroflotation
Hydrogen and oxygen bubbles are generated during water
electrolysis (Matis et al. 1993). More precisely, hydrogen is
released at the cathode surface while oxygen is released at the
anode surface as shown in Equations (1) and (2).
Anode : 2H2 OðlÞ ! O2ðgÞ þ 4H þ ðaqÞ þ 4e
Cathode : 4H þ ðaqÞ þ 4e ! 2H2 ðgÞ
The cell voltage between two electrodes during water electro-
lysis is the summation of the equilibrium potential difference,
the anodic and cathodic overpotentials, and ohmic potential
drop of the aqueous solution.
The standard free energy of reaction, ΔG0 ; can be
expressed in terms of the thermodynamic potential (E0 ) of
water decomposition as:
ΔG0
E0 ¼
nF
where n is the number of exchanged electrons and F is
Faraday’s constant (96,485 C/mol).
Since the decomposition of water at standard temperature
and pressure requires a theoretical minimum of 237.13 kJ/mol
of electrical energy input (Chen and Chen 2010), it follows
from Equation (3) that the minimum voltage necessary for
electrolysis is about 1.23 V. Although the equilibrium poten-
tial difference required for the decomposition of pure water
into hydrogen and oxygen −1.23 V, a potential difference of
> 2 V is often required in practice due to the contributions of
overpotantial and ohmic potential drop (Chen et al. 2002).
Hydrogen and oxygen molecules generated by electrolysis
forms bubbles but can also dissolve into the bulk solution by
convective diffusion. For example, Müller et al. (1989) found
that at a current density of 3000 A/m2, up to 85% of hydrogen
generated forms hydrogen gas bubbles. The mechanism of
formation of bubbles at electrode surfaces involves three
sub-processes: bubble nucleation, bubble growth, and bubble
detachment from the electrode. Bubble sizes also increase due
to the diffusion of gas through bubble surfaces. These sub-
processes are discussed below.
2.1 Bubble Nucleation on an Electrode
The nucleation of a bubble on an electrode surface occurs
when the bubble attains a radius that is larger than the critical
bubble radius (r ), which is defined by the Gibbs-Thompson
equation as:
2σΩ
r ¼ (4)
kTlnðp=p0 Þ
where σ, Ω, k, and T are the interfacial tension, the molecular
volume, the Boltzmann’s constant, and the temperature,
respectively; p0 is the vapor pressure of a flat sample of
infinite radius, while p is the vapor pressure of a sub-critical
nucleus of radius, r . As can be seen in Equation (4), the
increase in p leads to decrease in r .
In electroflotation, nucleation of bubbles occurs on solid
electrodes. The rate of heterogeneous bubble nucleation, J, is
given by (Lubetkin 1995):


Φ0 ðθÞ ΔG
J ¼ Cexp (5)
kT
where C is pre-exponential factor, Φ0 ðθÞ is the fractional
reduction in the volume of the critical sized bubble when it
(1)
forms on a surface:
(2) Φ0 ðθÞ ¼ ð1 þ cosθÞ2 ð2  cosθÞ=4 (6)

The free energy barrier to the phase change, ΔG , is given by:
 2
ΔG ¼ 16πσ 3 Ω2 =3 pb  p (7)
and pb is the pressure inside the bubble.
Bubble nucleation rate depends on electrode surface inhomo-
geneity, the diameter of an electrode wire, and current density
(Glas and Westwater 1964; Janssen and Hoogland 1973). The
inhomogeneity of the electrode surface (e.g. cracks and
scratches) results in the increase in bubble nucleation rate due
to atomic ledges and thus higher energy points on the electrode
(3)
surface. The smaller diameter of the electrode wire also leads to
higher bubble nucleation rate probably because bubbles
detached from wire with a small diameter have a smaller size
than those detached from wire with a larger diameter (Sarkar
et al. 2010). Thus, the detachment rate of bubbles from the wire
with smaller diameter results in more nucleation sites on the
wire surface. Finally, the increase in current density leads to
higher bubble nucleation rate probably because the generation
of molecules is more pronounced at a higher current density (i.e.
the concentration of dissolved gas increases).
2.2 Bubble Growth on an Electrode
Bubbles can grow if bubble size is higher than the critical
bubble size. Another reason for bubble growth is coalescence
with other bubbles on electrode surfaces (Sides and Tobias
1985). A number of factors influence the bubble growth rate
including the molecular diffusion of gas to the interface of the
bubble, inertia, viscosity, and surface tension. Bubble growth
kinetics can be described using the power law model
(Brandon and Kelsall 1985):
rðtÞ ¼ η0 t l (8)
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 3

where rðtÞ is the bubble radius at time t after nucleation, η0
is the growth coefficient, t is time and l represents the time
coefficient. It is important to note that the higher the time
coefficient, the faster the bubble growth. It was proposed
(Brandon and Kelsall 1985) that there are three regions of
bubble growth based on bubble growth time i.e. Region I,
Region II, and Region III as shown in Figure 1.
Region I (t < 10 ms): The bubble growth is the fastest
during the initial period (i.e. where the value of l is between
0.6 and 0.8 in Figure 1) due to the high local saturation of gas
forming molecules. The lower the surface tension of liquid,
the faster the bubble growth rate. In other words, the decrease
in surface tension of liquid increases the internal bubble
pressure and thus the bubble growth rate rises.
Region II (10 < t < 100 ms): When time is between 10
and 100 ms, the bubble growth rate decreases dramatically
(i.e. l = 0.5) due to the reduced local saturation of gas
forming molecules. Thus, the controlling step of bubble
growth is the diffusion of dissolved molecules to the bubble
surface.
Region III (t > 100 ms): When time is longer than 100 ms,
the bubble growth rate is more reduced than that in Region II
(i.e. l = 0.33). In this region, gas penetrates through the bubble
on electrode surfaces while diffusion of gas to the bulk solu-
tion is negligible.
The growth coefficient (η0 ) for hydrogen and oxygen
evolution was found to be dependent on current density,
faradaic charge and electrode rotation speed but indepen-
dent on solution pH, electrode material (Pt or Ag) and the
addition of sodium dodecyl sulphate or dodecyl-trimethyl-
ammonium bromide (Brandon and Kelsall 1985; Brandon
et al. 1985).
2.3 Detachment of Bubble from an Electrode Surface
Following the aforementioned nucleation and growth pro-
cesses, the bubble eventually detaches from the electrode
surface. Bubble detachment is dependent on the balance of
adhesion and detachment forces acting on the bubble (Jones,
1999a). At equilibrium,
Fd þ Fs ¼ Fi þ Fp þ Fb (9)
Where Fd is the drag force, Fs is the surface tension force,
Fi is the inertial force, Fp is the pressure force, and Fb is the
buoyancy. At relatively low growth rates, Equation (9) can be
written as:
Fs ¼ Fp þ Fb (10)
Thus, bubbles separate from an electrode when the detach-
ment force (i.e. the sum of the buoyancy force and the
pressure force inside the bubble) is higher than the attach-
ment force between the bubble and the electrode (i.e. surface
tension force). It should be noted that although there is no
experimental evidence showing the importance of the electro-
static forces during bubble detachment from an electrode,
these forces may also play a role in the bubble detachment
process (Brandon and Kelsall 1985; Lubetkin 1995).
By using the scheme shown in Figure 2 and balancing the
attachment force with the detachment forces, the radius of the
detaching bubble from an electrode can be determined as
follows (Sarkar et al. 2010):
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u 24σsin2 θ
u
db;d ¼ t   (11)
g ρf  ρG ð2 þ 3cosθ  cos3 θÞ
and
ω
θ¼   (12)
1 þ sin1 db;d =de
where de is the diameter of the electrode, ω is the liquid
surface tension, db;d is the diameter of the detached bubble,
θ is the contact angle, ρf and ρG are the density of the liquid
and gas, respectively. The diameter of the detached bubble can
be calculated by combining Equation (11) with Equation (12).

1.0

Region I
0.8

Region II
Time Coefficient

0.6
Region III

0.4

0.2

0.0
0.01 0.1 1
Time (s)
Figure 2. Geometry of bubble on curved electrode surface which is used to
Figure 1. Change in time coefficient (l) during hydrogen bubble growth on a calculate bubble detachment diameter where h is the height from the top of the
25 µm diameter Pt electrode at pH 1.4 (Brandon and Kelsall 1985). detaching bubble to the electrode surface (Sarkar et al. 2010).
4 B. TADESSE ET AL.
300
H2 (-2.2 V, 10 µA)
250 H2 (-1.08 V, 1 µA)
Bubble detachment diameter (µm)
O2 (3.2 V, 10 µA)
O2 (2.1 V, 1 µA)
200
150
100
50
0 where Sb (m2) represents the bubble surface area, kG is mass
0 2 4 6 8 10
pH
Figure 3. Effect of pH on bubble detachment diameter of hydrogen and oxygen
on a 10 µm diameter platinum electrode (Brandon and Kelsall 1985).
Experimental results show that in surfactant-free solu-
tions the detachment diameter of hydrogen bubbles was
large at low pH and small at high pH while the opposite
trend was observed for oxygen bubbles as shown in
Figure 3 (Brandon and Kelsall 1985). The reason behind
these observations was explained by the electrostatic inter-
action between the charged electrodes from which the bub-
bles are generated and the charges on the bubbles.
Electrolytically generated hydrogen and oxygen bubbles
have been shown to possess a net charge except at the
point of the zero charge at pH 2–3 (Brandon et al. 1985).
At pH < 2, bubbles are positively charged while they are
negatively charged at pH > 3. Thus, at pH < 2 the electro-
static interaction between a negatively charged cathode and
the positively charged hydrogen bubbles results in large
hydrogen bubble detachment diameters, while the opposite
is true at pH > 3 (Figure 3). By contrast, the interaction
between a positively charged anode and positively charged
oxygen bubbles led to smaller departure diameters at pH
< 2. Larger oxygen detachment diameters are expected from
the interaction between the positively charged anode and
the negatively charged oxygen bubbles at pH > 3 as seen in
Figure 3 (Brandon and Kelsall 1985; Brandon et al. 1985).
However, the influence of pH on departure diameter of
both hydrogen and oxygen bubbles is less pronounced in
the presence of surfactants such as sodium dodecyl sulphate
or dodecyl-trimethyl-ammonium bromide. Departure dia-
meter decreases with increasing concentration of surfac-
tants. It was suggested that the adsorption of surfactants
at the gas-liquid interface decrease the electrostatic attrac-
tion between bubble and electrode which reduces the effect
of pH on the departure diameter (Brandon and Kelsall
1985; Brandon et al. 1985).
Sarkar et al. (2010) reported that the detachment diameter of
hydrogen bubbles was not dependent on current density when
the current density is between 150 and 350 A/m2 while the
detachment diameter increased with increasing Pt wire diameter.
2.4 Diffusion of Gas Through Bubble Surface
Some fraction of the gas generated during electrolysis can
diffuse into bubbles separating from the electrode surface,
causing an increase in bubble sizes. Once the bubble is
detached from the electrode surface it grows rapidly as it
moves through the bulk solution (Sarkar et al. 2010). This
growth was attributed to a number of factors including hydro-
static pressure variation and diffusion of hydrogen, water
vapor and other dissolved gases into the bubble.
The diffusion rate (n, mol/s) can be described as follows
(Jones et al. 1999b):
dn
¼ Sb kG ðCb  Csat Þ (13)
dt
12 14 transfer coefficient; Cb (mol/m3) and Csat (mol/m3) are the
molar concentration in the bulk liquid and the saturated
molar concentration on the liquid–gas interface, respectively.
The mass transfer coefficient can be determined using
Equation. (14) (Vogt 1984):
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2lnð2ÞD  ρG
kG ¼ 0:5  (14)
tMG ðCb  Csat Þ
where D (m2/s) represents the mass diffusivity, ρG is the
density of gas (kg/m3) and MG (kg/kmol) is the molecular
mass of the gas molecules.
The gas concentration in the bulk liquid changes with time and
position in relation to an electrode. For example, in the case of a
wire cylindrical electrode, gas concentration (including dissolved
molecules) in the bulk liquid is given by (Sarkar et al. 2010):

 !

dw ðr2 þ ðdw =2Þ2 rdw
Cðr; t Þ ¼ N exp I0 (15)
4Dt 4Dt 4Dt
where Cðr; t Þ (mol/m3) is the gas concentration at radial
position, r, from the cylindrical electrode, t is diffusion time,
dw is diameter of the cylindrical electrode, N (mol/m2) is
strength, and I0 is the modified Bessel function of the first
kind of order zero.
3. Bubble Size in Electroflotation
Bubble size measurements in electroflotation have been con-
ducted mainly using photographic techniques (Glas and
Westwater 1964; Brandon and Kelsall 1985). These measure-
ments were performed for hydrogen bubbles, oxygen bubbles
or bubbles generated during electroflotation (i.e. hydrogen
and oxygen bubbles without distinguishing among them).
Given that researchers measured bubble sizes using various
bubble generation techniques, measurement positions, and
electrode materials, differing observations for bubble sizes
have been reported. Figure 4 shows various factors affecting
electrolytically generated bubble diameter (Venkatachalam
1992). The main factors that affect bubble sizes such as pulp
pH, current density, and type of the electrode (i.e. electrode
material, geometry, and roughness) will be discussed below.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 5

Figure 4. Factors affecting electrolytically generated bubble size (Venkatachalam 1992).

3.1 Effect of Pulp pH 100

Llerena et al., 1996
The size of electrolytically generated hydrogen bubbles as a Glembotsky et al., 1975
Brandon and Kelsall, 1985
function of pH has been investigated by Brandon and 80 Jimenez et al., 2010
Kelsall (1985) who found that hydrogen bubble size is
larger in acidic solutions due to the higher amount of
Bubble Diameter (µm)

hydrogen ions in these solutions. By contrast, smaller oxy- 60

gen bubbles are produced in acidic media while larger
oxygen bubbles are generated in higher pH conditions
(Glembotsky et al. 1975; Brandon and Kelsall 1985). Other
studies suggest that strongly acidic (pH 2) and strongly
alkaline (pH 14) media lead to the formation of larger
bubbles while a larger number of smaller sized bubbles
were obtained at neutral pH (Jiménez et al. 2010). By
contrast, other authors have not observed any relationship
between hydrogen bubble size and pulp pH (Llerena et al.
1996). The dependence of hydrogen and oxygen bubble size
on pulp pH under various experimental conditions is sum-
marized in Figures 5–6.
3.2 Effect of Current Density
The amount of hydrogen and oxygen gas generated from
electrodes is directly proportional to the current density. For
that reason, the rise in current density results in the increase
in bubble sizes probably due to more pronounced bubble
coalescence (Landolt et al. 1970; Ben Mansour et al. 2007).
Jiménez et al. (2010) found that a large number of small
bubbles were generated at higher current densities while a
small number of large bubbles were observed at lower current
densities. Other studies have suggested no clear linkage
between bubble size and current density (Burns et al. 1997).
It can be concluded that while current density might play
some role in controlling bubble sizes and bubble concentra-
tion, it is necessary to take into account the effect of other
factors such as electrode material and geometry, and pulp
chemical environment in order to establish the relationship
40
20
0
0 2 4 6 8 10 12 14
pH
Figure 5. Variation of electrolytically generated hydrogen bubble size (diameter)
as a function of electrolyte pH as reported in various studies (Glembotsky et al.
1975; Brandon and Kelsall 1985; Jiménez et al. 2010) as shown by symbols.
between current density and bubble size. The influence of
current density on bubble size under various experimental
conditions is summarized in Figure 7.
3.3 Effect of Electrode Material, Geometry and
Roughness
The selection of electrode material affects bubble size of both
hydrogen and oxygen bubbles. For example, iron electrodes
produced smaller hydrogen bubble sizes than platinum elec-
trodes (Glembotsky et al. 1975). The reason is probably that the
iron electrode suppressed the growth and coalescence of hydro-
gen bubbles while the opposite is true in the case of the plati-
num electrode. It is worth mentioning that the effect of
6 B. TADESSE ET AL.

100 Table 1. Bubble sizes generated on various electrode materials during electro-
Glembotsky et al., 1975 lysis (Modified from Chen and Chen 2010).
Brandon and Kelsall, 1985 Size range (µm) Electrode Reference
80 H2 15–65 Al Han et al. (2002)
H2 19–38 Graphite Burns et al. (1997)
H2 20–89 Steel wire screen Ren et al. (2014a)
Bubble Diameter (µm)

H2 15–23 Pt Sarkar et al. (2010)

60 H2 68–105 Ti Jiménez et al. (2010)
62–88 Stainless steel
H2 25–55 Pt Glembotsky et al. (1975)
17–40 Fe
25–35 C
40
O2 25–55 Pt
H2 22–34 Stainless steel plate Ketkar et al. (1991)
28–39 200 mesh
32–45 100 mesh
20 37–49 60 mesh
O2 42–48 Pt plate
38–50 200 mesh
O2 17–38 Graphite Chen et al. (2002)
0 O2 49–58 Pb-Ca-Sn alloy Al Shakarji et al. (2011)
2 4 6 8 10 12 14
pH

Figure 6. Variation of electrolytically generated oxygen bubble size (diameter)
as a function of electrolyte pH as reported in various studies. Adapted from
(Brandon and Kelsall 1985; Glembotsky et al. 1975) as shown by symbols.
160
of mesh electrodes resulted in large bubbles (Lumanauw
2000), while on the contrary, increased roughness on plate
electrodes led to the generation of smaller hydrogen bubbles
probably due to a larger number of nucleation sites (Jiménez
et al. 2010).

Burns et al. (1997)

140 4. Potential Application of Electrolytic Bubbles in
Jiménez et al. (2010)
Sarkar et al. (2010) Fine Particle Separation
Mean Bubble Diameter (µm)

120 Ben Mansour et al. (2007)

100
80
60
40
20
0 while another type of bubbles can be removed from the
0 13 26
2
Current Density (mA/cm )
Figure 7. Effect of current density on the size of bubbles generated by electro-
lysis. Adapted from (Burns et al. 1997; Ben Mansour et al. 2007; Jiménez et al.
2010; Sarkar et al. 2010). The symbols represent various references.
electrode material on the size of hydrogen and oxygen bubbles
should be considered in conjunction with other variables such
as electrolyte pH and pulp conditions, current density and the
bubble measurement techniques. A concise review of the influ-
ence of electrode material on bubble sizes is given in Table 1.
In addition to the type of electrode materials, electrode
geometry and roughness also influence bubble sizes generated
during electrolysis. For example, Ni mesh electrodes produced
smaller bubbles than Ni plate electrodes (Lumanauw 2000). In
the case of mesh electrode, the larger the diameter of the wires
of the cathode, the bigger the generated bubbles. The reason is
that two wires with large diameter have less overlapping sites
than those with a smaller diameter. Additionally, wires with
larger diameter have smaller curvatures. The higher roughness
Electroflotation experiments are commonly performed using a
modified Hallimond tube apparatus (Glembotsky et al. 1975;
Matis et al. 1993; Llerena et al. 1996) shown in Figure 8. The
apparatus has an electrolysis chamber which is located at the
bottom of a flotation chamber. In the electrolysis chamber, a
pair of electrodes is mounted one on each side of a permeable
membrane with the electrodes connected to a DC power
supply for the generation of hydrogen and oxygen gas bub-
bles. Such electrode arrangement allows for one type of bub-
bles (hydrogen or oxygen bubbles) to be used for flotation
39 electrolysis chamber together with the circulating electrolyte.
Electrolytic bubbles have different properties than bubbles
produced during dispersed-air flotation. It should be noted
that dispersed-air flotation can be performed using Hallimond
tubes, mechanically agitated cells, or columns. This section
discusses advantages and disadvantages of using electrolytic
bubbles to recover fine mineral particles.
4.1 Advantages of Electroflotation
4.1.1 Improved Recovery for Fine and Ultrafine Particles
Electroflotation has some advantages over dispersed-air flota-
tion. The most important advantage of electroflotation is the
generation of significantly smaller bubbles than that produced
using dispersed-air flotation methods (see Table 2). Fine bub-
bles, generated during electroflotation, have lower buoyancy
and thus their residence time is longer, increasing the prob-
ability of collision between particles and bubbles. The increase
in the probability of collision particularly improves electro-
flotation recovery of fine particles. The reason is that fine
particles have very low settling rates and their small mass

Figure 8. Schematic diagram of a modified Hallimond tube electroflotation cell. 1, flotation chamber; 2, electrolysis chamber; 3, electrolyte inlet; 4, electrolyte outlet;
5, electrodes; 6, diaphragm; 7, float collection tube.
Table 2. Comparison of bubble size generated in various flotation cells (Sarkar
2012).
Cell type Bubble diameter (µm)
Mechanically agitated cell
Column flotation
Dissolved air flotation
Electroflotation: hydrogen bubble
Electroflotation: oxygen bubble
prevents detachment of particles from a bubble. For example,
Sarkar et al. (2011) found that the maximum recovery of silica
varied from 90 – 96% during electroflotation using Cetyl
trimethyl ammonium bromide collector at pH 10 for particles
in size range of 5.3 – 12.3 µm diameter. By comparison,
flotation recovery of silica during flotation using Rushton
turbine mechanically agitated cell in the presence of tri-
methylchlorosilane collector, and at pH 6 was around 60 –
70% for −10 µm size fraction particles (Shi and Fornasiero
2009). The high electroflotation recovery of silica for 5.3 –
12.3 µm particle size range was attributed to an optimisation
of collision and attachment efficiencies at this particle size
thereby leading to high collection efficiency as observed by
Dobby and Finch (Dobby and Finch 1987). A comparison of
flotation recovery of various minerals using electroflotation,
dissolved-air flotation and mechanical flotation in the fine
and ultrafine particle size range is given in Table 3.
Although the flotation experiments were conducted at differ-
ent conditions (such as pH, reagents used, pulp density,
bubble sizes etc.), it is believed that Table 3 will provide a
general comparison among these techniques.
Electroflotation resulted in better recoveries for both dolo-
mite and magnesite when compared with dispersed-air flota-
tion under similar conditions (i.e. particle size fraction
−45 + 10 µm, 20 mg/L fatty acid collector, and same pulp
pH) as seen in Figure 9a–b (Matis et al. 1993). Figure 9a
shows lower dolomite electroflotation recovery at pH 6 com-
pared with higher pH values. This observation is attributed to
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 7
the limited solubility of the fatty acid collector in acidic pH.
Fatty acid collectors form colloidal precipitate at low pH
(Joseph-Soly et al. 2015) which may lead to poor collector
500–2900
600–1500 performance and thus reduced flotation recovery. In the case
10–300 of magnesite, electroflotation recoveries were about three
5–65 times higher than that of dispersed-air flotation. The poor
15–95
floatability of magnesite using dispersed-air flotation method
might be attributed to the presence of ultrafine particles on
the surface of magnesite particles (Matis et al. 1993). That is,
the stirring action of impellers during the conditioning stage
of dispersed-air flotation promoted coating of magnesite par-
ticles with magnesite ultrafine particles.
Llerena et al. (1996) investigated the flotation behavior of
sphalerite fine particles (< 25 µm in diameter) using hydrogen
and oxygen bubbles generated by sparging and electrolytically.
It was reported that flotation recovery obtained by the elec-
trolytic bubbles was two times higher than that obtained by
sparging bubbles under the same rate of gas production. The
differences in flotation recovery were attributed to the differ-
ences in the size of gas bubbles used in the two flotation
experiments; hydrogen and oxygen bubbles sizes generated
by sparging and electrolytically were 200 µm and 16 µm in
diameter, respectively (Llerena et al. 1996).
According to Bhaskar Raju and Khangaonkar (1982), the
flotation of chalcopyrite ultrafine particles (average size of
4.42 µm) resulted in a recovery of up to 90% when electro-
lytically generated gas bubbles were used. In comparison,
under the same conditions, the chalcopyrite recovery was
30–33% when oxygen bubbles were generated by sparging. It
was suggested that finer bubble sizes in electroflotation made
the process more effective for ultrafine particles than those
generated by sparging even when a smaller gas flow rate was
used (Bhaskar Raju and Khangaonkar 1982).
A comparison between electroflotation and dispersed-air
flotation was also reported for the flotation of pyrite (25–
45 µm) (Kydros et al. 1994). In the presence of 15 ppm
8 B. TADESSE ET AL.

Table 3. Comparison of flotation recovery between electroflotation, dissolved-air Figure 10a is considered to be typical of pyrite as confirmed
flotation and mechanical flotation for some selected minerals in the fine and
ultrafine particle size range.
in previous studies (Fuerstenau et al. 1968; Fuerstenau and
Mishra 1981). By contrast, in the presence of 100 ppm
Feed Size Flotation Recovery (%)
KMnO4 and lime, electroflotation resulted in significantly
Mineral (µm) Condtions EF DAF MF Reference
higher pyrite recovery as compared with dispersed-air flota-
Pyrite 25–45 15 ppm KEX; 55 82 Kydros et al.
pH 8; 10 ppm 1994 tion in the pH range 5.0–9.0 as shown in Figure 10b. The
CuSO4; depressing action of permanganate ion on pyrite flotation was
10 ppm lime claimed to be because of the formation of some surface
25–45 15 ppm KEX, 80 45 Kydros et al.
100 ppm 1994 products facilitated by the presence of permanganate ions,
KMnO4, not because of xanthate oxidation (Rinelli et al. 1980).
10 ppm lime; Oxidation of pyrite due to the presence of oxygen bubbles is
pH 8
−45 20 ppm KEX; 63 Matis et al. not expected to be significant in the presence of KMnO4.
50 ppm 1993
2+
Cu ; pH 8
Chalco- −20 140 mg/l KEX; 90 33 Bkaskar and 4.1.2 Control of Bubble Sizes and Bubble Flux
pyrite pH 8.0; Khangaonkar,
4% Na2SO4, O2 1982 Bubble size and bubble flux can be controlled by adjusting
gas pulp pH, current density, pulp composition (e.g., type and
−20 0 KEX; pH 11; > 75 Trahar 1981 concentration of reagents, etc.), electrode material, and elec-
PPG
10–22 wt% trode surface geometry (Bhaskar Raju and Khangaonkar 1982;
solids Ren et al. 2014b). High concentration of ultrafine bubbles
Sphalerite −25 pH 4; O2 gas; 70 50 Llerena et al. provides for better bubble distribution within a flotation cell
192 mg/L 1996
SIX; 123 mg/L which is not possible to achieve in mechanically agitated
CuSO4 flotation cells. It should be noted that given that mechanical
−25 pH 4; H2 gas; 95 85 Llerena et al. agitation is not used in electroflotation, mechanical entrain-
192 mg/L 1996
SIX; 123 mg/L ment of fine particles can be neglected.
CuSO4
−10 22 g/t KEX; 57 Trahar 1976
20 wt% solids; 4.1.3 Use of Electrolytic Hydrogen and Oxygen Bubbles
pH 11; 16 min
flotation
Hydrogen and oxygen bubbles, occurring during electrolysis, are
Quartz 3–15 4.46 × 10−5 M > 82 Sarkar et al. more active than air bubbles generated during dispersed-air
CTAB; pH 10 2011 flotation because oxygen and hydrogen can be adsorbed on
MIBC; 0.2 M
Na2SO4
mineral surfaces, causing various electrochemical reactions par-
10–30 2.5 mg/L 94 Ketkar et al. ticularly on surfaces of sulphide minerals (Venkatachalam 1992).
sodium oleate; 1991 As a result, the presence of electrolytically generated oxygen and
H2 gas; 0.5%
solids; pH 9.0 hydrogen bubbles might be beneficial to recover specific
4–10 2.5 mg/L 70 Ketkar et al. minerals.
sodium oleate; 1991 Another advantage of electroflotation is that hydrogen and
H2 gas; 2.5%
solids; pH 9.0 oxygen bubbles can be isolated and used separately for differ-
−10 TMCS; pH 6; 70 Shi and ent flotation conditions. For instance, it was reported that the
3.5 min Fornasiero floatability of sulphide minerals such as chalcopyrite (Bhaskar
flotation 2009
Dolomite 10–45 20 mg/L fatty 90 74 Matis et al. Raju and Khangaonkar 1982, 1984b) or pyrite (Glembotsky
acid; pH 10 1993 et al. 1975; Kydros et al. 1994) in the presence of xanthate
15–45 100 ppm CMC; 70 Matis et al.
pH 9.5 1993
collector were higher with electrolytically generated oxygen
bubbles as compared with hydrogen bubbles. The reason is
KEX = potassium ethyl xanthate; CTAB = Cetyl trimethyl ammonium bromide;
CMC = Carboxymethyl cellulose; SIX = sodium isopropyl xanthate; that oxygen is required for the formation of dixantogen or
PPG = polypropylene glycol; TMCS = trimethylchlorosilane metal xanthate on surfaces of sulphide minerals, rendering
EF = Electroflotation; DAF = Dissolved-air flotation; MF = mechanical flotation these minerals hydrophobic. It was reported that the rate of
adsorption of xanthate on pyrite and chalcopyrite increased
with increasing the oxygen concentration, even at relatively
potassium ethyl xanthate and 10 ppm copper sulphate, flota- high oxygen concentrations (Kuopanportti et al. 1997). Thus,
tion recovery obtained using electrolytic bubbles was lower the presence of dissolved oxygen facilitates the adsorption of
than that obtained by sparging bubbles in similar conditions collectors and increases sulphide mineral recovery, although
as seen in Figure 10a. The reason for that might be the prolonged oxidation could depress sulphide mineral flotation.
decomposition of copper (I) xanthate to copper (II) oxide at The pulp potential was also found to be strongly dependent
high oxidation potential during electroflotation, making pyrite on the dissolved oxygen concentration for both pyrite and
particles less hydrophobic (Woods et al. 1990). Depression of chalcopyrite. Generally, higher dissolved oxygen concentra-
pyrite flotation was observed at pH 3–6 range while activation tion led to more positive pulp potential (Kuopanportti et al.
of pyrite was found at pH > 6 for both electroflotation and 1997). It was suggested that the pulp potential may be the
dispersed-air flotation. The sinusoidal shape of the flotation driving force in xanthate adsorption in the flotation of sul-
recovery of pyrite in various pH conditions shown in phide minerals such as pyrite and chalcopyrite.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 9

100 100
a b
Electroflotation
Electroflotation
80 80
Recovery (%)

Recovery (%)
60 Dispersed-air flotation 60

40 40 Dispersed-air flotation

20 20

0 0
5 6 7 8 9 10 11 12 5 6 7 8 9 10 11 12
pH pH

Figure 9. Comparison between electroflotation (open circles) and dispersed-air flotation (filled circles) recoveries of (a) dolomite; (b) magnesite at various pulp pH;
both at particle size fraction of −45 + 10 µm and in the presence of 20 mg/L fatty acid collector (Matis et al. 1993).

100 100
a b Electroflotation
Electroflotation
Dispersed-air flotation Dispersed-air flotation

80 80
Recovery (%)
Recovery (%)

60 60

40 40

20 20

0 0
2 4 6 8 10 12 14 2 4 6 8 10 12 14
pH pH

Figure 10. Comparison between electroflotation and dispersed-air flotation recoveries of fine pyrite (a) in the presence of 15 ppm KEX and 10 ppm CuSO4; and (b) in
the presence of 15 ppm KEX, 100 ppm KMnO4 and lime at different pulp pH (Kydros et al. 1994).

In regards to oxide minerals such as cassiterite (Hogan
et al. 1979) and quartz (Lumanauw 2000), hydrogen bub-
bles led to higher flotation recoveries as compared with
oxygen gas bubbles. In the case of electroflotation of cassi-
terite with electrolytic hydrogen bubbles, increased flotation
recovery and grade was observed due to surface reduction
of cassiterite by electrolytic hydrogen, making cassiterite
surfaces more hydrophobic (Hogan et al. 1979).
4.2 Disadvantages of Electroflotation
The main disadvantage of electroflotation is that it requires
the use of electrical energy for bubble generation which
increases production costs (Montes-Atenas et al. 2010).
The energy consumption during electroflotation depends
on a range of factors such as the nature of electrodes
used and the distance between them, electrolyte conductiv-
ity, pulp density, floatability of the particles, pH, and also
operational factors to a large extent. Nevertheless, Llerena
et al. expressed the energy consumption during electroflo-
tation as (Llerena et al. 1996):
Energy per ton of floatable particles
Cell voltage ðV Þ  Current ðAÞ  timeðhÞ
¼ (16)
weight of particles floated ðtÞ
Based on Equation (16), and at a current of 5 A, the cell voltage
of 9.8 V, flotation time of 4 min, and using electrolytic hydrogen
at pH 4, they estimated the energy requirement to be equal to 65
kWh/t for electroflotation of ZnS (Llerena et al. 1996). A sig-
nificantly lower estimated energy consumption of 3 kWh/t was
reported by the same authors for conventional flotation.
The generation of hydrogen ions at the cathode changes the
overall pH of the pulp around the vicinity of the electrodes
(Glembotsky et al. 1975; Llerena et al. 1996). Although this
localized change in pH may not be significant if constant mixing
is maintained, mineral surface hydrophobicity, dissociation rate
of reagents, and ionic composition of pulp may all be influenced
by small changes in pulp pH. The tight control of pulp pH is
needed because uncontrolled fluctuations in pulp pH have detri-
mental effects on flotation performance. Furthermore, at lower
pulp pH, metals may leach out of the minerals (Bhaskar Raju and
Khangaonkar 1982; Ren et al. 2014b) and stability of the flotation
reagents may deteriorate, substantially reducing mineral
10 B. TADESSE ET AL.
recovery (Llerena et al. 1996). It is also worth mentioning that, in
cases where the electrolysis electrolyte is not separated from the
pulp, the presence of inorganic salts in flotation pulp might have
a depressing effect on the flotation of some particles.
Sulphide minerals are prone to surface oxidation when
exposed to oxygen, and their flotation is greatly dependent
on the surface chemistry of the mineral particles in the pulp.
This is particularly of interest in electroflotation because oxy-
gen gas is generated at the anode. Electrochemical reactions
involving oxygen may be expected on the surface of mineral
particles especially in a set up where the electrodes are within
the flotation chamber. For instance, it is reported that sul-
phide minerals undergo physicochemical changes in an elec-
troflotation cell (Glembotsky et al. 1975). Chalcopyrite
undergoes electrochemical oxidation in alkaline conditions
and forms thin layer of Cu(OH)2, Fe(OH)3, CuO, and Fe2O3
on its surface (Yin et al. 2000), particularly in cases where
bubbles are generated in the pulp.
CuFeS2 þ 5OH  ! CuðOH Þ2 þ FeðOH Þ3 þ 2S þ 5e (17)
2CuFeS2 þ 10OH  ! 2CuO þ Fe2 O3 þ 5H2 O þ 4S
þ 10e (18)
These surface changes may reduce flotation recovery signifi-
cantly. Additionally, when common sulphide collectors such
as xanthates are used, xanthate might decompose to a certain
degree, reducing the ability of xanthate to make sulphide
minerals sufficiently hydrophobic. Due to chalcopyrite surface
oxidation to Fe oxides, and possible xanthate decomposition
during electroflotation, collectors such as sodium oleate which
are normally used in Fe oxide flotation (Joseph-Soly et al.
2015) were found to be effective in the electroflotation of
ultrafine chalcopyrite (Makuei et al. 2018). Thus, it can be
concluded that electroflotation may be more suitable in the
flotation of oxide minerals such as hematite, magnetite, and
other carbonate and silicate minerals where oxidation is not a
primary concern, as compare with sulphide minerals such
chalcopyrite and pyrite.
5. Electroflotation Models
The first-order flotation model can be used to predict the rate of
recovery of mineral particles in electroflotation cells. Recovery of
particles by flotation depends on the number of particles col-
lected in the concentrate which in turn is a function of the
number of free particles in the feed, the number of particles
attached to bubbles, and bubble–particle detachment rate. The
bubble–particle detachment rate can be neglected in electroflo-
tation processes because there is no agitation and fine particles
have very small mass (Yoon and Luttrell 1989). The number of
particles attached to bubbles (Np;a Þ in an electroflotation cell can
be expressed as (Koh and Schwarz 2006):
t several mathematical models have been developed (Flint and
Np;a ðt Þ ¼ ò k1 Np;f NbT ð1  βÞ (19)
0
where Np;f is the number of free particles, k1 (m3/s) is the
bubble–particle attachment rate constant and NbT is the total
number of bubbles. β is the average bubble loading parameter.
The average bubble loading parameter can be determined
using the following expression (Koh and Schwarz 2006):
4dp 2 Np;a
β¼ (20)
db 2 φNbT
where dp and db are the particle and bubble size, respectively;
Np;a is the number of particles attached to bubbles, and φ is
the fractional coverage of bubble surface. In practice, the
whole bubble surface may not be completely covered by
particles, and thus φ can be assumed to be 0.5. However,
Koh and Schwartz (2008) compared the experimental and
calculated recovery and found that the value of φ of 0.2
matched experimental data better than a value of 0.5.
Equation (19) can be used to calculate the number of
particles attached to bubbles when the
bubble–particle attachment rate constant is known.
Therefore, in this section, a brief description of calculation
of bubble–particle attachment rate constants is given.
Additionally, the available models for prediction of the max-
imum floatable particle size in electroflotation are also
presented.
5.1. Bubble–Particle Attachment Rate Constant
The bubble–particle attachment rate constant can be pre-
dicted using the theory by Koh and Schwarz (2006):
k1 ¼ Z 1 P (21)
where Z1 is the bubble–particle collision frequency, and P is
the probability of collection of particles by bubbles.
Given that there is no mechanical agitation during electro-
flotation, Z1 can be expressed by (Nguyen and Schulze 2004):


db þ dp 2
Z1 ¼ π Vrel (22)
2
where Vrel is the relative velocity between the bubble (vb ), and
the particle (vp ).
The probability of collection can be expressed as (Yoon
2000):
P ¼ P c P a ð1  P d Þ (23)
where Pc ; Pa ; andPd are the probability of collision, attach-
ment, and detachment, respectively.
For fine particles, Pd can be negligibly small due to the low
inertia of fine particles, and thus Equation (23) may be sim-
plified as:
P ¼ Pc Pa (24)
5.1.1. Bubble–Particle Collision
The relationship between the probability of collision, and bubble
and particle sizes has been a subject of extensive research, and
Howarth 1971; Gaudin et al. 1942; Sutherland 1948; Reay and
Ratcliff 1973; Yoon 1993). For very small bubbles (< 100 μm)
such as those encountered in electroflotation, Stokes flow might
occur around air bubbles. In the case of Stokes flow, the prob-
ability of collision is directly proportional to the square of the

particle size and inversely proportional to the square of the
bubble diameter (Yoon 2000).

2
dp
Pc ¼ 1:5 (25)
db
Intermediate flow around air bubbles can also occur during
electroflotation due to the mixing action of electrolytic bub-
bles. The probability of collision can be derived using the
stream function (Weber and Paddock 1983; Ralston et al.
1999):


2
3 4Re0:72 dp
Pc ¼ þ b
(26)
2 15 db
Reb is the Reynolds number of bubbles.
The decrease in particle size and the increase in bubble size
result in lower Pc, suggesting that fine particles are less likely
to be captured by large bubbles. By contrast, fine bubbles
enhance the probability of collision with fine particles which
leads to increasing the probability of collection.
5.1.2. Bubble–Particle Attachment
Bubble–particle attachment is the central process in froth
flotation (Ralston et al. 1999; Verrelli and Albijanic 2015).
Flotation thermodynamics is used to predict the possibility
of the attachment of a particle to a bubble. In electroflota-
tion, where solid particles and bubbles are suspended in
liquid medium, the total surface free energy is equal to the
balance between the solid, liquid, and vapor interfacial
tensions and interfacial areas. The relationship between
the Gibbs free energy and the three surface forces is given
by (Laskowski 1989):
ΔG ¼ γsv  γsl  γlv
where is γsv the solid–vapor interfacial tension, γsl is the
liquid–solid interfacial tension, γlv is the liquid–vapor inter-
facial tension, respectively. The Gibbs free energy change for
attachment must be negative for a bubble–particle attachment
to be feasible thermodynamically. Equation (27) can be con-
verted, with the introduction of Young’s equation, to the well-
known thermodynamic criterion for flotation:
ΔG ¼ γlv ðcosθ  1Þ
where θ denotes contact angle between the bubble and parti-
cle surface. From Equation (28) it can be seen that bubble–
Figure 11. Schematic representation of possible bubble–particle attachment mechanism in electroflotation of fine particles: (a) flocculation of particles by bubble
bridging; (b) particles coated with fine bubbles; and (c) two-stage bubble–particle attachment (Zhou et al. 1997).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 11
particle attachment is only thermodynamically feasible if θ
> 0. The contact angle is used to describe the hydrophobicity
of mineral surfaces.
Bubble–particle aggregates occur when hydrophobic parti-
cles collide with bubbles, followed by the drainage and rup-
ture of the liquid film between the bubble and the particle,
and the expansion and relaxation of the gas–liquid–solid
contact line (Ralston et al. 1999). The time scale of the
drainage of the liquid film is defined as the induction time.
Given that the drainage of the liquid film controls the bubble–
particle attachment mechanism, the induction time is
required to determine the probability of attachment. For
example, Yoon and Luttrell (1989) used the stream function
and the induction time to derive the following expression for
the probability of attachment:
"  ! #
1  45 þ 8Re0:72
b vb ti
Pa ¼ sin 2tan exp
2   (29)
15db 1 þ db =dp
where ti is the induction time and vb is the bubble rise
velocity.
Ren et al. (2014a) investigated bubble–particle attach-
ment mechanism between fine cassiterite particles and elec-
trolytic hydrogen bubbles and found that the presence of
small bubbles may cause flocculation of fine particles
through a bubble-bridging mechanism by capillary action
(Figure 11a). Thus, the apparent particle size increases,
leading to higher probability of bubble–particle collision.
In addition to this, fine particles might be coated with
electrolytic microbubbles thereby modifying surface proper-
ties of the particles (Figure 11b). It was suggested that these
bubbles act as flotation carriers, and lead to improved
(27) flotation efficiencies (Ahmadi et al., 2014; Tussupbayev
et al. 2016). For instance, the effect of microbubbles on
the selective flotation of ultrafine chalcopyrite (80% passing
12 µm, 50% passing 4 µm) using laboratory pneumomecha-
nical and column flotation cells was investigated by
Tusupbajev et al. (2016). In comparison with the absence
of microbubbles, the introduction of 16 L of microbubbles
per 1 kg of chalcopyrite in a pneumomechanical type cell
resulted in an increase in the copper recovery from 60% to
72%. Similarly, it was observed that the presence of micro-
(28)
bubbles in flotation column increases the copper recovery
by 15.8% compared with conventional column flotation
(Tusupbajev et al., 2016).
12 B. TADESSE ET AL.
Fine particles coated with ultrafine bubbles may attach to a
large bubble, resulting in the formation of a bubble–bubble–
particle aggregate (Dziensiewicz and Pryor 1950) as shown in
Figure 11c. The attachment of large bubbles to a mineral particle
frosted with tiny bubbles, typically in the range of about 1–10 µm,
is highly probable because tiny bubbles forming on the particle
surface facilitate the attachment of larger bubbles (Klassen 1960).
A range of bubble sizes with diameter from < 10 µm to > 100 µm
are known to form in electroflotation and thus this mechanism
may be favored for a number of reasons. For instance, particle
surface frosted by bubbles is expected to be less hydrated as
compared with the surface of mineral particles because bubbles
are more hydrophobic than solid particles. Thus, the coalescence
of a bubble to a particle covered by bubbles is more favored than
the attachment of a bubble to a solid particle.
5.2. Limits of Particle Size in Electroflotation
The maximum floatable particle size was derived using the
balance of the capillary force, the pressure force, the buoyancy
force, and the gravitational force (Nguyen 2003):

1
  3σ ð1  cosθÞ 2
dp max;d ¼ (30)
Δρðg þ bm Þ
where dp max is the maximum diameter of floatable particles,
Δρ ¼ ρp  ρl , ρp and ρl are the particle density (kg/m3) and
the liquid density (kg/m3), respectively, θ is the particle con-
tact angle, σ is the liquid surface tension (N/m), g is the
acceleration due to gravity (m/s2) and bm is the machine
acceleration (m/s2).
Given that machine acceleration is negligible in electroflo-
tation, Equation (30) can be simplified as (Sarkar 2012):

1
  3σ ð1  cosθÞ 2
dp max;d ¼ (31)
gΔρ
Therefore, if θ, Δρ and σ are known the maximum particle
size can be calculated.
Another model to predict the maximum floatable particle
size is derived for the case when the mass of the particles
attached to the bubble prevents the ability of the bubble–
particle aggregate to rise into the froth phase (Wark 1933).
More precisely, the model is based on the buoyancy criteria:
!1
  ρpulp  ρg 3
dp max;b ¼ db (32)
ρp  ρpulp
where ρg; ρpulp ; ρp are the density of gas, pulp and particle,
respectively. Thus, Equation (32) shows that the maximum
size of floatable particle can be estimated when
ρg; ρpulp ; ρp anddb are known.
6. Future Outlook of Electroflotation in Fine Particle
Recovery
The advantages of electroflotation over dispersed-air flotation lie
not only in the smaller bubble sizes generated by electrolysis but
also in the ease of control bubble sizes by varying operating
variables. Gas bubbles generated in electroflotation are also
more active than those generated by dispersed-air flotation
methods. The particle surface modifications resulting from inter-
action with electrolytic gas bubbles were reported to result in
better floatability of pyrite and chalcopyrite even in the absence
of collectors (Glembotsky et al. 1975). Another important feature
of electroflotation is its ease of operation. Electroflotation can be
operated in combination with electrocoagulation particularly in
fine and ultrafine particles flotation (Chen 2004). In such con-
figuration, the electrocoagulation process mainly plays the role
of destabilizing and aggregating the fine particles, while the
electroflotation part is used to float the resulting flocs. A com-
bined electrocoagulation-electroflotation system has been found
to be effective for large-scale applications (Chen 2004).
Although electroflotation can lead to improved selectiv-
ity and recovery, small bubbles cause high water recovery,
and the entrainment of gangue minerals, although mini-
mized, cannot be avoided altogether (Trahar and Warren
1976). In acidic pH, metallic ions may leach out in to
solution during electroflotation and may form species that
deactivate the surface of minerals, consequently depressing
flotation recovery (Llerena et al. 1996). Thus, electroflota-
tion may not be as effective in low pH range. Although
large-scale electroflotation cells have been designed for
waste water treatment, similar scale cells for mineral parti-
cle recovery purposes are scarce. Furthermore, the greater
energy requirement during water electrolysis for bubble
generation poses constraints to its widespread use for
mineral beneficiation on an industrial scale (Bhaskar Raju
and Khangaonkar 1984b). However, the following factors
were identified as compensation for the extra expenditures
incurred by electroflotation (Glembotsky et al. 1975):
(1) Lowering or elimination of collector consumption
(e.g. 98% recovery of pyrite during electroflotation
with oxygen bubbles were obtained without any
reagent addition (Glembotsky et al. 1975); high chal-
copyrite recovery was achieved in the absence of
collector during electroflotation (Bhaskar Raju and
Khangaonkar 1984a)).
(2) Improved flotation rate
(3) Improved grade of target mineral in the concentrate
(4) Applications in non-conventional flotation separa-
tions (e.g. recovery of fine salt-type minerals (Matis
et al. 1993); removal of toxic heavy metals from
wastes (Il’in et al. 2014); and separation of microbes
from wastewater (Neto et al. 2014)).
7. Conclusions
The challenges in the froth flotation of fine and ultrafine
particles are well recognized. Several experimental and theo-
retical studies have been published aiming at improving the
recovery of this particle size range. The main cause for
reduced recovery of fine and ultrafine particles in conven-
tional flotation methods is the poor collision efficiency
between the fine particles and large bubbles. Methods invol-
ving small bubbles are considered to be more suitable for the
recovery of ultrafine particles. Electroflotation has been

proved to be a promising method in the beneficiation of fine
and ultrafine mineral particles because of its ability to produce
gas bubbles of < 100 µm in size. Compared with dispersed-air
flotation, electroflotation has been found to be more effective
in the recovery of carbonates such as dolomite and magnesite.
Recoveries in excess of 90% have been reported for the elec-
troflotation of ultrafine silica particles using electrolytic
hydrogen bubbles. A two-stage bubble–bubble–particle
attachment is proposed as the main attachment mechanism
in electroflotation. Despite its advantages in the ease of bubble
size control, electroflotation requires additional energy for gas
bubble generation. This additional energy cost needs to be
adequately compensated by the improved recovery in order to
realize the application of electroflotation on an industrial
scale. Further research on exploring equipment design
requirements is essential.
Disclosure statement
The authors report no conflicts of interest. The authors alone are
responsible for the content and writing of the article.
Funding
The financial assistance of the Department of Mining Engineering and
Metallurgical Engineering, Western Australian School of Mines, Curtin
University is gratefully acknowledged.
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