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Article history: A feature of electroflotation is the ability to create very fine bubbles, which are known to improve flota-
Available online 22 September 2010 tion performance of fine particles. This study was aimed at determining the hydrogen bubble size gener-
ated as a function of current density and electrode geometry. Experiments were performed in a viewing
Keywords: cell that allowed direct visualization of hydrogen bubbles being generated and transported away from
Electroflotation platinum wire electrodes of 90, 120 and 190 lm in diameter. The detached bubble diameters varied
Detached bubble diameter between 15 and 23 lm in diameter, and for each wire diameter, were little influenced by the applied cur-
Bubble generation rate
rent in the range 150–350 A/m2. The measurements were consistent with those predicted from a simple
force balance analysis based on a H2–Pt–0.2M Na2SO4 contact angle of 0.18°. Interestingly, upon detach-
ment, the bubble size increased rapidly, recording up to an 8-fold increase in volume in the first few mil-
limeters of rise, before approaching the steady state diameter of between 30 and 50 lm in the bulk. This
increase in bubble size was found to be mostly due to the transfer of dissolve hydrogen into growing bub-
ble while moving through the electrolyte super saturated by dissolved hydrogen gas. The equilibrium
bulk diameter was found to be a function of the rate of hydrogen production, bubble nucleation rate,
and dissolved gas concentration field. Consequently, electroflotation cells need to be designed to optimise
the contact between the supersaturated liquid and the rising bubble plume. By doing this, the volumetric
flux of bubbles will be maximised leading to improved flotation performance.
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction Allum (1984) reported that at the time the bubble size in most
industrial flotation circuits within Australia were of the order
In the past 40 years there have been numerous studies that 1000 lm. While there have been improvements in overall cell de-
focusing on the flotation of fine mineral particles (e.g. Flint and sign since then, the reliance on a mechanical agitator to create
Howarth, 1971; Reay and Ratcliff, 1975; Anfruns and Kitchener, the bubbles has meant that the bubble size produced has remained
1977; Ahmed and Jameson, 1985; Yoon and Luttrell, 1989; Dai et relatively unchanged. Consequently, alternative flotation method-
al., 1998; Ramirez and Davis, 2001; Tao, 2004; Nguyen et al., ologies capable of producing bubbles sizes less than 100 lm have
2006; Miettinen, 2007; Waters et al., 2008). For the latest review been investigated, namely dissolved air flotation (e.g. Rodrigues
of the literature on fine particle flotation see Miettinen et al. and Rubio, 2007; Rubio et al., 2007; Englert et al., 2009) and
(2010). Many of the studies listed have reported that the recovery electroflotation.
of particles in the diameter range of 1–10 lm is increased with The focus of this study is on electroflotation, and their have been
decreasing bubble size, which is largely the result of the increased a number of studies involving mineral flotation. Raju and Kha-
collision efficiency between the particles and the bubbles (e.g. ngaonkar (1984) reported 74–81% recovery of 4 lm chalcopyrite
Nguyen and Schulze, 2004; Sarrot et al., 2007). with electrolytically-generated hydrogen bubbles at current den-
While it is widely acknowledged that the recovery of fine parti- sity in the range of 490–1470 A/m2. Ketkar et al. (1991) reported
cles is generally enhanced by using fine bubbles, it is also recog- more than 60% recovery of +4–10 lm quartz with hydrogen bub-
nized that conventional mechanically agitated and sparged bles of 22 lm diameter. Llerena et al. (1996) reported almost
column flotation cells produce bubbles that are too large, i.e. greater 100% recovery of 25 lm sphalerite after 4 min of electroflotation
than 500 lm, to obtain this benefit. The review by Jameson and with mean bubble diameter of 16 ± 2 lm generated using a stain-
less steel screen of wire diameter 115 lm and operated at current
density of 500 A/m2 at solution pH of 4. Han et al. (2006) used
⇑ Corresponding author. Tel.: +61 2 49215897; fax: +61 2 49216920.
electroflotation to generate very fine bubbles with 27 lm mean
E-mail addresses: M.Sarkar@uon.edu.au (M.S.K.A. Sarkar), Geoffrey.Evans@
diameter to obtain 98% recovery of 28 lm flocculated kaolin parti-
newcastle.edu.au (G.M. Evans), Scott.Donne@newcastle.edu.au (S.W. Donne). cles. Most recently, Sarkar et al. (2010) obtained more than 70%
1
Tel.: +61 2 49215573; fax: +61 2 49216920. recovery of 13 lm silica particles with electrolytically-generated
0892-6875/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2010.08.015
M.S.K.A. Sarkar et al. / Minerals Engineering 23 (2010) 1058–1065 1059
25
450
20
350
db,d (µm)
15
x (µm)
250
10
150
5
50
0
0 100 200 300 400
-50 10 20 30 40 50 60 70
I (A/m 2)
d b (µm)
Fig. 4. Bubble detachment diameter vs current density [Pt: D = () 90, (j) 120, and
Fig. 3. Bubble diameter vs distance from top of electrode [Pt: D = () 90, (j) 120, (d) 190 lm; platinised: D = (s) 190 lm].
and (d) 190 lm; I_ = 354 A/m2; photograph: D = (a) 90, (b) 120 and (c) 190 lm].
Eqs. (5) and (6) were applied, using a fitted contact angle, to pre-
distance, xb,d, below the top of the electrode surface (x = 0 m). The
dict the diameter of the bubble at the point of detachment. The
projection was required as many of the generation sites were be-
comparison is given in Table 3, where it can be seen that predic-
low the top of the electrode and it was only possible to view the
tions were within ±20% of the experimental values over the range
bubbles once they had risen into the field of view of the camera.
investigated. The predictions were based on a single fitted contact
Consequently, the following expression:
angle, x, of 0.18° for all four wires. This value was consistent with
those from other studies, which ranged from 0° (Bewig and Zisman,
db ðxÞ ¼ db;d þ db;d 1 eKðxþxb;d Þ=db;d ; ð13Þ
1965; Brandon and Kelsall, 1985; Gardner and Woods, 1977) to 10°
(Gardner and Woods, 1974), depending on the cleaning procedure
was fitted to the experimental rising bubble diameter measure- of the platinum surface. Also given in Table 3 is the predicted db,d of
ments to obtain average values for the detachment diameter for 21 lm for a flat surface. Again, this value is consistent with Janssen
each wire diameter and range of current densities. The fitted values, and Hoogland (1973) who reported a hydrogen bubble size of
including for K and xb,d are given in Table 2. 26 lm produced from a platinum disc electrode of 11.2 mm diam-
It can be seen from Table 2 that xb,d varied between experi- eter at current density of 40 A/m2. Similarly, Han et al. (2002)
ments, reflecting the fact that bubbles can nucleate anywhere on reported hydrogen bubbles of 15–65 lm produced from a flat alu-
the electrode surface. Similarly, the exponent, K, values varied from minium electrode with average diameter of 22 lm.
0.07 to 0.26, resulting in a range of growth rates for the bubbles
once they have detached from the wire. Reasons for the variation 4.3. Bubble nucleation rate
are given later in the paper. While xb,d and K might have varied be-
tween different nucleation sites the projected detachment diame- Hydrogen bubble nucleation rate on the cathode surface is
ter values were quite consistent. shown in Fig. 5 as a function of current density for both the Pt
and platinised wires. It can be seen that bubble nucleation rate
4.2. Bubble diameter at detachment (per m2 of surface area) increased with increasing current density
for all of the wire diameters. This is not surprising, given the in-
The db,d values reported in Table 2 are plotted as a function of crease in hydrogen formation with increasing current while the
current density in Fig. 4. It can be seen that for each wire diameter bubble detachment diameter remained relatively constant. More-
the detachment diameter of the bubble remained relatively con- over, the bubble flux will depend on number of nucleation sites,
stant over the current density range investigated. Similarly, platin- and in accordance with Murakawa (1957), more nucleation sites
isation of the wire surface made little difference to the detachment are expected to become active at higher current density as the
diameter. However, for a given current density the detachment solution adjacent to the electrode surface becomes more supersat-
diameter increased with increasing wire diameter. urated. The intent of investigating the platinised surface was the
Table 2
Fitted coefficients for Eq. (13).
Table 3 50
Average experimental and predicted detached bubble diameter.
db,b (µm)
90 18.0 15.2 ± 1.4 18
30
120 18.2 18.3 ± 2.5 1
190c 18.9 21.7 ± 2.9 13 20
1d 21.0
a
Using fitted contact angle of 0.18 deg, which is the average of 0.15, 0.18, 10
0.21 deg for 90, 120, 190 lm wires.
b
Taken as the average value for the three current densities given in Table 2 (±
0
values are for 95% confidence interval).
c 0 100 200 300 400
Average of both platinum and platinised 190 lm wires.
d
Equivalent to a flat surface. I (A/m2)
Fig. 6. Bulk bubble diameter vs current density [Pt: D = () 90, (j) 120, and (d)
190 lm; platinised: D = (s) 190 lm].
6.E+08
5.E+08
The bulk diameter measurements reported in Fig. 6 represent
nb,d (1/m2.s)
bulk the fraction of hydrogen utilised as bubbles was higher for the for the same times at x = 550 lm (for 190 lm Pt wire). These levels
platinised wire. Given that the platinised wire also produced smal- of supersaturation are consistent with the study by Shibata (1978).
ler bubbles (see Fig. 6), and at higher frequency (see Fig. 5), it Also shown in the figure is the position of the bubble overlayed
would seem to be a significant advantage in electroflotation to onto the dissolved gas concentration gradient, generated at
operate with a platinised surface cathode. t = 30 s after the current source was switched on. The bracketed
The bubble diameter in the bulk can be predicted from Eqs. (7) values are the diameter measurements as the bubble rises away
to (12) provided the dissolved gas concentration profile is known. from the wire surface; whereby the increase in diameter due lar-
From Fig. 7, it was shown that the fraction, w, of hydrogen remain- gely to the high levels of supersaturation in the surrounding liquid.
ing in solution was 0.79 (190 lm Pt wire), and 0.83 (90 and 120 lm Knowing the dissolved hydrogen gas concentration profile the
Pt wires). Assuming these values, the concentration profile of dis- model equations can be solved simultaneously to obtain the bub-
solved hydrogen gas, calculated from Eq. (10), for the Pt wires ble diameter as a function of distance from the top surface of the
(90, 120 and 190 lm diameter) and current density of 354 A/m2 electrode. The experimental measurements are compared with
(N_ = 1.833 mmol/m2 s) is shown in Fig. 8. In accordance with un- predicted bubble diameter values in Fig. 9 for the Pt wires at a cur-
steady diffusion theory for a constant flux source, the concentra- rent density of 354 A/m2. There are three predictive curves illus-
tion increases with increasing time at the surface, and decreases trated: Firstly, the prediction using Eq. (13) shows good
with increasing distance away from it. Given that the saturation agreement with the measurements, which is hardly surprising
concentration of hydrogen gas at atmospheric pressure is
0.78 mol/m3, the normalised (C/Csat) corresponding supersatura-
tion values in the figure are: 5, 33 and 52 at the surface 1,000
(x = 0 lm), at times 0, 10 and 30 s, respectively; and 0, 1 and 7
---Ψ = 0.3
800 Eq. (13) ----
1,000
x (µm)
600
800
t = 30s --- Ψ = 0.83
400
600
x (µm)
(30)
(30)
400 200
(29)
t = 10s (28)
200 (24) 0
t = 1s (22) 0 10 20 30 40 50 60
(19)
0 d b (µm)
0 10 20 30 40
C b (x,t) (mol/m3) 1,000
--Ψ = 0.3
1,000 800 Eq. (13) ----
800
x (µm)
600
t = 30s
600
x (µm)
--- Ψ = 0.83
(34) 400
400 (33)
t = 10s 200
(31)
200 (29)
(27)
(25)
t = 1s
(18) 0
0 0 10 20 30 40 50 60
0 10 20 30 40
3 d b (µm)
Cb (x,t) (mol/m )
1,000
1,000
Eq. (13) ----
800 800
t = 30s
x (µm)
x (µm)
600 600
(41)
400 (41) 400
t = 10s
(40) --- Ψ = 0.79
200 (38)
(34) Ψ = 0.35 ----
t = 1s
(29) 200
(24)
0
0 10 20 30 40 0
3 0 10 20 30 40 50 60
C b (x,t) (mol/m )
d b (µm)
Fig. 8. Dissolved hydrogen gas concentration vs time and distance above wire [Pt
wire; I_ = 354 A/m2; w = 0.79 (D = 190 lm): 0.83 (D = 90 and 120 lm); bubble Fig. 9. Measured and predicted bubble diameter vs distance above wire [Pt wire;
location and diameter (lm): D = () 90, (j) 120, and (d) 190 lm]. I_ = 354 A/m2; measured: D = () 90, (j) 120, (d) 190 lm].
1064 M.S.K.A. Sarkar et al. / Minerals Engineering 23 (2010) 1058–1065
given the equation parameters K, xb,d, and db,d are fitted to the of the cathode surface, and smaller bubbles were produced with
experimental data. Secondly, the prediction from solution of Eqs. reducing the cathode wire diameter. Finally, the observation that
(7)–(12), and using w = 0.79 (190 lm Pt wire), and 0.83 (90 and bubble diameter was a function of position, time, dissolved gas
120 lm Pt wires) for the dissolved gas concentration profile as concentration profile and electrode surface treatment, as helped
shown in Fig. 8, leads to an over-prediction of bubble diameter to explain why there is such wide variation in reported measure-
with increasing distance from the top of the wire. The reason for ments across the literature.
the discrepancy is thought to be the result of the diffusion of the
dissolved hydrogen taking place radially in all directions from Acknowledgement
the electrode wire surface, whereas the bubbles move only in the
upward direction. Consequently, the rising bubbles are in contact Shahjahan Sarkar gratefully acknowledges the financial support
with the dissolved hydrogen that is in the liquid above the wire from the University of Newcastle.
and the dissolved hydrogen below the wire will remain in the li-
quid. As a consequence, the actual concentration of dissolved References
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