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Chemical Engineering and Processing 40 (2001) 269 275

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Froth flotation: kinetic models based on chemical analogy


F. Hernainz *, M. Calero
Departamento de Ingeniera Qumica, Facultad de Ciencias, Uni6ersidad de Granada, 18071 Granada, Spain
Received 2 March 2000; received in revised form 31 July 2000; accepted 31 July 2000

Abstract
This paper studies several kinetic aspects of flotation of celestite and calcite in a mechanical cell with sodium dodecylsulphate
as the collector agent, using pure minerals ranging in average particle size between 137 and 74 mm, respectively, with a constant
pH 3 in the flotation bath in all experiments. The results obtained indicate that both minerals float rapidly and that the flotation
rate constant responds to a non-integral order equation. Likewise, a linear relationship exists between flotation rate and particle
diameter. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Flotation kinetic; Froth flotation; Flotation rate; Particle

1. Introduction
In froth flotation, air bubbles are injected into a
moving stream of aqueous slurry containing a mixture
of particles, so that only hydrophobic ores are collected
on the bubble surface and exit the stream. Owing to its
simplicity, the process is widely used for separating a
great variety of solid particles. However, a number of
complex chemical and physical interaction aspects is
involved in the flotation process. An extensive work is
reported in the literature on the study of this process,
which has been studied from different angles. Of these,
kinetic approach has been highly instrumental in better
understanding leading to reasonably accurate
predictions.
The quantification of kinetic parameters is of increasing importance in industrial flotation to shed light on
the speed of the process. Numerous researchers have
studied the kinetic aspects of froth flotation paying
special attention to particle size, bubbles and their
complex interactions (Trahar and Warren [1]; Jameson
[2]; Radoev et al. [3]; Loewenberg and Davis [4]).
Arbiter and Harris [5] found that the flotation kinetics is the study of the variation in amount of froth
overflow product with flotation time, and the quantita-

tive identification of all rate-controlling variables. With


such variables maintained constant, the algebraic relationship between the proportion of mineral floated and
flotation time is a flotation rate equation. This contains
the constant values of all the rate determining variables
implicit in one or more rate constants, which must be
evaluated from experimental data.
In a recent review of flotation kinetics (Mehrotra and
Padmanabhan [6]), the mathematical models describing
froth flotation as a rate process are classified into six
categories, kinetic models based on chemical analogy,
probabilistic and stochastic models, multiphase models,
mechanistic models, kinetic models with distributed
rate constant and continuous flotation models.
This paper aims to determine the flotation rate of
celestite and calcite with sodium dodecylsulphate
(SDS), using the kinetic models based on chemical
analogy. Likewise, this study supplements a previous
work (Hernainz and Calero [7]) in which the flotation
rate of both minerals was determined using sodium
oleate as collector agent.

2. Experimental

2.1. Mineral species


* Corresponding author. Tel.: + 34-58-243315; fax: + 34-58248992.
E-mail address: hernainz@goliat.ugr.es (F. Hernainz).

Celestite, SrSO4, and calcite, CaCO3, from two different mines were used for this research study.

0255-2701/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
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F. Hernainz, M. Calero / Chemical Engineering and Processing 40 (2001) 269275

The celestite was taken from the Cerro de Montevives mine, located in Las Gabias, 12 km southwest of
the city of Granada (Spain). The mineral, fragmented
and selected again by hand to collect only the purest
samples, thus guaranteeing a concentration of 97%, as
shown by acid leach analysis. The calcite was taken
from a deposit near Torredonjimeno (province of Jaen,
Spain), with a concentration in CaCO3, over 99.6%.

2.2. Flotation agents


2.2.1. Collector agent
Sodium dodecylsulphate supplied by Merck with a
99% purity. The solutions were dissolved in water. The
solute was then weighed on a METTLER AJ150 precision balance, and the desired solution obtained by
successive dilutions as the agent concentrations used
were very small.
2.2.2. Foaming agent
Daksa M-1 pine oil was used with a constant concentration of 0.01407 g/l, sufficient to stabilise the foam.
2.2.3. Modifying agents
HCl and NaOH (Fluka, puriss. p.a.) were used as pH
modifiers in the cell, and control was effected by means
of a digital pH meter.

2.3. Experimental conditions, apparatus and


calculations
The mineral, previously ground to the appropriate
size, was added to stainless steel tank, fitted with an
agitator and a reducer, which provided gyration at 60
rpm. The density of the pulp was then adjusted in the
proportion ore:water=80:1250 g, and the collector, pH
modifier and foaming agent were added, almost at the
same time. This mixture was agitated for a 10-min
conditioning period before being subjected to flotation
in a mechanical cell for another 5-min period.
In the flotation experiments, a DENVER-D12 mechanical cell with a 1.25-l stainless steel tank was used.
The speed of impeller was adjusted to 1000 rpm suction
caused by the impeller provided the aeration required
for the formation of foam. The froths were manually
skimmed to the overspill with an aluminium blade and
collected by a collector in glass tanks where the mineral
was decanted. The temperature in the bath was maintained between 291 and 293 K.
The floated mineral was vacuum filtered through a
ceramic funnel lined with appropriate filter paper. The
sample was dried by a heating stone at 383 K to a
constant weight. The percentage of recovery was obtained easily since pure mineral was used.

3. Results and discussion

3.1. Influence of the concentration of SDS

Fig. 1. Flotation recovery of celestite vs. concentration of SDS and


two different particle sizes.

First of all, the influence of SDS concentration on


two different average particle sizes of celestite were
determined, namely 74 and 137 mm, which are the usual
limits in flotation operations.
Experiments were performed at pH 3, as this pH has
proved to be the most appropriate for SDS as a flotation agent on celestite and calcite according to previous
papers (Cabrerizo [8]; Navarro [9]; Hernainz and
Navarro [10]), although calcite undergoes a certain
degree of solubilisation at this pH, under 0.8% in all
cases, as revealed experimentally. The SDS concentration range selected also applies to the collectors use in
industrial flotation operations.
The recovery percentage of celestite was plotted
against SDS concentration in M (mol/l) in Fig. 1. Even
at very low concentrations of the agent, the mineral is
seen to respond well to flotation at sizes below 74 mm.
An increase in the collector concentration above
1.3310 4 M barely alters the celestite recovery percentage, which remains at around 90%.
For the mineral size 137 mm, however, recovery
gradually rises as SDS concentration is increased. At
concentrations approaching 4.4 10 5 M, the recovery
percentage is very low (10%), at 1.3310 4 M, the

F. Hernainz, M. Calero / Chemical Engineering and Processing 40 (2001) 269275

271

maintained for calcite and considerably lessened for


celestite (a difference of 20%). Both above and below
these two concentrations, either the difference in response to flotation for the two concentrations is poor,
as in the case of celestite, or the recovery percentages
are relatively low, as in the case of calcite.
The two concentrations, namely 1.3310 4 and
2.22 10 4 M, were selected for the kinetic study
detailed below.

3.2. Flotation kinetics

Fig. 2. Flotation recovery of calcite vs. concentration of SDS and two


different particle sizes.

percentage rises to 48%, while at 2.66 10 4 M, recovery percentage exceeds 80%. At this latter concentration, the values found for both sizes used are very
similar, indicating that this parameter (i.e. size) ceases
to be a limiting factor when there is an excessive
collector concentration as revealed by Taggart [11], and
Pereda and Hernainz [12].
Fig. 2 shows the results obtained for calcite using the
same sizes and SDS concentrations as those used for
celestite. For calcite size of 74 mm, the recovery percentage of the mineral rises as the SDS concentration is
increased up to a value of approximately 1.3310 4
M. From this point onwards, an increase in agent
concentration does not enhance the mineral recovery
percentage, which remains constant at around 70%.
Low recovery rates, between 15 and 17%, are obtained from calcite flotation for a size of 137 mm and
throughout the SDS concentration ranges studied.
These results suggest that size is clearly one of the
factors influencing recovery of this mineral, what coincides with that indicated by Trahar [3].
From a comparative study between celestite and calcite recovery (Figs. 1 and 2), it is seen that certain agent
concentrations allow kinetic constants to be determined, given that there is a noticeable separation between both sizes as well as good results in mineral
recovery. For example, at 1.33 10 4 M, for both
minerals, the difference in separation of the smallest
and the largest sizes is of importance (a difference of
over 40%) and at 2.2210 4 M the difference is

Flotation kinetics studies the variation of floated


mineral mass according to flotation time. If all operational variables are kept constant, the algebraic relationship between the parameters mentioned above is a
flotation rate equation. The ways, in which rate equations may be evaluated can be based on assumptions or
on facts established about the mechanism of the process, or, more commonly, determined empirically or by
analogy with similar rate processes (Arbiter and Harris
[5]).
By analogy with chemical kinetics, the equation representing flotation kinetics may be expressed thus,
dC
= kC n
dt

(1)

where C is the concentration of solids, t flotation time,


n order of the process, and k is the flotation rate
constant.
From the kinetics point of view, concentration C in
Eq. (1) comes from,
C=

M
V

(2)

so that, if it is assumed that the volume is not modified


during flotation (which is not strictly true as there is
always a small loss of liquid when the mineralised
froths are collected), the problem becomes considerably
simpler, as we may take C as the mineral mass, which
remains in the cell as the operation proceeds.
Therefore, if we assume that the volume is not altered during operation, the value for the flotation rate
constant may be obtained. This constant is complex
since it includes operational parameters such as inducement time, aeration, reagent concentration, particle
size, prior treatment, design of the flotation cell, etc.
Three approaches may be used to calculate this constant, namely,
1. first-order equation (n= 1);
2. second-order equation (n=2);
3. non-integral-order equation.
The integration for obtaining the constant of flotation rate in the three approaches is described in a
previous work (Hernainz and Calero [7]).

F. Hernainz, M. Calero / Chemical Engineering and Processing 40 (2001) 269275

272

Fig. 3. Flotation recovery of celestite vs. flotation time, with 1.33


10 4 M SDS and five different mineral fractions.

Fig. 4. Flotation recovery of celestite vs. flotation time, with 2.22


10 4 M SDS and five different mineral fractions.

3.2.1. Celestite
Fig. 3 shows the recovery percentage plotted against
flotation time at pH 3 and 1.3310 4 M of SDS for
the following average particle sizes, 137, 115, 96.5, 81
and 74 mm.
The flotation rate is very fast for all sizes studied,
with the greatest part of the mineral having floated
within 3 min.
These experiments also reveal that a decrease in size
increases mineral recovery as pointed out by Trahar
[13] when using other minerals. An increase in flotation
rate is also seen to occur as size decreases, although for
81 and 74 mm, results are very similar as indeed occurs
for 115 and 96.5 mm.
Fig. 4 shows the results obtained using an SDS

concentration of 2.22 10 4 M. The recovery percentage is seen to increase considerably, reaching maximum
recovery within 3 min. It may also be seen that particle
size becomes less important than in the previous case
where SDS concentration was 1.33 10 4 M (Fig. 3).
The results for four of the five sizes used are very
similar in order to the recovery percentage.
The values obtained for the three assumptions under
consideration are shown in Table 1.
The correlation coefficient, r 2, obtained for kl indicates that the operation may not be assimilated in order
1 at either of the two SDS concentrations used.
For order 2, the correlation coefficients give acceptable values in some cases, mainly with the smaller sizes
used.

Table 1
Celestite
SDS (M)

1.33104

2.22104

Average particle size (mm)

137
115
96.5
81
74
137
115
96.5
81
74

n=1

n=2

n-non-integral

k1 (min1)

r2

k2 (g1 min1)

r2

kq (min1)

r2

0.1313
0.2954
0.3418
0.3617
0.3741
0.2880
0.4378
0.4518
0.4812
0.5006

0.76
0.82
0.88
0.82
0.79
0.76
0.85
0.89
0.85
0.89

0.00237
0.00820
0.01060
0.01463
0.01688
0.00829
0.01875
0.02204
0.02766
0.03415

0.78
0.88
0.94
0.93
0.91
0.85
0.94
0.96
0.98
0.99

47
73
79.8
87
90.1
77
88
90
94
96

0.8506
1.1542
0.8325
0.7010
0.6240
0.7794
1.0561
0.8777
0.7021
0.6589

0.92
0.98
0.97
0.94
0.93
0.91
0.99
0.96
0.93
0.98

F. Hernainz, M. Calero / Chemical Engineering and Processing 40 (2001) 269275

273

Fig. 6. Flotation recovery of calcite vs. flotation time, with 2.22


10 4 M SDS and five different mineral fractions.

Fig. 5. Flotation recovery of calcite vs. flotation time, with 1.33


10 4 M SDS and five different mineral fractions.

It may be seen that relatively high recovery rates are


achieved for size of 74 mm. It is also clear that as size
increases, in all cases, recovery percentage decreases.
Table 2 shows the results obtained again checking the
adjustment by first-, second- and non-integral-order
equations.
In this case, the correlation coefficients indicate that
the representative kinetics of the process also correspond to a non-integral order.

However, it is in the non-integer order that the


correlation coefficient gives the best results, and, therefore, kq may be taken as representative of the process.
The values for kq lessen with a decrease in the mineral
size, for the two SDS concentrations used, which
mainly agrees with results found for other minerals by
other researchers (Trahar [13]; Laplante et al. [14,15]).
However, those found by Hernainz and Calero [7] for
the same mineral with sodium oleate are different, since
kq is similar for all the particle sizes.

3.3. Flotation rate and particle diameter


3.2.2. Calcite
Recovery percentages for calcite are shown in Figs. 5
and 6, plotted against flotation time at pH 3 for the five
average particle sizes of mineral selected using 1.33
10 4 and 2.22 10 4 M of SDS, respectively.

The flotation rate of fines particles is low relative to


that of other sizes, primarily as a result of the decreased
probability of collision between particles and air bubbles as the particle size is reduced (Trahar [13]; Ready

Table 2
Calcite
SDS (M)

1.33104

2.22104

Average particle Size (mm)

137
115
96.5
81
74
137
115
96.5
81
74

n= 1

n =2

n-non-integral

k1 (min1)

r2

k2 (g1 min1)

r2

kq (min1)

r2

0.0061
0.0173
0.0197
0.0354
0.1434
0.0226
0.0230
0.0544
0.0716
0.2018

0.67
0.72
0.73
0.75
0.75
0.71
0.81
0.85
0.78
0.82

8.2564105
2.4962104
2.8397104
5.3479104
0.00345
3.1278104
3.3492104
7.4449104
0.001194
0.005357

0.67
0.73
0.74
0.76
0.82
0.71
0.82
0.82
0.80
0.89

9.2
14.9
16.6
22.9
62
13.6
15.4
25.5
35
68

1.4274
1.4816
1.2141
1.0991
0.8290
1.6855
1.2361
1.0968
0.9800
0.7450

0.87
0.94
0.97
0.98
0.98
0.97
0.98
0.98
0.98
0.94

F. Hernainz, M. Calero / Chemical Engineering and Processing 40 (2001) 269275

274

and Ratcliff [16]). However, the form of the relationship between flotation rate and particle size is not yet
clear. The most recent theoretical analyses suggest that,
k8d

(3)

where k is a suitable measure of the flotation rate, d the


particle diameter, and m is the number between 1.5 and
2.
Fig. 7 shows the rate constant, kq, plotted against
average particle size for the celestite and calcite at
1.33 10 4 and 2.2210 4 M of SDS. In this figure,
the kq with r 2 lower of 0.93 has not been represented.
The results shown in Fig. 7 support a roughly linear
relationship between flotation rate and particle diameter. In this sense, Table 3 shows the results obtained
checking the adjustment.
The correlation coefficient, r 2, obtained indicates that
a linear relationship exists between flotation rate and
particle diameter. Likewise, the values of m are between
1.1 and 1.35, what is lightly inferior to that found for
other minerals by other researchers (Jameson [2]; Trahar [13]).

4. Conclusions
1. The flotation rate is very fast for both minerals and
for all sizes studied, with the greater part of the
mineral having floated within 3 min.
2. The results obtained on flotation of celestite and
calcite indicate that the representative kinetics of the
process correspond to a non-integral order although
the correlation coefficient gives the best results
(r 2 \ 0.93 in the most cases), and, therefore, kq may
be taken as representative of the process. The value
for kq lessens with a decrease in the mineral size, for
the two SDS concentrations used. The values of kq
are between 1.1542 and 0.624 min 1 for celestite,
and 1.6855 and 0.745 min 1 for calcite.
3. Likewise, the correlation coefficient, r 2, obtained of
the kq plotted against average particle size indicates
that a linear relationship exists between flotation
rate and particle diameter (r 2 \ 0.98 for celestite and
r 2 \ 0.91 for calcite).

Appendix A. Nomenclature

n
R

mass of mineral remaining in the machine (g)


diameter of particle (mm)
flotation rate constant
first-order flotation rate constant (min1)
second-order flotation rate constant (g1 min1)
non-integral order flotation rate constant
(min1)
order of the process
recovery of mineral at infinite time

flotation time (min)

C
d
k
k1
k2
kq

References

Fig. 7. Variation in flotation rate constant with particle size of


celestite and calcite.

Table 3

Celestite
Calcite

SDS (M)

r2

1.33104
2.22104
1.33104
2.22104

1.35
1.10
1.18
1.15

0.98
0.99
0.91
0.94

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