Canadian Metallurgical Quarterly

The Canadian Journal of Metallurgy and Materials Science

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A New Approach to Classification of Flotation

Collectors

J.S. Laskowski

To cite this article: J.S. Laskowski (2010) A New Approach to Classification of Flotation
Collectors, Canadian Metallurgical Quarterly, 49:4, 397-404

To link to this article: http://dx.doi.org/10.1179/cmq.2010.49.4.397

Published online: 18 Jul 2013.

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 397

Canadian Metallurgical Quarterly, Vol 49, No 4 pp 397-404, 2010

© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

A New Approach to Classification of Flotation Collectors

J.S. Laskowski

NB Kevil Institute of Mining Engineering,

The University of British Columbia,
Vancouver, B.C., Canada, V6T 1Z4
e-mail: jsl@apsc.ubc.ca

(Received in revised form August, 2010)

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Abstract — A collector is needed at the point of particle to bubble attachment and can be brought to this
point either on the surface of particles, bubbles or both. In order for this to happen the collector must first
be introduced into the flotation pulp. The water-soluble collectors are utilized as aqueous solutions,
water-insoluble oily hydrocarbons must be dispersed in water and are used as emulsions, while water-
insoluble amphipathic compounds can spread at the gas/water interface. The rational classification of
flotation collectors based on such observations is presented in this paper. The analysis of the accompa-
nying phenomena leads to the conclusion that in all these mechanisms a very important and not always
recognized part is played by the surface of bubbles. The role of bubbles in transportation of collectors to
the point of particle-to-bubble attachment is especially important for the two types of water-insoluble col-
lectors: oily hydrocarbons and long-chain amphipathic compounds.

Résumé — On a besoin d’un collecteur au point d’attachement entre la particule et la bulle et on peut
l’amener à ce point soit à la surface des particules, des bulles ou des deux. Afin que cela se produise, on
doit d’abord introduire le collecteur dans la pulpe de flottation. Les collecteurs hydrosolubles sont utili-
sés en solutions aqueuses, alors que l’on doit disperser dans l’eau les hydrocarbures huileux insolubles,
utilisés comme émulsions, et que les composés bipolaires insolubles peuvent se répandre à l’interface
gaz-eau. Dans cet article, on présente la classification rationnelle des collecteurs de flottation en se basant
sur de telles observations. Grâce à l’analyse des phénomènes d’accompagnement, on peut conclure que,
dans tous ces mécanismes, une partie très importante et pas toujours reconnue se joue à la surface des
bulles. Le rôle des bulles dans le transport des collecteurs vers le point d’attachement particule à bulle
est particulièrement important pour les deux types de collecteurs insolubles dans l’eau: les hydrocarbures
huileux et les composés bipolaires à longue chaîne.

INTRODUCTION functional group with such ligand atoms as S, N, O and also

Many different chemical additives, referred to as flotation
reagents, are utilized in the flotation process. The most
important group includes collectors, the reagents needed to
make given mineral(s) floatable. Classification of flotation
collectors is usually based on chemical composition of these
compounds. An example of such a classification is shown in
Figure 1.
New collectors are chemical reagents that adsorb at
solid/liquid interfaces by chemisorption. A majority of new
developments in collector chemistries involve a functional
group that contains two donor atoms capable of bonding a
metal species and of forming a ring structure known as a
chelate. Chelating-type collectors contain a reactive
P, in positions capable of bonding the same metal atom
through two or more different ligand atoms to form a hetero-
cyclic ring [1,2,3]. This relatively new group of flotation
collectors has been introduced to a traditional classification
of collectors in Figure 1. Such a classification, while more
complete, is however not consistent since some sulphur-
containing compounds appear twice, in the group of
thio-collectors and also in the group of chelating collectors.
This controversy calls for a different classification
system which should be based on the mechanism of action
rather than on the collector chemical composition. The basic
point in such an approach is the fact that collector is needed
at the point of the particle-to-bubble attachment. If so then
it can be carried on to this point either on the surface of solid

Canadian MetallurgiCal Quarterly, Vol 49, no 4

 398 J.S. Laskowski
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Fig. 1. Classification of flotation collectors.
particles, or on the surface of bubbles, or on both. In both
cases the collector first must be introduced into the flotation
pulp. If collectors are soluble in water, they are added to the
pulp in the form of aqueous solution. If these are ‘oils’, i.e.,
insoluble hydrocarbons, they must be dispersed in water and
then added to the pulp in the form of an oil-in-water
emulsion. Amphipathic water-insoluble compounds, i.e.,
long chain surfactants, can form molecular films at the
water/gas interface and so they can be introduced to the
flotation system on the surface of bubbles. Thus, from the
point of view of the mode of operation of these agents the
most logical would be classification of the flotation
collectors into:
1. water soluble compounds,
2. water insoluble “oily” collectors,
3. water insoluble amphipathic compounds which form
molecular films at water/gas interface.
SOLUBLE COLLECTOR FLOTATION
Diffusion of collector ions or molecules toward solid surfaces
and selective adsorption on to solid surfaces is a main
mechanism of the action of the soluble flotation collectors. In
order for the flotation to be selective, the collector adsorption
must be selective. In this mechanism the collector must be
soluble in water (in this text this mechanism will be referred
to as soluble collector flotation).
By writing Young’s equation in the form:
Canadian MetallurgiCal Quarterly, Vol 49, no 4
 SV   SL (1)
cos  
 LV
where  is the contact angle and SV, SL and LV are the
interfacial tensions at the solid/vapour, solid/liquid and
liquid/vapour interfaces, respectively, it becomes obvious that
for an initially hydrophilic solid ( = 0, cos  = 1 and SV  SL
= LV), the contact angle can increase (solid will become
hydrophobic) only if, as a result of surfactant adsorption, SV
decreases more than SL, so that
 SV   SL   LV (2)
This may happen only when
(3)
 SV   SL
where SV and SL stand for the adsorption at solid/vapour and
solid/liquid interfaces.
This exercise leads to the conclusion that “an increase
in contact angle results from surfactant only if the surfactant
adsorption is greater at the mineral-air interface than at the
mineral-water interface” [4]. This result indicates that for
better flotation, one should look at the adsorption at the
liquid/gas interface and solid/gas interface rather than just at
the solid/liquid interface, as is usually done.
 A New Approach to Classification of Flotation Collectors 399

While solid/vapour ( SV) and solid/liquid ( SL)

interfacial tensions cannot be measured experimentally, it is
possible to measure the adhesion tension ( =SV –SL), the
numerator in Equation 1, that is the difference between these
two. Using the Wilhelmy plate method, Yaminsky and
Yaminskaya [5] measured the adhesion tension on silica
plates in cetyltrimethylammonium bromide (CTAB)
solutions. They showed that the adhesion tension initially
decreases with concentration and that over this concentration
range the surface is hydrophobic. This indicates that at the
lower concentration range adsorption at the solid/gas
interface is larger than at the solid/liquid interface and that
only in the CTAB concentration range over which the
adsorption difference between the adsorption at solid/vapour
and solid/liquid interfaces was positive was the silica plate
Fig. 2. Adsorption of the surfactant brought by a bubble on to solid (Leja-
hydrophobic. Similar results were published by Kelebk et al.
Schulman penetration theory).
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[6] who showed that adhesion tension measured in the

system galena-decyl xanthate initially sharply decreases,
passes through a minimum and then increases at higher decyl preparation stage commonly involves filtration and in this
xanthate concentrations. The tests carried out with gold- process, the solution/gas interface makes contact with solid
hexyl mercaptan system by Aplan and de Bruyn [7] particles and whatever is adsorbed at this interface ends up on
confirmed the importance of adsorption at the mineral/gas the surface of the solid particles. It is then logical to postulate
interface. that while the chemisorbed part results from the adsorption at
As observed by Smolders [8], in the flotation systems, the solid/liquid interface, the physisorbed part results from
the higher adsorption of reagents at the solid/gas interface the contact with the bubbles carrying some agents. It is
than at the solid/liquiod interface can be explained by the therefore logical to expect that the portion of the collector that
penetration theory of Leja and Schulman [9,10]. In this is physisorbed on to the solid particles represents the part
theory, in the moment of particle-bubble collision and which under flotation conditions is brought on the surface of
attachment, the collector adsorbed on the mineral particle is bubbles.
postulated to interact with the species (e.g. frother) carried by There are many flotation observations which are exactly
a bubble. This leads to the situation shown in Figure 2 which in line with the approach discussed in this paper. Taggart and
agrees very well with theoretical conditions for successful Hassialis [18] showed that the presence of frother, namely
attachment given by Equations 1 to 3. cresol, leads to the immediate establishment of a contact
In total agreement with the Leja-Schulman theory, Digre angle on sphalerite partially coated with xanthate, whereas an
and Sandvik [11] demonstrated that the adsorption of C12, air bubble fails to make contact in a potassium ethyl xanthate
C14 and C16 amine hydrochlorides on to quartz more than solution alone. Krasowska and Malysa [19] with the use of a
doubled when the conditioning of the quartz suspension was high-speed camera were able to show that while bubbles do
carried out in the presence of gas bubbles. Doczkal [12] found not easily attach to a very hydrophobic Teflon® surface, the
much higher adsorption of alcohols on to coals in the attachment becomes much easier in the presence of traces of
presence of bubbles. n-hexanol.
Eigeles with his co-workers [13,14,15] used tagged
atoms and in direct measurements showed that some colloidal
species that appear in flotation systems accumulate on the
surface of bubbles. The presence of such species on the
surface of bubbles affects very strongly flotation performance
indicating how important the role is of that part of the
reagents which is carried by bubbles [16].
Collectors can both chemisorb and physisorb on to solid
particles and the total adsorption density includes both forms.
Using different solvents, Abramov [17] showed that for each
successful flotation there is a clear ratio between these two
forms of adsorption. These results demonstrate that both
adsorption forms are needed for a mineral to exhibit a good
floatability. In the adsorption experiments, the solid particles
after conditioning with the collector solution of known
concentration must be separated from this solution which is
then used to determine the final collector concentration. The Fig. 3. Solid-liquid separation by filtration in the adsorption experiments.

Canadian MetallurgiCal Quarterly, Vol 49, no 4

 400 J.S. Laskowski

WATER-INSOLUBLE OILY COLLECTOR

FLOTATION

In another mechanism, the collector appears in the form of

droplets (as in the case of emulsion flotation with an oily
collector) which collides with mineral particles as a result of
conditioning and can get attached to the solid surfaces. For
the attachment to be possible, the solid must to some extent
be hydrophobic (this mechanism will be referred to as
insoluble oily collector flotation). Flotation selectivity in this
case then results from the selective attachment of oily
droplets to mineral surfaces. As shown by Taubman and
Yanova [20], only hydrocarbons which are insoluble in water
can operate in this way.
The model tests described by Zettlemoyer et al. [21] in
which a smooth Teflon® disc was placed under water and a
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drop of the mineral oil (Drakenol-10) was submerged and

placed in contact with the Teflon® plate (the contact angle of
water on this disc was 108° confirming that it was very
hydrophobic) well describes the situation in the flotation
process in which an oily collector is added to the pulp
containing mineral particles suspended in water. In the
Zettlemoyer et al. experiments, the oil droplet in water
exhibited a finite contact angle of 37° (measured through oil),
i.e., the oil does not displace water from the Teflon®. Water
height was then gradually lowered and when the oil/air
interface was established the water spontaneously receded to
the edge of the disc leaving oil droplets on the Teflon® surface
(contact angle of 52° measured through the oil phase). When
the sequence of the stages was reversed however, the oil
droplet was placed on a dry Teflon® surface and then the
system submerged in water, the oil contact angle was zero.
This probably results from the contact angle hysteresis. These
observations also explain why it is commonly assumed that
oil forms a film on the surface of hydrophobic particles in
flotation systems. The mechanism described by Zettlemoyer
et al. agrees very well with the mechanism postulated by
Klassen and his co-workers in a series of publications on the
mechanism of action of water-insoluble oily collectors [22].
This mechanism is sketched in Figure 4.
One noticeable effect of the oily collector is an
increased size of floated particles. As maintained by Melik-
Gaykazyan [23], the location of the oil as a thread at the line
of contact of the three phases (Fig. 4d) remarkably increases
the bubble-particle adhesion force.
In the discussed collector classification, the flotation
agents which are weak electrolytes (e.g. fatty acids, amines)
are somewhere in between the soluble and oily insoluble
collectors. Ionization of these agents strongly depends on pH
and while the molecular forms of these agents are very
insoluble in water (solubility of oleic acid is about 10-8
mole/L), they may be quite soluble when ionized. This is
quite obvious on the domain diagrams of these agents [24].
The fact that the weak electrolyte type collectors depending
on pH appear in the flotation system either in the form of
emulsion or as a solution explains some peculiar flotation
properties of such agents. It is well established that the
Fig. 4. Attachment of a bubble to a hydrophobic particle in the presence of
oil droplet on the solid surface [based on Zettlemoyer et al. [21]).
flotation with water-insoluble oily collectors requires long
conditioning time [25,26,27]. On the other hand, an
adsorption equilibrium is established fairly quickly for an
ionized collector and so, in the pH zone in which the collector
is ionized the effect of conditioning time should be negligible.
Kulkarni [28] observed that while at pH 8 adsorption of oleate
on hematite attained its constant value after less than 2
minutes, at a pH of 4.8 the equilibrium adsorption was not
reached even after 4 hours. As shown in Figures 5 and 6,
flotation tests confirm entirely such conclusions [29].
Figure 5 shows the effect of conditioning with sodium
oleate on flotation response of fluorite. At pH 9.5 the fluorite
recovery increases dramatically over the first few minutes
and then remains almost constant. This is very different at a
pH of 4 and thus while at short conditioning times the
flotation in the alkaline solution is better, this picture changes
dramatically when the conditioning time is long enough.
Figure 6 shows similar results for the flotation of magnesite
with sodium oleate.
These results demonstrate that the transportation of the
collector species toward mineral particles is a flotation
controlling step in the emulsion flotation. Because of very
low solubility of oleic acid, in the acidic pH ranges the oleic
acid droplets appear in the system and a typical emulsion
flotation ensues. Slow diffusion of the collector droplets is
apparently responsible for the pronounced effect of
conditioning time on flotation in the acidic pH range. In the
alkaline range the collector is ionized and as a result of the
fast diffusion of such ions the adsorption equilibrium is
reached quickly. Consequently the optimum on the flotation
recovery – pH curves shifts towards lower pH values when
the experiments are preceded by longer conditioning times.

Canadian MetallurgiCal Quarterly, Vol 49, no 4

 A New Approach to Classification of Flotation Collectors
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Fig. 5. The effect of conditioning time on the flotation of fluorite under
acidic and alkaline conditions at a sodium oleate concentration of 10-5 M
[29].
It is also to be pointed out that oil droplets can spread at
the air/gas interface. This can also be shown using thermo-
dynamic data. The spreading of oil on the surface of bubble is
given by:
Sow   wv   ov   wo (4)
If n-octane is used as an oil phase, ov = 21.8 mJ/m2, wo = 50.8
mJ/m2 [30] and putting for water wv = 72.8 mJ/m2 gives Sow
= 0.2 > 0 indicating that the spreading on the bubble surface
will likely take place. This is thus different from hydrophobic
solid surfaces submerged in water; oil does not spread on
Fig. 6. The effect of conditioning time and oleate concentration on the
flotation of magnesite at pH 3.5 and 10.5 [29].
401
such surfaces but adheres to them in the form of droplets
(Figure 4). It is also to be pointed out that Equation 4 and the
provided numbers give the initial spreading coefficient. When
two substances are in contact, they will become mutually
saturated, so that wv and ov will change. The resulting final
spreading coefficient is often negative, thus a rapid initial
spreading will then be followed by a retraction of the oil
phase into lenses. However, the water surface left behind is
not pure as indicated by much lower surface tension
corresponding to the adsorption monolayer.
The studies on reactive oily-bubbles [31], i.e., the air
bubbles coated with a thin film of oily collector, demonstrated
again how beneficial it is when the collector is brought to the
point of particle-bubble attachment on the surface of bubbles.
Misra and Anazia [32] compared the results of coal flotation
tests carried out with fuel oil No. 2, which was either added
directly into a Denver flotation cell in an ultrasonically
emulsified form or as aerosol in the stream of air entering the
cell. The results indicate that the introduction of collector on
the surface of bubbles produces superior results. Misra and
Anazia also demonstrated that the induction time needed for
the oil-coated bubbles to attach to coal specimen was many
times shorter in comparison with the induction time measured
for the oil-free bubbles.
WATER-INSOLUBLE AMPHIPATHIC COLLECTORS
Amphipathic compounds, insoluble in water, form molecular
films at the water/gas interface (also known as Langmuir-
Blodgett films). The monolayer films of fatty acids were
heavily studied. Gaines [33] demonstrated that with long-
chain amines (e.g. C22 amine) condensed monolayers are
formed in a wide range of conditions. The stability of
monolayers depends on solubility; fatty acids form stable
monolayers on water in acidic solutions when they are not
ionized, while long-chain amines form stable monolayers on
water in an alkaline pH range [34]. Spreading of monolayer
from a solid requires detachment of molecules into the
surface film which occurs only at the periphery of the crystal.
The process, therefore, strongly depends on temperature and
becomes extremely slow below certain temperatures, but
increased solubility or evaporation make the films unstable if
temperature is high.
Arsentiev and Leja [35] studied the monolayers of
amines and fatty acids spread and compressed on saturated
salt solutions. They used hexanol (or 1:1 mixture of benzene
and ethyl alcohol) to dissolve the tested surfactants in the
spreading procedure. In the spreading rate measurements [36]
it was shown that while the spreading rates on saturated salt
solutions were negligible for pure long-chain amines, these
rates increased dramatically when the amines were mixed
with alcohols. (e.g. hexanol). The tested flotation frothers
such as MIBC and DF-250 behaved similarly to hexanol. The
spreading rates for C16-C18 amines mixed with hexanol were
in the range from 300 to 400 mm/s. The KCl plates brought
from underneath adhered strongly to the amine films, NaCl
Canadian MetallurgiCal Quarterly, Vol 49, no 4
 402
plates did not (Figure 7). There was no adhesion between KCl
plates and the branch-chain amine films.
Potash Ore Flotation System
Long-chain primary amines utilized as a collector in potash
ore flotation are practically insoluble in water. The amines are
therefore melted by heating up to 70 to 90°C, they are then
neutralized with hydrochloric or acetic acids and such a hot
emulsion/dispersion is introduced into the flotation pulp
(NaCl-KCl saturated brine at room temperature). According
to all reported observations, a white precipitate immediately
appears when the hot emulsion of amine is added to the
potash flotation pulp. Introduction of a hot amine dispersion
into a pulp at a temperature which is much lower than the
Krafft temperature for the utilized amine must result in
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precipitation of the amine [37].
For the last ten or so years we have been reporting that
the use of a frother (e.g. MIBC) in the amine preparation/
dispersion dramatically enhances the performance of amine
in the potash ore flotation [38,39]. The hot amine dispersion
when prepared with the addition of MIBC exhibits quite
different properties, also the size and morphology of the
precipitating amine particles when it is introduced to the
flotation pulp differ [40].
Since the long-chain amines are insoluble in brine, it is
possible to place the amine dispersion directly on the surface
of KCl plate or on the surface of bubble. Figure 8 shows the
contact angles on freshly cleaved KCl plates measured in a
saturated brine with amine collector either placed on the
surface of KCl plate or on bubble, both in the presence and
absence of MIBC [41]. When amine dispersion is physically
placed on the surface of the KCl plate, which is then
contacted with a bubble, the obtained contact angle values
exhibited a very high degree of scatter. Such a KCl surface
coated with amine particles is obviously very heterogeneous
and it is only slightly hydrophobic. However, when the amine
is placed on the surface of the bubble which is then contacted
with KCl plate, the plate becomes remarkably hydrophobic.
The contact angle measurements in such a case are very
reproducible and this obviously results from the much more
homogeneous deposition of amine. This homogeneity is even
more obvious when the amine is prepared with an addition of
MIBC. It is obvious that in the mode of action of the water-
NaCl
Fig. 7. The adhesion tests between the amine film, spread on a saturated NaCl-KCl brine and either NaCl or KCl plates [35].
Canadian MetallurgiCal Quarterly, Vol 49, no 4
J.S. Laskowski
Amine on bubbles Amine + MIBC on bubbles
Amine on particles Amine + MIBC on particles
No amine
Frequency
Advancing contact angle (deg)
Fig. 8. Contact angle measurements on KCl plates in NaCl-KCl saturated
brine. The 1% amine dispersion was placed directly on to the surface of the
capillary used to generate the bubble or on to the surface of KCl plate [41].
insoluble collectors described in this paper the liquid/gas
interface plays an essential role.
Flotation of coarse sylvite particles is very important in
the potash industry since the coarse concentrate is saleable
without any additional particle-size enlargement operations.
The flotation of coarse fractions is usually achieved with the
use of an extender oily collector. As we showed in our paper
presented at the 24th IMPC [39] while the coarse sylvite
particles float poorly when the amine is prepared in a conven-
tional way (without a co-surfactant), such a flotation is quite
satisfactory when it is carried out with the amine prepared with
MIBC. The results presented in this paper offer an obvious
explanation. Since the coarse particles can float only when very
hydrophobic, this is much more likely to happen when amine
is prepared with MIBC. Observations indicate that the amine
particles precipitating in the pulp when the amine dispersion is
damped in the pulp accumulate at the liquid/gas interface and
armour bubbles. This makes a very flotation-active mixture
when the amine is prepared with MIBC since amine under such
conditions may spread and form the amine monolayer film on
the surface of bubbles. Much better flotation of coarse KCl
particles under such conditions confirms this conclusion.
KCl
 A New Approach to Classification of Flotation Collectors
It is to be pointed out that the spreading rate of amine
molecular films at a liquid/gas interface is fast if amine is
accompanied by a co-surfactant, but it is a very slow process
for a pure amine [36]. It is then likely that while such film can
form under flotation conditions on bubbles in the potash
flotation system when amine is prepared with MIBC, the
kinetics of the process does not allow formation of the amine
film in the case of pure amine. The major conclusion evident
from the results of potash ores flotation tests is that the
colloidal species of amine prepared in the presence of MIBC
form a dispersion which spreads into amine monolayer on the
surface of the bubbles when such particles collide and attach
to bubbles. The presence of such films on the surface of
bubbles leads to a drastic improvement in the flotation of the
coarse sylvite particles.
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CONCLUSIONS
This study highlights the mode of action of flotation
collectors as a basis for rational classification of the
collectors. The collector is needed at the point of attachment
of a particle to a bubble and by analysis of the mode of action
of the collectors classified into water soluble, water insoluble
oily compounds and water insoluble amphipathic compounds;
it becomes clear that in all these cases the surface of bubbles
plays a very significant role.
ACKNOWLEDGEMENTS
The author would like to acknowledge the support provided
by Natural Sciences and Engineering Research Council
(NSERC) through a Discovery Grant
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