Froth flotation

Froth flotation
Flotation is a separation process that exploits the differences in surface properties of the
minerals.

Mineral surface can be two types:

1) Hydrophilic: Readily wetted with water If a mixture of hydrophobic and hydrophilic particles are
2) Hydrophobic: water repellent suspended in water, and air is bubbled through the
suspension, then the hydrophobic particles will tend to
attach to the air bubbles and float to the surface.
The froth layer that forms on the surface will then be
heavily loaded with they hydrophobic mineral, and
can be removed as a separated product.

The hydrophilic particles will have much less

tendency to attach to air bubbles, and so it will
remain in suspension and be flushed away
 θ θ

θ-= small (<<90 C) Θ >> 90

The attachment of the bubbles to the surface is determined by the interfacial energies between the solid, liquid, and gas
phases. This is determined by the Young/Dupre Equation,

where γlv is the surface energy of the liquid/vapor interface,

γsv is the surface energy of the solid/vapor interface,
γsl is the surface energy of the solid/liquid interface, and
‘θ’ is the “contact angle”, the angle formed at the junction
between vapor, solid, and liquid phases

If the contact angle (‘θ’) is:

1) very small, then the bubble does not attach to the surface, θ
2) While a very large contact angle results in very strong bubble attachment.
3) A contact angle near 90° is sufficient for effective froth flotation in most cases. Θ= 90
Froth flotation process
• The agitator provides enough
turbulence in the pulp phase to
promote collision of particles and
bubbles, which results in the
attachment of hydrophobic particles to
bubbles (forming bubble particle
aggregates) and their transport into
the froth phase for recovery.
• In flotation concentration, the
valuable mineral is usually transferred
to the froth, or float fraction, leaving
the gangue in the pulp or tailings.
• A function of the froth phase is to
retain the collected particles and
transport them to the overflow.
 Flotation reagents

The mineral particles can only attach to the air bubbles if they are to some extent hydrophobic.

• All minerals are not hydrophobic- need to convert the hydrophilic minerals to hydrophobic.
• The air bubbles only continue to support the mineral particles if they can form a stable froth, otherwise they will burst
and drop the mineral particles.

To achieve these conditions, it is necessary to use the numerous chemical compounds known as flotation reagents.

Flotation reagents include:

1. Collectors: which adsorb on mineral surfaces, rendering them hydrophobic and facilitating bubble attachment.
2. Regulators : are used to control the flotation process; these either activate or depress mineral attachment to air
bubbles and are also used to control particle dispersion and the pH of the system.
3. Frothers: help to produce the fine bubbles necessary to increase collision rates and to help maintain a reasonably
stable froth.
Collectors: which adsorb on mineral surfaces, rendering them hydrophobic and facilitating bubble
attachment.

• Collectors are reagents that are used to selectively adsorb onto Collector film

the surfaces of particles. Hydrophobic

nature
• They form a monolayer on the particle surface that essentially
makes a thin film of non-polar hydrophobic hydrocarbons. Particle
(hydrophilic)
• The collectors greatly increase the contact angle so that bubbles
will adhere to the surface.

• Collectors can either chemically bond to the mineral surface

(chemisorption), or be held on the surface by physical forces (physical
adsorption).

• Selection of the correct collector is critical for an effective

separation by froth flotation.
 • Collectors can be generally classed depending on their ionic charge: they can be
a) Non-ionic:
b) Anionic,
c) Cationic.
• The non-ionic collectors are simple hydrocarbon oils, while the anionic and cationic collectors consist
of a polar part that selectively attaches to the mineral surfaces, and a non-polar part that projects out
into the solution and makes the surface hydrophobic.

Collectors can either chemically bond to the mineral surface (chemisorption), or be held on the surface
by physical forces (physical adsorption).

Chemisorption:
In chemisorption, ions or molecules from solution undergo a chemical reaction with the surface,
becoming irreversibly bonded. This permanently changes the nature of the surface.

Physisorption:
In physisorption, ions or molecules from solution become reversibly associated with the surface, attaching
due to electrostatic attraction or van der Waals bonding. The physisorbed substances can be desorbed from the
surface if conditions such as pH or composition of the solution changes.
Sodium oleate
and fatty acids Less-used than fatty acids. Less Carbon is tetravalent, has four bonds; phosphorus is
with this polar collecting power, higher selectivity pentavalent with five bonds. Sulfur atoms
group occur in chemically bond to sulfide mineral surface.
vegetable oils.
Collector for
hematite and
other metal
oxide minerals. Figure: Basic collector types: In the structures, “R” represents a
Strong
collector, low hydrocarbon chain, different collectors will use different
selectivity hydrocarbons for “R”
 Nonionic Collectors
• Hydrocarbon oils, and similar compounds, have an affinity for surfaces that
are already partially hydrophobic.
• They selectively adsorb on these surfaces, and increase their hydrophobicity.
• The most commonly-floated naturally-hydrophobic material is coal.
• Collectors further enhances the hydrophobicity of the coal particles without
affecting the surfaces of the minerals.
1. Fuel oil
2. Kerosene

• Fuel oil and kerosene have the following advantages :

I.They have low enough viscosity to disperse in the slurry and spread over the coal particles easily, and
II.They are very low-cost compared to other compounds which can be used as coal collectors.
• This improves the recovery of the coal, and increases the selectivity between coal particles and mineral
matter.
• In addition to coal, it is also possible to float naturally-hydrophobic minerals such as molybdenite, elemental
sulfur, and talc with nonionic collectors.
 Anionic Collectors
Anionic collectors are weak acids or acid salts that ionize in water, producing a collector that has a
negatively-charged end that will attach to the mineral surfaces, and a hydrocarbon chain that extends out into
the liquid

Solid particle

Fig: Adsorption of anionic collector onto a solid surface. The anionic portion is responsible for the attachment of the
collector molecule to the surface, while the hydrophobic part alters the surface hydrophobicity.
 Anionic Collectors for Sulfide Minerals.. PbS, ZnS, Pyrite (FeS2), ...etc
• The most common collectors for sulfide minerals are the sulfhydryl collectors, such as the various
Xanthates and dithiophosphates.
• Xanthates are most commonly used, and have structures shown in Figure.
• Xanthates are highly selective collectors for sulfide minerals, as they chemically react with the sulfide
surfaces and do not have any affinity for the common non-sulfide gangue minerals.
Minerals:
PbS, ZnS, FeS2

Structure of a typical xanthate collector (ethyl xanthate)

• The OCSS- group attaches irreversibly to the sulfide mineral surface. Using xanthates with longer hydrocarbon chains
tends to increase the degree of hydrophobicity when they adsorb onto the surface.

• Other highly-selective collectors for use with sulfide minerals, such as dithiophosphates, have somewhat different
adsorption behavior and so can be used for some separations that are difficult using xanthates.
Anionic Collectors for Oxide Minerals
• The collectors available for flotation of oxide minerals involves the attachment to the surface by
electrostatic attraction rather than by chemically bonding to the surface.
• A typical anionic collector for oxide mineral flotation is Sodium oleate, the sodium salt of oleic acid,
which has the structure shown in Figure.

The structure of oleic acid, a very commonly-used anionic collector

• The anionic group responsible for attaching it to the mineral surface is the carboxyl group, which dissociates in
water to develop a negative charge. The negatively-charged group is then attracted to positively-charged mineral
surfaces.
Cationic Collectors
• Cationic collectors use a positively-charged amine group to attach to mineral surfaces.
• Since the amine group has a positive charge, it can attach to negatively-charged mineral surfaces.
• Cationic collectors therefore have essentially the opposite effect from anionic collectors, which attach
to positively-charged surfaces.
• Cationic collectors are mainly used for flotation of silicates and certain rare-metal oxides, and for
separation of potassium chloride (sylvite) from sodium chloride (halite).

Primary, secondary, and tertiary amine groups that can be used for cationic collectors
Frothers
Frothers are compounds that act to stabilize air bubbles so that they will remain well-dispersed in the
slurry, and will form a stable froth layer that can be removed before the bubbles burst.
Frothers have three main functions in flotation :
1. Aid formation and preservation of small bubbles: Reduction in bubble size increases the number and total
surface area of bubbles, which increases collision rate with particles and thus increases flotation kinetics.
2. Reduce bubble rise velocity: Reducing rise velocity increases the residence time of bubbles in the pulp
which increases the number of collisions with particles and thus further increases kinetics.
3. Aid formation of froth: Formation of a froth means the bubbles do not burst when they reach the top of
the pulp, which enables the collected particles to overflow as the float product.

• The most commonly used frothers are: Alcohols, MIBC (Methyl Isobutyl Carbinol), or 4- methyl-2-
pentanol.
• Water-soluble polymers based on Propylene oxide (PO) such as Polypropylene glycols.
 Working principle

• Most frothers are heteropolar compounds comprising a polar

(i.e., hydrophilic) group, typically hydroxyl, and a hydrophobic
hydrocarbon chain.

• When surface-active molecules are in water, the water dipoles

combine (H-bond) readily with the polar groups, but there is
practically no reaction with the nonpolar hydrocarbon group, the
tendency being to force the latter into the air phase.

• Thus, the heteropolar structure of the frother molecule leads to

its adsorption at the airwater interface, with the non-polar groups
oriented toward the air and the polar groups toward the water.

• Frother, thus controls the properties of the air-water interface.

Regulators or Modifiers
• Regulators are chemicals reagents that influence the way that collectors attach to mineral surfaces.
Types:
• Activator: A reagent that increases the adsorption of collector onto a given mineral called activators.
• Depressant: A reagent that prevent the adsorption of collector onto a given mineral called depressants.
 It is important to note that just because a reagent is a depressant for one mineral/collector
combination, it does not necessarily follow that it is a depressant for other combinations.
 For example, Sodium sulfide is a powerful depressant for sulfide minerals being floated with xanthate,
but does not affect flotation when sulfide minerals are floated with the collector hexadecyl trimethyl
ammonium bromide.
Collector
film
Minerals:
Particle
PbS, ZnS, FeS2
(hydroph
ilic)
An example of an activator: Metal-sulfide minerals

Copper sulfate (CuSO4) as an activator for Sphalerite (ZnS) flotation with Xanthate collectors.

When untreated, Xanthate cannot attach to the sphalerite surface because it forms a Zinc-Xanthate compound
that quickly dissolves:
ZnS(s) + Xanthate  S(s) + ZnXanthate (aq) Xanthate
ZnS

The surface of the sphalerite can be activated by reacting it with a metal ion that does not form a soluble
xanthate, such as soluble copper from dissolved copper sulfate:
CuS
Xanthate
ZnS
ZnS(s) + CuSO4(aq)  CuS(s) + ZnSO4(aq)

This forms a thin film of copper sulfide on the sphalerite surface, which allows for stable attachment of the
xanthate, rendering the sphalerite particle hydrophobic and floatable.
Depressants Minerals: PbS, ZnS, FeS2

Depressants have the opposite effect of activators, by preventing collectors from adsorbing onto particular
mineral surfaces. Their typical use is to increase selectivity by preventing one mineral from floating, while
allowing another mineral to float unimpeded.

Cyanide (CN):
CN is a particularly useful
depressant in sufide mineral flotation. Its
activity is believed to be due to its ability to
complex with, and in some cases dissolve, a
number of metal ions, preventing them from
attaching to the Xanthate molecules.

In particular, it is a strong depressant for

pyrite (FeS2), and can be used to
“deactivate” sphalerite that has been
activated by copper ions in solution

Effect of cyanide depressant on flotation of minerals as a function of pH. It is interesting to note

that flotation of galena (PbS) is unaffected by the presence of cyanide.
• Lime:
Lime is added as either CaO or Ca(OH)2, and when it dissolves it contributes calcium ions that can
adsorb onto mineral surfaces. In combination with its strong alkaline nature, this makes it particularly useful
in manipulating sulfide flotation.

• Organic Depressants:
A large number of organic compounds are useful as flotation depressants. These tend to be soluble
polymers (such as starch) that selectively coat mineral surfaces and prevent collector from attaching.

An example of this is in the “reverse flotation” of silica from iron ore, where the silica tailings are floated
using a cationic collector at a pH of 8.5 - 11, leaving behind the iron oxide minerals.

Starch acts as a depressant for iron oxide in this process, preventing it from being floated by the cationic
collector.
pH Control

The simplest modifiers are pH control chemicals. The surface chemistry of most minerals is affected by the pH.
For example, in general, minerals develop a positive surface charge under acidic conditions and a negative
charge under alkaline conditions. Since each mineral changes from negatively-charged to positively-charged at
some particular pH, it is possible to manipulate the attraction of collectors to their surfaces by pH adjustment.
There are also other, more complex effects due to pH that change the way that particular collectors adsorb on
mineral surfaces.

Sulfhydryl collectors such as xanthate ions compete

with OH- ions to adsorb on mineral surfaces, and so
adsorption is a function of pH. This makes it possible
for sulfhydryl collectors to be used to progressively
separate specific minerals. The pH where the
xanthate ion wins the competition with OH- ions
depends both on the concentration of xanthate in
solution, and on the specific sulfide mineral present
 Flotation machines
Flotation machines are designed to ensure flow of the pulp into good, active contact of particles with
bubbles and levitation of mineral-laden air bubbles to the top of the cell, allowing entrapped particles to be
removed.
1) Mechanical machines: Here dispersion of the pulp through agitation by the mechanical driven impeller.
Mechanical machines employ one of the two types of pulp flow and aeration systems:
• Cell-to-Cell flow with adjustable wiers between cells or
• Open flow without the wiers and air intake via suction resulting from the rotation of the impeller or an
external blower.
Flotation tank profiles of Open-flow machines
Flotation cell impeller mechanisms
Column flotation:
• The technique uses the countercurrent
principle to improve separation by reducing
entrapment of particles .
• Important difference with others cell are, no
impeller or any agitation mechanism.
• Here the ore is fed into the column via
distributor located at 2/3 of the height of
cell.
• air bubbles are generated at the bottom of
the column by the porous sparger.
• The tails are removed from the bottom,
• Concentrates are overflow at the top.
Floatation circuit:
Flotation is carried out as a continuous operation in a series or bank of cells. This increases the floating time, allowing
ample opportunity for particle-bubble attachment to occur. The rate at which the particles float will depend on particle
composition, pulp density, particle size and degree of turbulence in the cell. The arrangement of a number of cells in
series allows the collection of different products from the various cells.
Cleaner circuit: Quite often the grade of concentrate recovered
from a single stage of flotation is not high enough and requires re-
floating in one or more stages of flotation referred to as cleaner or
recleaner stages.
The cleaner stage experiences milder flotation conditions
of lower pulp density and lower reagent concentrations to reduce
entrainment in the froth and to ensure only the high grade
particles will float.
Rougher stage: The series of cells that produce the initial
concentrate is called the rougher stage.
Scavenging: The subsequent retreatment of the rougher tailings is
referred to as scavenging.
The scavenger section of the flotation circuit is given
higher reagent dosages and long flotation time to float as much
valuable mineral as possible and maximise recovery.
https://www.youtube.com/watch?v=dCRYqSoDznQ