Flotation

General Theory
What is Flotation?

A method of wet concentration of

ores in which separation of valuable
minerals from gangue is effected by
utilizing the surface-chemical
properties of the minerals to enable
physical separation
What is Flotation?
 Generally, separation is made possible by
attaching a mineral to a bubble and letting
it float above the bulk phase, leaving the
other “unwanted” mineral submerged
 Vise-versa, in the case of REVERSE
FLOTATION
Types of Flotation Processes
 Film Flotation
 aka Skin Flotation
 Oil Buoyancy Flotation
 Froth Flotation
 Theonly flotation process which is of
commercial importance

*Oil Flotation and Film Flotation will help

us understand Froth Flotation!
Froth Flotation
 When air bubbles are passed through a
slurry containing fine mineral particles, with
certain minerals capable of attachment
to the bubble
 The attached minerals levitate with the gas
bubble to the surface of the bulk, forming
the FROTH
Froth Flotation

 The process exploits the fact that

either:
 The minerals differ naturally in terms of
their affinity to water and air
 The surface of the minerals may be
altered so as to attain the same
aforementioned effect, using surfactants
Froth Flotation

THEORY:
THEORY The driving force for
the attachment of the particles
to the gas bubbles is the
reduction of the surface
energy of the system
Features of Froth Flotation

 capable of concentrating selectively

and successively a number of
different minerals which originally
coexisted in a given ore deposit
 Complex Ore: CuFeS2, PbS, ZnS, and FeS2
 Sphalerite,
chemically identical to allotrope
Wűrtzite, may be concentrated separately
Keys to Froth Flotation

 Flotationis UNIQUE among

applications in metallurgy, as it
involves all possible interfaces:
 Air-Water (Gas-Liquid)
 Mineral-Water (Solid-Liquid)

 Air-Mineral (Gas-Solid)
AIR-WATER Interface
 Consider: A certain amount of water in a
container, exposed to the atmosphere

Molecule A:
w/in the bulk

Molecule B:
@ the surface
AIR-WATER Interface
 Consider: A certain amount of water in a
container, exposed to the atmosphere
Molecule A:
 Interior
molecules
surrounded by same
molecules
 Uniformly bound from all
directions
AIR-WATER Interface
 Consider: A certain amount of water in a
container, exposed to the atmosphere
Molecule B:
 Bounded on one side by
like molecules from the
bulk
 Bounded on the other by
molecules of a different
substance i.e. air
AIR-WATER Interface
 Forces at work:
Molecule A:
 Uniform field
attraction due to
surrounding
molecules
 Forces of attraction
are well
compensated from
all directions
AIR-WATER Interface
 Forces at work:
Molecule B:
 Inward attraction is
NOT compensated
by an equal
attraction from a
widely dispersed
molecules from the
vapor
It may be said that…
“Surface portion of the liquid have HIGHER
FREE ENERGY”

Extra Free Energy

SURFACE TENSION
Surface Tension

 Is the force acting parallel to the

surface of a bulk of substance, which
opposes any effort to extend the
interfacial area
 The natural tendency of a liquid to
decrease its surface
 Denoted by γ
FROTHING

 Froth– Collection of bubbles;

governed by the equation:
n

 bubbles   froth
i 1
i

 Frothing – maintenance of a body of

bubbles at and above the upper
surface of the pulp
Purpose of FROTHING
 The froth effectively
changes the effective Bubble, ↓ρ
density of attached
minerals
 It permits differential
draining of gangue back Mineral, ↑ρ

into the pulp

 It also maintains a body of
ore particles above the Mineralized
pulp long enough to froth, ↓ρ

permit separation
FROTHING

 prolonging the bubble life is an

essential element of frothing
 Sufficiently long time is necessary to
give time for gangue draining and
horizontal transport
 However, further life may prove to be a
nuisance
Frothing Agents
 also referred to as FROTHERS
 These are a group of substances which
dissolve in the liquid to change the air-
water interfacial tension
 Generally separated into two groups:
Organic and Inorganic Frothers
Frothers
 Frothers does not necessarily lower the
ST of the solution!
 Organic – lowers ST; the reagent concentrates
at the bubble surfaces
 Inorganic – increases ST; they concentrate
away from the surface
Chemical Structure of Frothers
 Most common frothers: Polar Organic
Compounds
 It has the form RA
R – hydrocarbon radical of any type; normally
having >6 carbon atoms
 A – polar solubilizing group; examples are
COOH, NH2, OH, and CO
Chemical Structure of Frothers
 Solubilizing effect of principal polar groups,
i.e.:
 for –alkyl compounds:
COOH > NH2 > OH > CO
 for –aryl compounds:
OH > NH2 > CO > COOH
 Stronger solubilizing effect ≈ better frother
Chemical Structure of Frothers
 Orientation of Surface Films –
hydrocarbon groups turned toward the gas
phase; polar groups towards the bulk of
the solution
 Good frothers – high proportion of (CH)
bulk to resist pull of polar radical; however,
not high enough to effect insolubility
Ideal Frothing Agent

 No collecting property
 Intensely surface active
 Should be independent of kind and
quantity of solutes present in the pulp
Theories of FROTHING
 Adsorption of Frothing Agent
 Film formation of liquids – due to
viscosity and surface tension
 Frothers concentrate at the gas-liquid
interface
Theories of FROTHING
 Effect of electrolytes to frothing
 Acids – decrease froth volume due to
flocculation of ore particles
 Alkali – increase frothing

 Neutral – no effect; except when it

reacts with the frothing agents
Characteristics of a mineral-bearing froth

 Should carry the mineral load without

collapse or excessive showering
 Should not be so tight nor tough
 Should be sufficiently small-bubbled
COLLECTION
 Using Surface-active Chemicals
 The collectors are generally organic
molecules that are selectively adsorbed
into the mineral surface
 It changes the mineral’s behavior in water
Chemical Structure of Collectors
 Similar in nature to FROTHERS
 Composed of two parts with very distinct
properties
 Non-polar end – hydrocarbon radical;
hydrophobic
 Polar end – compounds that has sufficient
activity in water; hydrophilic
Classification of Collectors

 Non-Ionizing – does not dissociate

with H2O; limited use
 Ionizing– polar compound end
dissociates with H2O; general type of
collectors
Ionizing Collectors
 Have the most commercial importance
 May easily be applied to a variety of
minerals by using knowledge in zeta
potentials
 “Heteropolar” – 2 functional groups
 Divided into two types:
 Anionic

 Cationic
Ionizing Collectors

 Both the Anionic and Cationic

collector have the same structure,
composed of:
 Hydrocarbon Radical – chains of (CH2)
 Solidophil group – dissociated ions
H H H S
H C C C O C
S-
H H H
Solidophil
Hydrocarbon
Group
Radical
Anionic Collectors
 Remarkable selectivity and strong
attachment to mineral
 Three most common types (by
application):
 Xanthates

 Dithiophosphates

 Carboxyl
Xanthates
 Applied for flotation of Sulfide minerals
 No collector action for oxides

S
R O C
S-
Dithiophosphates
 Commercial name: Aeroflot
 Applied also to sulfide minerals
 Not as widely used as xanthates

R O S
P
R O S-
Carboxyl Groups
 Applied to alkali earth minerals
 Also for some carbonates and oxides

O
R C
O-
Cationic Collectors
 Principal polar compound: amino group
 Relatively weak adsorption as compared
to anionic collectors
 Applied for silicates and certain metal
oxides
R NH2
Collector Attachment

 theadsorption of collectors from

solution to the S/L interface is
dependent on:
 Chemisorption – due to chemical
reactions between adsorbing species
(mineral) and ions (solidophil)
 Physical Adsorption – due to counter-
ions in the EDL
Adsorption
 Surface-chemical reactions involves the
adsorption of ions; especially free-flowing
ions to a solid surface
 This occurrence is present in mineral-
water couple in Flotation
Adsorption
 The ADSORPTION of ions from solutions
at the mineral-water surface is dependent
on:
 Chemical composition and Structure of
mineral surface
 Electrical interactions of ions at the locality of
the interface
Adsorption
 Adsorption in this mechanism occurs
through:
 Chemisorption – adsorption due to chemical
reaction
 Physical Adsorption – as a function of
electrical behavior of ions
Surface Adsorption
 occurs as a confluence of both
CHEMISORPTION and PHYSICAL
ADSORPTION
 This explains the fact that solids tend to
attain surface charges when introduced in
water
Electrical Double Layer

 Thistheory deals with the distribution

of ions; hence, with the magnitude of
electric potentials w/c occurs in the
locality of the charged surface
Electrical Double Layer

 Ittells us that if an ionic species is

adsorbed at an interface, then for
ELECTRONEUTRALITY, counter
ions must be adsorbed
Significance of Specifically Adsorbed Ions

 In cases of strong specific adsorption of

ions takes place on a charged surface → a
reversal of electric potential occurs
 Specific Adsorption is the most important
topic and the study of EDL
Electrical Double Layer
Physical Adsorption

 Consider: a galena mineral to be

floated using Lead Ethyl Xanthate
(PbEXt)
 Pb ions dissociate in solution from the
EXt, forming the EDL
Physical Adsorption
H H H H
H C HH C H H C HH C H
H C HH C H H C HH C H
O O O O
C S S C C S S C
S S S S

EDL
Pb Pb

S Pb S
Chemisorption

 Consider: flotation of Potash (KCl)

using Dodecyl Amine Chloride (DAC)
 Chlorine ions dissociate in solution
 Chloride component of R-NH3CL
substitute in the lattice formation
Chemisorption
Hey! I belong!
Bubble-Particle Contact
 3 stages:
 Bubble-particleapproach
 Thinning of water film

 Equilibrium contact
 Bubble-Particle Approach

 Probability of collision, Pc:

Pc  3rp rbCnbVbp

Where: Pc = probability of collision

Cnb = bubble concentration
Vbp = relative velocity
Thinning of Water Film
 Consider a Bubble – Particle system:

Water Water

Air
Air

Mineral Mineral
Disjoining Pressure, Pd

 The water film

behaves as though an Water

excess pressure, Pd,

is acting normal to the Air
film and opposing the
thinning of the film
Mineral
Disruption of Van der Waals
 Area of effect → due to hydrophobicity

Water

Mineral
London Van der Waals?
H
H
O O
H H
H H
O H
H
O
O H
H

H H H H
O O O O
H H H H
Induction Life, ti

 “Film life”
 Time required for the disjoining film to
drain such a thickness prior to rupture
 Should be less than contact time for
flotation to be possible!
Recall… Contact Angle
 Interaction of Interfacial Forces

Water

Air γAW

γAM θ

γWM
Mineral

 AM   MW   AW cos 
Contact Angle
 When a drop of water or liquid is placed on
a solid surface (metallic mineral), it would
give a profile of:
Contact Angle
 Contact Angle:
Angle angle between the solid-
liquid interface and the tangent of the
gas-liquid interface at the meeting point
of air, gas, and solid, in a plane passing
through the center of the liquid drop and at
right angle to the solid surface
Contact Angle

Θ = Contact Angle

Θ
Contact Angle

Θ = Contact Angle

Θ
Equilibrium State (Vector Diagram)

Θ
A O C

 Equation of Equilibrium:
OA = OC + OBcosΘ
 Therefore: OA > OC!
Equilibrium State (Vector Diagram)

Θ
A
O C

 Conversely;
OA + OBcosΘ = OC
 Therefore: OA < OC!
Contact Angle

 Experiments show that the relative

magnitude of OA and OC are different
for minerals against water
 The difference in magnitudes of OA
and OC, in effect, results in the
changes in CONTACT ANGLE
Gibbs Adsorption Law

 Surface adsorption of surfactant as a

function of concentration and surface
tension :
1   
U   
RT   ln C 
 Surface tension decreases correspondingly
with increase in surface adsorption density
Application
 Gibbs Adsorption Equation, applied to
interaction of interfacial forces:

 AM   MW   AW cos 
increase
decrease
Application
 As adsorption density increases

Water

Air γAW

γAM θ

γWM
Mineral
Application

 (γAM – γWM) decreases

Water

Air γAW

γAM θ

γWM
Mineral
Application
 θ increases

Water

γAW

Air
γAM θ

γWM
Mineral
 This increase in θ is accompanied by the
“spreading” of the bubble over the mineral
surface
 The adsorption of collector at the mineral
surface (up to equilibrium) changes the
stability of the bubble-particle attachment
Interpenetration Theory
 Introduced by Leja and Schulman
 Theory of attachment based on sulfide
mineral-collector-frother systems
 Limited to systems where reagent
starvation occurs (frother leaves the
solution)
Interpenetration Theory
 To obtain a bubble-particle adhesion:
A sulfide particle must first be coated with
monolayer of collector
 The collector molecules abstract (extract)
frother molecules from solution (by ionic
interaction, EDL)
Interpenetration Theory
Interpenetration Theory
 To obtain a bubble-particle adhesion:
 The frothers will intermingle with the collector
molecules already on the mineral surface
 The nascent bubble (generated by
hydrodynamic mechanisms) is nucleated by
organic discontinuities on the mineral surface
Interpenetration Theory
Modulation of Collection
Activators, Depressants, and
Regulators
Conditioning
 The essential prerequisite to separation by
flotation is selective collector-coating
 Necessity for conditioning becomes
apparent as:
 The pulp is a highly complex system of similar
but competing chemical and physical
interactions
 The collector has to selectively coat the wanted
mineral while other reactions occur
Resurfacing Controls

 Resurfacing of mineral particles in

order to improve the selectivity of the
flotation process is the most important
and most complex function performed
by any modifying agent
 Also known as MODIFIERS
Modifiers

 Reagents used in flotation to control

the action of a collector on minerals,
in order to intensify or reduce its
water repellent effect on the mineral
surface
CONTROLLER or MODIFIERS

 Depressants
 Activators
 Regulators
Depression

 Chemically altering the surface of a

mineral that is exhibiting natural
floatability
 Making a naturally hydrophobic
mineral hydrophilic
Activation

 Essentiallythe semantic opposite of

Depression
 Enabling a mineral that has
previously no activity with a collector
to adsorb collector ions for bubble
attachment
To recap…
 To be effective, the resurfacing agent
must be selectively attached to one
mineral or group of minerals in the ore
 This results in either activation or
depression of the resurfaced mineral
depending on the collector reaction with
the resurfacing agent adsorbed
Regulators

 Regulators make collector action

more selective with regard to
minerals, thus ensuring a reasonably
sharp separation from each other in
flotation
 Most important: pH Modification
pH Modification
 One of the primary objects of flotation
research is to discover the optimum pH for
any given combination of reagents and ore

 Most flotation plants treating sulfide ores

operate with an alkaline pulp to give
optimum metallurgy as well as to keep
corrosion at a minimum