Flotation 1

Flotation
See also → Solid – Solid Separation, Introduction
Baki Yarar, Colorado School of Mines, Golden, Colorado 80401, United States

1. Introduction . . . . . . . . . . . . . . . 2 2.4.2. Adsorption – Desorption of Organic

1.1. Interfacial Energies Reagents . . . . . . . . . . . . . . . . . . 10
and Contact Angle . . . . . . . . . . . 2 3. Electrical Phenomena . . . . . . . . . 11
1.2. Hydrophobic and 4. Bubble – Particle Interactions . . . . 14
Hydrophilic Solids . . . . . . . . . . . 3 5. Flotation Processes . . . . . . . . . . . 15
2. Flotation Reagents . . . . . . . . . . . 3 5.1. The Gamma Flotation Process . . . 16
2.1. Functional Classification of Flota- 5.2. Design of Flotation Operations . . . 17
tion Reagents . . . . . . . . . . . . . . . 3 5.3. Flotation Machines . . . . . . . . . . . 18
5.4. Industrial Applications . . . . . . . . 20
2.2. Chemical Classification . . . . . . . . 4
5.4.1. Sulfide Mineral Flotation . . . . . . . . 21
2.3. Surface and Solution Chemistry . . 7 5.4.2. Nonsulfide Flotation . . . . . . . . . . . 24
2.3.1. Solubility . . . . . . . . . . . . . . . . . . 7 5.4.3. Coal Flotation . . . . . . . . . . . . . . . 25
2.3.2. Surface Activity . . . . . . . . . . . . . . 8 5.4.4. Flotation of Precipitates and Ions . . . 26
2.4. Interactions between Flotation 5.4.5. Use of Oil Droplets instead of Air Bub-
Reagents and Solids . . . . . . . . . . 8 bles . . . . . . . . . . . . . . . . . . . . . 27
2.4.1. Adsorption – Desorption of Inorganic 6. Future Trends . . . . . . . . . . . . . . 27
Reagents . . . . . . . . . . . . . . . . . . 10 7. References . . . . . . . . . . . . . . . . . 28

Symbols γ SL = solid – liquid interfacial tension

ε = dielectric constant
C = equilibrium concentration of surfactant
ζ = zeta potential
in solution
η = viscosity of aqueous medium
E = electric field between electrodes apply-
θ = contact angle
ing the field
πD = disjoining pressure
k = Boltzmann constant
p = pressure inside a bubble
po = pressure of the bulk of the liquid
Pa = probability of particle-bubble adhesion 1. Introduction
Pc = probability of particle-bubble collision
Pf = probability of flotation General Aspects. Flotation is one of the
Ps = probability of formation of a stable well-established physicochemical separation
particle-bubble aggregate processes, widely applied in mineral concentra-
S = spreading coefficient for air on solid tion and recovery operations; other applications
T = temperature include water treatment and purification, the re-
Ve = electrophoretic velocity of particle cycling of secondary materials, and the recovery
W = work of adhesion of ionic and colloidal materials from aqueous so-
Γ = surface excess concentration of surfac- lutions.
tant measured in quantity per unit area Various forms of this process are known as
(e.g., molecules/cm2 ) froth flotation, ion flotation, precipitate flotation,
γ = specific surface energy of liquid film piggyback flotation, flotoflocculation, skin flota-
γ0 = specific surface energy of an infinitely tion, column flotation, and two-liquid flotation
thick film of a liquid [1–8]. Gamma flotation is based on the control
γ LG = liquid – gas interfacial tension of liquid – vapor interfacial tension to facilitate
γ SG = solid – gas interfacial tension the particle – bubble adhesion process [9].

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b02 23
2 Flotation

Because most flotation processes are applied

γSG −γSL =γLG cosθ (1)
with water as the principal liquid, and the widest
area of applications is in the field of mineral pro- W =γLG (1 − cosθ) (2)
cessing, mostly systems containing water and S =γSL − (γLG +γSG ) (3)
minerals are discussed here.
where γ SG = solid – gas interfacial tension,
γ SL = solid – liquid interfacial tension, γ LG = liq-
uid – gas interfacial tension, θ = contact angle,
1.1. Interfacial Energies and Contact S = spreading coefficient for air on solid, and
Angle W = work of adhesion. For particle – bubble ad-
hesion the conditions W > 0, S > 0, and θ > 0
The flotation process relies primarily on the fact are satisfied.
that hydrophilic particles are wetted by water, Figure 2 describes the mechanical equilib-
whereas hydrophobic particles are wetted by oils rium among the three interfacial tensions indi-
and air bubbles; therefore, if air bubbles are in- cated as vectors applied to point C, known as the
troduced into an aqueous slurry, the bubbles ad- three-phase contact point; the contact angle θ is
here to the hydrophobic solid particles. As a measured in the liquid phase. The two variables
result, air – solid aggregates are carried to the cos θ and γ LG are readily accessible by experi-
surface, forming a froth layer; this explains the ment. Contact angles on minerals in various me-
name froth flotation. The froth layer can be re- dia are given in Table 1. The significance of the
moved manually or mechanically; the result is contact angle arises from the fact that it is a mea-
the separation of hydrophobic from hydrophilic sure of surface wettability; θ > 0 indicates a hy-
particles. For further information on detergency, drophobic solid. Contact angle values of θ > 10◦
see also → Laundry Detergents, Chap. 2.1. usually indicate that particles can form bubble –
particle contacts strong enough to resist turbu-
lence in a conventional flotation cell, enhancing
the probability of flotation as decribed in Chap-
ter 4.

Table 1. Contact angles of solids in water and various aqueous

media

Solid Contact Solution conditions

angle
(degrees)

Colemanite 43 5×10−3 M oleate ∗

solution
Copper metal 93 in 50 mg/L oleate ∗
solution
Fluorite 91 in 10−5 M oleate ∗,
pH = 8.1
Galena 60 in 10−3 M ethyl xanthate
solution
Graphite 96 water
Figure 1. Processes occurring in a flotation cell (Schematic) Ilmenite 80 treated with oleate ∗,
A) Flotation cell a) Froth overflow; b) Froth layer; c) Pulp; pH = 8, T = 75 ◦ C
d) Rotor for pulp agitation Colorado oil shale with 59.5 water
B) Mineralized air bubbles within flotation cell 28 % organic carbon
Paraffin wax 108 water
Silica 81 2.5 mg dodecylammonium
The principal processes occurring in a slurry- chloride per L solution,
containing vessel known as a flotation cell are pH = 10
shown in Figure 1. Equation (1), known as the Teflon 160 water
Teflon 0 methanol – water solution
Young–Dupré equation, and Equations (2) and with surface tension
(3) are used to describe the relationship of phys- <20 mN/m
icochemical variables to particle – bubble adhe- ∗ Sodium oleate.
sion.
 Flotation 3

Frothers. Frothers promote the formation of

a metastable froth phase that facilitates the re-
moval of particles carried by air bubbles to
the top of the flotation cell. They also reduce
the induction time; that is, they allow collid-
ing particles and bubbles to establish contact
Figure 2. Equilibrium contact angle more rapidly. The usual induction times in sul-
a) Captive bubble in water; b) Hydrophobic solid
fide flotations are of the order of milli- or mi-
Cosθ= γSGγ −γSL
LG croseconds [12]. Examples of frothers are pine
oil, long-chain alcohols, and polyoxypropylene
derivatives.
1.2. Hydrophobic and Hydrophilic
Solids Auxiliary Reagents. These reagents include
depressants, which are used to prevent solids
Although most naturally occurring minerals are from becoming hydrophobic, and activators,
hydrophilic, some are hydrophobic. Examples which promote the adsorption of reagents onto
of the latter include graphite, sulfur, antimonite selected solids. For example, high pH impedes
(Sb2 S3 ), molybdenite (MoS2 ), talc, and high- the flotation of sulfide minerals by xanthates.
rank coals such as anthracite. Many polymers, Thus, reagents used to increase pH, e.g., NaOH
such as Teflon and Nylon, are also hydrophobic. or Ca(OH)2 , would be depressants in this con-
Hydrophilic materials can be made hy- text. Sulfide ions similarly impede the flotation
drophobic by the adsorption of chemicals. For of sulfides in the same system, and Na2 S used
example, calcite (CaCO3 ) can be readily made as a source of sulfide ions would act as a de-
hydrophobic by treating it with low concentra- pressant. Other depressants include starch and
tions of sodium oleate (C17 H33 COONa). Sil- quebracho.
ica (SiO2 ) can be made hydrophobic by treat- On the other hand, sphalerite (ZnS) does not
ment with dodecylamine (C12 H25 NH2 ). A solid readily become hydrophobic in the presence of
made hydrophobic by chemical treatment can xanthates unless copper (II) ions are introduced
revert to the hydrophilic state on further chem- into the aqueous pulp. In this case CuSO4 , used
ical change. For example, galena (PbS), in to supply copper (II) ions, is an activator. Other
contact with 25 mg/L potassium ethyl xanthate examples of activation are provided by divalent
(potassium O-ethyldithiocarbonate) [140-89-6] ions such as barium or calcium in the flotation of
(C2 H5 OCSSK) solution, is hydrophobic at pH silica by fatty acids. In this case, silica is inert to
below 10.8, but hydrophilic at higher pH. Teflon these reagents unless a divalent cation is intro-
is highly hydrophobic in most aqueous media, duced into the pulp at alkaline pH. Thus, CaCl2
but behaves like a hydrophilic solid if the sur- or Ba(NO3 )2 used as sources of these divalent
face tension is reduced below 20 mN/m by the cations and NaOH used to raise the pH would
addition of methanol [10]. Chemicals used to af- be activators of silica for flotation by fatty acids.
fect the hydrophobic – hydrophilic properties of The terms collector and frother do not precisely
solids are known as flotation reagents. describe the action of such reagents in all sys-
tems.
Although oleic acid acts primarily as a col-
2. Flotation Reagents lector in the flotation of solids such as scheel-
ite (CaWO4 ) it also exhibits excellent frothing
2.1. Functional Classification of properties when present in sufficient quantities.
Flotation Reagents On the other hand, nonanol [143-08-8], a well-
known frother, is the sole reagent required for
Collectors. These are used primarily to make the flotation of talc or high-rank coals, where
solids hydrophobic and promote adhesion to air it acts simultaneously as frother and collector.
bubbles or oil droplets. Common examples are The same is true for activators and depressants.
fatty acids, sulfonates, xanthates (dithiocarbon- For example, sodium sulfide was cited previ-
ates), amines, and dithiophosphates.
4 Flotation

ously as a depressant for sulfide minerals in the into all categories of the functional classifica-
presence of xanthate reagents. In fact, heavily tion. The organic reagents can be classified as
oxidized (tarnished) sulfide minerals are treated follows:
with sodium sulfide before the introduction of
Polar:
xanthates for flotation, making Na2 S an activa-
anionic: polar group is an anion, e.g., oleate,
tor in this type of flotation pulp (see Fig. 3).
CH3 (CH2 )7 CH=CH(CH2 )7 COO−
cationic: polar group is a cation, e.g., RNH+3
amphoteric: anionic or cationic, depending
on pH, e.g., alkylaminocarboxylic acids,
RNH(CH2 )x COOH
nonionic: polar group is not ionized, e.g.,n-
hexanol, CH3 (CH2 )4 CH2 OH
Nonpolar: e.g., saturated hydrocarbons

Table 2. Inorganic auxiliary flotation reagents

Compound Composition Common

Applications

Lime CaO pH regulator,

depressant
Sodium carbonate Na2 CO3 pH regulator,
(soda ash) dispersant
Sodium hydroxide NaOH pH regulator,
(caustic soda) dispersant
Sodium sulfide Na2 S sulfide depressant and
ore sulfidizer
Sodium bisulfide NaHS sulfide depressant and
ore sulfidizer
Sulfuric acid H2 SO4 pH regulator
Sodium cyanide NaCN sulfide depressant
Calcium cyanide Ca (CN)2 sulfide depressant
Sodium dichromate Na2 Cr2 O7 PbS depressant
Cupric sulfate CuSO4 ZnS, FeAsS, Sb2 S3
activator
Lead acetate Pb (CH3 COO)2 Sb2 S3 activator
Sodium ferrocyanide Na4 Fe (CN)6 depressant in Cu – Mo
sulfide circuits
Potassium KMnO4 FeS2 depressant in
permanganate FeAsS flotation
Sulfur dioxide SO2 activated ZnS
depressant
Sodium thiosulfate Na2 S2 O3 SO2 source in acid
circuits
Sodium silicate Na2 SiO3 siliceous gangue
Figure 3. Activation Processes dispersant
A) Activation of malachite [CuCO3 · Cu (OH)2 ] by sodium Sodium fluosilicate Na2 SiF6 depressant in
sulfide a) In the presence of 0.43 mol/L ethyl xanthate; b) In iron-flotation circuits
the presence of 0.43 mol/L isoamyl xanthate a, b Sodium e.g., (NaPO3 )6 dispersant
B) Activation of ZnS by CuSO4 in the presence of 25 mg/L polyphosphates
potassium ethyl xanthate c Sodium fluoride NaF activator in silicate
a With permission of [7]. b Excessive quantities of sulfide flotation
Nokes reagent complex mixture of general depressant in
reduce the recovery. c Redrawn from [11].
molybdenite
P2 S5 , As2 O3 , flotation circuits
Sb2 O3 , NaOH, etc. except for MoS2

2.2. Chemical Classification

Organic flotation reagents are also classified
Flotation reagents may be inorganic or organic. by functional group, including fatty acids, car-
The former are largely used as auxiliary reagents boxylic acids, thiols, xanthates, sulfates, sul-
(Table 2), whereas the latter (Tables 3 and 4) fall fonates, and amines.
 Flotation 5
Table 3. Organic reagents commonly used as flotation collectors
6 Flotation
Table 4. Organic chemicals used in flotation as depressants, slime depressants, and flocculants

Figure 4. Micelle formation

A) Spherical micelle B) Straight-chain surfactant (amphipatic) molecule
a) Polar end; b) Nonpolar end C) Laminar micelle
 Flotation 7

The following organic reagents are commonly taining more than eight carbon atoms are insol-
used as flotation frothers: uble in water and are used as frothers.
Most ionic or polar flotation reagents are
sufficiently soluble in water. Solubility is lim-
ited mainly by the tendency of such compounds
to form molecular aggregates in the aqueous
medium known as micelles when present in high
concentrations (Fig. 4, see previous page). The
concentration at which micelles form is known
as the critical micelle concentration (cmc).

2.3.2. Surface Activity

The ability of reagents to alter the liquid – vapor

interfacial tension, γ LG , of aqueous solutions is
called surface activity (see also → Surfactants).
For example, although the surface tension of dis-
tilled water is about 72 mN/m at room tempera-
ture, the introduction of a flotation reagent such
as sodium dodecyl sulfate at a concentration of
0.005 mol/L reduces this value to 48.5 mN/m.
Such organic reagents contain two chemical
groups: a nonpolar moiety, usually a saturated
hydrocarbon, and a polar moiety, which may be
ionic (e.g., −COO− , −SO− −
3 , −SO4 ) or non-
ionic (e.g., −OH, −NH2 , >C=O).
The quantitative relationship between the
concentration of an amphipatic molecule and its
effect on the surface tension at concentrations
below the cmc is described by the Gibbs adsorp-
tion equation:
dγLG T
=− Γk (4)
dC C
where γ LG = solution surface tension,
C = equilibrium concentration of surfactant in
2.3. Surface and Solution Chemistry solution, k = Boltzmann constant, Γ = surface
excess concentration of surfactant measured in
2.3.1. Solubility quantity per unit area (e.g., molecules/cm2 ), and
T = temperature.
Inorganic reagents used in flotation are always Based on Equation (4), the variation of so-
highly soluble in water whereas organic reagents lution surface tension can be discerned to be as
may not be. Nonpolar oils, for example, are in- shown in Figure 5, which predicts that some sub-
soluble in water and must be added to the flota- stances ought to increase surface tension, creat-
tion cell or the preceding conditioning tank, at ing a surface deficiency, as opposed to surface
high shear created by intense agitation of the excess concentration. This condition is met by a
pulp. Alternatively, these reagents can be pre- number of inorganic compounds shown in Fig-
pared as emulsions or sometimes dissolved in an ure 6.
alcohol such as methanol before addition to the Not all amphipatic flotation reagents exhibit
flotation system. Straight-chain alcohols con- pronounced surface activity, as demonstrated by
8 Flotation

Figure 5. Variation of solution surface tension by solutes

according to the Gibbs adsorption equation (Schematic)
A) Effect of organic surfactants on γ LG and Γ . Condition
of surface excess concentration
B) Effect of inorganic solutes on γ LG and Γ . Condition for
surface deficiency.
γ H2 O = Surface tension of pure water; γ = Surface tension
of solution; Γ = Surface excess concentration

Figure 6. Compounds that lower the surface ten-

sion of water are not necessarily surface ac-
tive, although their structures may indicate am-
phipatic properties. Short-chain alcohols, ace-
tone, and simple ethers fall into this category
(see Fig. 7 on top of next page).
Figure 6. Effects of inorganic salts and organic flotation
reagents on the surface tension of water
a) Sodium hydroxide a ; b) Sodium chloride a ; c) Potas-
2.4. Interactions between Flotation sium ethyl xanthate b d) Polyoxyethylene n-decanol with 30
ethylene oxide groups b ; e) Cetyltrimethylammonium bro-
Reagents and Solids mide c ; f) Sodium oleate d ;
a Drawn from data in [13]. b With permission from [14]. c

As a general rule, for alteration of the hydropho- Drawn from data in [15]. d Redrawn from data in [16].
bic – hydrophilic properties of solids in a flota-
tion pulp, adsorption or desorption at the sur- Silica, treated with trimethylchlorosilane
face is a prerequisite. Thus, for a solid to be- (Si (CH3 )3 Cl) shows hydrophobic – hydrophilic
come hydrophobic or hydrophilic it must first transitions that depend on time, pH, and tem-
take up ions or molecules from the medium or re- perature [17]. In all the experimental cases re-
lease them into it. Alternatively, a solid made hy- ported for this system, whether the solid was
drophobic by the adsorption of a reagent changes hydrophilic or hydrophobic, the organic reagent
only by the action of other species which alter the was present at the solid surface. The variation
surface properties. This may or may not require of hydrophobic – hydrophilic properties was at-
the desorption of the species originally present. tributed to the tenacity of the aqueous layer at the
For example, at a given pH, a given sulfide min- solid – liquid interface; the desorption of species
eral requires a minimal concentration of flotation that confer hydrophobic characteristics is not al-
collector before stable bubble – particle contact ways essential for a solid to exhibit hydrophilic
(flotation) can occur [8] (Fig. 8, see next page). properties.
 Flotation 9

Figure 7. Surface tension of aqueous solutions of acetone

and methanol
a) acetone; b) methanol

Naturally hydrophobic solids need to be con-

sidered a special case of this general rule, be-
cause they may require no surfactant uptake
from the medium to become hydrophobic, but
can be made hydrophilic by adsorbed reagents. Figure 8. Role of carbon chain length in flotation
For example, most wetting agents, e.g., Aerosol A) Sphalerite (ZnS) in the presence of various chain-length
OT, (sodium dioctylsulfosuccinate) [577-11-7], xanthates at pH = 3.5 ∗
a) 6 Carbons, hexyl xanthate; b) 4 Carbons, isopropyl xan-
eliminate the natural hydrophobicity of graphite. thate; c) 2 Carbons, ethyl xanthate
B) Quartz (SiO2 ) flotation by alkylammonium acetate solu-
tions; chain lengths indicated at their natural pH ∗∗
∗ With permission [18]. ∗∗ With permission [19].

2.4.1. Adsorption – Desorption of Inorganic

Reagents

In general, the chemical reactions of inorganic

flotation species in aqueous solution can be
described in terms of solubilities. The classi-
cal equilibrium constant (solubility product) ap-
plies:
MA2
M 2+ + 2 A− (5)


2
Ksp = M2+ A− / [MA2 ] (6)

Figure 9. Cation concentrations derived from the dissolu- where M 2+ indicates the cation (metal) concen-
tion of some metal hydroxides at different pH [21]
∗ Calculations made assuming that the solubility product
tration in solution, A− the anion concentration,
expression given in Equation (6) applies; more elaborate and K sp the solubility product. Figure 9 shows
calculations including other hydrolytic species can also be the relationships of hydrolysis and precipitation
made [22, 23] that occur in the aqueous phase for various ions
10 Flotation

in accordance with the solubility product princi- spectroscopy shows that the calcium oleate
ple. Traces of ions or their hydrolysis products formed by the interaction of oleic acid with
many play important activator roles in flotation calcite or fluorite is not identical to the calcium
[20]. salt of oleic acid, Ca (C17 H33 COO)2 , obtained
from CaCl2 and sodium oleate [28].

2.4.2. Adsorption – Desorption of Organic Hydrophobic Bonding. Association of the

Reagents hydrocarbon ends of amphipatic substances
leads to the formation of micelles (Sect. 2.3.1).
Organic reagents and solids suspended in a flota- Similarly, many saturated hydrocarbons, such
tion pulp interact by one or more of the mech- as kerosene or fuel oils, are readily adsorbed
anisms given below. Some processes, such as on naturally hydrophobic solids, e.g., graphite
hydrogen bonding, are also important in the sol- or freshly cleaved bituminous coal. Such in-
ubilization of polar substances in aqueous me- teractions are mainly a result of London – van
dia. der Waals forces. Furthermore, the hydrocarbon
ends of surfactants, such as dodecylbenzenesul-
Hydrogen Bond Formation. This bond fonate, and dodecylbenzenesulfate, associate at
(strength ca. 21 – 29 kJ/mol), usually associated the solid – liquid interfacial region, resulting in
with the physical properties of ice and water, low-energy structures known as hemimicelles
is favored when a group contains hydrogen at- [29].
tached to a highly electronegative element such The strength of association is a function of
as F, O, S, or N. Thus, the adsorption of an amide the hydrocarbon chain length and is of the order
group, present in proteins or nonionic polyacry- of 1 kT per −CH2 -group (where k = Boltzmann
lamide (a depressant), on fluorite or silica is due constant and T = temperature). The unique bond
to this bond [24, 25]. The interaction of elemen- that leads to such adsorptions and molecular as-
tal sulfur and alcohols probably also takes place sociations is called the hydrophobic bond. Al-
by hydrogen bond formation. though the term has been criticized [30], it has
been generally accepted.
Electrostatic Interactions. Such interac-
tions are nonspecific, occurring between groups Multiple Dipole Interaction Bonds
that carry electrostatic charges of opposite sign. (Crystal-field Interactions). The adsorption
Bond formation occurs by charge attraction. of tannins (depressants in flotation) or poly-
A typical example in flotation systems is the acrylamide on fluorite has been attributed to the
adsorption of amines that carry cationic po- formation of a bond in which an active group
lar groups on silica, which carries a net nega- of the reagent is held in the crystal field of the
tive electric charge at pH > 2. Many treatments adsorbing solid [31]. Little information on such
of reagent – solid interactions in flotation sys- bonds is available.
tems tend to exaggerate the importance of elec-
trostatic interactions, overlooking other mecha- Collector Fitting into Solid Lattices. The
nisms. separation of similar salts, such as NaCl and
KCl, by the use of amines is a well-established
Chemical Bond Formation. Chemical industrial practice. Although a number of mech-
bonds are characterized by their strength (typ- anisms have been suggested for the selective in-
ically greater than ca. 42 kJ/mol) and usually teraction between KCl and primary amines, the
lead to the formation of saltlike structures at most widely accepted is that the amine fits into
solid – liquid interfaces. A surface compound is spaces on the KCl lattice vacated by K+ because
not necessarily identical to a compound formed the ionic sizes of −NH+ +
3 and K are compara-
in the bulk of the solution [26, 27]. Examples ble. Thus, KCl is made selectively hydrophobic,
of such bonds include the interaction of fatty whereas NaCl is not (Fig. 10).
acids, which carry the polar carboxylate group In many systems more than one mechanism
(−COO− ), with sparingly soluble solids such may act simultaneously and synergistically. The
as calcite (CaCO3 ) or fluorite (CaF2 ). Infrared
 Flotation 11

term adsorption is used here for the accumula-

tion of a dissolved species on a solid particle. The
term sorption is preferred by some authors. The
terms physical adsorption or physisorption and
chemisorption are also used to distinguish bet-
ween bonds with strengths less than 20 kJ/mol
and those greater than 42 kJ/mol, respectively.

Figure 10. Schematic representation of the selective adsorp-

tion of amine ions on sylvite (KCl) [32]
A) Potassium chloride (KCl)
B) Sodium chloride (NaCl)
a) Cl− b) NH+ +
3 ; c) K ; d) Na
+

3. Electrical Phenomena
The main phenomena to be considered in this
connection are those associated with the solid –
liquid interfacial region. On contact of the solid
with the aqueous medium, ionization, ion dis-
solution, or ion adsorption occurs, resulting in
charging of the particle surface. Hydrolysis in
the aqueous medium may also alter the charac-
ter of the ionic species passing into it. The pre-
dominant phenomena here relate to the fact that
cations are hydrated more than anions and that Figure 11. Crystal structures and mode of cleavage of min-
thermal energy promotes ion mobilization in the erals
system. Ruptured bonds and the lattice parame- A) Fluorite (CaF2 ) and its cleavage plane
ters also affect the properties of the solid – liquid a) Calcium; b) Fluorine
B) Graphite
interface. The cleavage of fluorite, graphite, and C) Chalcopyrite (CuFeS2 ) which cleaves irregularly, some-
chalcopyrite are shown in Figure 11. times at the (011) plane
Within short periods of contact, a double a) Copper; b) Iron; c) Sulfur
layer (usually referred to as the electric double
layer), consisting of the charged surface of the consists of a surface with fixed charge whereas
solid and counter ion, is established. Although the ionic cloud countering it is diffuse [33]. The
earlier theories considered this charge arrange- overall system, consisting of the solid and the
ment to be in the form of a simple plate capaci- ionic medium surrounding it, conforms to the
tor, colloid science showed that the double layer principle of electroneutrality.
12 Flotation

Zeta potential is widely used to describe the

role played by the electrical double layer in flota-
tion. It corresponds to the potential that exists at
the so-called shear plane, which is created when
a charged particle moves under the influence of
an external electric field.
Zeta potential can be measured by elec-
trophoresis, sedimentation potential, streaming
potential, and electroosmosis. In the first two of
these methods the shear plane is created by the
motion of the particle; in the other two, the par-
ticle (more precisely, a porous bed consisting of
many charged particles) is fixed [34, 35]. Equa-
tion (7) correlates the zeta potential with the Figure 12. Relationship between iep and flotation properties
of goethite (FeO (OH)) [36]
electrophoretic mobility of the particles under • = Sodium dodecyl sulfate or -sulfonate;
= Dodecyl-
the influence of an external electric field: ammonium chloride;
= iep
∗ Courtesy USBM; zeta potential measurements made in
4πη Ve 10−4 M NaCl; note that minimum flotability occurs at the
ζ= (7)
ε E pH of iep and anionic reagents act as collectors at ζ > 0
whereas cationic reagents collect goethite at ζ < 0.
where
ζ = zeta potential
η = viscosity of the aqueous medium
ε = dielectric constant
V e = electrophoretic velocity of particle
E = electric field between electrodes applying
the field
At 25 ◦ C and η = 0.895 mPa · s, Equation (7) re-
duces to
ζ = 12.8 V e = 12.8 u where u = electrophoretic
mobility.
The significance of the zeta potential becomes
apparent where electrostatic interactions play a
major role in flotation reagent adsorption, as
shown in Figure 12. The condition at which ζ = 0
is known as the isoelectric point (iep), some-
times, less accurately, the zero point of charge
(zpc). In principle, although an iep can be de-
fined for each solid for numerous conditions,
the variable most frequently used to describe the
ionic conditions at which iep occurs is pH.
Adsorption mechanisms correlate with zeta
potential; that is, physical adsorption affects the
magnitude of the zeta potential. A change of sign
in the presence of an appropriate concentration Figure 13. Representation of the fact that zero zetapotential
does not necessarily indicate zero surface potential (ψ o ) [35,
of adsorbate (see Fig. 13) is taken as an indi- p. 221]
cation of a chemisorption-type reagent uptake Dashed line = Inner Helmholz plane; wiggled line = Shear
[38]. As seen from Figure 13, the iep does not plane
necessarily indicate zero potential at the surface ∗ Although ψ o1 and ψ o2 are positive and ψ o3 is negative,
all conditions indicate ζ = 0; inner Helmholz plane passes
of the particle, only that the potential at the shear through the centers of unhydrated, specifically adsorbed
plane is equal to zero. ions.
 Flotation 13

Depending on the mechanism of reagent – cles. Particle flotability can be treated as a prob-
solid interaction, many systems exhibit corre- ability [39]:
lations between system variables and zeta po-
tential (Fig. 14). Pf = Pc ·Pa ·Ps (8)
where
Pf = probability of flotation
Pc = probability of particle – bubble collision
Pa = probability of particle – bubble adhesion
Ps = probability of formation of a stable parti-
cle – bubble aggregate
In some methods, such as vacuum flotation,
where dissolved gases become the bubble
source, or in situ bubble-generation processes,
where acids generate bubbles of carbon dioxide
from carbonate-containing pulp, the probability
treatment needs to be modified. Equation (8),
however, is widely applied, because most flota-
tion systems rely on extraneously introduced air
bubbles. Particle – bubble aggregates are shown
in Figure 15.

Figure 14. Correlation of commonly measured flotation and

surface chemical variables in the quartz-dodecylammonium
acetate system
– = % Recovery; – · – = Zeta potential; ◦–◦ = Con-
tact angle; • – · · – • = Monolayer
∗ With permission [37].

Figure 15. Different forms of particle – bubble aggregates

The following isoelectric points (ζ = 0) are [7, 41]
observed in the absence of other substances. A) Particle attached to bubble
B) Multiple bubble attached to large particle (common in
AgCl pAg+ = 4
vacuum flotation)
AgBr pAg+ = 5.4
C) Particle – bubble flocculation in pulps containing fine par-
Ag2 S pAg+ = 10.2
ticles
CuSiO3 · 2 H2 O pCu2+ = 4, at pH = 7
CaF2 pCa2+ = 3
Fe2 O3 pH = 6.5 and 8.2 Solids to be floated carry an aqueous film,
FeS2 pH = 7 which may have a thickness as low as tens of
FeS2 pH = 5 (30 mg NaCN/L)
PbS pH = 3.5
nanometers [40]. The stability of this film deter-
SiO2 pH = 2 – 3.7 mines whether a particle will adhere to a bub-
SiO2 neutral pH in the presence of ble on collision within the slurry: if the film
3×10−3 mol dodecylam-
monium acetate/L
thins, ruptures, and recedes, adhesion is facil-
itated. The time taken for the film to undergo
these processes is known as the induction time.
Film stability has been quantified in terms as
4. Bubble – Particle Interactions disjoining pressure [27].

The ultimate objective of a flotation process is πD =p −

∞ po (9)
the selective removal of solid particles from the γ =γ0 πD dh (10)
aqueous medium, which is accomplished by the h
adhesion of air bubbles to the hydrophobic parti- where
14 Flotation

π D = disjoining pressure Disjoining pressure depends on the summa-

p = pressure inside bubble tion of electrical double-layer effects (π E ), sol-
po = pressure of the bulk of the liquid vation effects (π s ), and London – van der Waals
γ = specific surface energy of the liquid film forces (π v ); i.e., π D = π E + π s + π v , as well as on
γ0 = specific surface energy of an infinitely the heterogeneity of the solid surface [42]. The
thick film of the same liquid role of frothers is to make π D more positive, i.e.,
The conditions for film stability are shown in reduce film resistance to rupture.
Figure 16.

For stable films: ∂π D
<0

∂π T
∂h
5. Flotation Processes
For unstable films: ∂h T > 0
D

The phenomena described so far relate to the

froth flotation process. The following variations
and techniques are also used:

Collectorless flotation:
froth flotation using the natural hydrophobicity
of some minerals

Two-liquid flotation:
variant of froth flotation, using oil droplets in-
stead of air bubbles and an oil layer instead of
froth

Column flotation:
variant of froth flotation, employing columns 3 –
9 m high with 0.3 – 1.5 m cross-section

Microbubble flotation:
variant of column flotation, employing bubbles
10 – 50 µm in diameter

Dissolved-air flotation:
air bubbles are generated by applying vacuum
to air-saturated slurries

Gamma flotation:
liquid – vapor surface-tension control is used to
separate hydrophobic particles

Piggyback flotation:
also known as carrier flotation: uses the mutual
coagulation of solids; when one is floated,
the other (usually more difficult to float on
its own) is also collected

Skin flotation:
Figure 16. The concept of disjoining pressure [40] hydrophobic particles are removed without
A) Schematic representation of a disjoining film between a froth, but at a layer approximately one par-
particle and a bubble
B) Relation of film stability to disjoining pressure
ticle thick
a) Stable film; b) Metastable film; c) Unstable film
 Flotation 15

5.1. The Gamma Flotation Process

The gamma flotation process is characterized by

emphasis on the control of solution surface ten-
sion. The critical surface tension of wetting of
solids is based on a plot of the cosine of contact
angle θ against the surface tension of the solu-
tion in contact with a solid [43]. Each hydropho-
bic solid exhibits cos θ = 1 (zero contact angle)
at a given solution surface tension as shown in
Figure 17. Difficulties in contact-angle measure-
ments on powdered solids, as used in flotation
practice, can be overcome by a technique where
flotation recoveries are plotted against solution
surface tension [10, 44, 45]. The γ LG at which
flotation recovery is equal to zero is taken as
the critical surface tension of wetting, γ c , of the
solid under investigation. The two techniques
[43–45] are equivalent [10]; the proof of this
constitutes an independent demonstration of the
thermodynamic basis of the flotation process
[46].

Figure 17. Schematic of critical surface tension of wetting Figure 18. Schematic of physical basis of the gamma flota-
by contact-angle measurement tion process [9]∗
A) Adhesion tension vs. solution tension for two solids with
different critical surface tension or wetting
Figure 18 shows the use of critical surface B) Relation of flotation recovery to solution surface tension
tension differences of two hydrophobic solids for two solids with different critical surface tension or wet-
by controlling the surface tension of the solu- ting
γ c1 = Critical surface tension of wetting of solid 1;
tion in which they are suspended. This method γ c2 = Critical surface tension of wetting of solid 2;
is called gamma flotation [9]. The value of the ∗ Lines a, b, and c obtained by substituting values into the
process has been demonstrated for a number adhesion tension equation, e.g., [γ LG cos θ].
of flotation systems including oil shale, sulfide ∗∗ In the shaded area solid 1 with γ c1 floats, whereas solid
2 with γ c2 is completely wetted by the aqueous solution.
16 Flotation

Figure 21. Flotation in high surface tension solutions ∗ [9]

a) NaCl; b) Na2 SO4
∗ This method is also known as salt flotation [7, p. 338, 339],
[13].

Figure 19. Separation of Colorado oil shale sizes fractions

by exploiting the kinetic aspects of gamma flotation [47]
a) <13 µm; b) 18 – 13 µm; c) 26 – 18 µm; d) 38 – 26 µm;
e) 48 – 38 µm

Figure 22. System variables that affect the flotation process

[9]

salts raise the surface tension of water to val-

Figure 20. Separation of a mixture of silica and magnetite ues above the usual 72 mN/m. Figure 21 demon-
by gamma flotation ∗ strates the relationship between solution surface
a) SiO2 ; b) Fe3 O4 tension modified by salts and flotation results
∗ Powders have been initially made hydrophobic by treat- obtained with various coals [9].
ment with appropriate surfactants and mixed after filtration
[49]

minerals, and others [48–50] (see Figures 19 5.2. Design of Flotation Operations
and 20). Salt flotation, which has been used in
coal processing, is a variant of gamma flotation Flotation testing is generally preceded by geo-
in which the natural hydrophobicity of coal is logical, engineering, and mineralogical work.
exploited and the surface tension of the solution The overall flotation system is a complex com-
is controlled by salts. Figure 6 shows that some bination of variables outlined in Figure 22, but
 Flotation 17

laboratory testing is based on mineral character- 5.3. Flotation Machines

istics and reagent properties. Recovery is “the
percentage of total values contained in the ore Flotation machines consist of a chamber (cell)
which is recovered in the concentrate”; grade equipped with entry and exit ports and an agi-
refers to “assay of values in the concentrate.” tation assembly that keeps the pulp in constant
Recovery and grade tend to vary inversely. motion during the separation. These machines
Laboratory tests are designed to establish fulfill the following functions: (1) mixing and
crushing and grinding conditions and optimize agitation of the slurry, (2) aeration and promo-
such variables as pulp density, reagent addition, tion of particle – bubble collisions, (3) formation
pH, and auxiliary reagent concentration before of a froth layer and its removal for product re-
the pilot plant stage. An important laboratory covery, and (4) continuous discharge of tailings,
test is the “locked-cycle test”, which simulates consisting of components not collected in the
pilot plant conditions (Fig. 23) [1]. froth layer [53].
The design of a flotation machine (or cell) is
largely empirical and aims at maintaining high
throughput subject to the previously stated cri-
teria; the Wemco flotation machine is shown in
Figure 24. Flotation cells can reach volumes of
20 – 25 m3 [54]. Figure 25 is an outline of con-
temporary flotation machine types; Figure 26
shows cell geometries and paddle designs in
mechanically agitated flotation machines. Flota-
tion machines used in water treatment are not al-
ways mechanically agitated but may rely on the
quieter conditions provided by the generation of
air bubbles in the system.

Figure 24. Wemco flotation machine ∗

a) Motor; b) Weir level; c) Rotor submergence; d) Rotor top;
e) Adjustable collar; f) False bottom; g) Draft tube; h) Rotor;
i) Disperser; j) Hood; k) Stand pipe; l) Air inlet duct
Figure 23. Schematic of locked-cycle test [51] ∗ With permission [53]

Flotation machine variables, such as volume, Such methods include vacuum flotation, in
area, throughput, aeration rate, and cell layout which air-saturated water is subjected to a vac-
are considered at the plant-design stage. Sim- uum for bubble generation. Pressure flotation, on
ulation studies using computer modeling tech- the other hand, does not require the application
niques have gained increasing acceptance [1, of vacuum, since air bubbles are released after
52]. The final plant layout provides for prod- saturation of water under pressure. Electroflota-
uct handling, filtration, dewatering, tailings dis- tion has also been used to a limited extent. In
posal, and plant-water recycling. this method hydrogen and oxygen bubbles are
generated by electrolysis [57].
18 Flotation

Figure 25. Types of flotation machines, their modes of operation, and representative manufacturers [54–56]

A new version of an old flotation cell has Peripheral speed: S = π ND ∝ Da (a ∼ 0 – 0.5)

led to the development of column flotation (see Power (constant viscosity and density)
Fig. 27) [58–60]. Column cells seem to perform Net power consumption: P ∝ N 3 D5 /N c D2c
best with highly hydrophobic solids. They are (c ∼ 0 – 0.33)
used for the recovery of sulfides and coal, and Aeration
to recover valuable particles rejected in the tail- Air-flow number: N (Q) = Q/AND ∝ Df (f ∼ 0)
ings of conventional, mechanically agitated, bat- Impeller diameter is the parameter of machine
teries. Column flotation offers the following ad- size
vantages: Geometry: L ∝ D1−r ; A ∝ D 2 (1−r) ;
n (1−r)
V∝D
1) reduction of gangue entrainment in froth,
Power: P ∝ D(a+1) (3−c)−1
2) increase of bubble residence times in the
Aeration: Q ∝ Da+f+2 (1−r)
pulp,
Power intensity or specific power:
3) improved selectivity,
P/V ∝ D (a+1) (3−c)−n (1−r)−1 ∝ D b
4) energy economy per unit weight of values
Nominal residence time of air:
recovered, and
V/Q ∝ D (2−n) (r−1)−(a+f) ∝ Dq
5) improved control and instrumentation.
N = Impeller rotational speed in rpm;
The following relationships are used in the de-
D = Impeller diameter; L = Tank length. Expo-
sign of flotation machines [56]:
nents are experimental parameters characteristic
Geometrical of specific machine design.
Effective volume: V ∝ L n (n ∼ 2 – 3)
Froth area: A ∝ L 2
Impeller/tank aspect ratio: D/L ∝ Dr (r ∼ 0 –
0.5)
Impeller speed
 Flotation 19

Figure 26. Schematic of impeller and tank geometries of mechanically agitated flotation cells [55]
a) Air port; b) Diffuser; c) Impeller; d) Standpipe; e) Shaft; f) Propeller; g) Aerating impeller; h) Recirculation well; j) Pulp
entry; k) Rotor; m) Disperser hood

5.4. Industrial Applications and sulfur removal from coal, separation of sol-
uble minerals such as halite (NaCl) and sylvite
Various methods of separation exploit differ- (KCl) from each other, and recovery of fine gold
ences in size, relative density, and magnetic and [6–8, 61].
electrostatic properties. Flotation, however, ex- Water-treatment applications include the re-
ploits two unique controllable properties of par- moval of oily components and colloidal matter
ticulates (Table 5): (1) it operates at very fine from industrial waters, water recycling, and the
particle sizes, and (2) it is based on inherent or removal of color and metal ions.
modified surface properties of solids.
Since its discovery in the late 19th century, Mineral Flotation. Minerals containing
the flotation process has been used principally valuable elements can be recovered econom-
in the minerals industry. At present, it is used ically by flotation (Table 6) in the following
to treat several thousand million tonnes of ore stages:
annually. Most of the minerals-related applica-
tions aim at recovering ore values, rejecting the Crushing and grinding. These steps reduce
rest as tailings. particle size and mechanically liberate the
Applications of flotation in the minerals in- desired minerals. Some deposits, such as
dustry are diverse and include recovery of sul- beach sands or placers, do not require crush-
fide minerals, upgrading phosphates ores, ash ing, which is usually effected by jaw or gyra-
20 Flotation

tory crushers. For grinding, equipment such Table 5. Physical properties of particulates and size ranges suitable
as ball mills and rod mills is employed. for separation technology
Classification and sizing. As can be seen
Physical property Physical separation Approximate
from Table 5, the optimal size range for flota- technique particle size range,
tion is 10 – 500 µm. Coal particles can be mm
floated at the upper limit, and copper sul- Color or radiation sorting 10 – 100
fide particles at the lower. Particles of non- Size dry or wet screening 0.01 – 10
sulfide minerals finer than 50 µm, however, Size, shape, wet or dry cyclones 0.005 – 1
density
interfere with flotation. Such fines are sepa- sedimentation and 0.003 – 3
rated by hydrocyclones, sedimentation tanks, hydraulic classification
and other classification equipment; they are centrifugation 0.001 – 0.05
Density heavy media 1 – 10
discarded as slimes (Figure 28). Size, density jigging 5 – 50
Conditioning. In the conditioning opera- tabling 0.005 – 3
tion the ore powder is slurried with water Magnetic wet or dry magnetic 0.001 – 5
susceptibility separation
and flotation reagents, forming the flotation Surface or bulk electrostatic separation 0.05 – 5
slurry. In the flotation step, air is introduced conduction
to transfer hydrophobic particles to a froth Surface chemistry flotation 0.001 – 0.5
spherical agglomeration 0.01 – 0.5
layer, which is skimmed away mechanically selective coagulation and 0.05 – 0.001
by paddles. selective flocculation

The solids content of the pulp, known as pulp

density, averages 20 – 40 %, but may be 3 – 10 %
in some systems, such as coal flotation. In the
preparation of potable water, the solids content
may be well below 1 %.
The mineral flotation process is carried out in
interconnected batteries of flotation cells, where
slurry flow occurs by gravity and the level of the
slurry is controlled by gates or weirs.
The arrangement of flotation cells, some-
times with intermittent grinding of the products,
leads to flotation circuits of which five basic
types have been identified [62] (Fig. 29).

5.4.1. Sulfide Mineral Flotation

Sulfide minerals such as those of copper

(CuFeS2 ), lead (PbS), and zinc (ZnS) are com-
monly found in the same ore. Xanthates (dithio-
carbonates) and dithiophosphates are used as
collectors in sulfide mineral flotation; frothers
include pine oil and synthetic commercial com-
pounds such as Dowfroth 250. Some qualified
generalizations apply to sulfide mineral flota-
tion:
Figure 27. Pilot plant size flotation column 1) Xanthates and dithiophosphates are collec-
a) Wash water flow meter; b) Conditioner; c) Valve; d) Con- tors for sulfides.
centrate discharge; e) Porous glass diffuser; f) Air regulator;
g) Air flow meter; h) Tails discharge 2) The chemisorption of xanthates and the pres-
ence of oxygen are essential for the flotation
of sulfide minerals such as galena [63–65].
 Flotation 21
Table 6. Elements contained in minerals recovered by flotation

Element Mineral Composition Element Mineral Composition

Al bauxite Al2 O3 · xH2 O (Fe,Mn,Ti) Mn pyrolusite MnO2

Al kaolinite Al2 Si2 O5 (OH)4 Mo molybdenite MoS2
As arsenopyrite FeAsS2 Na halite NaCl
Au native gold P fluorapatite Ca5 F (PO4 )3
B colemanite Ca2 B6 O11 · 5 H2 O S native sulfur
Ba barytes BaSO4 Si quartz SiO2
C diamond carbon Sn cassiterite SnO2
C graphite carbon Sr strontianite SrCO3
Ca calcite CaCO3 Th fergusonite (Y,Ce,U,Th,Ca) (Nb,Ta,Ti) O4
Cr chromite FeO · Cr2 O3 Ti rutile TiO2
Cu chalcopyrite CuFeS2 U carnotite K 2 O · 2 U 2 O3 · V2 O5 · 2 H 2 O
F fluorite CaF2 V vanadinite Pb5 ClV3 O12
Fe hematite Fe2 O3 W scheelite CaWO4
Hg cinnabar HgS Y monazite (Ce,Y) PO4
K sylvite KCl Zn sphalerite ZnS
Li spodumene LiAl (SiO3 )2 Zr zircon ZrSiO4
Mg magnesite MgCO3

Figure 28. Characteristics of slimes [7]

This correlates well with the electrochem- conditions. The ratio of concentration of xan-
istry of the system and the stability of species thate to hydroxide for such a critical transi-
that collect at the solid surface (Fig. 30). tion usually conforms to the Barsky relation-
3) Other variables being constant, an increase ship: [X− ]/[OH− ] = constant
in chain length for a homologous series of 5) The ions OH− , S2− , CN− , Cr2 O2−
7 are com-
reagents strengthens them as collectors; this mon sulfide mineral depressants for selectiv-
rule also applies to other minerals; see Fig- ity control in flotation; Cu2+ is an activator
ure 14. for ZnS in flotation by xanthates. Figure 31
4) At a given constant collector concentration, is a flow diagram of a sulfide flotation plant.
a critical pH for each sulfide mineral deter-
mines the boundary of flotation – no flotation
22 Flotation

Figure 29. Flotation circuit configurations ∗

A) Type 1; B) Type 2; C) Type 3; D) Type 4; E) Type 5
∗ With permission [62].
 Flotation 23

5.4.2. Nonsulfide Flotation

Nonsulfide ores include those of iron, phos-

phate, fluorite, magnesite, and beach sand. Some
ores may contain sulfur-bearing minerals as sec-
ondary components. Collectors in these systems
are generally fatty acids and their salts, sul-
fonates, and sulfates. Amines are also used, es-
pecially in iron-bearing ores and in silicate flota-
tion. Figure 32 shows the separation of lead car-
bonate, barium sulfate, and calcium fluoride in
a 100 t/d plant; the main gangue is siliceous ma-
terial.
Phosphate-ore concentration plant flow
sheets are shown in Figures 33 and 34. Their
difference lies in the run-of-mine grades and the
complexity of gangue minerals.
Figure 30. E h -pH Diagram of thermodynamically stable An interesting application of nonsulfide min-
species and associated experimental data in the galena – eral flotation is the separation of soluble salts
oxygen – xanthate flotation system [42] from brines (Fig. 35). Primary amines are well-
x = Strong bubble contact; o = Feeble bubble con-
tact;v = Oxidizing depression by potassium chromate; established selective collectors and have long
∧ = Reducing depression by sodium sulfite-ferrous mixture; been used in the production of KCl from the
. . . . . = Xanthate (10−3 M) – dixanthogen (saturated); Dead Sea. In some cases, clays interfere with
- - - - - = Galena – dixanthogen system in equilibrium with
10−3 M xanthate ion; E = Electrical potential

Figure 31. Flow sheet of plant treating 30 000 t/d of molybdenite ore, Henderson Mill, Colorado ∗
a) Gyratory crusher; b) Self-cleaning magnet; c) Ore storage bin; d) Semiautogenous mill; e) Pump box; f) Thickener;
g) Cleaner; h) Tailing pond; i) Concentrate holding tank; j) Pump; k) Disc filter; l) Dryer
∗ Courtesy of Denver Equipment Co.
24 Flotation

Figure 32. Flow sheet for PbCO3 , CaF2 , and BaSO4 concentration ∗
a) Coarse ore bin; b) Apron feeder; c) Jaw crusher; d) Belt conveyor; e) Fine ore bin; f) Ball mill; g) Cyclone; h) Conditioner;
i) Reagent feeders; j) Sampler; k) Flotation machine; l) Concentrate thickener; m) Pump; n) Disc filter; o) Screw conveyor;
p) Elevator and storage bins; q) Fluorspar filter; r) Dust cyclone; s) Dryer
∗ Courtesy of Denver Equipment Co.

the flotation and need to be depressed by the ad- whole mass subjected to flotation without re-
dition of starch, lignin, or cellulose derivatives. course to primary gravity separation. The natu-
ral hydrophobicity of freshly ground coal is an
asset which minimizes the use of collectors. A
5.4.3. Coal Flotation small quantity of MIBC or pine oil (50 – 100 g
Coal is cleaned by gravity separation to reduce per tonne of mineral) acts as both collector and
ash and pyrite content [69]. These methods in- frother.
clude jigging, tabling, and heavy-media separa- On extended storage, or if the coal seam has
tion. The fines (ca. 400 µm, 35 mesh) are treated been in contact with air for geological time peri-
by flotation. To liberate ash and sulfur-bearing ods, coal loses its hydrophobicity and is referred
components, the run of mine coal is sometimes to as “weathered coal”. In such cases, MIBC, low
ground to ca. 600 µm (28 mesh) or finer, and the pH, and the addition of hydrocarbon oils such as
 Flotation 25

Figure 33. Flow sheet for phosphate ore flotation in Brazil ∗

a) Slime thickener; b) Rod mill; c) Ball mill; d) Cleaner; e) Rougher; f) Scavenger; g) Conditioner; h) Concentrate regrinder;
i) Concentrate thickener; j) Tailing thickener; k) Tailing pond
∗ The main mineral of value is apatite; the gangue contains barytes, iron oxides, and silicates; fatty acid flotation generates
concentrates assaying an average of 36 % P2 O5 , with recoveries of 62 – 63 %; with permission [66].

kerosene or fuel oil make coal matter floatable 5.4.4. Flotation of Precipitates and Ions
[42,70].
Sometimes, pyrite is first removed by conven- Precipitate flotation is based on the same prin-
tional sulfide mineral flotation using xanthates ciples as mineral flotation. For example, in the
as collectors. This is followed by the flotation of preparation of potable water, the adjustment of
coal matter and the rejection of ash-forming ma- pH to precipitate ferric ions as hydroxides elim-
terials such as silica, silicates, and carbonaceous inates most of the iron and colloidal matter by a
shale. subsequent flotation step. In this case, the water
Unlike other minerals, coal exhibits a high contaminants render the hydrolysis product suf-
degree of variation with respect to origin, age, ficiently hydrophobic for bubble – particle adhe-
rank, moisture content, degree of weathering, sion to permit flotation under quiescent condi-
physical and chemical structure, and nature of tions.
gangue. As a result, it is difficult to develop a Alternatively, dissolved ions can be electro-
unified flotation strategy from sample to sam- statically attached to selective cations, which in
ple. Even samples of the same origin undergo turn can be collected in a foam layer (Fig. 37).
surface chemical changes to different extents on The recovery of Au, Pd, Pt, and Ir by such foam
prolonged storage. fractionation methods, as well as the removal of
Nonetheless, generalized strategies are pos- uranium from aqueous solutions by the use of
sible (Table 7). Figure 36 shows a flow sheet of amines, has been demonstrated [73–75].
coal flotation [71]. Figure 38 shows a foam fractionation (ion
flotation) assembly. At times of increasing en-
vironmental concern, the removal of heavy
metal ions and toxic substances such as PCBs
26 Flotation

Figure 34. Flotation flow sheet for Finnish low grade apatite ore ∗ [67]
a) Silo; b) Feed bin; c) Rod mill; d) Ball mill; e) Hydrocyclone; f) Cone classifier; g) Conditioner; h) Pressure filter
Head ore = 3.9 % P2 O5 ; Concentrate grade = 36.5 % P2 O5 ; Recovery = 75 – 79 %
∗ Gangue minerals include calcite, dolomite phlogopite [(KMg3 (AlSi3 ) O10 (OH,F)2 ], and mica.

(polychlorinated biphenyls) seems a promising assemblies similar to those used in conventional

area for further application of ion flotation and flotation technology.
foam fractionation techniques. This method has been used for alumina
(Al2 O3 ), hematite (Fe2 O3 ), cassiterite (SnO2 ),
and artificial diamonds, by first making the pow-
5.4.5. Use of Oil Droplets instead of Air ders hydrophobic with an amine or a sulfonate,
Bubbles followed by extraction into an oil phase [76,
77]. The thermodynamics of the system apply
Surfaces to which air bubbles can adhere are equally well to the now well-established process
also readily wetted by hydrocarbon oil droplets of coal cleaning by oil agglomeration.
in preference to water. This has been demon-
strated thermodynamically and experimentally.
Although micrometer-size solid particles may 6. Future Trends
adhere nonselectively to air bubbles, the replace-
ment of air by hydrocarbon oils provides better The decline in the mining and metallurgical in-
selectivity, as proved experimentally. These con- dustries has shifted emphasis away from conven-
siderations have given rise to the development of tional flotation technology. Nonetheless, under-
two-liquid flotation for extraction of finely di- standing of the fundamentals of flotation is by
vided solids into an oil phase (oil extraction) in no means complete and development of sophis-
 Flotation 27

Figure 35. Potash treatment flow sheet as practiced by the Potash Corporation of Saskatchewan, Canada [68]

ticated instrumentation is leading to combined of flotation chemicals is also under development

research on materials science and on surface fun- and wider application of flotation in recycling
damentals of flotation [78]. industries is at its early stages.
As new applications, such as control of the
so-called pulp potential, control of redox condi-
tions, E h , use of critical surface tension of wet- 7. References
ting, and flotation of ions and dissolved species,
such as toxic and hazardous materials, become 1. B. Yarar, Z. Dogan (eds.): Mineral Processing
more widespread, froth flotation will be em- Design, Martinus-Nijhof, Dordrecht, The
ployed more and more. Netherlands 1987.
Computer technology and instrumental con- 2. B. Yarar: “Investigation of the Recovery of
trol now make larger plants possible with higher- Cellulose from Difficult to Process Sources,
grade products and more complete recoveries. Using Surface Chemical Principles,” Proc. 4th
Furthermore, pyrometallurgy and hydrometal- Recycling World Congress, New Orleans, La.,
lurgy are now used together with flotation for 1982.
3. B. Yarar, D. J. Spottiswood (eds.): Interfacial
recovery of metals from slags or melts [79].
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28 Flotation

Figure 36. Flotation flow sheet applicable to oxidized coals Figure 38. Schematic of continuous-flow foam fractionation
or low pyrite-content coal ∗ column [72]
a) Cyclone; b) Conditioner, 6 %; c) Conditioner, 25 %; a) Ion storage; b) Surfactant storage; c) Pump; d) Mix tank;
d) Fine rougher float, 6 %; e) Coarse rougher float, 15 %; e) Saturator; f) Moisture trap; g) Flow meter
f) Drier; g) Disc filter
∗ With permission [71].

Metals, Melbourne 1955.

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 Flotation 31

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Flour → Cereals and Cereal Products

Flouranthene → Hydrocarbons