Introduction

Without reagents there would be no flotation, and without flotation the mining industry, as
we know it today, would not exist. Reagents in mineral processing are therefore an insep-
arable part of the flotation process. Many books, articles and patents exist on development
of reagents, reagent chemistry and reagent application. In spite of all this, researchers and
those who work on the development of reagent schemes for the treatment of new ores or
improvement in existing operations still rely heavily and almost exclusively on the advise
of chemical companies and their technical services to select specific collectors or depres-
sants for the plant. Unfortunately, the reagent schemes do not consist of only collectors and
frothers. Pulp chemistry in an operating plant is a complex system involving the interac-
tion of all additives, including collectors, depressants, activators, pH regulators, frothers
and, most of all, soluble components of the ore and altered mineral surfaces.
In 1992, R. D. Crozier advocated that those who work on reagent scheme development
must understand surface chemistry. This may be true for those dedicated to fundamental
research using pure minerals, but not for those who are involved in applied research.
Surface chemistry has been and will remain an important part of the flotation process, but
even if we understand the surface chemistry of pure minerals, the same minerals in natu-
ral settings can be vastly different. What does this means in terms of reagent scheme
development and development of new reagents? It means that we have to learn how to
interpret the interactive effects of flotation reagents in a plant setting in order to develop
or improve reagent schemes for given plant feeds. Would knowledge of flotation funda-
mentals help us solve these problems? Yes, to some degree, when we are dealing with a
relatively simple ore. The real test arises when a particular reagent does not do what it is
"supposed" to do; for example, if cyanide does not depress sphalerite or a particular col-
lector is not as selective as described in the manufacturer's book, then one would say "the
ore did not read the book."
A huge database exists on operating flotation plants, treating large quantities of sulfide
ores such as porphyry copper ores and single or multiple base metal ores. When the matrix
of the ore becomes complex by introduction of predominantly iron sulfides, these data-
bases become statistics on production but not on treatment schemes.
This text is a condensed form of the fundamental knowledge of chemical reagents com-
monly used in flotation and is addressed to the researchers and plant metallurgists who
employ these reagents. Flotation reagents are not only collectors and frothers, but include
equally large groups of modifiers, regulators, depressants and activators. This latter group
of flotation reagents is often neglected in basic research studies. It is not the intention of
this text to prescribe recipes for particular ores, but is an attempt in some way to summa-
rize the experience of many years of laboratory and plant studies of different reagent
schemes.
xii Introduction

Those who believe that flotation technology has evolved by "trial and error in operating
mills, and that very little is based on fundamental research" may have forgotten that these
operating plants also produce erroneous metallurgical results. It should be remembered
that fundamental research has provided guidelines for those researchers and engineers
involved in process design and development.
Confusion, however, arises from the fact those flotation properties of a given mineral
often change when present in different ore matrices. This can be best illustrated by exam-
ining the flotation behavior of chalcopyrite found in porphyry ores, massive sulfide ores
and mixed ores. Chalcopyrite from porphyry copper ore floats readily with any thiol col-
lector with usually high recovery. However, the flotation property of chalcopyrite from a
massive sulfide ore is vastly different and the floatability depends on the type of collector
used, pH and modifier/depressant type. The floatability of chalcopyrite is further reduced
in the presence of pyrrhotite.
Since all components in the ore have a pronounced effect on the flotation properties of
a particular mineral, it is not possible to apply only basic research to develop a treatment
process. The main purpose of applied research is to combine the fundamental knowledge
of the chemical and physical aspects of flotation with the experience gained from plant
operations to interpret the responses of an ore to conditions applied in the laboratory or the
plant.
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Classification of Flotation Reagents

Reagents are the most important part of the flotation process. In the early stage of the
development of the flotation process, the major advances were due to better flotation
reagents. In developing a treatment process, much time, energy and attention is spent on
the selection of reagents to give the most effective separation and concentration results. In
commercial plants, the control of reagent additions is the most important part of the flota-
tion strategy.
Modern classification of the reagents is based on the function of a particular reagent. On
this basis, reagents are divided into collectors, frothers, regulators and depressants. Several
thousands of chemicals were either tested or suggested as flotation reagents. Nowadays,
there are only a few hundred of these reagents that are extensively used in flotation.
Collectors are a fairly large group of organic chemical compounds, which differ in
chemical composition and function. The basic purpose of the collector is to selectively
form a hydrophobic layer on a given mineral surface in the flotation pulp and thus provide
conditions for attachment of the hydrophobic particles to air bubbles and recovery of such
particles in the froth product.
According to the ability of collectors to dissociate in water, they can be divided into dis-
tinct groups. Ionizing collectors consist of heteropolar organic molecules. Depending on
the resulting charge, the collector assumes the character of a cation or anion. Anionic col-
lectors are further classified into oxhydryl and sulfhydryl collectors on the basis of their
solidophilic property.
Cationic collectors are chemical compounds in which the hydrocarbon radical is pro-
tonized. These reagents are amines from which the primary amines are the most important
flotation collectors (i.e. R-NH2).
Non-ionizing collectors are also divided into two groups. The members of the first group
are the reagents containing bivalent sulfur. The second group contain non-polar hydrocar-
bon oils.
Frothers are heteropolar surface-active compounds that lower the surface tension of
water and have the ability to adsorb on the air bubble–water interface. Their presence in
the liquid phase increases the film strength of the air bubbles, thus providing better
attachment of hydrophobic particles to the bubbles. Surface tension also affects the size
of the air bubbles. The effectiveness of some of the frothers is very much dependent
on pulp pH. Their performance is optimum when frother is in the molecular form.

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2 1. Classification of Flotation Reagents

For example, cresol at high pH is converted into an ionized compound, which does not
act as a frother:

−
CH3 CH3

+ NaOH

OH O Na+

Quinoline in acid pH forms ions, which have poor frothing properties:

+ HCl
N N
−
H Cl

On the basis of the effectiveness of frothers at different pH values (i.e. the pH at which
the frother is most effective), they can be divided into: acidic, when frothing ability is
reduced with an increase in pH from acid to alkaline and neutral, when the performance
of the frother does not depend on pH value of the pulp.
The acidic frothers are chemicals that belong to two basic groups: phenols (cresol,
xylenol) and alkylsulfonates (surfactants).
The most important group of frothers is the neutral type of frothers. These frothers are
divided into the following groups: cyclic alcohols, aliphatic alcohols, alkoxy paraffins and
glycols.
Regulators: Activators, depressants and pH regulators are often referred to in the litera-
ture as modifiers or regulators of the flotation process. The main purpose of these reagents
is to modify the action of the collector on mineral surfaces and as a consequence govern
the selectivity of the flotation process. In the presence of regulators, the collector only
adsorbs on particles that are targeted for recovery.
In some cases, a regulator reacts directly with the mineral surface (copper sulfate with
sphalerite) and provides conditions for interaction of this mineral with the collector. These
reagents are known as activators. Some regulators may reduce conditions for hydropho-
bization of a particular mineral with the collector, or they can make the surface
hydrophilic. These reagents are called depressants. Both activators and depressants can be
either inorganic or organic compounds.
The third group of modifiers is pH regulators. The purpose of these is to regulate the
ionic composition of the pulp by changing the concentration of the hydrogen ion in the
pulp. Consequently, this results in improvement in collector interaction with the selected
mineral and reduces collector interaction with undesirable minerals. The pH regulators can
also be depressants at the same time (e.g. lime and some organic acids).
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1. Classification of Flotation Reagents 3

This classification of regulators is very arbitrary. For example, regulators under certain
conditions act as depressants and under other conditions as activators. Other important
groups of reagents, which cannot be included in any group of regulators, are dispersants
because of the multiplicity of functions that they can fulfill. Dispersants added to a pulp
containing slimes or clay act as a cleansing medium and can improve the rate of flotation
of particular minerals and reduce excessive collector consumption.
Flocculants are natural or synthetic polymers with different polar groups. Normally,
they have molecular weights ranging from 20,000 to several millions, and they can be elec-
trolytes and non-electrolytes. On the basis of the way they dissociate in water, flocculants
can be loosely classified into the following groups:

(a) Anionic polyelectrolytes dissociate in water into complex polymer anions and
simple cations (Na⫹, NH⫹4 , K⫹, etc).
(b) Cationic polyelectrolytes dissociate into polymer cations and anions (Cl⫺, SO⫺4 ,
CH3COO⫺).
(c) Amphoteric polyelectrolytes are polymers that contain both anionic and cationic
groups.
(d) Non-ionic polymers contain polar groups without attached an anion or cation.
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Collectors

2.1 CLASSIFICATION

On a broad basis, collectors can be defined as organic chemical substances in which the
molecular structure is divided into a non-polar and a polar group.
The non-polar portion of the collector molecule is a hydrocarbon radical, which does not
react with water and is therefore water-repellent. In contrast to the non-polar part of the
molecule, the polar part can react with water. A typical example of such a heteropolar
molecular structure is sodium oleate (Figure 2.1).
The collector structure and composition determines its activity in relation to water
dipoles. In the adsorption process of the collector on the mineral surface, the non-polar
group of the collector is oriented toward the water phase and the polar parts toward the
mineral surface. With this orientation, the mineral surface is rendered water-repellent
(hydrophobic). Chemicals that are apolar hydrocarbon liquids (without a heteropolar struc-
ture) and that do not dissociate in water are also used as collectors.
Because the purpose of collectors is to render minerals water-repellent, these
reagents are usually classified according to their ability to dissociate into ions in aque-
ous solution and having regard to which type of ions (anion or cation) gives the water-
repelling effect [1].
When a collector dissociates into cation and anion, the one that is the direct cause of the
water-repellent action, may be called the active repellent ion, and the other the non-active
(non-repellent) ion. The repellent ion structure always includes a hydrocarbon radical, the
presence of which ensures that the mineral is rendered water-repellent. These radicals
cannot exist in the free state and do not directly attach themselves to the mineral surface.
Therefore, the repellent radical includes another group of atoms attached to the carbon
radical, which forms a connection between the radical and the mineral surface. This con-
nector group is called a “solidophilic” group.
The water-repellent effect of the collector is directly related to the length and
structure of the hydrocarbon radical, whereas the effect of the solidophil group
depends on (a) the nature of the reaction with the mineral surface, (b) the strength
of the collector attachment, and (c) selectivity, all of which are dependent on the
solidophilic group’s composition and structure. According to their ion dissociation

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6 2. Collectors

Molecule
Non-polar group Polar group
Anion Cation
Hydrophobic group
Solidophilic Hydrophilic
Hydrocarbon radical group group

Figure 2.1 Molecular structure of sodium oleate.

properties, the mineral and solidophil group, Al. Glembocki and Plaksin [2] have
classified collectors into the following two groups:

1. Ionizing compounds, which dissociate into ions in water.

2. Non-ionizing collectors, which are non-polar compounds, principally hydrocarbon
compounds, insoluble in water. It is believed that these collectors render the mineral
water-repellent by covering its surface with a thin film.

The larger group of collectors are ionizing, and are divided into the two following
groups (Figure 2.2):

1. Anion collector, where the anion renders the mineral water-repellent.

2. Cation collector, where the cation renders the mineral surface water-repellent.

Anionic collectors are the group most widely used in flotation. These collectors are fur-
ther subdivided based on the structure of the solidophilic group into oxhydryl collectors,
when the solidophilic group is based on organic and sulfo-acid ions, and sulfhydryl col-
lectors, when the solidophilic group contains bivalent sulfur.
The newest versions of anionic collectors are organic sulfides, R-S-R, containing an
active sulfur atom but no other electron donors [3]. From this point of view, these collec-
tors are something in between oxhydryl and sulfhydryl groups. What is not common to the
above group of collectors is that the sulfur in the R-S-R position can share its lone pair of
electrons for bond formation with metals on sulfide mineral surfaces. Because the sulfur
is the only electron-donating atom, the effectiveness of these collectors is strictly related
to pulp chemistry.
Groups that are not covered by this classification, are amphoteric compounds and
chelating collectors.

2.2 OXHYDRYL COLLECTORS

Oxhydryl collectors are the largest group of anionic collectors, yet only a limited number
of these reagents have found application in industrial practice. This is mainly due to the