Principles and practice of sulphide mineral
flotation
R. Herrera-Urbina
J. S.Hanson
G . H. Harris
D. W. Fuerstenau
Department of Materials Science and Mineral Engineering, University of California
at Berkeley, Berkeley, California, U.S.A.
SYNOPSIS
This paper presents both the fundamentals of sulphide
mineral flotation and the practical aspects of sulphide
ore flotation. The fundamental aspects of the flotation
of sulphide minerals both in the absence and presence of
thiol collectors are discussed in relation to their crystal
structure, surface chemistry and electrochemical
characteristics. Since the electrochemistry of the
sulphide mineral/aqueous solution interface and of
various sulphide mineral/aqueous thio-compound
systems has been amply investigated over the past two
decades, the results of these modem electrochemical
studies are briefly reviewed. Mechanisms of the action
of various flotation reagents, including collectors,
activators and depressants, commonly used in sulphide
mineral flotation are discussed in terms of the chemical
and electrochemical principles presented within this
paper. Simplified flow sheets of representative flotation
plant operations are given to illustrate how these
principles are applied for the commercial separation of
sulphide minerals from their ores. Various novel
techniques that take advantage of controlling the
electrochemical and physical behaviour of the flotation
system are also presented.
The practice of sulphide minerals flotation is as old as
the flotation process itself. In the United States, for
example, the first froth flotation plant began operation
in 1911 at the Butte and Superior Copper mill in Basin,
Montana and recovered sphalerite from slimes
(material 92% finer than 150 meshl.I Although in 1911
sphalerite was the only sulphide mineral concentrated
commercially by flotation, over the years the industrial
flotation of sulphides has grown impressively in size,
complexity and importance. According to statistics
87
P. M. J. Gray et al. (eds.), Sulphide deposits—their origin and processing
© The Institution of Mining and Metallurgy 1990
compiled recently by the United States Bureau of Mines,
the largest tonnage of ores treated by flotation
corresponds to sulphide ores, which also consume the
largest amount of reagents.2 Today, froth flotation of
sulphide ores constitutes the single most important
operation for the concentration of sulphide minerals.
Current flotation practice often involves the separation
of three or four sulphides from the same ore.
Industrially important sulphide minerals include
galena, chalcopyrite, sphalerite, pyrite, chalcocite and
molybdenite. Traditionally, these minerals have been
separated from each other using relatively simple
flotation schemes to process high-grade, coarse-gra ined
ores. Because of the depletion of these easy-to-process
ores, however, flotation scientists and engineers are
now confronted with the need to exploit existing low-
grade sulphide deposits with complex mineralogical
composition and finely disseminated values. As a result
of this need, in recent years the flotation of complex
sulphide ores has been the topic of a number of
symposia and workshops.3-5
In contrast to the extensive amount of progress
that has been gained ind ustrially, a clear understanding
of the basic principles of the flotation of sulphide
minerals has not yet been achieved though most of the
early fundamental flotation research involved
investigation of the flotation behaviour of this group of
minerals. The way by which those sulphides that do not
exhibit natural flotability are made to respond to
flotation has been perhaps the aspect investigated more
intensively and in the greatest detail. This aspect
involves the interaction of the mineral with
amphiphatic surfactants, which are called collectors in
flotation term inology, that adsorb at the solid/solution
interface and make the attachment of an air bubble to
the mineral surface thermodynamically favourable.
Since the discovery in 1925 by Keller6 that the alkali
xanthates act as collectors of sulphide minerals, these
thio-eompounds have become the universal collectors
for sulphide minerals other than molybdenite. In spite
of over half a century of continued research on the
interaction of this thiol collector and sulphide minerals,
this system is nowyielding both new results and
problems as new experimental techniques are
introduced in modem flotation research and ultimately
into flotation plant practice. In addition to xanthates,
such thio-eompounds as dithiophosphates (patented by
Whitworth in 1926) and thiocarbamates (patented by
Harris and Fischback in 1954) are also common sulphide
minerals collectors. Although the interaction of thiol
collectors and sulphide minerals is not completely
understood, both its chemical and electrochemical
nature has been amply documented. Galena, bornite
and chalcocite, for example, interact chemically with
thiol collectors producing a surface metal thiolate.7 On
the basis of modem electrochemical studies, on the
other hand, it has been possible to propose a mixed-
potential model to rigorously explain the electro-
chemical nature of this interaction. This model states
that the hydrophilic/hydrophobic transformation of the
sulphide mineral surface by the interaction with a thio-
compound involves simultaneous electrochemical
reactions. The cathodic step is usually the reduction of
oxygen, while the anodic step involves the oxidation of
the collector.8
Apart from the issue of how thiol collectors
interact with sulphide minerals making them amenable
to flotation, various aspects of these flotation systems
remain unclear. For example, the role of oxygen has
become the most controversial issue mainly because of
lack of adequate oxygen control in many investigations.
Based on the most recent results on electrochemical
research, however, it is now widely recognized that an
electron transfer is associated with the adsorption of a
thiol collector to make most sulphide surfaces
hydrophobic. Industrially, oxygen acts as the electron
acceptor but can be substituted by other oxidizing agents
such as sodium hypochlorite,9 or by anodic oxidation .
After many years of being denied as a real phenomenon,
the flotation response of sulphide minerals in the
absence of collectors and under certain conditions is
now well documented. lO Mildly oxidizing
environments render some sulphide minerals
amenable to flotation without collectors.
This paper presents both the fundamentals of
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sulphide minerals flotation and the practical aspects of
sulphide ores flotation . Since the crystal structure and
surface chemistry of sulphides determine their response
to flotation, the nature of the sulphide mineral surface
will be examined first to delineate the effect of crystal
structure on the inherent hydrophobicity of some of
these minerals. For sulphide minerals that do not
exhibit natural flotability, approaches to render their
surfaces hydrophobic and the phenomena involved are
discussed. How the surfaces of sulphides interact with
thiol collectors, depressants and activators used
commercially for the concentration of sulphide
minerals by flotation are analysed. Over the past two
decades, the electrochemical aspects of these interactions
have received considerable attention. Results of these
studies will be reviewed briefly and discussed to the
extent that various working hypotheses can be applied
to plant practice. To illustrate how these fundamental
aspects of flotation chemistry are applied for the
separation of sulphide minerals from their ores,
simplified flowsheets of representative commercial
operations will be given. In addition, various novel
techniques that take advantage of controlling the
electrochemical and physical aspects of the system are
also presented.
CRYSTAL STRUCTURE AND SURFACE CHEMISTRY
OF SULPHIDES
Surface chemistry is the very basis of flotation.
Therefore, a complete understanding of the physical-
chemical characteristics of solid surfaces is essential to
better understand the complex phenomena taking place
during flotation . These surface characteristics are
determined by such crystal properties as the types of
forces that hold the solid together, that is the chemical
bonding, and its atomic or molecular structure. Surfaces
created by the rupture of bonds other that van der Waals
bonds contain very reactive, ionic sites, while those
surfaces created by the rupture of van der Waals bonds
are capable of reacting with the environment only
through van der Waals type interactions. Furthermore,
the interaction between the surfaces of solids and their
environment depends on the solid's cleavage
characteristics, which are determined by the type of
bonds that are most susceptible to breakage during size
reduction. Using such techniques as X-ray diffraction
and 8 -a solution diffractometry, Lindqvist and Stridh ll
have demonstrated that the flotation behaviour of
galena, pyrite and sphalerite is directly related to a