Minerals Engineering 9697 (2016) 214

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Evolution of flotation chemistry and chemicals: A century of innovations

and the lingering challenges q
D.R. Nagaraj , R.S. Farinato
Cytec-Solvay Group, Technology Solutions, 1937 West Main St., Stamford, CT 06902, United States

a r t i c l e i n f o a b s t r a c t

Article history: The history of mineral flotation is a record of over a century of impressive innovations, especially in the
Received 2 January 2016 development of flotation chemistry and chemicals, the principles of their action, their manufacture and
Revised 14 June 2016 the role they play in sustaining efficiencies and productivities even as the quality and grade of ores
Accepted 15 June 2016
decline, and the severity of the challenges increases. We emphasize the major innovations that have
Available online 8 July 2016
directed progress on this subject, especially those innovations that have positively impacted industrial
scale applications. An analysis is given that organizes the evolution of flotation chemistry and reagents
Keywords:
into four historical and one emerging period. As in many other technology areas, flotation chemistry
Flotation
Flotation chemistry
research and development have reached a plateau in the face of mounting industry challenges related
Flotation chemicals to water and energy consumption, decline in the ore quality, economic uncertainty, and health, safety
Reagents and environmental (HSE) aspects. Elevating us off this plateau will require several necessary steps,
Flotation innovations including more detailed, holistic understanding of practical systems, better integration of chemical
Flotation chemicals history effects into flotation models, a more robust education system to produce adequate numbers of qualified
Sustainability engineers, development of novel technologies and chemical schemes that address the challenges identi-
fied above, and a stronger commitment by mining companies to actually adopt those innovations.
Success in developing novel technologies will be greatly improved when we can confront the chemical
complexity in flotation systems. This in itself is one of the grand challenges in the emerging period.
We outline some directions to achieve this goal. The mineral processing industry must take the initiative
towards these goals in order to bring about the necessary transformation if we are to maintain a sustain-
able technology.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
The evolution of flotation chemical technology over the past
100 years is reflected in the growth in diversity and tonnage of
chemicals used, which has mirrored features of the ores treated.
Innovation in the development and use of chemicals has gone
hand-in-hand with innovation in the development of flotation
technology. The introduction of chemicals made the flotation pro-
cess practical and widely applicable; conversely, developments in
flotation technology made possible the use of a wider variety of
chemicals. The resulting positive feedback of this relationship led
to the development of improved flotation operations. Flotation
q
This article was written as a keynote address (Flotation 15, Cape Town) to
commemorate the centenary of Cytec (formerly American Cyanamid) mining
chemicals franchise
Corresponding author.
E-mail addresses: d.r.nagaraj@solvay.com (D.R. Nagaraj), raymond.farinato@
solvay.com (R.S. Farinato).
reagents have thus played a critical role in mineral resource recov-
ery; this criticality stems from the fundamental fact that successful
flotation necessarily depends on creating differences in the surface
chemistries of the minerals being separated.
Nagaraj and Farinato (2014) provided an overview of the flota-
tion reagent innovations of industrial (practical) relevance over
the past 100 years. They observed that these innovations were
greatly influenced by the general zeitgeist and paradigms existing
in the broader field of chemistry at any one time. They also identi-
fied five distinct periods of innovations and developments (see
Table 1), the fifth (emerging) period is one where emphasis is
placed on increasing the sustainability of mining separation oper-
ations. The aim of the present paper is to make a more comprehen-
sive critical assessment of the progress made over the last
100 years and challenges that exist going forward, both lingering
and emerging. An extensive survey of patents, journal articles, con-
ference papers, and plant practice was made in order to identify
and emphasize innovations that have made a substantial impact
on practice. The first four historical periods will be discussed only

http://dx.doi.org/10.1016/j.mineng.2016.06.019
0892-6875/ 2016 Elsevier Ltd. All rights reserved.
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
Table 1
Periods in the evolution of flotation reagent innovations and developments of practical importance.
briefly in order to provide a context for the major focus of this
paper, which is a discussion of the challenges and possible ways
to address those sustainability challenges that face us in the fifth
(emerging) period.
Innovations in flotation chemicals and chemistry can be viewed
in terms of concepts, products and/or application modalities. These
forms of innovation, individually or together, have led to: (i) a rad-
ical change in the way the flotation process is practiced; (ii) an
expansion of reagent choice, processable ore types, and tonnage
treated; (iii) a gradual improvement in productivity and efficiency;
and (iv) reduction in variability of plant performance. Over the dec-
ades, the first two have received reasonable attention and recogni-
tion in the industry and in the published literature; however, the
last two have often been either unrecognized or underemphasized,
although they are important, contribute significantly to value cre-
ation in the plant and form the basis for large innovations.
2. A chronology of major innovations
A highly compressed schematic of the historical progress of
innovations that had a significant impact on practice is given in
Fig. 1. The details are discussed below. At a gross level we can rec-
ognize four distinct periods of development plus an emerging fifth
period. Above each numbered period we list key concepts impor-
tant during that period, and below each numbered period we list
some of the major drivers for radical change. There were certainly
numerous innovations between periods, but they were compara-
tively small and gradual. We believe that we are currently on a pla-
teau and transitioning into what we call an emerging period, which
is poised for another radical leap in progress. This will be discussed
in greater detail in the final section.
3
2.1. First period (18601 1920)
In the first period (18601920), the innovations centered on
the need to improve processes through engineering, reduce con-
sumption of oil (typically fatty oils, see Table 2 below) that was
used as the buoyant medium, and to improve selectivity of separa-
tion through the use of chemicals (modifiers) that were readily
available. Order of magnitude reductions in reagent consumption
due to the introduction of air and improved flotation chemicals is
illustrated in Fig. 2.
With the reduction in oil consumption, inherent differences in
the frothing and collecting powers of various oils were noted,
which led to improvements in flotation efficiency. The next set of
innovations was in terms of selective or differential flotation with
the use of inorganic compounds (which eventually were described
as modifiers) through trial and error testing of virtually any readily
available chemical. Examples of these include soda ash, copper sul-
fate, sulfur dioxide, sulfosalts, hydrogen sulfide and sodium sulfide,
polysulfides, colloidal S, lime, ammonia, bleach, dichromate, per-
manganate, sodium phosphates, persulfate, sodium silicate,
sodium hydroxide, other inorganic soluble salts. Many of the
modifiers discovered in this period are still used today. Such efforts
led to the discovery that alkaline circuits could provide greater per-
formance leverage in terms of lower overall reagent consumption
and differential flotation which were not possible in the previously
popular (sulfuric) acid circuits. Indeed, by the end of the 1920s
most of mineral flotation was conducted in alkaline circuits.
Towards the end of this first period several investigators,
notably Perkins, Sayre and co-workers (Perkins, 1917, 1919;
1
Although the concept of flotation can be traced back to 1860, froth flotation as
practiced today in the mineral industry began in 1905 with the deliberate
introduction of air.
4 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214

Fig. 1. Flotation reagents historical perspective.

Table 2
Small organic compounds to replace fatty oils.

Naphthylamine Naphthol Diazo-aminobenzene

Fatty oils Replaced by ?

Amino thiophenol Thiuram disulfide Thiocarbanilide (diphenyl thiourea)
S

NH NH

100 Their work also established that neutral or slightly alkaline con-
Period 1 (1860 1920) and slightly beyond ditions improved the efficiency of these collectors. As more small
organic chemicals were investigated, it was evident that chemicals
10 could be put into two distinct categories: those that predominantly
collector dose (kg/t)

promoted differential flotation on minerals (collectors, e.g. thiocar-

1 banilide) and those that predominantly facilitated stable froth
formation (frothers; e.g. cresol or pine oil); indeed, Perkins et al.
(Sayre, 1924) noted such classification in their patents. Addition-
0.1 ally, essential molecular features (e.g. those containing both
N and S) became evident for organic compounds that made them
0.01 good collectors for sulfide minerals (i.e. organic, slightly water-
soluble, chemically reduced, easily oxidized, and non-frothing)
and the manner in which they cause mineral collection (Taggart
0.001 et al., 1930). These features are quite evident from structures of
oil oil & air improved 1921 > 1921 amino thiophenol, thiuram disulfide and thiocarbanilide. Of the
small organic collectors compounds listed in Table 2, only thiocarbanilide was used com-
Fig. 2. Collector dose reduction during the first period (18601920) and slightly
mercially for many decades, especially to improve recovery of Ag
beyond. values. The reduced form of thiuram disulfide, viz. the dialkyl
dithiocarbamate (Sayre, 1924) is still in use.

Perkins and Sayre, 1921; Sayre, 1924), established that slightly-
soluble, small organic compounds (see examples in Table 2), which
included some chelating agents, were effective collectors and could
replace the large amounts of fatty oils and soaps (see Fig. 2) that
were in widespread use.
2.2. Second period (19211950)
The innovation noted above marked the beginning of a long
string of innovations in the subsequent (second) period
(19211950) in the development of new and highly effective
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
non-frothing collectors that are still used today; indeed modern
reagents still have roots in this innovation. The 1920s were espe-
cially intense and productive. Two main themes are evident in
the second period: discovery and expansion. The discovery part
was characterized by exploring (screening) the application of
chemicals (or, in some cases, an entire line of chemicals derived
from a primary feed stock) developed in other major industry or
market segments (for e.g. tanning, agriculture, petroleum, rubber,
textiles (dyes), food, soaps, detergents and explosives). In this
available derivatives of building block chemicals approach, the
chemical feed stock or a building block is at the core, with several
derivatives emerging out of this core. Some intermediates in this
scheme that were used as additional building block chemicals also
found direct use as flotation reagents. Examples of such core che-
mistries or building blocks are: ammonia, cyanamide, acrylonitrile,
aniline, cyanide, S-compounds, P2S5, fatty amines, alcohols, etc.
One example of the hierarchy of building block chemicals and their
derivatives that have found use in flotation is carbon disulfide,
which is used to manufacture xanthates. Xanthates found direct
application as flotation reagents. Xanthates were used as building
blocks to make other derivatives for other chemical industries
(e.g. rubber). Some of these derivatives were also used directly as
flotation reagents (e.g. xanthogen formates, xanthate esters and
thionocarbamates).
Such a model based on available building block chemicals and
their derivatives persisted well into the 1960s in many industrial
chemical segments, and was later supplanted by the applica
tion-centric approach wherein a chemical product was developed
essentially to address a specific application need in the mineral
processing industry (see Periods 4 and 5). The availability of chem-
icals for flotation was subject to the influences of these other
industries, as well as the prevailing state of war or peace. Never-
theless the phenomenal innovations and developments during this
period firmly established the so-called era of chemical flotation, and
revolutionized flotation.
The expansion theme of this period was exemplified by the
exploration of more effective ways to apply flotation techniques
and the reagents invented to a wide variety of natural resource
separations. Indeed the vast majority of general schemes for min-
erals separation and recovery that are in use today were developed
in the second period.
Examples of short-chain (C2 C6) organic molecules developed
as collectors (many of which were water-soluble), specifically for
sulfide minerals, are given in Table 3. Most notable of these
structurally and functionally similar collectors were: xanthates
(Keller and Lewis, 1925); potassium salt of dithiocarbamic acid
(Sayre, 1924); cresyl dithiophosphoric acid (Whitworth, 1926);
the sodium salts of aliphatic dithiophosphates (Christmann,
1930); and mercaptobenzothiazole (Bolton, 1928). Xanthates and
dithiophosphates, and to a lesser extent the mercaptobenzothiazole,
found immediate acceptance in the industry and within a few years
Table 3
Collectors based on short-chain organic molecules.
Xanthates Dialkyl Trithiocarbonates
S S
R R R'
O S- Na+ S S
Dialkyl xanthogen formates Dialkyl dithiophosphates
S O R S
R R' O P S- Na+
O S O NH
O O
R'
5
became the workhorses in sulfide flotation. Dithiocarbamates, on
the other hand, were not widely adopted (their usage is still
relatively small). The reagents named in many patents in this
period all contained either sulfur or nitrogen or both (the signifi-
cance of this was noted by Taggart et al. (1930)); these elements
are most preferred in reagents for sulfide systems. This led to
search for other sulfur compounds such as alkyl xanthogen
formates (Douglass, 1927), alkyl ester xanthogen alkyl amide
(aka dialkyl thionocarbamates) (Douglass, 1928a); and dialkyl
trithiocarbonate (Douglass, 1928b).
Trithiocarbonates (whether dialkyl or monoalkyl) never quite
enjoyed wide application perhaps owing to their instability,
stench, and lack of any unique features over xanthate or dithio-
phosphate. Alkyl mercaptans were developed during this time,
but they found only sporadic and limited use. Although thionocar-
bamates were patented in 1928 (Douglass, 1928a), they remained
obscure until a manufacturing process patent from Dow in 1954
(Harris and Fischback, 1954). They became popular soon there-
after. Xanthogen formate enjoyed only limited use, perhaps
reflecting its limited capability and stability. Mixtures of collectors,
with the intention of exploiting any synergism, e.g. those of
thiocarbanilide, mercaptobenzothiazole and dithiophosphates, were
developed and commercialized during the 1930s (Christmann
and Jayne, 1936; Christmann and Falconer, 1936) and these and
many other mixtures continue to be important today.
Although efforts in reagent development tend to be skewed in
favor of collectors and receive much attention, innovations in the
development of modifiers and process schemes to facilitate differ-
ential flotation are no less impressive. Building on the many impor-
tant discoveries in the 19101920 period involving the use of
inorganic modifiers such as sulfosalts, dichromate, etc. to achieve
selective or differential flotation, Sheridan and Griswold (1922a,
b) demonstrated that a small amount of cyanide caused a marked
decrease in the floatability of zinc and iron sulfides compared to
those of copper and lead. This revolutionized the processing of
complex Pb-Cu-Zn-Fe ores. This second era, especially in the
19201940s, saw other modifiers placed in the flotation reagent
arsenal (see Table 4) in addition to sodium cyanide, such as
synthetic dyes and a new class of modifiers drawn from natural
products such as dextrin, tannin, starch and dyes (Moyer, 1958;
Gutzeit, 1946).
Reagent development in non-sulfide flotation came much later
than it did in sulfide flotation since the focus on reagents in the
1920s and early 1930s was on sulfide ores. As a result, the early
record of innovation for the treatment of non-sulfides is relatively
sparse. There are at least two important reasons for this: (a) the
greater need and value for base and precious metals, and (b) the
large diversity of non-sulfide ores and the perceived difficulty in
non-sulfide mineral separations (how could one float non-
sulfides if all the collectors were floating sulfides away from
them?). The thrust of the innovation in non-sulfide flotation,
Dithiocarbamates, Na salt Mercaptobenzothiazole Alkyl Mercaptans
S N R-SH
R S- Na+
N S- Na+ S
R'
Dialkyl thionocarbamates Dicresyl dithiophosphoric acid Na alkyl trithiocarbonates
S S
S
R R' O P SH R
O S S- Na+
6 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214

Table 4
Innovations in the development of modifiers for differential flotation.

Year Reagents Application

19101921 CuSO4, SO2, sulfosalts, H2S, polysulfides, Na2S, Colloidal S, Mostly flotation of sulfides from gangue;
Na2CO3, Lime, NH3, bleach, dichromate, permanganate, selective
Na phosphates, persulfate, Na silicate, NaOH, FeCl3, ZnSO4, separation of sulfides
other inorganic soluble salts
1921, 1930, Dextrin, tannin, starch Depression in coal, non-sulfide, and sulfide flotation
1922 NaCN (with Na2CO3) Pyrite depression in Pb-Zn-Cu flotation
19251927 Starch, glue, gelatin Gangue depression in sulfide flotation
1928 Polythionates Separation of sulfides
1929 Gum Arabic Gangue depression (e.g. mica)
1930 Mineral lattice ions Reduce solubility and floatability (e.g. NaF to depress cryolite)
1933 Hydrofluosilicic acid or metal fluosilicate Slime depressant; Oxidized ores
1933, 1943 Tannin Mn ores; Barite ores
1934 Ferrocyanide Cu-Zn separation
1934 Zn cyanide ZnS and FeS2 depression in Pb-Cu flotation
1935 Ammonium thiophosphates Gangue depressant in flotation of oxidized Pb ores
1935, 1938, 1949 Lignin sulfonate Depression of ZnS, Carbonaceous matter; Dispersant and
depressant in sulfide flotation
1937 Starch-NaOH and Dyes Depression of Mo in Cu-Mo separation
1939 Dextrin Depression of carbonaceous matter
1940 Naphthalene sulfonic acid condensation product Depression of Mo in Cu-Mo separation
1940 Dyes Depression of carbonaceous matter
1949 Dextrin, Tannin Depression in iron ore flotation

therefore, was identifying and developing suitable modifiers, condi-
tions and schemes to achieve selective separations while employing
rather non-selective collectors such as soaps and amines. The impor-
tant work at the U.S. Bureau of Mines and other institutions
(Gaudin et al., 1928; Coghill and Clemmer, 1935; Ralston, 1938)
beginning in the late 20s in the flotation separation of oxide, car-
bonate and phosphate minerals from quartz and silicate gangues
by means of anionic collectors such as fatty acids is noteworthy.
Many developments occurred in the1930s and 1940s in reagents
(see Table 5) and schemes for the selective separations in a wide
variety of non-sulfide systems including energy minerals. These
reagents and schemes are still used today. A general description
can be found in Taggart (1951), Falconer and Crawford (1947),
Rogers et al. (1946), Falconer (1960), Thom (1962). The majority
of collectors used for non-sulfide flotation were found to be rather
non-selective, thus requiring ingenuity in selecting appropriate
modifiers and conditions. This is largely true even today. The rea-
sons for this can be found in Aplan and Fuerstenau, 1962; and in
Nagaraj and Ravishankar, 2007. However, research during this per-
iod lead to the identification of several new chemical classes with
benefits as collectors for non-sulfide ores, including hydroxamates
(Ppperle, 1941) and chelate forming reagents (Gutzeit, 1946).
Commercialization of some of these selective collectors occurred
only in the 1980s due to a variety of reasons related to economics,
importance of the need and lack of practical manufacturing
processes.
Although several companies were active in reagent develop-
ment in the period 19211950, American Cyanamid was the most
prolific in this period: over 180 patents covering both sulfide and
non-sulfide flotation (see Fig. 3). If one considers only those
patents that resulted in plant usage, then the ranking is even more
heavily skewed in favor of Cyanamid. Much of the flotation reagent
work that came out of American Cyanamid from the mid-1920s
and beyond was likely accelerated by the expansion of chemicals
derived from building blocks, and technologies that were brought
under the same roof during periods of business diversification.
While some flotation reagents patented early in the game derived
from adjacent areas of research, these successes spawned more
deliberate and specific for-purpose efforts.
A perusal of the literature reveals that almost all of the reagent
development occurred in companies, well before a fundamental
understanding of reagent interaction with minerals was developed.

Table 5
Innovations in reagents for non-sulfide flotation.

Year Reagents Application

19101921 Use of oils and soaps (neutral to alkaline circuit; sodium silicate, Flotation of oxidized Cu, Pb ores, non-metallic ores,
sodium phosphate, sodium carbonate) phosphate ores
1921 Sulfonated fatty acids Sn and W ores
1923 Taurocholic acid, cupferron, and others Sn, V ores; oxidized Pb ores
1923 Fatty acids (as-is or emulsified); sod. silicate to disperse gangue Iron ore
19281936 Fatty acids; soaps; pitch; sulfonated oils; with sod silicate and soda Barite ore, Sn ore, phosphate ore, Mn ore, fluorspar,
ash, tannin, metaphosphate Ba/Ca ores with clay
1933, 1937 Quaternary ammonium compounds General non-sulfide flotation
19341935 Fatty acid and fuel oil; Sulfate black liquor tall oil Phosphate ore
1935 Fatty acid soap (with Pb acetate) U ore
193638 Fatty acid soap Potash ore; Zircon, magnesite
19371940 Primary amines including guanidine; with hydrocarbon oil Potash ore; feldspars; phosphate ore; limestone
19381939 Fatty acid, mineral oil, emulsified with alkyl sulfate; pre-saponified Mn ore, calcite, phosphate
19381941 Sulfonated oils and fatty acids Phosphate, calcite, barite, glass sands, and others
1939 Alkyl phosphate Phosphate
19391944 Condensate amines; imidazolines Phosphate ore and others
1945 Sulfosuccinates General non-sulfide flotation
19431946 Petroleum sulfonates General non-sulfide flotation
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214 7

180 paper (Gutzeit, 1946). He noted the importance of applying

160 knowledge of specific chelate-forming organic analytical reagents,
140 particularly in the selection of reagents for flotation, which
120 included collectors and depressants. He noted that many of these
# patents

100 specific reagents are uneconomical. Some of them could be used

80
60
40
20
0 During this period innovations in flotation reagents were of
Fig. 3. Flotation reagent patent statistics: 19211950.
Indeed to a large extent this is still the case. The seminal work of
Taggart and his co-workers in the 1920s (Taggart et al., 1930) laid
the foundation for identifying and establishing chemical functional
group features of collectors, depressants, and frothing agents. This
work coupled with the fundamental studies of Gaudin (1957),
Wark, Sutherland (Sutherland and Wark, 1955), and others was
an important conceptual advance that brought the much needed
scientific understanding. Taggart et al. (1930) noted the following:
Soluble organic collecting agents function by reacting chemically
with the surface substance of the mineral particle to be collected,
thereby forming an organic reaction product that is insoluble in
water in the concentration present, and adheres at the reacting
surface and thereby changes that surface, for all practical purposes,
to an organic surface with water-repelling properties.
This surface chemical reaction theory is valid for chemisorb-
ing reagents, e.g. the dominant collectors in sulfide flotation, and
the majority of modifiers (simple and polymeric) interacting with
minerals.
2.3. Third period (19512000)
The structural features required for reagents to impart selectiv-
ity in separation were well articulated by Gutzeit in his influential
at low cost, if their efficiency were proved to be outstanding.
Indeed Gutzeits paper appeared to anticipate the arrival of the
third period (19512000) of Rational, Targeted Design for
collectors and modifiers.
quite a different character: a gradual shift from screening and
expansion exploratory type of research (utilizing available
building block chemicals and their derivatives) to efforts in design-
ing reagents de novo for specific separation challenges (operational
need-centric or mineral-centric) based on advanced understanding
of organic, polymer and coordination chemistry. The aim of much
of this led to rational targeted design, based on specific chemical
interactions between reagents and minerals. This kind of inquiry
applied equally to research on macromolecules, especially syn-
thetic polymers, which were a burgeoning field during this period.
Polymers offered unique features and advantages, including
improved HSE profiles. There was growing recognition of the
power and efficiency of polymers, and the great flexibility they
offered for tailored design, especially as this allows use of a wider
array of functional groups.
The rational targeted design approach was founded on donor-
acceptor concepts that arose from the original work of Lewis in
the early 1920s and subsequent refinements over the next several
decades. These concepts were also applied to mineral systems dur-
ing the period 19701985 (details found in Nagaraj, 1987). In that
paradigm, reactions between acids (electron acceptors minerals)
and bases (electron donors flotation reagents) are viewed in
terms of a redistribution of valence electrons.
A greater degree of predictive power was realized via the donor-
acceptor paradigm, making it now part of the conventional frame-
work by which we understand and develop reagents that bind
selectively to either metal ions in solution or mineral surfaces in
suspension. While this scheme was originally applied to binary
interactions between reagent and target mineral, it has also been
extended to rationalizing behavior in more complex mixtures
where competitive adsorption is the central feature. The
donor-acceptor model has been very successful and it resulted in

Table 6
Examples of reagents developed by rational design using donor-acceptor.

Alkoxycarbonyl alkyl thionocarbamates Alkoxycarbonyl thioureas Dithiophosphinates Allyl alkyl thionocarbamates

O S S O S S
R R' R R' R P S- Na+ R
O NH O NH NH O NH O
R'
Dialkyl thionocarbamates Allyl xanthate esters Alkyl phosphonates Monothiophosphates
S S O
Na + R S

R R' R R P O- O P O- Na+
NH O O S
O- Na+ R'
O

Alkyl hydroxamates Synthetic polymeric modifiers Synthetic polymeric modifiers

O R1 R1 R1 R1 R1
+ x y z x y z
O- Na
R N O O O O O
H
H2N HN OM H2N HN OM
OH S
R2 NH2

R1 = H or CH3 R1 = H or CH3
R2 = H or COOM M = Na
M = Na
8 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
numerous innovations in both collectors and modifiers. These
innovations rested squarely on the conceptual innovation that
emphasized the role of the functional group rather than attributes
like charge (ionic, neutral), solubility, hydrolysable, oxidizable,
etc. Some important examples of new classes of collectors and
modifiers developed in this period using the donor-acceptor model
are given in Table 6 (detailed description can be found in Nagaraj
and Avotins, 1988; Nagaraj et al., 1988, 1989; Nagaraj, 1997, 2000).
Most of these reagents are still in commercial use today. The
1980s was a period of intense activity in flotation reagent develop-
ment, much like the intense periods of developments seen in the
1920s and 1940s. Significant efforts by R&D groups in chemical
companies during the 1980s were focused on developing
reagent-mineral characterization data and extensive structure-
property-performance relationships which led to subsequent
numerous innovations. A review of literature shows that many
companies were active during this period, especially American
Cyanamid (see patent statistics in Fig. 4). As previously observed
in the second period, if one considers only those patents that
resulted in plant usage, then the ranking is even more heavily
skewed in favor of Cyanamid.
As in the Discovery-Expansion period, the majority of reagent
innovations in the rational targeted design period have been in
the area of sulfide flotation. The innovative concept was that in
systems where the driving force for adsorption of collectors,
organic modifiers or polymers on minerals is based on chemical
bond formation (i.e. chemisorption), the reagent properties
(strength and selectivity) could be designed by exploiting and
manipulating the functional group (type, position, and number of
donor atoms) and the hydrophobic portion of the molecule (type,
length and branching). Donor atom properties could additionally
be modified by introducing electron withdrawing/donating groups
and by manipulating substituents in the molecules, thereby creat-
ing the optimal complex-forming functional groups. While this
degree of manipulating chemical structure still produces innova-
tions in reagents operating by chemical bond formation, collectors
operating by electrostatic adsorption (e.g. amines, sulfonates,
sulfates, and to some extent fatty acids) leave little room for
improving their molecular composition. Application of donor-
acceptor principles can also be used to make the choice of simple
inorganic, organic and polymeric modifiers more rational.
Since chemical interactions have the highest adsorption ener-
gies, changes in structure of the reagent molecule can potentially
result in large changes in the strength of adsorption, selectivity,
interfacial properties, and flotation response. Structure-property
relationships take on added dimensions in polymers in terms of
Flotaon Reagent Patents (1951 2000)
160
140
120
# patents
100
80
60
40
20
0 ing this problem is the exponential growth in environmental
Fig. 4. Flotation reagent patent statistics for the period 19512000.
complexity and possibilities. In addition to changes in functional
group, factors such as molecular weight, degree of substitution,
location and distribution of functional groups, and conformation
in solution and at the interface become critical.
Many innovations occurred in the development of efficient and
economical manufacturing processes for certain flotation reagents
and these had a profound impact in the industry by catalyzing the
much needed widespread applications of the specific reagents in
many innovative ways. Three examples can be cited: (a) a practical
process for dialkyl thionocarbamate (Douglass, 1928a) in 1954 by
Dow (Harris and Fischback, 1954), (b) manufacture of dithiophos-
phinate by American Cyanamid using a novel process based on the
unique phosphine chemistry (Wystrach and Peters, 1964), and (c) a
practical process for making alkyl hydroxamates, which facilitated
their widespread plant use (Wang and Nagaraj, 1989).
In terms of simple modifiers, the majority of developments had
occurred in the second period (prior to 1951). A major innovation
in the third period, however, was the successful application of the
donor-acceptor concepts in the development of water-soluble,
synthetic polymeric modifiers with targeted molecular architec-
ture and mineral-specific functional groups capable of targeting
specific sites on minerals (via complexation or chelation) (see
Table 6). Although such a task appears rather straightforward in
principle, there was a truly significant challenge in developing
robust, practical and economical manufacturing routes to produce
such polymers with consistent structural features.
2.4. Fourth period (2000 present)
Paradoxically, the innovations and successes in the rational tar-
geted design of flotation reagents derived from the enthusiasm and
intense R&D activity in the 1980s, created a crisis for the chemical
manufacturers by 1990 resulting from a lack of application under-
standing and a rational scheme for selecting and optimizing
reagents from this new arsenal of chemicals. This paved the way
for intense activity to develop new methodologies and approaches
for reagent selection and optimization (the fourth period). The
crisis arose from a lack of large scale implementation of new tech-
nology in the industry. There were many important factors (some
impacting the whole industry and others impacting chemical
usage) driving this situation, which resulted in a recognizable
trend that exists even today. These factors were well articulated
in several publications in an SME symposium in 1994
(Cappuccitti, 1994; Klimpel, 1994; Malhotra, 1994; Nagaraj,
1994), and discussed in greater detail more recently (Nagaraj and
Ravishankar, 2007, see Table 12 therein; Nagaraj, 2010). There
was a growing recognition that the traditional approach to flota-
tion reagent selection and optimization had become subjective,
reductionist, and fraught with misunderstanding and largely based
on personal experience, with no accepted standard of practice in
place (Nagaraj and Bruey, 2003; Nagaraj, 2005). Such an approach
was very costly because the failure rate was high in implementing
new chemistries. Even when the best reagent is developed for an
unmet need in the industry, it is deemed a failure if we fail to apply
it properly on the large scale. This issue becomes acute when one
considers the high overall cost ($510 million from concept to
commercialization) and the long time required (510 years) to
develop and implement new reagents and technology. Compound-
regulations and the high upfront cost of regulatory registration
for new chemicals (as much as $2 million in 8 countries for a single
chemical). Adding to the confusion, the plant metallurgist is
presented with a large variety of chemistries, differentiated not
only by major functionalities but also by many other features. This
complexity naturally reflects the complexity of mineral flotation,
but it creates a challenge for reagent selection and optimization.
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
The critical innovation that emerged from this situation was the
development, beginning in the mid-1990s, of a holistic approach,
called Flotation Matrix 100TM to reagent selection and optimization
(Nagaraj 2005, 2008, 2010; Franzidis, 2005). Such an approach con-
fronts and deals with the complexity of ore flotation systems,
rather than circumvent it. This was facilitated by the development
of rule-based expert system reagent selection software employing
a database of structure-performance relationships, the use of quan-
titative mineralogy, and the use of advanced statistical tools and
techniques for dealing with variability and complexity, both at
lab scale and plant scale. On the whole, the holistic approach incor-
porated the ideas of best practices, plant needs and expansion of
the knowledgebase, with the ultimate goal of developing a robust
and optimized tool that is suitable for dynamic and variable plant
systems, and which has the highest probability of successful
chemical implementation to capture a greater percentage of the
otherwise lost value minerals.
The importance of analyzing, modeling, and controlling the
froth zone, which is central to flotation and strongly influenced
by chemistry, was increasingly recognized during this period;
however, a detailed picture of the dynamic physical micro-
processes involved in the transport of particles of different
wettabilities, shapes and sizes through and by a network of liquid
lamellae is still unavailable. While there has been appreciation by
some researchers of the various contributions to the physical state
of the froth zone, this level of understanding is not taken into
account by the wider industrial community. There is a common
belief that frother chemicals act independently of other functional
chemicals (e.g. collectors and modifiers), minerals, and physical-
mechanical factors. This completely ignores factor interactions
which are quite often very significant.
There is still a disproportionate focus on behavior in 2-phase
systems (i.e. aqueous phase containing a frother and air; without
minerals), which has no direct relevance to practical flotation.
Similarly, understanding the dynamics and complexity of water
chemistry, and modeling these features remains a great challenge.
This is a subject that is certainly ripe for critical innovations. We
can learn from ongoing work in the area of predicting scale forma-
tion in brines found in petroleum production as an example of how
taking water chemistry into account can lead to better prediction.
While a host of sophisticated techniques to characterize ores and
study the mineral-solution interface and interaction of reagents
with mineral surfaces are available, techniques that can provide
in situ real-time information are not available. This is another
roadblock to progress.
2.5. Fifth period (emerging)
Although plant metallurgists have begun to realize the potential
benefits of a holistic approach, and some progress has been made
in the past ten years, adoption of this methodology has been rather
slow. Attempts to implement this approach broadly have revealed
persistent and large gaps in the knowledgebase necessary for
implementation. This is true both in the research and industrial
communities. This situation has been brought into the spotlight
by the magnitude of the sustainability challenges facing the
mineral processing industry. It demands a new paradigm to
reshape our research and technology transfer efforts to meet these
challenges. Business as usual would not leave us with a sustainable
future. A survey of the literature and conferences (e.g. recent IMPC
and SME keynote addresses) confirms the need for a change in
paradigm and the high level of attention being given to the
topic of grand challenges and sustainability. We see this as the
emergence of a new era in flotation reagent and flotation
chemistry the fifth period.
9
Current challenges in the mineral processing industry are well
expressed in the literature (for example, see Batterham, 2013;
Ralston, 2014; van Deventer, 2014): processing low-grade and
poor-quality ores with complex mineralogy; maximizing resource
utilization; improving water usage efficiency and water resource
management; better energy efficiency; waste reduction and
remediation; complying with and exceeding increasingly restric-
tive health, safety and environment (HSE) regulations; the need
for more environmentally benign chemicals; and minimizing over-
all environmental impact and ensuring social license to operate.
These challenges are very broad, complex, and independent of
the industry boom and bust cycles. They are linked to the three
pillars of sustainability societal, environmental, and economic
which rely heavily on technological (rather than traditional
economy-of-scale) solutions, generally engineering-based and/
or chemistry-based. We focus on the latter because they epitomize
a kind of disparity (great commercial importance vs. lack of appli-
cation knowledge and industry acceptance) which must be fixed in
order to address sustainability challenges in a meaningful way.
Chemistry-based solutions will undoubtedly play a pivotal role
in addressing most of these challenges. They provide optimal
metallurgical performance on a day-to-day process level (routine
variability in operational factors, comminution and mineralogy).
Given all the physical-mechanical and operational constraints, the
plant operators rely heavily on chemicals to optimize performance.
i. They allow a plant to process different ore types, especially
when faced with low-grade, poor quality ores. Only chemi-
cals can address this predicament. A different suite of
reagents might be necessary; however, that sort of change
is more manageable than redesigning the flow sheet and/
or installing new equipment, thereby incurring large capital
expenditures.
ii. Chemicals provide excellent flexibility to the operators,
especially if the flotation strategy must change; e.g. bulk
flotation followed by separation vs. sequential flotation.
iii. They provide a means to devise the majority of solutions to
HSE issues.
Compared to physical-mechanical methods, chemical solutions
to mineral separation problems are much easier to implement and
control. Many problems can be solved more efficiently and eco-
nomically via chemistry (e.g. selectivity in separation, processing
poor-quality ores, processing with low-quality waters, improving
energy efficiency, improving HSE profiles, dealing with toxic ele-
ments and deleterious gangue minerals, etc.). In addition, chemical
innovations can enable and enhance innovations in equipment and
processing strategies. Independent of whether these solutions
require development of new or implementation of existing
technologies, successfully addressing the challenges will require
robust application knowledge and technology acceptance by the
mineral processing industry. Unfortunately, currently we have
problems with both.
Our application knowledgebase and research framework from
which such knowledge is generated are both outdated and
inadequate. Many of the classical problems in flotation that were
recognized in the first half-century of flotationfor example, the
effect of water chemistry, the adverse effect of altered silicates
and slimes, recovery of coarse and fine particles, difficult mineral
separations, and numerous others have remained largely
unsolved.
A review of scientific journals and conference proceeding over
the past several decades may lead one to conclude that there has
been little innovation and that progress has been incremental.
However, we would arrive at a different conclusion if we consider
the innovations made in industrial labs and in plants (as evidenced
10 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
in plant practice), some of which are captured in this paper. One
important reason for this conflicting perspective is that industrial
research and development, and plant practices are not widely
published, advertised or shared. The research community is mostly
in the dark on such progress. Coupled with this is the significant
erosion in comprehensive chemistry knowledge across the aca-
demic and industrial communities involved in flotation, including
subjects such as: reagent chemistry, chemical factor interactions
in the pulp and froth zones, the role of aquatic chemistry, and
reagent-mineral interactions in practical systems (i.e. of represen-
tative mineralogical complexity). Reasons for this have been
discussed in Nagaraj, 2010. This has resulted in a very simplistic,
unbalanced, misguided and inaccurate view of the subject; often
leaving us with an assortment of myths and misconceptions to sort
out. All told, there are many missed opportunities to advance the
field, especially since most of the commercially relevant innovations
in flotation reagents and their application have come from indus-
trial research. The situation has not substantially changed since
Fuerstenaus observation twenty years ago (Fuerstenau, 1995):
The flotation process did not come into being as the result of an
intensive fundamental research effort but, in a manner similar to
the development of so much of the other technology used in the
processing of raw materials, it was developed over the years
through a great deal of empirical and intuitive work on complex
ores. As a result, most of the basic research in this field has been
concerned with the problem of explaining why existing processes
work so well. We are now at the stage where any further substan-
tial extension of the flotation process will demand even more
profound understanding of the fundamental principles on which
it is based. Current knowledge of flotation fundamentals is still
far from the stage where processes can be designed, optimized,
and controlled from first principles. Because of the complexity of
the interactions between minerals and reagents, basic research in
flotation has involved primarily working with simplified and some-
what idealized experimental systems.
Nagaraj (2010) expanded on this and provided a detailed cri-
tique of state of research and technology transfer, argued for an
overhaul of current research paradigm, and suggested a new
framework based on a systems approach (holistic approach). This
was summed up as: Our research effort over the decades has sus-
tained itself, but often it has little to do with sustainability in mineral
processing. Research efforts must be both more coordinated and
integrated so that the research and plant work are designed appro-
priately to fill the Grand Canyon of knowledge gaps.
When naturally complex problems are modeled as idealized
systems (i.e. a reductionist approach), too often the results are sim-
plistic and of limited utility. Fragmentary and uncoordinated
research efforts compound the issue. Attempts to model the kind
of complex systems found in flotation operations have been rea-
sonably successful at the engineering level (see for example King,
2001; Nguyen and Schulze, 2003); however, these models do not
yet incorporate information on mineral surface chemistry and the
interplay between multiple dissolved and dispersed components in a
flotation pulp and in the froth phase. Integrating such physical-
chemical details into process models would constitute a significant
contribution and a major innovation, providing an antidote to the
perception that chemical effects play only a minor role.
Modeling flotation has been a lofty goal for many decades.
While significant advances have been made in modeling
physical-mechanical aspects of flotation, the absence of chemical
aspects is a particularly glaring omission given that successful
flotation is leveraged through interfacial chemistry, which in turn
is affected by mineral/solution chemistry. Almost all flotation mod-
els either ignore chemistry or collapse it all into a single number
(e.g. contact angle), where it is convoluted with a panoply of other
non-chemical factors. Other such model parameters that dont
account for the natural distribution of these quantities, or the
manner in which they change in response to changes in the chem-
ical environment that exists in a flotation cell include the single
mineral zeta potential or surface potential (or electrode potential
in the case of sulfides), Hamaker coefficient, hydrophobic force
decay length, etc. This reductionist practice is the equivalent of
characterizing a population of people by their average shoe size!
While there has been good progress in cell design based on a
refined understanding of physico-mechanical fundamentals, there
has been significantly less useful fundamental knowledge transfer
into the practice of reagent optimization. Flotation models might
be improved by invoking richer parameterization of the contact
angle, e.g. accounting for contact angle distributions, taking into
account spatial heterogeneity and/or dynamical aspects in the
bubble-particle contact process (Chau et al., 2009). However, this
still buries chemical factors amongst a host of physical factors,
and it neglects kinetics aspects of the chemically evolving system
(e.g. mineral dissolution, hydrolysis, surface oxidation, and reagent
reactions). In addition to the difficulty of accounting conceptually
for more realistic chemistry, we are faced with the even greater
challenge of determining quantitative parameter estimates that
characterize this chemical complexity. In situ methods for analyz-
ing the mineral-solution interface during a bubble-particle colli-
sion in a turbulent fluid are not currently available. However,
this fact should not deter efforts in the research community to
begin to develop and incorporate a more robust set of chemical fac-
tors into flotation models to make them meaningful and useful.
This should be a new goal. Other fields with similar chemical com-
plexity have made considerable progress. It must be recognized,
however, that developing these more complete models would be
fruitful only when operations are motivated to make necessary
changes based on the insights gained.
Recently there has been a great surge in the use of computa-
tional chemistry modeling to understand reagent-mineral interac-
tions, driven perhaps by factors such as glamor, ease of study (no
need for lab infrastructure) and publication, and perceived scien-
tific merit. Unfortunately, this is going backward, as the myriad
model assumptions necessary to facilitate computation make the
systems far more idealized than even the single mineral systems,
which fail to capture the complexity of the practical systems. These
studies also suffer from incomplete inclusion of parameters
characterizing the mineral environment, a focus on inappropriate
questions, and unrealistic expectations and promises. None of
these issues are insurmountable for the computational chemist;
and we believe that great strides may be made by using modeling
tools more wisely.
Among the sustainability challenges listed earlier, HSE and
Regulatory aspects loom large, accentuated by the ambiguity and
tepidity with which we acknowledge and approach this elephant
in the room. More restrictive regulations are inevitable because
of increasing expectations from society and a genuine concern
for improving HSE conditions. Chemical manufacturing companies
have experienced a dramatic increase of more stringent
regulations for chemicals well in advance of the mineral industry
and many leading chemical companies are accounting for HSE
factors in their technology portfolios. The regulatory landscape is
rapidly changing and becoming more complex, eventually impact-
ing the mining industry. Given the large amounts and types of
chemicals used in mineral processing, many of which are
hazardous, HSE aspects are of critical importance. This should drive
adoption of safer and more environmentally-friendly chemicals if
they already exist, or the development of new ones a major
challenge in itself. In either case, acceptance by industry is the
key. Some operations have already begun to make changes. Many
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
operations, however, prefer the current paradigm (focus on cost
rather than sustainability) and wait for regulations. Others may
be motivated to change, but may not have sufficient understanding
of the impact and benefits of particular chemicals on HSE.
Since the process of developing a solution can be long and
expensive, the industry would ideally develop a satisfactory
chemical solution in anticipation of a regulation. If no satisfactory
solution exists within the available pool of chemicals in the mar-
ket, then a new, greener chemical and the associated application
technology would have to be developed a very long and expen-
sive effort indeed.
Chemicals that have been used for a very long time and
thought to be safe might be subsequently judged as unsafe or toxic
because the accepted threshold exposure limits or concentrations
were lowered, either as a result of concern over worker safety
and health risks or over impact on the environment (through water
and air).
The development and use of greener chemicals and processes
are important, industry-wide issues. Their importance and, in some
cases, urgency combined with the desire to achieve step-change
technology leading to more sustainable solutions should drive
research efforts. However, an initiative with broader impact must
come from the mineral industry, since individual chemical compa-
nies are not likely to have sufficient resources and risk tolerance to
develop industry-wide chemical solutions. Currently chemical
companies are only able to develop greener reagents on a case-
by-case basis. Some examples of this include polymeric modifiers
as alternatives to NaSH (Bhambhani et al., 2014) and cyanide
(Nagaraj, 2000), and replacing xanthate with other less hazardous
collectors, for example dithiophosphinates (Guitard et al., 2015).
The impact and benefit of the greener chemicals or processes
can only be assessed by considering the overall system, not just
parts of it. This requires a completely different thinking and
approach in research (and practice) and to enable successful
technology transfer from the laboratory to the plant. It would also
require a very effective, strategic collaboration and coordination of
efforts.
Prudence requires the mineral industry to stay ahead of regula-
tions by making wise choices and investments, thereby avoiding
major penalties, closures or incurring substantial losses. Chemical
suppliers should educate the industry on these HSE aspects. There
is a great opportunity for all of us to tackle this big HSE challenge
and to realize substantial gains for both industry and society,
independent of boom/bust cycles. This would be both profitable
and sustainable.
3. Concluding remarks
The bursts of activity characterizing each historical period in
the evolution of flotation reagents have each brought the science
and technology to increasingly elevated plateaus where wrestling
with the next set of challenges must be taken up anew and with
zest. We are currently engaged in such a struggle. Declining ore
qualities continue to erode operational profitability, especially for
those clinging to a conventional and limited set of reagents and
practices. HSE and sustainability issues throw more light into pre-
viously dark corners that can no longer be ignored. High quality
water is less and less available, and this impacts both the engineer-
ing and chemical components of a separation strategy. Simply
throwing more high quality energy at the problem will not bring
us to the next technological level. A full frontal acknowledgment
of the high degree of complexity in mineral flotation processes
must be followed by earnest efforts to confront this complexity
and tame it sufficiently to progress to more efficient and sustain-
able operations.
11
Impediments to real progress in the use of chemicals to address
sustainability challenges in the mineral processing industry
include:
 Incomplete (and inadequate) schemes for evaluating proposed
chemical and associated process changes: for example, a full
accounting of all the pros and cons of adding a new reagent
across an entire operation requires more upstream and down-
stream information, and more sophisticated algorithms to
monetize the effects in order to put them all on a comparable
basis. This will lead to a better informed decision.
 Inadequate communication of efforts in introducing chemical
innovations, especially successes with safer chemicals, to
address HSE issues. Better communication, within the mineral
processing community and to the general public, is needed
and essential to improve the value and visibility of chemical
innovations with respect to economic, environmental and
societal sustainability.
 Slow (and low) rate of acceptance and adoption in the industry:
Efforts by suppliers to generate technological improvements
will become progressively mundane without acceptance and
adoption of clearly beneficial offerings.
 The current large knowledge gap between research and prac-
tice, coupled with a general decline in chemistry knowledge
in the field and a shaky knowledge transfer framework (from
research to practice) all conspire to bog down our progress.
Only some of these issues can be addressed by improving the
education system; however, thats a good place to start.
Knowledge, inventiveness and actualization are all required to
make effective and lasting improvements in mineral processing.
The attention required to be paid to health, safety and environ-
mental issues has grown exponentially in the last decades, judging
by the increasing community and regulatory pressures (e.g.
Europes REACH regulation and the UNs Globally Harmonized
System for Hazard Communication). Perspectives on these multi-
faceted issues can vary greatly depending on the measuring stick,
if any, being applied. This can lead to significant differences of
opinion about the need for and pace of action to be taken. To state
some obvious non sequiturs: (i) historical usage of a product does
not mean it is currently considered safe or green; (ii) a product
manufactured using green methods (e.g. according to the
12 Principles of Green Chemistry) does not necessarily mean the
product is green or safe when used; (iii) although a substance is
generally regarded as safe (GRAS) today, it may lose that status
in the future after more in depth inquiry.
The rapidly changing landscape has required more response
from operating companies and their suppliers. Many of these
responses are crafted on a case-by-case basis; a situation that
would benefit from a more concerted effort. HSE issues are inde-
pendent of the boom-and-bust cycles that the mineral processing
industry faces, suggesting that a sustained, co-operative effort
would be a sensible approach.
The leverage that can be obtained from the proper use of
flotation chemicals in existing or new equipment and separation
processes should be incorporated in the design of solutions to
address the current challenges faced by the mineral processing
industry. By leverage in this instance we mean the substantial
improvements in mineral separation operation effectiveness that
can be achieved at relatively low cost/performance ratios when
optimal flotation chemicals are employed. Benefits are achievable
in the following categories.
 Health, Safety and Environment (HSE)
 Processing low-grade poor-quality ores
 Water usage
12 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
 Enabling new equipment/processes
 Energy efficiency
 Processes other than flotation
Fundamental studies of the sub-processes that make up the
flotation process have yet to make a serious impact on the plant
operator whose froth has just collapsed for no apparent reason,
or the metallurgist who must decide how to select or alter the
reagent suite in order to best deal with the natural swings in ore
composition. Elegant physical models developed from principles
in fluid mechanics, surface & colloid chemistry and chemical
engineering have yet to reach the stage of completeness and
integration where even guidelines for emergent features of daily
interest to the plant operator, such as optimizing recovery and
grade, or dealing with ore variability, are reliable. One important
reason for this is the low level of chemistry taken into account.
Most models collapse the complex set of chemical factors and
interactions into one scalar parameter the contact angle. Clearly
there is a need to unfold this dimension of the problem via an
integration of chemical and physical aspects. By doing this there
is a high likelihood of having a positive impact on not only
understanding flotation better, but also giving better guidance to
plant operators.
One reason for importance of this better representation of
chemistry in flotation models is that fundamentally the mineral-
mineral separation that occurs in flotation is linked to differences
in surface chemistry of the various minerals, which in turn is
affected by the chemistry of the environment of those surfaces.
Chemical factor interactions can dominate the overall performance
in an operation.
Facing the complex nature of mineral flotation systems can
easily dampen the spirits of someone attempting to get to the
bottom (and top) of it all. We can try looking towards other disci-
plines that have made better progress in dealing with complexity
and hope to find a door to penetrate through the wall. There are
several general areas of scientific research that we might turn to
in this regard.
Several disciplines have sprung up around the ability to grapple
with big data; including proteomics, petroleomics and genomics.
The basis for these tour-de-force approaches is usually sophisti-
cated analytical methods to quantify the myriad species involved,
combined with software and computing power sufficient to make
sense of the large amount of data involved. As a first pass one
can gain insight at the dominant factors level via quantitative
structure-property relationships derived from methods such as
principle components analysis or the use of genetic algorithms.
Crafting a comparable approach in flotation would require sub-
stantially more detailed chemical information than we commonly
acquire in flotation systems. Two important kinds of data are rarely
gathered in flotation systems: (a) dynamics and interactions at
different levels of complexity (most information we have is for highly
idealized models), and (b) large-scale measurements of the whole
system and at least an empirical description of the whole system
which provides the context and the rationale for research at any level
of complexity. If we are to make headway, the required information
would, at a minimum, comprise the spatial (i.e. throughout various
zones in a flotation cell) and temporal (i.e. accounting for kinetic
effects) distributions of species concentrations (intended and
unintended) in the aqueous phase, at the various co-existing
mineral surfaces, and at liquid-gas interfaces.
Molecular biology and its applications in pharmacology have
evolved from a science and technology based on functional
descriptions to one based on molecular details. That level of detail
has only percolated up through to the organism level in a
few instances; however, the march in that direction continues
unabated. In order to begin following a similar path in flotation a
greater level of chemical detail must be brought into our picture.
The biological sciences began to study more than a cell, a protein,
or a strand of DNA at a time because they recognized emergent
properties; i.e. properties that are the result of a multiplicity of
interactions in a system. This does not suggest that chemistry
should at last throw off its physics-envy and move on to biology-
envy, but it does bring credibility to the proposal of a holistic
approach in tackling the sustainability challenges in mineral
processing.
Combinatorial and systems chemistry has been applied in many
fields (Li et al., 2013; Ludlow and Otto, 2008; Hunt and Otto, 2011),
especially in instances where a panoply of chemicals or materials
have to be generated and sifted through in order to find the needle
in the haystack that proves efficacious. Beyond the obvious exam-
ples in molecular biology and drug design (see any issue of the
journals Combinatorial Chemistry & High Throughput Screening or
Combinatorial Science), this approach has also been used in a vari-
ety of material science, catalysis, and surface science applications
(Rajan, 2008; Li et al., 2013). What currently prevents greater use
of this approach in flotation applications is the lack of high
throughput screening methods.
Flotation operations are dynamical systems, whose trajectory
through myriad possible states would be nearly impossible to
predict, no less to even catalog, due to the inherent sensitivity of
that path to initial conditions. However, a more faithful represen-
tation of the general character of flotation would likely come from
including nonlinear behaviors that are characteristic of such
systems. A key step to achieving such a model would be inclusion
of chemical and chemical kinetics effects in any primary descrip-
tion of the micro-processes.
Mineral processing must take its place in the league of disci-
plines that have embraced the complexity of natural systems in
their research.
Paradigm shifts occur when we challenge dogma and conven-
tion. Adopting a framework based on a holistic approach would
constitute a paradigm shift in mineral processing, as it was in the
biological sciences. A holistic approach does not reject studies of
parts or model systems. Indeed such studies are necessary in
parallel with the study of the whole system. Such an approach will
serve to bridge the widening gulf between research and practice. It
will also provide an exciting platform through which we may
inspire students to consider the links between science and practice.
A holistic approach also requires that a balanced set of skills be
applied to the problem if it is to succeed. The atrophy of chemical
knowledge in our field must be rectified.
The crisis in mineral processing education has been recognized
for a number of years (Cilliers et al., 2013). Efforts are being made
to correct this deficiency. Such efforts must include re-establishing
and advancing the lost chemistry knowledge so foundational to
understanding flotation and providing improved solutions in plant
operations.
Since sustainability goals and challenges are multi-faceted,
broad and complex, they require a confluence of expertise from
many disciplines in order to create a paradigm shift in our thinking
and approach in order to produce breakthrough innovations and to
effectively organize and integrate research effort and output. How
would such an effort be fueled? Academic research is supported by
a grant structure that inhibits radical idea generation, where peer
assessments have the perverse effect of inhibiting radical idea
generation by conditioning researchers to not stray too far from
the norm (van Deventer, 2014). A large collaborative effort and
increased funding do not guarantee that the right information is
generated to build the required knowledgebase. The research
efforts must be guided by and consistent with the challenges in
 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
the industry and society, and must have the right context and
relevance.
There are multiple possible paths that could be taken in the
emerging period (see Fig. 1). If we dont do anything, i.e. business
as usual, then we will be taking the downward trajectory a
travesty considering how far mineral processing has climbed in
the last 100 years. If we address the sustainability challenges on
an individual, case-by-case basis, then we will be taking a trajec-
tory that delivers modest progress and will soon reach another pla-
teau in the short-term, which may easily erode under the weight of
the challenges outlined. Again, this is not a satisfactory solution.
The most preferred trajectory would be a persistent, ascending
one, as seen in previous periods of strong innovation. This goal is
certainly within our capacity to actualize. There has been
phenomenal progress in chemistry both in design and manufac-
ture. There are many new concepts and tools on which we can
capitalize. However, in order to take this preferred path, we have
to overcome the impediments weve discussed.
Here are some steps that can be taken now to create a better
trajectory in the near future.
 Develop metrics to make more holistic economic assessments
so that one can better decide how to capitalize on all the lever-
age of chemicals, new design concepts & new manufacturing
strategies that are offered. And then adopt the new technologies
that make sense from a holistic data evaluation.
 Take a systems approach to confronting the complexity in
mineral processing operations. An example of this is to
integrate chemical effects into physical models.
 Prioritize and act on HSE and other challenges that are indepen-
dent of boom-and-bust cycles; i.e. improving sustainability
requires a sustained effort.
 Enhance strategic collaboration; for example, could professional
societies play a greater role?
 Enhance education for mineral processing scientists and
engineers, especially regarding aspects of chemistry.
The necessary cultural change must come from industry, even
in the face of short-term economic uncertainty that might be used
as a justification for postponing implementation of sustainable
solutions. Industry has to provide the motivation and initiative
for such a paradigm shift. In our opinion, many of the factors that
could motivate such cultural change are precariously close to crit-
ical thresholds and action by the mineral processing industry is
necessary to keep us on the right trajectory for the future.
Acknowledgments
The authors wish to acknowledge Prof. Barry Wills for inviting
and encouraging us to deliver the keynote address (on this topic)
in Flotation15. The authors thank the management of Cytec-
Solvay Group for their support and permission to publish this
paper.
References2
Aplan, F.F., Fuerstenau, D.W., 1962. Principles of Nonmetallic Mineral Flotation. In:
Froth Flotation 50th Anniversary Volume Edited by. Ch. 7.
Batterham, R.J., 2013. Sustainability in Minerals: Ever More Important.
Sustainability. CETEM, Rio de Janeiro, Brazil.
Bhambhani, T., Nagaraj, D.R., Gupta, P., Lawrence, A., Peart, M., Zarate, P., 2014.
Practical Aspects of Cu-Mo Separations and Alternatives to NaSH and Nokes
Reagent. IMPC XXVII, Santiago, Chile.
Bolton, E.K., 1928. Process Ore Concentration. CA281647.
2
It should be noted that there are some inconsistencies in the way references are
catalogued in the electronic media; for e.g. Gutzeit reference appears as both 1946
and 1947.
13
Cappuccitti, F.R., 1994. Current trends in the marketing of sulfide mineral collectors.
In: Mulukutla, P.S. (Ed.), Reagents for Better Metallurgy. Littleton, CO: SME., Ch. 8.
Chau, T.T., Bruckard, W.J., Koh, P.T.L., Nguyen, A.V., 2009. A review of factors that
affect contact angle and implications for flotation practice. Adv. Colloid Interf.
Sci. 150 (2), 106115.
Christmann, L.J., 1930. Flotation Agent. CA302752.
Christmann, L.J., Falconer, S.A., 1936. Oxide flotation. US2029156.
Christmann, L.J., Jayne, D.W., 1936. Flotation Reagent, US2043192.
Cilliers, J., Drinkwater, D., Heiskanen, K. (Eds.), 2013. Minerals Industry: Education
and Training, The Indian Institute of Mineral Engineers and International
Mineral Processing Congress (IMPC) Council.
Coghill, W.H., Clemmer, J.B., 1935. Soap flotation of the nonsulfides. Trans. AIME,
449465.
Douglass, W.A., 1927. Process of concentrating ores and minerals by flotation
US1652099.
Douglass, W.A., 1928a. Process of Concentrating Ores and Minerals by Flotation
US1674166A.
Douglass, W.A., 1928b. Process of concentrating ores and minerals by flotation
US1659396.
Falconer, S.A., 1960. Non-sulfide flotation with fatty acid and petroleum sulfonate
promoters. Trans AIME 217, 207215.
Falconer, S.A., Crawford, B.D., 1947. Froth flotation of some nonsulphide minerals of
strategic importance. Trans. AIME, 527542.
Franzidis, J.P., 2005. Integration of science and practice in mineral flotation. Min.
Mag., May: 1217
Fuerstenau, D.W., 1995. Where We Are in Flotation Chemistry After 70 Years of
Research. Proceedings of XIX I.M.P.C. Flotation Operating Practices &
Fundamentals Ch. 1, pp. 317.
Gaudin, A.M., 1957. Flotation. McGraw Hill.
Gaudin, A.M., Glover, H., Hansen, M.S., Orr, C.W., 1928. Flotation Fundamentals. I.
University of Utah Technical Papers 1, 78101.
Guitard, E., Bruce, T., Bruey, F., Nagaraj, D.R., Riccio, P., Thomas, W., 2015.
AEROPHINE 3418A PROMOTER The Canadian Collector 50 Years of
Improved Metallurgy in Various Applications. Canadian Mineral Processors,
Ottowa, Canada.
Gutzeit, G., 1946. Chelate-Forming Organic Compounds As Flotation Reagents. In:
Mining Technology, AIME, pp. 272286.
Harris, G.H., Fischback, B.C., 1954. Process for the manufacture of dialkyl
thionocarbamates. US2691635.
Hunt, R.A.R., Otto, S., 2011. Dynamic combinatorial libraries: new opportunities in
systems chemistry. Chem. Commun. 47 (3), 847858.
Keller, C.H., Lewis, C.P., 1925. Improvements in or relating to the concentration of
ores by froth-flotation. GB223860A.
King, R.P., 2001. Modeling and Simulation of Mineral Processing Systems.
Butterworth-Heinemann.
Klimpel, R.R., 1994. A discussion of traditional and new reagent chemistries for the
flotation of sulfide minerals. In: Mulukutla, P.S. (Ed.), Reagents for Better
Metallurgy. Littleton, CO: SME., pp. 5966, Ch. 7.
Li, J., Nowak, P., Otto, S., 2013. Dynamic combinatorial libraries: from exploring
molecular recognition to systems chemistry. J. Am. Chem. Soc. 135 (25), 92229239.
Ludlow, R.F., Otto, S., 2008. Systems chemistry. Chem. Soc. Rev. 37 (1), 101108.
Malhotra, D., 1994. Reagents in the mining industry: commodities or specialty
chemicals? In: Mulukutla, P.S. (Ed.), Reagents for Better Metallurgy. Littleton,
CO: SME, pp. 7580, Ch. 9.
Moyer, S.P., 1958. Flotation: the art of utilizing modifying agents. Mining Mag. 98,
916.
Nagaraj, D.R., 1987. The chemistry and applications of chelating or complexing
agents in mineral separations. In: Somasundaran, P., MoudgilReagents, B.M.
(Eds.), in Mineral Technology, Ch. 9, pp. 257334.
Nagaraj, D.R., 1994. A Critical Assessment of Flotation Agents. Reagents for Better
Metallurgy. Littleton, CO: SME, pp. 8190, Ch. 10.
Nagaraj, D.R., 1997. Development of new flotation chemicals. Trans. Indian Inst.
Met. 50 (5), 355363.
Nagaraj, D.R., 2000. New synthetic polymeric depressants for sulfide and non-
sulfide minerals. In: Proceedings of the XXI International Mineral Processing
Congress, Rome, Italy: Elsevier. Developments in Mineral Processing Series 13:
C8b-1C8b-8.
Nagaraj, D.R., 2005. Reagent selection and optimizationthe case for a holistic
approach. Miner. Eng. 18 (2), 151158.
Nagaraj, D.R., 2008. New Approach to Reagent Development and Applications in the
Processing of Base and Precious Metals Ores. XXIV International Mineral
Processing Congress, Beijing, pp. 15031512.
Nagaraj, D.R., 2010. Chemical Aspects of Sustainable Mineral Processing and a
Framework for Research and Technology Transfer. XXV International Mineral
Processing Congress, Brisbane, pp. 91100.
Nagaraj, D.R., Avotins, P.V., 1988. Development of new sulfide and precious metals
collectors. In: Proceedings of the II International Minerals Processing
Symposium, Eylul University, Izmir, Turkey, Izmir, Turkey, p. 399.
Nagaraj, D.R., Basilio, C., Yoon, R.H., 1989. The chemistry and structure-activity
relationships for new sulphide collectors. In: Rao, G.S.D.R. (Ed.), Processing of
Complex Ores, Amsterdam, Pergamon, pp. 157166.
Nagaraj, D.R., Bruey, F., 2003. Reagent Optimization in Base Metal Sulfide Flotation
Pitfalls of Standard Practice. Flotation and Flocculation from fundamentals
to applications. In: Proceedings of the Strategic Conference and Workshop, Kona
Hawaii: University of South Australia, Ian Wark Research Institute, Adelaide,
Australia, p. 257.
14 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214
Nagaraj, D.R., Farinato, R.S., 2014. Major Innovations in the Evolution of Flotation
Reagents. In: Anderson, C.G., Dunne, R.C., Uhrie, J.L. (Eds.), Mineral Processing
and Extractive Metallurgy: 100 Years of Innovation, SME, Englewood, CO, pp.
159175.
Nagaraj, D.R., Lewellyn, M.E., Wang, S.S., Mingione, P.A., Scanlon, M.J., 1988. New
sulfide and precious metals collectors: For acid, neutral and mildly alkaline
circuits. In: XVl lnternational Mineral Processing Congress, Sweden: Elsevier.
Developments in Minerals Processing", vol. 10B, pp. 12211232.
Nagaraj, D.R., Ravishankar, S.A., 2007. Flotation reagentsa critical overview from
an industry perspective. In: Fuerstenau, M.C., Jameson, G.J., Yoon, R.-H. (Eds.),
Froth Flotation: A Century of Innovation, pp. 375424.
Nguyen, A., Schulze, H.J., 2003. Colloidal Science of Flotation. Taylor & Francis.
Perkins, C.L., 1917. US1240598, US1240597, CA180528, CA180529.
Perkins, C.L., 1919. US1302966, US1322816, US1394639, US1364304, US1364305,
US1364306, US1364858.
Perkins, C.L., Sayre, R.E., 1921. US1364307, US1364308, US1364859.
Ppperle, J., 1941. Verfahren zur Schwimmaufbereitung von Erzen (Method for
flotation of ores) DE700735.
Rajan, K., 2008. Combinatorial materials sciences: experimental strategies for
accelerated knowledge discovery. Annu. Rev. Mater. Res. 38 (1), 299322.
Ralston, J., 2014. 21st Century Challenges in the Chemistry of Mineral Processing. G
D Delprat Distinguished Lecture Series. AusIMM Metallurgical Society.
Ralston, O.C., 1938. Flotation and Agglomerate Concentration of Nonmetallic
Minerals. Bureau Of Mines Bureau Of Mines Report of Investigations 1938
RI 3397.
Rogers, J., Sutherland, K.L., Wark, E.E., Wark, I.W., 1946. Principles of Flotation-
Paraffin Chain Salts as Flotation Reagents. In Mining Technology. Edited by:
AIME. X.
Sayre, R.E., 1924. Concentration of Ores. US1497699A.
Sheridan, G.E., Griswold, G.G.J., 1922a. Concentration of ores by flotation
US1421585.
Sheridan, G.E., Griswold, G.G.J., 1922b. Concentration of ores US1427235.
Sutherland, K.L., Wark, I.W., 1955. Principles of Flotation, second ed. Australasian
Inst. Mining & Metallurgy.
Taggart, A.F., 1951. Elements of Ore Dressing. Wiley.
Taggart, A.F., Taylor, T.C., Ince, C.R., 1930. Experiments with flotation reagents.
Trans. AIME 87, 285368.
Thom, C., 1962. Standard flotation separations. In: Fuerstenau, D.W. (Ed.), Froth
Flotation 50th Anniversary Volume. AIME, New York.
van Deventer, J., 2014. A Crystal Ball Vision of Innovation in Mineral Processing.
IMPC 2014, 27th International Mineral Processing Congress. Santiago, Chile.
Wang, S.S.-N., Nagaraj, D.R., 1989. Novel collectors and processes for making and
using same EP 311759.
Whitworth, F.T., 1926. Art of concentration of mineral ores by flotation. US1593232.
Wystrach, V.P., Peters, G.A., 1964. Salts of 2-cyanoethyl phosphinodithioic acids
US3138605.