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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 reagents have thus played a critical role in mineral resource recov-
ery; this criticality stems from the fundamental fact that successful
The evolution of flotation chemical technology over the past flotation necessarily depends on creating differences in the surface
100 years is reflected in the growth in diversity and tonnage of chemistries of the minerals being separated.
chemicals used, which has mirrored features of the ores treated. Nagaraj and Farinato (2014) provided an overview of the flota-
Innovation in the development and use of chemicals has gone tion reagent innovations of industrial (practical) relevance over
hand-in-hand with innovation in the development of flotation the past 100 years. They observed that these innovations were
technology. The introduction of chemicals made the flotation pro- greatly influenced by the general zeitgeist and paradigms existing
cess practical and widely applicable; conversely, developments in in the broader field of chemistry at any one time. They also identi-
flotation technology made possible the use of a wider variety of fied five distinct periods of innovations and developments (see
chemicals. The resulting positive feedback of this relationship led Table 1), the fifth (emerging) period is one where emphasis is
to the development of improved flotation operations. Flotation 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
q
This article was written as a keynote address (Flotation 15, Cape Town) to 100 years and challenges that exist going forward, both lingering
commemorate the centenary of Cytec (formerly American Cyanamid) mining and emerging. An extensive survey of patents, journal articles, con-
chemicals franchise
Corresponding author. ference papers, and plant practice was made in order to identify
E-mail addresses: d.r.nagaraj@solvay.com (D.R. Nagaraj), raymond.farinato@
and emphasize innovations that have made a substantial impact
solvay.com (R.S. Farinato). 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 3

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 2.1. First period (18601 1920)
paper, which is a discussion of the challenges and possible ways
to address those sustainability challenges that face us in the fifth In the first period (18601920), the innovations centered on
(emerging) period. the need to improve processes through engineering, reduce con-
Innovations in flotation chemicals and chemistry can be viewed sumption of oil (typically fatty oils, see Table 2 below) that was
in terms of concepts, products and/or application modalities. These used as the buoyant medium, and to improve selectivity of separa-
forms of innovation, individually or together, have led to: (i) a rad- tion through the use of chemicals (modifiers) that were readily
ical change in the way the flotation process is practiced; (ii) an available. Order of magnitude reductions in reagent consumption
expansion of reagent choice, processable ore types, and tonnage due to the introduction of air and improved flotation chemicals is
treated; (iii) a gradual improvement in productivity and efficiency; illustrated in Fig. 2.
and (iv) reduction in variability of plant performance. Over the dec- With the reduction in oil consumption, inherent differences in
ades, the first two have received reasonable attention and recogni- the frothing and collecting powers of various oils were noted,
tion in the industry and in the published literature; however, the which led to improvements in flotation efficiency. The next set of
last two have often been either unrecognized or underemphasized, innovations was in terms of selective or differential flotation with
although they are important, contribute significantly to value cre- the use of inorganic compounds (which eventually were described
ation in the plant and form the basis for large innovations. 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-
2. A chronology of major innovations manganate, sodium phosphates, persulfate, sodium silicate,
sodium hydroxide, other inorganic soluble salts. Many of the
A highly compressed schematic of the historical progress of modifiers discovered in this period are still used today. Such efforts
innovations that had a significant impact on practice is given in led to the discovery that alkaline circuits could provide greater per-
Fig. 1. The details are discussed below. At a gross level we can rec- formance leverage in terms of lower overall reagent consumption
ognize four distinct periods of development plus an emerging fifth and differential flotation which were not possible in the previously
period. Above each numbered period we list key concepts impor- popular (sulfuric) acid circuits. Indeed, by the end of the 1920s
tant during that period, and below each numbered period we list most of mineral flotation was conducted in alkaline circuits.
some of the major drivers for radical change. There were certainly Towards the end of this first period several investigators,
numerous innovations between periods, but they were compara- notably Perkins, Sayre and co-workers (Perkins, 1917, 1919;
tively small and gradual. We believe that we are currently on a pla-
teau and transitioning into what we call an emerging period, which 1
Although the concept of flotation can be traced back to 1860, froth flotation as
is poised for another radical leap in progress. This will be discussed practiced today in the mineral industry began in 1905 with the deliberate
in greater detail in the final section. 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- 2.2. Second period (19211950)
soluble, small organic compounds (see examples in Table 2), which
included some chelating agents, were effective collectors and could The innovation noted above marked the beginning of a long
replace the large amounts of fatty oils and soaps (see Fig. 2) that string of innovations in the subsequent (second) period
were in widespread use. (19211950) in the development of new and highly effective
D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214 5

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

Table 3
Collectors based on short-chain organic molecules.

Xanthates Dialkyl Trithiocarbonates Dithiocarbamates, Na salt Mercaptobenzothiazole Alkyl Mercaptans


S S S N R-SH
R S- Na+
R R R'
O S- Na+ S S N S- Na+ S
R'

Dialkyl xanthogen formates Dialkyl dithiophosphates Dialkyl thionocarbamates Dicresyl dithiophosphoric acid Na alkyl trithiocarbonates
S O R S S S
S
R R' O P S- Na+ R R' O P SH R
O S O NH O S S- Na+
O O
R'
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- (Ppperle, 1941) and chelate forming reagents (Gutzeit, 1946).
tions and schemes to achieve selective separations while employing Commercialization of some of these selective collectors occurred
rather non-selective collectors such as soaps and amines. The impor- only in the 1980s due to a variety of reasons related to economics,
tant work at the U.S. Bureau of Mines and other institutions importance of the need and lack of practical manufacturing
(Gaudin et al., 1928; Coghill and Clemmer, 1935; Ralston, 1938) processes.
beginning in the late 20s in the flotation separation of oxide, car- Although several companies were active in reagent develop-
bonate and phosphate minerals from quartz and silicate gangues ment in the period 19211950, American Cyanamid was the most
by means of anionic collectors such as fatty acids is noteworthy. prolific in this period: over 180 patents covering both sulfide and
Many developments occurred in the1930s and 1940s in reagents non-sulfide flotation (see Fig. 3). If one considers only those
(see Table 5) and schemes for the selective separations in a wide patents that resulted in plant usage, then the ranking is even more
variety of non-sulfide systems including energy minerals. These heavily skewed in favor of Cyanamid. Much of the flotation reagent
reagents and schemes are still used today. A general description work that came out of American Cyanamid from the mid-1920s
can be found in Taggart (1951), Falconer and Crawford (1947), and beyond was likely accelerated by the expansion of chemicals
Rogers et al. (1946), Falconer (1960), Thom (1962). The majority derived from building blocks, and technologies that were brought
of collectors used for non-sulfide flotation were found to be rather under the same roof during periods of business diversification.
non-selective, thus requiring ingenuity in selecting appropriate While some flotation reagents patented early in the game derived
modifiers and conditions. This is largely true even today. The rea- from adjacent areas of research, these successes spawned more
sons for this can be found in Aplan and Fuerstenau, 1962; and in deliberate and specific for-purpose efforts.
Nagaraj and Ravishankar, 2007. However, research during this per- A perusal of the literature reveals that almost all of the reagent
iod lead to the identification of several new chemical classes with development occurred in companies, well before a fundamental
benefits as collectors for non-sulfide ores, including hydroxamates 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 at low cost, if their efficiency were proved to be outstanding.
60 Indeed Gutzeits paper appeared to anticipate the arrival of the
40 third period (19512000) of Rational, Targeted Design for
20 collectors and modifiers.
0 During this period innovations in flotation reagents were of
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
Fig. 3. Flotation reagent patent statistics: 19211950.
of this led to rational targeted design, based on specific chemical
interactions between reagents and minerals. This kind of inquiry
Indeed to a large extent this is still the case. The seminal work of applied equally to research on macromolecules, especially syn-
Taggart and his co-workers in the 1920s (Taggart et al., 1930) laid thetic polymers, which were a burgeoning field during this period.
the foundation for identifying and establishing chemical functional Polymers offered unique features and advantages, including
group features of collectors, depressants, and frothing agents. This improved HSE profiles. There was growing recognition of the
work coupled with the fundamental studies of Gaudin (1957), power and efficiency of polymers, and the great flexibility they
Wark, Sutherland (Sutherland and Wark, 1955), and others was offered for tailored design, especially as this allows use of a wider
an important conceptual advance that brought the much needed array of functional groups.
scientific understanding. Taggart et al. (1930) noted the following: The rational targeted design approach was founded on donor-
Soluble organic collecting agents function by reacting chemically acceptor concepts that arose from the original work of Lewis in
with the surface substance of the mineral particle to be collected, the early 1920s and subsequent refinements over the next several
thereby forming an organic reaction product that is insoluble in decades. These concepts were also applied to mineral systems dur-
water in the concentration present, and adheres at the reacting ing the period 19701985 (details found in Nagaraj, 1987). In that
surface and thereby changes that surface, for all practical purposes, paradigm, reactions between acids (electron acceptors minerals)
to an organic surface with water-repelling properties. and bases (electron donors flotation reagents) are viewed in
terms of a redistribution of valence electrons.
This surface chemical reaction theory is valid for chemisorb- A greater degree of predictive power was realized via the donor-
ing reagents, e.g. the dominant collectors in sulfide flotation, and acceptor paradigm, making it now part of the conventional frame-
the majority of modifiers (simple and polymeric) interacting with work by which we understand and develop reagents that bind
minerals. selectively to either metal ions in solution or mineral surfaces in
suspension. While this scheme was originally applied to binary
2.3. Third period (19512000) interactions between reagent and target mineral, it has also been
extended to rationalizing behavior in more complex mixtures
The structural features required for reagents to impart selectiv- where competitive adsorption is the central feature. The
ity in separation were well articulated by Gutzeit in his influential 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 complexity and possibilities. In addition to changes in functional
innovations rested squarely on the conceptual innovation that group, factors such as molecular weight, degree of substitution,
emphasized the role of the functional group rather than attributes location and distribution of functional groups, and conformation
like charge (ionic, neutral), solubility, hydrolysable, oxidizable, in solution and at the interface become critical.
etc. Some important examples of new classes of collectors and Many innovations occurred in the development of efficient and
modifiers developed in this period using the donor-acceptor model economical manufacturing processes for certain flotation reagents
are given in Table 6 (detailed description can be found in Nagaraj and these had a profound impact in the industry by catalyzing the
and Avotins, 1988; Nagaraj et al., 1988, 1989; Nagaraj, 1997, 2000). much needed widespread applications of the specific reagents in
Most of these reagents are still in commercial use today. The many innovative ways. Three examples can be cited: (a) a practical
1980s was a period of intense activity in flotation reagent develop- process for dialkyl thionocarbamate (Douglass, 1928a) in 1954 by
ment, much like the intense periods of developments seen in the Dow (Harris and Fischback, 1954), (b) manufacture of dithiophos-
1920s and 1940s. Significant efforts by R&D groups in chemical phinate by American Cyanamid using a novel process based on the
companies during the 1980s were focused on developing unique phosphine chemistry (Wystrach and Peters, 1964), and (c) a
reagent-mineral characterization data and extensive structure- practical process for making alkyl hydroxamates, which facilitated
property-performance relationships which led to subsequent their widespread plant use (Wang and Nagaraj, 1989).
numerous innovations. A review of literature shows that many In terms of simple modifiers, the majority of developments had
companies were active during this period, especially American occurred in the second period (prior to 1951). A major innovation
Cyanamid (see patent statistics in Fig. 4). As previously observed in the third period, however, was the successful application of the
in the second period, if one considers only those patents that donor-acceptor concepts in the development of water-soluble,
resulted in plant usage, then the ranking is even more heavily synthetic polymeric modifiers with targeted molecular architec-
skewed in favor of Cyanamid. ture and mineral-specific functional groups capable of targeting
As in the Discovery-Expansion period, the majority of reagent specific sites on minerals (via complexation or chelation) (see
innovations in the rational targeted design period have been in Table 6). Although such a task appears rather straightforward in
the area of sulfide flotation. The innovative concept was that in principle, there was a truly significant challenge in developing
systems where the driving force for adsorption of collectors, robust, practical and economical manufacturing routes to produce
organic modifiers or polymers on minerals is based on chemical such polymers with consistent structural features.
bond formation (i.e. chemisorption), the reagent properties
(strength and selectivity) could be designed by exploiting and 2.4. Fourth period (2000 present)
manipulating the functional group (type, position, and number of
donor atoms) and the hydrophobic portion of the molecule (type, Paradoxically, the innovations and successes in the rational tar-
length and branching). Donor atom properties could additionally geted design of flotation reagents derived from the enthusiasm and
be modified by introducing electron withdrawing/donating groups intense R&D activity in the 1980s, created a crisis for the chemical
and by manipulating substituents in the molecules, thereby creat- manufacturers by 1990 resulting from a lack of application under-
ing the optimal complex-forming functional groups. While this standing and a rational scheme for selecting and optimizing
degree of manipulating chemical structure still produces innova- reagents from this new arsenal of chemicals. This paved the way
tions in reagents operating by chemical bond formation, collectors for intense activity to develop new methodologies and approaches
operating by electrostatic adsorption (e.g. amines, sulfonates, for reagent selection and optimization (the fourth period). The
sulfates, and to some extent fatty acids) leave little room for crisis arose from a lack of large scale implementation of new tech-
improving their molecular composition. Application of donor- nology in the industry. There were many important factors (some
acceptor principles can also be used to make the choice of simple impacting the whole industry and others impacting chemical
inorganic, organic and polymeric modifiers more rational. usage) driving this situation, which resulted in a recognizable
Since chemical interactions have the highest adsorption ener- trend that exists even today. These factors were well articulated
gies, changes in structure of the reagent molecule can potentially in several publications in an SME symposium in 1994
result in large changes in the strength of adsorption, selectivity, (Cappuccitti, 1994; Klimpel, 1994; Malhotra, 1994; Nagaraj,
interfacial properties, and flotation response. Structure-property 1994), and discussed in greater detail more recently (Nagaraj and
relationships take on added dimensions in polymers in terms of 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
Flotaon Reagent Patents (1951 2000)
160 on personal experience, with no accepted standard of practice in
140 place (Nagaraj and Bruey, 2003; Nagaraj, 2005). Such an approach
120 was very costly because the failure rate was high in implementing
# patents

new chemistries. Even when the best reagent is developed for an


100
unmet need in the industry, it is deemed a failure if we fail to apply
80
it properly on the large scale. This issue becomes acute when one
60 considers the high overall cost ($510 million from concept to
40 commercialization) and the long time required (510 years) to
20 develop and implement new reagents and technology. Compound-
0 ing this problem is the exponential growth in environmental
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,
Fig. 4. Flotation reagent patent statistics for the period 19512000. but it creates a challenge for reagent selection and optimization.
D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214 9

The critical innovation that emerged from this situation was the Current challenges in the mineral processing industry are well
development, beginning in the mid-1990s, of a holistic approach, expressed in the literature (for example, see Batterham, 2013;
called Flotation Matrix 100TM to reagent selection and optimization Ralston, 2014; van Deventer, 2014): processing low-grade and
(Nagaraj 2005, 2008, 2010; Franzidis, 2005). Such an approach con- poor-quality ores with complex mineralogy; maximizing resource
fronts and deals with the complexity of ore flotation systems, utilization; improving water usage efficiency and water resource
rather than circumvent it. This was facilitated by the development management; better energy efficiency; waste reduction and
of rule-based expert system reagent selection software employing remediation; complying with and exceeding increasingly restric-
a database of structure-performance relationships, the use of quan- tive health, safety and environment (HSE) regulations; the need
titative mineralogy, and the use of advanced statistical tools and for more environmentally benign chemicals; and minimizing over-
techniques for dealing with variability and complexity, both at all environmental impact and ensuring social license to operate.
lab scale and plant scale. On the whole, the holistic approach incor- These challenges are very broad, complex, and independent of
porated the ideas of best practices, plant needs and expansion of the industry boom and bust cycles. They are linked to the three
the knowledgebase, with the ultimate goal of developing a robust pillars of sustainability societal, environmental, and economic
and optimized tool that is suitable for dynamic and variable plant which rely heavily on technological (rather than traditional
systems, and which has the highest probability of successful economy-of-scale) solutions, generally engineering-based and/
chemical implementation to capture a greater percentage of the or chemistry-based. We focus on the latter because they epitomize
otherwise lost value minerals. a kind of disparity (great commercial importance vs. lack of appli-
The importance of analyzing, modeling, and controlling the cation knowledge and industry acceptance) which must be fixed in
froth zone, which is central to flotation and strongly influenced order to address sustainability challenges in a meaningful way.
by chemistry, was increasingly recognized during this period; Chemistry-based solutions will undoubtedly play a pivotal role
however, a detailed picture of the dynamic physical micro- in addressing most of these challenges. They provide optimal
processes involved in the transport of particles of different metallurgical performance on a day-to-day process level (routine
wettabilities, shapes and sizes through and by a network of liquid variability in operational factors, comminution and mineralogy).
lamellae is still unavailable. While there has been appreciation by Given all the physical-mechanical and operational constraints, the
some researchers of the various contributions to the physical state plant operators rely heavily on chemicals to optimize performance.
of the froth zone, this level of understanding is not taken into
account by the wider industrial community. There is a common i. They allow a plant to process different ore types, especially
belief that frother chemicals act independently of other functional when faced with low-grade, poor quality ores. Only chemi-
chemicals (e.g. collectors and modifiers), minerals, and physical- cals can address this predicament. A different suite of
mechanical factors. This completely ignores factor interactions reagents might be necessary; however, that sort of change
which are quite often very significant. is more manageable than redesigning the flow sheet and/
There is still a disproportionate focus on behavior in 2-phase or installing new equipment, thereby incurring large capital
systems (i.e. aqueous phase containing a frother and air; without expenditures.
minerals), which has no direct relevance to practical flotation. ii. Chemicals provide excellent flexibility to the operators,
Similarly, understanding the dynamics and complexity of water especially if the flotation strategy must change; e.g. bulk
chemistry, and modeling these features remains a great challenge. flotation followed by separation vs. sequential flotation.
This is a subject that is certainly ripe for critical innovations. We iii. They provide a means to devise the majority of solutions to
can learn from ongoing work in the area of predicting scale forma- HSE issues.
tion in brines found in petroleum production as an example of how
taking water chemistry into account can lead to better prediction. Compared to physical-mechanical methods, chemical solutions
While a host of sophisticated techniques to characterize ores and to mineral separation problems are much easier to implement and
study the mineral-solution interface and interaction of reagents control. Many problems can be solved more efficiently and eco-
with mineral surfaces are available, techniques that can provide nomically via chemistry (e.g. selectivity in separation, processing
in situ real-time information are not available. This is another poor-quality ores, processing with low-quality waters, improving
roadblock to progress. 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
2.5. Fifth period (emerging) processing strategies. Independent of whether these solutions
require development of new or implementation of existing
Although plant metallurgists have begun to realize the potential technologies, successfully addressing the challenges will require
benefits of a holistic approach, and some progress has been made robust application knowledge and technology acceptance by the
in the past ten years, adoption of this methodology has been rather mineral processing industry. Unfortunately, currently we have
slow. Attempts to implement this approach broadly have revealed problems with both.
persistent and large gaps in the knowledgebase necessary for Our application knowledgebase and research framework from
implementation. This is true both in the research and industrial which such knowledge is generated are both outdated and
communities. This situation has been brought into the spotlight inadequate. Many of the classical problems in flotation that were
by the magnitude of the sustainability challenges facing the recognized in the first half-century of flotationfor example, the
mineral processing industry. It demands a new paradigm to effect of water chemistry, the adverse effect of altered silicates
reshape our research and technology transfer efforts to meet these and slimes, recovery of coarse and fine particles, difficult mineral
challenges. Business as usual would not leave us with a sustainable separations, and numerous others have remained largely
future. A survey of the literature and conferences (e.g. recent IMPC unsolved.
and SME keynote addresses) confirms the need for a change in A review of scientific journals and conference proceeding over
paradigm and the high level of attention being given to the the past several decades may lead one to conclude that there has
topic of grand challenges and sustainability. We see this as the been little innovation and that progress has been incremental.
emergence of a new era in flotation reagent and flotation However, we would arrive at a different conclusion if we consider
chemistry the fifth period. 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 (e.g. contact angle), where it is convoluted with a panoply of other
important reason for this conflicting perspective is that industrial non-chemical factors. Other such model parameters that dont
research and development, and plant practices are not widely account for the natural distribution of these quantities, or the
published, advertised or shared. The research community is mostly manner in which they change in response to changes in the chem-
in the dark on such progress. Coupled with this is the significant ical environment that exists in a flotation cell include the single
erosion in comprehensive chemistry knowledge across the aca- mineral zeta potential or surface potential (or electrode potential
demic and industrial communities involved in flotation, including in the case of sulfides), Hamaker coefficient, hydrophobic force
subjects such as: reagent chemistry, chemical factor interactions decay length, etc. This reductionist practice is the equivalent of
in the pulp and froth zones, the role of aquatic chemistry, and characterizing a population of people by their average shoe size!
reagent-mineral interactions in practical systems (i.e. of represen- While there has been good progress in cell design based on a
tative mineralogical complexity). Reasons for this have been refined understanding of physico-mechanical fundamentals, there
discussed in Nagaraj, 2010. This has resulted in a very simplistic, has been significantly less useful fundamental knowledge transfer
unbalanced, misguided and inaccurate view of the subject; often into the practice of reagent optimization. Flotation models might
leaving us with an assortment of myths and misconceptions to sort be improved by invoking richer parameterization of the contact
out. All told, there are many missed opportunities to advance the angle, e.g. accounting for contact angle distributions, taking into
field, especially since most of the commercially relevant innovations account spatial heterogeneity and/or dynamical aspects in the
in flotation reagents and their application have come from indus- bubble-particle contact process (Chau et al., 2009). However, this
trial research. The situation has not substantially changed since still buries chemical factors amongst a host of physical factors,
Fuerstenaus observation twenty years ago (Fuerstenau, 1995): and it neglects kinetics aspects of the chemically evolving system
(e.g. mineral dissolution, hydrolysis, surface oxidation, and reagent
The flotation process did not come into being as the result of an reactions). In addition to the difficulty of accounting conceptually
intensive fundamental research effort but, in a manner similar to for more realistic chemistry, we are faced with the even greater
the development of so much of the other technology used in the challenge of determining quantitative parameter estimates that
processing of raw materials, it was developed over the years characterize this chemical complexity. In situ methods for analyz-
through a great deal of empirical and intuitive work on complex ing the mineral-solution interface during a bubble-particle colli-
ores. As a result, most of the basic research in this field has been sion in a turbulent fluid are not currently available. However,
concerned with the problem of explaining why existing processes this fact should not deter efforts in the research community to
work so well. We are now at the stage where any further substan- begin to develop and incorporate a more robust set of chemical fac-
tial extension of the flotation process will demand even more tors into flotation models to make them meaningful and useful.
profound understanding of the fundamental principles on which This should be a new goal. Other fields with similar chemical com-
it is based. Current knowledge of flotation fundamentals is still plexity have made considerable progress. It must be recognized,
far from the stage where processes can be designed, optimized, however, that developing these more complete models would be
and controlled from first principles. Because of the complexity of fruitful only when operations are motivated to make necessary
the interactions between minerals and reagents, basic research in changes based on the insights gained.
flotation has involved primarily working with simplified and some- Recently there has been a great surge in the use of computa-
what idealized experimental systems. tional chemistry modeling to understand reagent-mineral interac-
tions, driven perhaps by factors such as glamor, ease of study (no
Nagaraj (2010) expanded on this and provided a detailed cri- need for lab infrastructure) and publication, and perceived scien-
tique of state of research and technology transfer, argued for an tific merit. Unfortunately, this is going backward, as the myriad
overhaul of current research paradigm, and suggested a new model assumptions necessary to facilitate computation make the
framework based on a systems approach (holistic approach). This systems far more idealized than even the single mineral systems,
was summed up as: Our research effort over the decades has sus- which fail to capture the complexity of the practical systems. These
tained itself, but often it has little to do with sustainability in mineral studies also suffer from incomplete inclusion of parameters
processing. Research efforts must be both more coordinated and characterizing the mineral environment, a focus on inappropriate
integrated so that the research and plant work are designed appro- questions, and unrealistic expectations and promises. None of
priately to fill the Grand Canyon of knowledge gaps. these issues are insurmountable for the computational chemist;
When naturally complex problems are modeled as idealized and we believe that great strides may be made by using modeling
systems (i.e. a reductionist approach), too often the results are sim- tools more wisely.
plistic and of limited utility. Fragmentary and uncoordinated Among the sustainability challenges listed earlier, HSE and
research efforts compound the issue. Attempts to model the kind Regulatory aspects loom large, accentuated by the ambiguity and
of complex systems found in flotation operations have been rea- tepidity with which we acknowledge and approach this elephant
sonably successful at the engineering level (see for example King, in the room. More restrictive regulations are inevitable because
2001; Nguyen and Schulze, 2003); however, these models do not of increasing expectations from society and a genuine concern
yet incorporate information on mineral surface chemistry and the for improving HSE conditions. Chemical manufacturing companies
interplay between multiple dissolved and dispersed components in a have experienced a dramatic increase of more stringent
flotation pulp and in the froth phase. Integrating such physical- regulations for chemicals well in advance of the mineral industry
chemical details into process models would constitute a significant and many leading chemical companies are accounting for HSE
contribution and a major innovation, providing an antidote to the factors in their technology portfolios. The regulatory landscape is
perception that chemical effects play only a minor role. rapidly changing and becoming more complex, eventually impact-
Modeling flotation has been a lofty goal for many decades. ing the mining industry. Given the large amounts and types of
While significant advances have been made in modeling chemicals used in mineral processing, many of which are
physical-mechanical aspects of flotation, the absence of chemical hazardous, HSE aspects are of critical importance. This should drive
aspects is a particularly glaring omission given that successful adoption of safer and more environmentally-friendly chemicals if
flotation is leveraged through interfacial chemistry, which in turn they already exist, or the development of new ones a major
is affected by mineral/solution chemistry. Almost all flotation mod- challenge in itself. In either case, acceptance by industry is the
els either ignore chemistry or collapse it all into a single number key. Some operations have already begun to make changes. Many
D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214 11

operations, however, prefer the current paradigm (focus on cost Impediments to real progress in the use of chemicals to address
rather than sustainability) and wait for regulations. Others may sustainability challenges in the mineral processing industry
be motivated to change, but may not have sufficient understanding include:
of the impact and benefits of particular chemicals on HSE.
Since the process of developing a solution can be long and  Incomplete (and inadequate) schemes for evaluating proposed
expensive, the industry would ideally develop a satisfactory chemical and associated process changes: for example, a full
chemical solution in anticipation of a regulation. If no satisfactory accounting of all the pros and cons of adding a new reagent
solution exists within the available pool of chemicals in the mar- across an entire operation requires more upstream and down-
ket, then a new, greener chemical and the associated application stream information, and more sophisticated algorithms to
technology would have to be developed a very long and expen- monetize the effects in order to put them all on a comparable
sive effort indeed. basis. This will lead to a better informed decision.
Chemicals that have been used for a very long time and  Inadequate communication of efforts in introducing chemical
thought to be safe might be subsequently judged as unsafe or toxic innovations, especially successes with safer chemicals, to
because the accepted threshold exposure limits or concentrations address HSE issues. Better communication, within the mineral
were lowered, either as a result of concern over worker safety processing community and to the general public, is needed
and health risks or over impact on the environment (through water and essential to improve the value and visibility of chemical
and air). innovations with respect to economic, environmental and
The development and use of greener chemicals and processes societal sustainability.
are important, industry-wide issues. Their importance and, in some  Slow (and low) rate of acceptance and adoption in the industry:
cases, urgency combined with the desire to achieve step-change Efforts by suppliers to generate technological improvements
technology leading to more sustainable solutions should drive will become progressively mundane without acceptance and
research efforts. However, an initiative with broader impact must adoption of clearly beneficial offerings.
come from the mineral industry, since individual chemical compa-  The current large knowledge gap between research and prac-
nies are not likely to have sufficient resources and risk tolerance to tice, coupled with a general decline in chemistry knowledge
develop industry-wide chemical solutions. Currently chemical in the field and a shaky knowledge transfer framework (from
companies are only able to develop greener reagents on a case- research to practice) all conspire to bog down our progress.
by-case basis. Some examples of this include polymeric modifiers Only some of these issues can be addressed by improving the
as alternatives to NaSH (Bhambhani et al., 2014) and cyanide education system; however, thats a good place to start.
(Nagaraj, 2000), and replacing xanthate with other less hazardous Knowledge, inventiveness and actualization are all required to
collectors, for example dithiophosphinates (Guitard et al., 2015). make effective and lasting improvements in mineral processing.
The impact and benefit of the greener chemicals or processes
can only be assessed by considering the overall system, not just The attention required to be paid to health, safety and environ-
parts of it. This requires a completely different thinking and mental issues has grown exponentially in the last decades, judging
approach in research (and practice) and to enable successful by the increasing community and regulatory pressures (e.g.
technology transfer from the laboratory to the plant. It would also Europes REACH regulation and the UNs Globally Harmonized
require a very effective, strategic collaboration and coordination of System for Hazard Communication). Perspectives on these multi-
efforts. faceted issues can vary greatly depending on the measuring stick,
Prudence requires the mineral industry to stay ahead of regula- if any, being applied. This can lead to significant differences of
tions by making wise choices and investments, thereby avoiding opinion about the need for and pace of action to be taken. To state
major penalties, closures or incurring substantial losses. Chemical some obvious non sequiturs: (i) historical usage of a product does
suppliers should educate the industry on these HSE aspects. There not mean it is currently considered safe or green; (ii) a product
is a great opportunity for all of us to tackle this big HSE challenge manufactured using green methods (e.g. according to the
and to realize substantial gains for both industry and society, 12 Principles of Green Chemistry) does not necessarily mean the
independent of boom/bust cycles. This would be both profitable product is green or safe when used; (iii) although a substance is
and sustainable. 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
3. Concluding remarks from operating companies and their suppliers. Many of these
responses are crafted on a case-by-case basis; a situation that
The bursts of activity characterizing each historical period in would benefit from a more concerted effort. HSE issues are inde-
the evolution of flotation reagents have each brought the science pendent of the boom-and-bust cycles that the mineral processing
and technology to increasingly elevated plateaus where wrestling industry faces, suggesting that a sustained, co-operative effort
with the next set of challenges must be taken up anew and with would be a sensible approach.
zest. We are currently engaged in such a struggle. Declining ore The leverage that can be obtained from the proper use of
qualities continue to erode operational profitability, especially for flotation chemicals in existing or new equipment and separation
those clinging to a conventional and limited set of reagents and processes should be incorporated in the design of solutions to
practices. HSE and sustainability issues throw more light into pre- address the current challenges faced by the mineral processing
viously dark corners that can no longer be ignored. High quality industry. By leverage in this instance we mean the substantial
water is less and less available, and this impacts both the engineer- improvements in mineral separation operation effectiveness that
ing and chemical components of a separation strategy. Simply can be achieved at relatively low cost/performance ratios when
throwing more high quality energy at the problem will not bring optimal flotation chemicals are employed. Benefits are achievable
us to the next technological level. A full frontal acknowledgment in the following categories.
of the high degree of complexity in mineral flotation processes
must be followed by earnest efforts to confront this complexity  Health, Safety and Environment (HSE)
and tame it sufficiently to progress to more efficient and sustain-  Processing low-grade poor-quality ores
able operations.  Water usage
12 D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214

 Enabling new equipment/processes unabated. In order to begin following a similar path in flotation a
 Energy efficiency greater level of chemical detail must be brought into our picture.
 Processes other than flotation The biological sciences began to study more than a cell, a protein,
or a strand of DNA at a time because they recognized emergent
Fundamental studies of the sub-processes that make up the properties; i.e. properties that are the result of a multiplicity of
flotation process have yet to make a serious impact on the plant interactions in a system. This does not suggest that chemistry
operator whose froth has just collapsed for no apparent reason, should at last throw off its physics-envy and move on to biology-
or the metallurgist who must decide how to select or alter the envy, but it does bring credibility to the proposal of a holistic
reagent suite in order to best deal with the natural swings in ore approach in tackling the sustainability challenges in mineral
composition. Elegant physical models developed from principles processing.
in fluid mechanics, surface & colloid chemistry and chemical Combinatorial and systems chemistry has been applied in many
engineering have yet to reach the stage of completeness and fields (Li et al., 2013; Ludlow and Otto, 2008; Hunt and Otto, 2011),
integration where even guidelines for emergent features of daily especially in instances where a panoply of chemicals or materials
interest to the plant operator, such as optimizing recovery and have to be generated and sifted through in order to find the needle
grade, or dealing with ore variability, are reliable. One important in the haystack that proves efficacious. Beyond the obvious exam-
reason for this is the low level of chemistry taken into account. ples in molecular biology and drug design (see any issue of the
Most models collapse the complex set of chemical factors and journals Combinatorial Chemistry & High Throughput Screening or
interactions into one scalar parameter the contact angle. Clearly Combinatorial Science), this approach has also been used in a vari-
there is a need to unfold this dimension of the problem via an ety of material science, catalysis, and surface science applications
integration of chemical and physical aspects. By doing this there (Rajan, 2008; Li et al., 2013). What currently prevents greater use
is a high likelihood of having a positive impact on not only of this approach in flotation applications is the lack of high
understanding flotation better, but also giving better guidance to throughput screening methods.
plant operators. Flotation operations are dynamical systems, whose trajectory
One reason for importance of this better representation of through myriad possible states would be nearly impossible to
chemistry in flotation models is that fundamentally the mineral- predict, no less to even catalog, due to the inherent sensitivity of
mineral separation that occurs in flotation is linked to differences that path to initial conditions. However, a more faithful represen-
in surface chemistry of the various minerals, which in turn is tation of the general character of flotation would likely come from
affected by the chemistry of the environment of those surfaces. including nonlinear behaviors that are characteristic of such
Chemical factor interactions can dominate the overall performance systems. A key step to achieving such a model would be inclusion
in an operation. of chemical and chemical kinetics effects in any primary descrip-
Facing the complex nature of mineral flotation systems can tion of the micro-processes.
easily dampen the spirits of someone attempting to get to the Mineral processing must take its place in the league of disci-
bottom (and top) of it all. We can try looking towards other disci- plines that have embraced the complexity of natural systems in
plines that have made better progress in dealing with complexity their research.
and hope to find a door to penetrate through the wall. There are Paradigm shifts occur when we challenge dogma and conven-
several general areas of scientific research that we might turn to tion. Adopting a framework based on a holistic approach would
in this regard. constitute a paradigm shift in mineral processing, as it was in the
Several disciplines have sprung up around the ability to grapple biological sciences. A holistic approach does not reject studies of
with big data; including proteomics, petroleomics and genomics. parts or model systems. Indeed such studies are necessary in
The basis for these tour-de-force approaches is usually sophisti- parallel with the study of the whole system. Such an approach will
cated analytical methods to quantify the myriad species involved, serve to bridge the widening gulf between research and practice. It
combined with software and computing power sufficient to make will also provide an exciting platform through which we may
sense of the large amount of data involved. As a first pass one inspire students to consider the links between science and practice.
can gain insight at the dominant factors level via quantitative A holistic approach also requires that a balanced set of skills be
structure-property relationships derived from methods such as applied to the problem if it is to succeed. The atrophy of chemical
principle components analysis or the use of genetic algorithms. knowledge in our field must be rectified.
Crafting a comparable approach in flotation would require sub- The crisis in mineral processing education has been recognized
stantially more detailed chemical information than we commonly for a number of years (Cilliers et al., 2013). Efforts are being made
acquire in flotation systems. Two important kinds of data are rarely to correct this deficiency. Such efforts must include re-establishing
gathered in flotation systems: (a) dynamics and interactions at and advancing the lost chemistry knowledge so foundational to
different levels of complexity (most information we have is for highly understanding flotation and providing improved solutions in plant
idealized models), and (b) large-scale measurements of the whole operations.
system and at least an empirical description of the whole system Since sustainability goals and challenges are multi-faceted,
which provides the context and the rationale for research at any level broad and complex, they require a confluence of expertise from
of complexity. If we are to make headway, the required information many disciplines in order to create a paradigm shift in our thinking
would, at a minimum, comprise the spatial (i.e. throughout various and approach in order to produce breakthrough innovations and to
zones in a flotation cell) and temporal (i.e. accounting for kinetic effectively organize and integrate research effort and output. How
effects) distributions of species concentrations (intended and would such an effort be fueled? Academic research is supported by
unintended) in the aqueous phase, at the various co-existing a grant structure that inhibits radical idea generation, where peer
mineral surfaces, and at liquid-gas interfaces. assessments have the perverse effect of inhibiting radical idea
Molecular biology and its applications in pharmacology have generation by conditioning researchers to not stray too far from
evolved from a science and technology based on functional the norm (van Deventer, 2014). A large collaborative effort and
descriptions to one based on molecular details. That level of detail increased funding do not guarantee that the right information is
has only percolated up through to the organism level in a generated to build the required knowledgebase. The research
few instances; however, the march in that direction continues efforts must be guided by and consistent with the challenges in
D.R. Nagaraj, R.S. Farinato / Minerals Engineering 9697 (2016) 214 13

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