International Journal of Mineral Processing 127 (2014) 62–69

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

An overview of the beneficiation of iron ores via reverse cationic flotation

L.O. Filippov a,b,⁎, V.V. Severov a, I.V. Filippova a,b
a
Université de Lorraine, GeoRessources UMR 7359 CNRS-CREGU, ENSG, 2 rue du Doyen Marcel Roubault TSA 70605, 54518 Vandoeuvre-lès-Nancy Cedex, France
b
National University of Science and Technology “MISIS”, Leninsky Prospekt 4, 119049 Moscow, Russia

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

Article history: Flotation is the most effective solution, both technologically and economically, when upgrading iron concen-
Received 24 September 2013 trates. Research regarding iron ore flotation began in 1931, demonstrating that reverse cationic flotation is a
Received in revised form 29 December 2013 very efficient method for beneficiating oxidised iron ores. This method can also be applied to reduce the silica
Accepted 11 January 2014
content in magnetite concentrates obtained using wet low-intensity magnetic separation. Several studies
Available online 25 January 2014
describing the processing of iron ores via reverse cationic flotation are reviewed. The predominate role of the
Keywords:
pulp mineralogy, as well as the type and molecular structures of the collectors and depressants, on flotation is
Iron ores discussed critically. The results concerning the role of the silicate mineralogy on the choice of reagents and flota-
Flotation tion processes are also discussed. Further development of the reverse cationic flotation of iron ores requires a
Amphiboles more detailed consideration of the nature of iron-bearing gangue minerals and the application of original
Ether amines approaches for the selective removal of these species.
Starch © 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2. Flotation routes for iron ores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3. Desliming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4. Cationic collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5. Mixed collector systems in reverse cationic flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6. Depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
7. Frothers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

1. Introduction
Iron is one of the most common elements in Earth's crust. The prima-
ry industrial types of iron-bearing minerals include oxides and hydrox-
ides and, to a lesser extent, carbonates: magnetite [Fe3O4], hematite
[Fe2O3], goethite [FeO(OH)], limonite [FeO(OH) × nH2O] and siderite
[FeCO3]. The genesis of iron ore deposits is variable, similar to numerous
other ore types. However, the major iron ore resources are composed of
metamorphosed iron formations called banded iron formations (BIFs).
Most of these formations are from the Early Proterozoic and Archean.
Smaller portions of the deposits are from the Late Proterozoic and
Early Paleozoic. Banded iron formations form extensive iron ore basins
(kilometres across and hundreds of metres in thickness) with a typical
layered structure composed of ore bodies. BIF areas are also associated
⁎ Corresponding author. Tel.: +33 383596358; fax: +33 383596339.
E-mail address: lev.filippov@univ-lorraine.fr (L.O. Filippov).
with weathering crusts (also called as bedded iron deposits) formed
by natural processes (hypogene and supergene Fe-enrichment). Bedded
iron deposits (BIDs) contain iron-rich hematite, goethite– and siderite–
magnetite, as well as martite (pseudomorph after magnetite)–goethite
and microplaty-hematite ores. The Kursk Magnetic Anomaly in Russia,
the Hamersley iron province in Australia, the Quadrilátero Ferrífero re-
gion in Brazil, the Anshan area in China, the province of Labrador in
Canada, the Krivoy Rog basin in Ukraine, the Lake Superior district in
the USA and the Singhbhum-North Orissa region in India are among
the largest of these types of rock formations. The share of these types
of ores compared to the overall commercial ore production exceeds
74%. Worldwide estimates of the iron reserves and mining are presented
in Table 1. Major iron ore storage locations are in Australia, Brazil, and
Russia. Nevertheless, most of the total iron ore production occurs in
China.
In general, magnetic separation is the most commonly used benefi-
ciation process for iron ores because the dominant iron minerals are

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 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69 63

Table 1 centrifuges) to use magnetic separation for its hematite processing

World iron ore production and reserves (million metric tons).a flowsheet. The flowsheet incorporates WHIMS and SLon separators at
Country Mine production Reserves the scavenger stage. The change from gravity-based to magnetic separa-
tion improved the iron grade and recovery by 2.95% and 13.80%,
2010 2011b
respectively.
United States 50 54 6900
Prasad et al. (1988) have studied iron ore slimes processed by mag-
Australia 433 480 35,000
Brazil 370 390 29,000 netic separation at the Kiriburu mines in India. A concentrate containing
Canada 37 37 6300 63% Fe and 3.3% Al2O3 with an iron recovery of 56% was obtained when
China 1070 1200 23,000 using WHIMS with slimes composed of hematite, goethite, and kaolinite
India 230 240 7000 after the classification via cyclone. Concurrently, Pradip (1994) found
Iran 28 30 2500
Kazakhstan 24 24 3000
that multigravity separation is the most effective method for processing
Russia 101 100 25,000 the slimes from the Indian ore to decrease Al2O3 content. However, Roy
South Africa 59 55 1000 and Das (2008) reported that this method is not very commercially
Sweden 25 25 3500 successful due to its low capacity. In some cases, the best results for sep-
Ukraine 78 80 6000
arating low-magnetic iron fines can be achieved when the magnetic
Others 87 91 17,800
Total (rounded) 2590 2800 170,000 separation in a medium-intensity field (MIMS) is combined with hydro-
a
phobic selective flocculation instead of WHGMS or WHIMS. Song et al.
Source: USGS, Mineral Commodity Summaries, January 24, 2012.
b
Estimated E Net exporter.
(2002) have named this process floc magnetic separation (FMS).
The industrial production of iron ore pellets and other high-quality
metallurgical raw materials, such as fluxed pellets and direct-reduced
ferro- and paramagnetic. However, iron ores should be processed accord- iron (DRI), requires pellet feed fines with limited contents of silica,
ing to its mineral composition, physical properties, character and degree aluminium oxide and other impurities. These requirements have led
of liberation of the iron-bearing minerals from the gangue. The gangue to the increased use of flotation (unlike gravity and magnetic separa-
minerals in BIF typically include quartz, several iron-bearing silicates as tion) to reduce the content of harmful impurities and produce iron
amphiboles, micas and pyroxenes, carbonates, feldspars, and clays. “superconcentrates”. The high potential of flotation for the beneficiation
Wet and dry low-intensity magnetic separation (LIMS) techniques of low-grade oxidised iron ores was emphasised by Iwasaki (1983).
are used to process ores that contain minerals with strong magnetic According to Peres and Mapa (2008), reverse cationic flotation is critical
properties, such as magnetite and titanomagnetite. For example, LIMS for producing pellet feed fines at all processing plants in Brazil.
separators are installed at the Kiruna plant KA1 in Sweden to process
a low phosphorus magnetite ore containing over 60% Fe (Söderman 2. Flotation routes for iron ores
et al., 1996). LIMS is also utilised in Section 2 of the Qidashan mineral
processing plant in China to extract magnetite from hematite– or Studies on iron ore flotation began in 1931 and revealed the following
limonite–magnetite ores (Zeng and Dahe, 2003). Various applications flotation routes: the direct anionic flotation of iron oxides and the reverse
of LIMS can be found during processing for the iron ores from Mesabi anionic or cationic flotation of quartz. The direct flotation of iron oxides
and Marquette Iron Ranges in the USA, in addition to the Savage River by anionic collectors such as petroleum sulphonates, fatty acids and
and OneSteel's Project Magnet operations in Australia (David et al., hydroxamates was the first to be tested and commissioned in 1950 at
2011). Wet high-gradient magnetic separation or wet high-intensity several processing plants, including the Humboldt mine and the Republic
magnetic separation (WHGMS/WHIMS) is used to separate the iron- mine in the USA, as well as the Anshan Iron & Steel Corporation in China
bearing minerals with weak magnetic properties as hematite, goethite (Iwasaki, 1983; Ma, 2012a).
and limonite from gangue minerals (Svoboda, 1987, 2001). Concurrently, In the early 1960s, the reverse flotation of silicates using anionic
Xiong et al. (1998) explained that the biggest problems facing conven- collectors that were primarily fatty acids has been developed. Reagent
tional WHGMS/WHIMS separators are matrix dogging and the mechani- regimes for the reverse anionic flotation of oxidised taconites from the
cal entrainment of non-magnetic particles when WHGMS/WHIMS was Lake Superior deposits have been designed at the Hanna Mining and
applied to treat metallic ores, including hematite ores, because these the U.S. Bureau of Mines laboratories (Bunge et al., 1977). Taconites
ores contain large portions of weakly magnetic minerals and relatively containing approximately 39% Fe, were ground to 60–100% of
coarse particles. These characteristics weaken the magnetic forces and − 44 μm and were floated without desliming. Calcium chloride
reduce the quality of the magnetic product. To solve these problems, (765 g/t) was used to activate the quartz, while dextrin (Gum 9072)
pulse high-gradient magnetic separation (PHGMS) has been in devel- (1.1 kg/t) was added to depress the flotation of the iron oxides. Acintol
opment since 1981 (Xiong et al., 1989; Liu et al., 1991; Yang et al., FA2 containing 97.8% tall oil (50% of oleic and 44% of linoleic acids) was
1993). Several models of the SLon vertical ring and pulsating high used as an anionic collector. The total collector dose was 720 g/t at
gradient magnetic separators have been designed since 1986. These pH 11.5; this pH was attained with NaOH (1.6 kg/t). The flotation con-
devices are successfully operated at 12 processing facilities for extracting centrate contained 60.3% Fe and 6.0% SiO2 to obtain a 90.5% Fe recovery.
hematite, limonite, siderite and other low-magnetic minerals. Finally, despite the successful flotation results, this route was not imple-
Tests over a 6-month period that were used to compare WHIMS- mented commercially due to the high cost of the reagents.
2000 and SLon-2000 separators for a low-grade oxidised iron ore at The flotation of apatite used to lower the levels of phosphorus from
the Gong Changling mineral processing plant have demonstrated the 0.1 to 0.025% of P2O5 in the LIMS magnetite concentrate is applied as a
high efficiency of SLon separators. These separators provided high- pellet feed with a fatty-acid-type collector called Atrac 1563 (mixture
grade magnetic products with an improved iron recovery and a low of 95–98% of ethoxylated tall oil ester of maleic acid and 2–5% of maleic
mass yield. Xiong et al. (1998) explained the increased grade and recov- anhydride) at 30–70 g/t at the Kiruna (KA2) and Malmberget plants in
ery of the iron using pulsating effects. Pulsations in the slurry increase Sweden. Sodium silicate (300–500 g/t) is added to disperse the fine par-
the rate of collisions between the magnetic particles and the matrix, ticles and to discourage magnetite flotation. However, the studies by
favouring the recovery of magnetic particles. However, the pulsations Forsmo et al. (2008) and Potapova et al. (2010) of the flotation concen-
increase the competitive forces acting on the non-magnetic particles. trates obtained in these facilities indicated that the adsorption of Atrac
This scenario is favourable for eliminating the mechanical trap for the on the magnetite surfaces seriously damaged the quality of the green
non-magnetic particles. For example, the Gushan iron mine completely pellets; an increasing amount of air bubbles became so strongly at-
stopped using gravity-based separation techniques (spirals and tached to particle surfaces that they could not be removed during
64 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69

compaction. The application of direct and reverse anionic flotation Table 3

routes of iron ores is summarised with several results from anionic Influence of desliming on the reverse cationic flotation of hematite containing tailings of
magnetic separation from magnetite ore at the Mikhailovsky plant, Russia (Filippov
collectors in Table 2. et al., 2010a).
Despite the recent success of the reverse anionic flotation of iron
ores in the Anshan province in China, reverse cationic flotation remains Desliming Products % wt. % grade % Fe recovery

the most popular flotation route used in the iron ore industry (Ma, Fe SiO2
2012a). Comparing reverse anionic and cationic flotation is difficult b10 μm Concentrate 58.5 39.2 35.8 72.8
because the processes are governed by the chemical, physical and Tailings 41.5 20.6 62.3 27.2
metallurgical properties of the iron ores. The major advantages of re- Magnetic product 100.0 31.5 46.8 100.0
verse cationic flotation over reverse anionic flotation include the higher b20 μm Concentrate 49.8 54.9 10.8 73.5
Tailings 50.2 19.6 66.5 26.5
flotation rate and superior results in hard water. Ma et al. (2011) have Magnetic product 100.0 37.2 38.8 100.0
shown that reverse anionic flotation has better results for the flotation
of fine particles (b10 μm) from the Vale iron ore than the cationic flota-
tion of the same material. The reverse cationic flotation of slimes did not 4. Cationic collectors
provide the required selectivity during separation. In contrast, when the
coarse particles (N210 μm) were floated, reverse cationic flotation Various amines are used as cationic collectors during the reverse
performs better. Finally, the research confirmed that reverse cationic flotation of iron ores. Previously, quaternary ammonium salts were
flotation is more sensitive toward desliming the flotation feed, while used during froth flotation, but the most effective cationic collectors
the anionic route is more sensitive toward the ionic composition of are hydrolysed reagents that present both ionic and molecular species
the pulp. in the aqueous phase. In this case, the ratio of the ionic and molecular
species will depend upon the pH of the solution and will determine
the mechanism of amine adsorption on mineral surfaces. Fuerstenau
3. Desliming and Modi (1959) showed that for the effective flotation of corundum,
the required concentration of dodecylamine could be 10 times lower
The importance of desliming before the reverse cationic flotation of than that of the trimethyldodecylammonium salt. However, Yuhua
iron ores was reported by Clemmer in 1947 (Clemmer, 1947). A high and Jianwei (2005) demonstrated that quaternary ammonium salts
content of fines increases the required cationic collector dose and exhibit better selectivity and collection ability than the dodecylamine
reduces the selectivity. Filippov et al. (2010a) reported that desliming salts when separating quartz from magnetite. Wang and Ren (2005)
at 10 μm of wet magnetic separation tailings when processing magne- also tested quaternary ammonium salts as collectors during the quartz
tite ores at the Mikhailovsky plant in Russia slowly improves the flotation from iron minerals. High selectivity and collectability of the
flotation selectivity of the reverse cationic flotation for hematite. quaternary ammonium salt surfactants were demonstrated.
When the fines b20 μm in size are removed from the flotation feed, The mechanism of the amine adsorption on mineral surfaces has
the selectivity increases dramatically. However, the hematite lost dur- been studied only for alkylamine adsorption on metal oxides and several
ing desliming increased from 7.6% to 16.6%. Finally, by using rougher silicates, such as quartz and feldspars. Until recently, the Gaudin–
and scavenger flotation tests, a hematite concentrate containing 54.9% Fuerstenau–Somasundaran model (Gaudin and Fuerstenau, 1955;
Fe and 10.8% SiO2 with an iron recovery of 73.5% was obtained (Table 3). Somasundaran and Fuerstenau, 1966) was used to explain the adsorp-
In fact, effective desliming requires a high dispersion of fine particles tion mechanism of amine on oxide or silicate surfaces at neutral pH
in the slurry. This state can be achieved by increasing the pH via the values. According this model, the amine cations adsorb from a solution
addition of alkali, increasing the electrostatic repulsion between the below the critical micelle concentration only on the negatively charged
equally charged particles. However, Peres et al. (2003) and Lima et al. oxide or silicate surfaces by means of electrostatic and hydrophobic
(2012) demonstrated that for all samples of Brazilian iron ore slimes, forces. At a certain amine concentration in the double electrical layer,
the dispersion at pH above 8 was not significantly increased. 2D aggregates of the amine cations called hemimicelle form at
Therefore, dispersants, such as sodium silicate, tripolyphosphate, etc., the solid–liquid interface. This amine concentration is the critical
should be used to prevent the non-selective coagulation of slimes during hemimicelle concentration (CHC). The same adsorption mechanism
the reverse cationic flotation of iron ores. In contrast, to reduce the losses has been postulated by Iwasaki et al. (1960) and Smith et al. (1973).
of iron oxides due to the overflow of the desliming apparatuses, selective However, the FTIR and XPS studies conducted by Chernyshova et al.
flocculants, such as high-molecular organic compounds, must be added (2000) and Vidyadhar et al. (2002) showed that ammonium ions can
(Colombo and Frommer, 1976; Colombo, 1980). interact with silanols on the quartz surface through hydrogen bonding;
However, Ma (2012b) reported that hematite pre-conditioned with these results are incompatible with the hemimicelle theory and cannot
dispersants hinders the hematite flocculation with starch. In contrast, be explained by this model.
hematite pre-conditioned with starch is not affected after adding After obtaining the adsorption isotherms for alkyl amine ions on bio-
dispersants. tite surfaces, Cases (1979) advocated the two-dimensional condensation

Table 2
Anionic collectors used during iron ore flotation.

Mineral floated Collector References

Hematite Lauric acid Keck et al. (1939)

Hydroxamates Fuerstenau and Pradip (1984)
Sodium alkylsulphate Iwasaki et al. (1960)
Sodium alkyl benzyl sulphonate Bibawy and Yousef (1982)
Sodium oleate Kulkarni and Somasundaran (1975)
Oleic acid Gutiérrez and Iskra (1977)
C6–C18 saturated fatty acids Quast (2006)
Apatite Mixture of ethoxylated tall oil ester of maleic acid and maleic anhydride Forsmo et al. (2008)
Quartz Sodium oleate Ye and Matsuoka (1993)
Alkylsulphate Smith and Rajala (1989)
 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69
theory; this theory is the basis for the admimicell hypothesis of
Scamehorn et al. (1982). Cases's theory indicates that the two-
dimensional condensation of a surfactant takes place at the interface
at the CHC. A two-dimensional phase should be chemically identical
to the three-dimensional hydrated crystal state or micelles of the
surfactant at temperatures below and above the Krafft point. This theory
predicts and the experimental results confirm that with a further in-
crease in the bulk surfactant concentration, a bilayer can form through
tail–tail interactions. Afterward, a three-dimensional condensation
occurs.
The importance of the molecular structure of surfactants on their
surface properties has been studied by Fuerstenau and Jia (2008). It
was analysed the influence of the molecular structure of cationic collec-
tors upon results of the flotation of quartz, which was supplied from
some Brazilian iron ore deposit. The following surfactants were tested
as collectors: dodecylammonium chloride, dodecylpyridinium chloride,
dodecyltrimethylammonium chloride, didodecyldimethylammonium
bromide, and 1,2-bis dodecylammonium ethane dibromide. The prop-
erties of the collector ions, such as the hydrocarbon chain length, the
number of hydrocarbon radicals and the type and amount of polar
groups, significantly affect the activity at the mineral surface. The
reagent has higher adsorption ability when its polar group can form
hydrogen bonds more easily on the mineral surfaces. The addition
of the second hydrocarbon chain to the collector molecule increases
the surface activity and reduces the amount of bulk reagent concen-
tration required to achieve a stable adsorption layer. The addition of
a second polar group to the molecule increases the reagent adsorp-
tion on the mineral surfaces due to electrostatic attraction and can
also maintain hydrocarbon chain interactions with the formation of
hemimicells due to the increased repulsions of the equally charged
functional groups.
Sekulić et al. (2004) tested various cationic collectors for the flota-
tion of feldspars, micas and other gangue minerals from the silica sand
of the Bujanovac and Kopovi-Ub operations in Serbia. Aero 3030C
(alkylamine acetate), Flotigam DAT (tallow fatty amine), Armoflot 64
(alkylamine acetate), Armac C (coco alkylamine acetate) were tested.
The anionic collector Aero 825 (petroleum sulphonate) was also tested
as an additive to Armac C. Armoflot 64 and Aero 3030C are the best for
the flotation of feldspars and micas from the Bujanovac sample. For the
feldspar flotation, a higher recovery was recorded with Aero 3030C
(19.6%) than was obtained with Flotigam DAT (6.2%). Similar results
were achieved for the reverse flotation of silica sand in the Kopovi-Ub
sample when Aero 3030C or combination of Armac C and Aero 825
was used. The concentrates from the silica sand contained 99.3% and
99.0% SiO2, respectively.
Liu et al. (2009) have proposed N-dodecylethylen-diamine as a
selective cationic collector:
C12 H25 NHðCH2 Þ2 NH2 :
The high selectivity of reverse cationic flotation without a depres-
sant at pH 10 was observed when N-dodecylethylen-diamine was
used for the flotation of single minerals, such as hematite, quartz,
calcite and calamine acquired from the hematite–magnetite ore
sample processing in the Qidashan processing plant in China. At an
N-dodecylethylen-diamine concentration of 1.83 × 10 − 4 M, the
hematite recovery remained below 55%. However, the quartz, calcite
and calamine recovery exceeded 90%.
Primary aliphatic amines, as well as their acetate and hydrochloride
salts, were used only during the early industrial applications of reverse
cationic flotation. Further progress regarding iron ore cationic flotation
was attributed to the use of oxygen-containing primary amines. These
reagents contain a covalent C\O bond and are known as primary
ether amines:
R−O−ðCH2 Þ3 −NH2 :
65
Araujo et al. (2005) found that if a polar hydrophilic group
О\(СН2)3 is present in the amine structure, the water solubility, ad-
sorption ability at liquid–gas interface and the dispersion properties of
the amine are higher. Additionally, the low sensitivity of the process to-
ward pH variations and the presence of slimes in the slurry was noted
when primary ether amines were used in place of the primary aliphatic
amines. Concurrently, the cost of primary ether amines is not higher
than that of aliphatic amines. To increase the solubility of primary
ether amines, they should be partially or completely neutralised with
acetic acid. The molar ratio of acetic acid to amine is called the
neutralisation degree. This factor is important because at a high
neutralisation degree, the amine is more soluble, but its hydrophobic
and frothing abilities are lower due to the low content of amine molec-
ular species. Most industrially used primary ether amines have
neutralisation degrees from 20 to 50% (Leja, 1982; Araujo et al., 2005).
A review of the processing plant practices indicates that the partially
neutralised ether monoamines are mostly used for the reverse cationic
flotation of iron ores. In contrast, the best results for coarse silicate par-
ticle flotation were achieved with ether diamines. Therefore, a mixture
of mono- and diamines may be more common for the flotation of iron
ores with a wide particle size distribution (Houot, 1983; Lindroos and
Keranen, 1985; Valine et al., 1997; Papini et al., 2001).
Weng et al. (2013) proposed a novel ester-containing quaternary
ammonium surfactant (M-302) after their studies on the reverse
cationic flotation of silicates from Chinese magnetite ores. M-302
was synthesised through a reaction between adipic acid and N-(2,3-
epoxypropyl) dodecyl dimethyl ammonium chloride; the latter was
synthesised from dodecyl dimethyl ammonium and epichlorohydrin.
The main advantages of M-302 compared to dodecylamine hydrochlo-
ride are its stronger collecting power, higher surface activity, lower
critical micelle concentration, higher solubilisation capacity and higher
foam stability during flotation.
5. Mixed collector systems in reverse cationic flotation
The use of mixtures containing cationic and anionic collectors and
also those with non-ionic surfactants was suggested to improve the
metallurgical results for the cationic flotation of silicates, including
iron-bearing silicates. This can provide increased flotation selectivity
and recovery compared to each separate reagent, as well as a significant
reduction in the amine consumption (Hanumantha Rao et al., 1990;
Hanumantha Rao and Forssberg, 1993, 1997).
The studies reported by Hanumantha Rao et al. (1990) and
Hanumantha Rao and Forssberg (1993) demonstrated an improved
selectivity during silicate flotation when a mixture of cationic and
anionic collectors is used. This phenomenon was explained by the
co-adsorption of an anionic collector on silicate surfaces through
hydrocarbon tail–tail interactions, increasing their hydrophobicity. The
ð1Þ metallurgical results for the reverse cationic flotation of iron ores can
also be improved by using a combination of cationic collectors and
non-ionic surfactants, such as fatty alcohols. According to Vidyadhar
et al. (2002, 2003), adding 1-dodecanol to the dodecylamine salt at
pH 6–7 causes a higher recovery of quartz and albite due to the co-
adsorption of the alcohol molecules on silicate surfaces. Vidyadhar
et al. (2002, 2003) reported that the adsorption of non-ionic surfactant
molecules reduces the electrostatic repulsion of the dodecylamine cat-
ions in the adsorption layer, leading to hemimicelle formation on the sil-
icate surfaces. This behaviour facilitates closer packing in the adsorption
layer to be created, increasing the silicate recovery at a lower dose of
dodecylamine.
Concurrently, few data are available regarding the use of mixtures
containing primary ether mono- or diamines with anionic collectors
or non-ionic surfactants during the flotation of quartz or other silicates.
Leal Filho and Rodrigues (1992) studied the mixture of a primary ether
monoamine with an oxyethylated nonylphenol (the chain lengths of
ð2Þ the oxyethylene groups were 2 and 4) and with an oxyethylated fatty
66 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69
alcohol for the flotation of Brazilian quartz. The floatability of quartz was
increased by approximately 20% at a 4:1 ratio of ether monoamine to
nonylphenol (with 2 oxyethylene groups). Additionally, adding
nonylphenol to flotation system decreased the surface tension at the
liquid–gas interface, reducing the froth depth during flotation.
Filippov et al. (2010b) showed that experimentally selected mix-
tures of dodecylamine or ether diamine with fatty alcohols (C13-rich
iso-alcohol) generate a hydrophobic adsorption layer on the surface of
the quartz and Fe-bearing amphibole pargasite at pH 10, even in the
presence of starch. Fig. 1 shows that adding 5 × 10− 5 M of iso-
alcohols to dodecylamine increases the quartz recovery from 13 to
71%. However, the flotation of pargasite remains unaffected under the
same conditions. The variations in the pargasite recovery are lower
than experimental error (estimated at 5%) during the flotation of a
single mineral. Only higher concentrations (10−4 M) of the iso-alcohol
increase the flotation recovery of the amphibole to 19% with
dodecylamine. Therefore, the effect of adding an iso-alcohol is more
significant for quartz flotation with dodecylamine in the presence
of starch. Ether diamine is a stronger collector than dodecylamine.
Therefore, adding iso-alcohols to ether diamine leads to the smallest
increase in quartz flotation recovery in the presence of starch. Never-
theless, adding iso-alcohols to ether diamine increases the quartz
flotation recovery from 52 to 84% at the iso-alcohol concentration
of 2.6 × 10− 5 M (Fig. 1). With a constant ether diamine concentra-
tion of 5.0 × 10− 5 M, adding 10− 4 M of iso-alcohols increased the
pargasite flotation recovery from 8 to 24%.
Filippov et al. (2012) suggested that adding iso-alcohols to ether di-
amine can also improve the floatability of Fe-bearing mica minerals,
such as biotite and muscovite, while reducing the amine consumption.
Fig. 2 depicts the flotation recovery of quartz, feldspars, micas and clay
minerals, such as palygorskite, at pH 8 with an ether diamine collector
with and without iso-alcohols (reagent PX 4826) in the system. Fig. 2a
shows that muscovite and biotite flotation is less favourable than
that for quartz and feldspars when the diamine concentration is below
10−4 mol/l. Therefore, the total removal of Fe-bearing silicates requires
a high reagent dosage, possibly impacting the flotation selectivity. In
contrast, adding iso-alcohols to ether diamine (1:1 molar ratio at a
total concentration of 10−4 M) reduces the concentration of ether di-
amine necessary for similar recovery of muscovite and biotite to that
for quartz and feldspars (Fig. 2b). Moreover, the recovery of muscovite
and biotite increases from 10 and 30% to 82 and 90%, respectively, at a
total concentration of 10−5 mol/l (1:1 molar ratio). Thus, a full recovery
Fig. 1. Quartz (solid line) and pargasite (dotted line) recovery as a function of alcohol ad-
dition in the presence of an amine (2.6 × 10−5 M for quartz and 5.0 × 10−5 M for
pargasite) and starch (100 mg/l) at pH 10.
of the silicates can be reached at a significantly lower concentration
of ether diamine. However, the palygorskite floatability increases in-
significantly after adding iso-alcohols with a collector concentration
below 10−3 mol/l. This phenomenon can also be used for the selective
flotation separation of clay minerals from other silicates.
Pereira et al. (2006) reported the possibility of a partial replacement
of ether amine with non-polar oils during the reverse cationic flotation
of Brazilian iron ore. The best results were obtained when the adding
diesel oil to ether amine with an 80%/20% amine/oil ratio and when
Tergitol TMN-10 was used as an emulsifier with a 95%/5% oil/emulsifier
ratio. An iron concentrate containing 0.7% SiO2 with an iron recovery of
74.4% was obtained from ore containing 49.1% Fe and 28.5% SiO2. The
flotation separation under these conditions had the highest Gaudin's
selectivity index (14.8).
6. Depressants
A common depressant used during the reverse cationic flotation of
iron ores is corn starch containing over 98% of amylose and amylopectin
due to its wide availability and good depressing abilities for iron oxides
(Araujo et al., 2005). Peres and Correa (1996) explained the importance
of the ratio of amylose to amylopectin in starch during hematite depres-
sion. Their paper showed that amylopectin reduces the hematite
flotation more profoundly than amylose when a primary ether amine
is used as a collector. Nevertheless, better results were achieved when
using starch with an amylopectin to amylose ratio of 75%/25% instead
of pure amylopectin. If the oil (triglycerides) content in the starch ex-
ceeds 1.8%, the starch performance drops during the reverse cationic
flotation of iron ores due to the potential for perturbations in froth
stability.
Amylose and amylopectin molecules are connected to each other via
hydrogen bonds in the starch molecules, forming 3 to 100 μm granules
that are insoluble in cold water. Therefore, alkali or thermal gelatinisation
is used for their dissolution. The mechanism for thermal gelatinisation is
based on the increased vibration of the hydrogen bonds in the starch
molecules and their rupture at high temperatures. Therefore, the starch
molecules gradually decrease in molecular mass until glucose monomers
are formed (Bertuzzi et al., 2007). Alkali gelatinisation is performed using
sodium hydroxide and can be conducted at low temperatures. This
method produces a homogeneous starch solution with a nearly full
destruction of the starch granules. However, alkali gelatinisation has
been studied less than the thermal method. The effectiveness of the alkali
gelatinisation is strongly affected by the starch/NaOH ratio (Broome et al.,
1951) and the dissolution technique (Iwasaki and Lai, 1965).
The two \OH groups on C-2 and C-3 of the glucose ring can partic-
ipate in complexation reactions (Davidson, 1967). Therefore, natural
starch, as well as dextrin, cellulose, and guar gum, can form complexes
with other compounds. The reaction between cuprammonium and
D -glucose is a classical example that results in the formation of a
five-membered ring complex involving the C-2 and C-3 positions in
the glucopyranose ring, the two oxygen atoms attached to them,
and a copper atom (Laskowski et al., 2007). However, during the
early studies, hydrogen bonding was proposed as the primary mech-
anism for polysaccharide adsorption on oxide surfaces (Balajee and
Iwasaki, 1969). Later, hydrophobic bonding was suggested by Wie
and Fuerstenau (1974). Pinto et al. (1992) described several possible
mechanisms for starch absorption on hematite, calcite, apatite and
quartz, emphasising adsorption via hydrogen bonding. Adsorption
via electrostatic interactions between the positively charged starch
molecules and negatively charged mineral surfaces of quartz and
hematite is also discussed. Numerous subsequent studies have sup-
ported the observation that unmodified natural polysaccharides,
such as dextrin or starch, are adsorbed on metallic mineral surfaces
through chemical interactions with superficial metal atoms. Khosla
et al. (1984) proposed that the starch adsorption mechanism on a he-
matite surface is a chemical complexation. This hypothesis was
 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69 67

Fig. 2. Flotation of quartz, biotite, muscovite, albite, orthoclase and palygorskite at pH 8 with ether diamine (PX 4817) in the absence (a) and presence (b) of a non-ionic reagent (PX 4826).

supported by Liu and Laskowski (1989) during their studies of dextrin
adsorption on chalcopyrite–galenite, as well as the studies of the starch
adsorption on hematite (Weissenborn et al., 1995) and the dextrin
adsorption on galenite, magnetite and certain salt-type minerals (Raju
et al., 1997). Starch adsorption on a calcite surface (Somasundaran,
1969) occurs through a chemical interaction between the calcium
cations and oppositely charged groups of starch molecules.
In contrast, Lima et al. (2013) proposed clathrate formation, possibly
explaining the quartz depression by starch observed during flotation by
ether amine for coarse fractions of −150 + 45 μm of a deslimed itabirite
iron ore. The term clathrate refers to a molecular compound in which
molecules of one species occupy the empty spaces in the lattice of
other species, resulting in the depression of hydrophobic minerals.
This explanation agrees with some the observations of Somasundaran
(1969): the starch-based depression of the calcite surfaces with the
adsorbed oleate can be related to the clathrate formed between the
starch and the oleate. Therefore, the starch helixes can package the
surfactants, yielding surface hydrophilicity.
Few studies are related to the effectiveness of starch as a depressant
during the flotation separation of iron oxides and iron-bearing silicates.
These silicates often reduce the quality of the iron concentrates during
reverse cationic flotation. Dogu and Arol (2004) showed that dark-
coloured minerals (sample contained Fe-bearing amphiboles, tourma-
line and biotite) rich in iron have a specific affinity toward starch and
that the adsorption of starch on this sample is pH-independent from
pH 2 to 12.
Accordingly, the research regarding the flotation activity of Fe-bearing
Based on flotation and contact angle studies, dos Santos and Oliveira
(2007) proposed the use of humic acid instead of starch for the hematite
depression. The reverse flotation of mixtures containing single minerals
with 75% hematite and 25% quartz from a deposit in Brazil used
dodecylamine as a collector and humic acid as a depressant for the
hematite supports, obtaining a concentrate containing 86% of hematite
with a 90.7% recovery. The use of carboxymethylcellulose (CMC) to re-
place starch was also studied during the cationic flotation of Brazilian
iron ores on a laboratory scale (Araujo et al., 2005). Finally, a high
grade iron concentrate was obtained, but the iron lost to the flotation
tailings was also increased.
Turrer and Peres (2010) also studied the flotation depressants used
for other mineral systems in the reverse cationic flotation of iron ores.
The tested reagents included corn starch (Cargill's Amilogill 2100), six
carboxymethylcelluloses (CMC), three anionic lignosulphonates, guar
gum and four humic acids. Most of these depressants have a low selec-
tivity because they depress both quartz and hematite flotation, increas-
ing the silica content in the flotation concentrate. Only one sample of
CMC, guar gum, and starch could obtain a concentrate with less than
2.5% SiO2 and an iron recovery above 40%. Using a polymer mixture
with a 1/3 ratio of CMC or guar gum to starch can be used during the
reverse cationic flotation of Brazilian iron ores.
100
90
80
70
Recovery (%)

amphibole pargasite in the presence of starch (Fig. 3) reveals that the

flotation of this mineral is not possible with dodecylamine (Filippov 60
et al., 2010c). The floatability of Fe-bearing amphibole pargasite with 50
ether monoamine and diamine is also affected when starch is used as a 40
depressant. 30
The major changes in the infrared and XPS spectra of pargasite ob-
20
served at pH 10 in the studies of Filippov et al. (2013) and Severov
10
et al. (2013) suggest that starch attaches to the amphibole surface via
hydrogen bonds with the surface hydroxyl groups (similar to quartz sur- 0
0 0.02 0.04 0.06 0.08 0.1 0.12
faces) and the formation of a surface chemical complex with the metal
Amine concentration (mM)
atoms (similar to magnetite surfaces). A starch adsorption mechanism
Dodecylamine Ether Amine Ether Diamine
based on the chemical complexation is proposed to explain the strong
depression effect of the starch during the magnetite and Fe–Mg–Al- Fig. 3. Recovery of pargasite as a function of the concentration of the amine acetate salt
bearing amphibole flotation with an amine compared to quartz. without (solid line) and with the addition of 0.1 g/l starch (dotted line) at pH 10.
68 L.O. Filippov et al. / International Journal of Mineral Processing 127 (2014) 62–69
7. Frothers
The use of frothers during the reverse cationic flotation of iron ores is
not a common practice because the partially neutralised ether mono-
and diamines used as collectors also act as frothers. However, several
alcohol-based frothers were used during the reverse cationic flotation
of iron ores in the USA and in Canada (Houot, 1983). To stabilise the
abundant foam formation, small quantities (20–30 g per 1 tonne of
crude ore) of Aerofroth 71 (mixture of C7 and C8 primary alcohols)
were added during the flotation of taconites with N-(n-tridecoxy-n-
propyl)-1,3-propylene diamine monoacetate at the Sept Iles processing
plant.
Araujo et al. (2005) reported that replacing approximately 10% of
the total amine dose with polyglycol-type frothers, such as Flotanol
D14 and Flotanol C7 increased the quartz recovery for the laboratory
scale single mineral and Brazilian iron ore flotation. However, these
results must be confirmed using industrial scale tests.
8. Conclusions
Wet low-intensity magnetic separation and high-intensity magnetic
separation are the best methods used to process magnetite and
hematite ores with a high iron content, a high degree of liberation of
iron oxides from gangue and quartz as the major gangue mineral.
Concurrently, flotation has significant advantages when processing
low-grade, finely grained iron ores containing iron-bearing silicates.
The most common flotation route used for the beneficiation of iron
ores is reverse cationic flotation. This process is the major technique
used to produce pellet feed fines at all Brazilian concentrators.
The advantages of reverse cationic flotation over anionic flotation
include the higher process selectivities and rates, as well as satisfactory
results when hard water is used. The flotation of silicates from iron ores
(or magnetic and gravity concentrates) is mainly conducted using pri-
mary ether monoamine or primary ether diamines with hydrocarbon
chain lengths of 10–16 carbon atoms, or mixtures of two ether amines.
Alkali-gelatinised corn starch is often used as a depressant for iron
oxides. Several studies have confirmed that the partial replacement of
starch with a type of CMC or guar gum is possible.
A universal reagent regime for the reverse cationic flotation of iron
ores cannot be proposed due to the variations in the mineral composi-
tion of different iron ore deposits. The major problem with the reverse
cationic flotation of low grade, finely grained iron ores is related to the
presence of iron-bearing silicates, such as amphiboles and pyroxenes;
the flotation recovery of these compounds is low when using common
reagent combinations. To facilitate the removal of silicates (including
iron-bearing silicates) during reverse cationic flotation, a collector
based on a mixture of primary ether amine and non-ionic surfactant,
such as fatty iso-alcohols, is recommended.
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