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Flotation of Iron Ores: A Review

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Flotation of Iron Ores: A Review

Xiaolong Zhang, Xiaotian Gu, Yuexin Han, N. Parra-Álvarez, V. Claremboux &

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
https://doi.org/10.1080/08827508.2019.1689494

Flotation of Iron Ores: A Review

Xiaolong Zhanga, Xiaotian Gua, Yuexin Hana, N. Parra-Álvarezb, V. Clarembouxb, and S. K. Kawatrab
a
School of Resources and Civil Engineering, Northeastern University, Shenyang, PR China; bDepartment of Chemical Engineering, Michigan
Technological University, Houghton, Michigan, USA

ABSTRACT KEYWORDS
A tremendous amount of research has been done on refining the flotation process for iron ore and Iron ore; flotation; desliming;
designing the reagents which go into it. This paper reviews the industrial practices and fundamental reagents; surface chemistry
research surrounding iron ore flotation. The advantages and disadvantages of direct flotation,
cationic reverse flotation, and anionic reverse flotation are reviewed. A novel stepped flotation
technique is discussed for the treatment of carbonate-rich iron ores. The necessity of desliming to
enable effective flotation is discussed in detail. Selective flocculation desliming is discussed in
particular detail as it is the primary deslime methodology used in industry. This paper also describes
a large variety of reagents commonly used or in development in each flotation route, covering
collectors, activators, depressants, dispersants, flocculants, and frothers. The impact of the zeta
potential and surface chemistry on flotation and deslime is also discussed. The aim of this paper
is to provide a well-detailed, well-referenced source for the current status of iron ore flotation, and
thus provide a useful guide to its future development and to further improve flotation performance
for iron ore.

1. Introduction
According to the U.S. Geological Survey there are approximately
170 billion tons of iron ore available in the world, representing
83 billion tons of metallic iron which could be extracted. The
majority of this iron ore is distributed between Australia (29.4%),
Russia (14.7%), Brazil (13.5%), and China (12.4%) (USGS 2017).
Among these four reserves, Russia and Brazil have higher iron
grades, while China has a lower iron grade (Tang et al. 2019; Yu
et al. 2019, 2019b; Zhang et al. 2019a).
Flotation is widely used as the primary beneficiation techni-
que for non-magnetic iron ores, and is often used for further
upgrading magnetic iron ores as well (Araujo, Viana and Peres
2005; Ma 2012; Nakhaei and Irannajad 2018). Flotation is fun-
damentally a surface selective separation that separates hydro-
phobic materials from hydrophilic materials. By using various
reagents, the hydrophobicity of mineral surfaces can be selec-
tively altered, allowing for a wide variety of separations to be
achieved (Carlson and Kawatra 2013; Iwasaki 1999; Rao 2013).
Because the success of flotation is mainly dependent on the
ability of air bubbles to carry the hydrophobized material to the
froth, it has significant advantages over gravity separation tech-
niques with very fine (<150 μm) particles. Magnetic separation
can also be made to work at fine particle sizes, but using mag-
netic separation alone will reject the non-magnetic portion of the
iron ore. While flotation is often more expensive than magnetic
separation, flotation also recovers the non-magnetic iron ore
fraction, and this increased recovery is often enough to offset
the additional cost.
Flotation can be performed in mechanical cells or flotation
columns. Flotation columns have become common in industry
for many applications (Dobby 2002). The key feature of column
flotation that was adapted by many more recent flotation cells is
the use of wash water to reduce entrainment (Dobby 2002). By
adding wash water to the froth layer, poorly hydrophobic mate-
rial can be rejected from the column overflow, increasing overall
selectivity. Care must be taken when scaling up flotation col-
umns between pilot and plant-scale, as the silica rejection must
be maintained at a very high level but the froth stability is
lowered by the increased flowrate of froth wash water (Dobby
2002). One major downside of flotation columns is that they are
difficult to control compared to mechanical cells, as the visible
surface of the column shows comparatively little information
about its performance. Another disadvantage of column flota-
tion is axial mixing – a set of 4 columns were installed in an
operating plant running cationic reverse flotation, but due to
axial mixing they did not perform well compared to the existing
flotation cells and were eventually removed.
In the beneficiation process flotation generally takes
place after comminution and any other separations, includ-
ing desliming, but before agglomeration and induration.
Because flotation operates on wet slurries while agglomera-
tion uses primarily solid material, a dewatering step is
necessary between the two. Different flotation routes can
also have an impact on the efficiency of the dewatering,
especially if performed via filtration, and on the subsequent
agglomeration steps.
Over the years, a tremendous amount of work has been
done to refine the flotation process, along with the reagents
and equipment used (Clemmer 1947; Filippov, Severov and
Filippova 2014; Zhu 1994).

CONTACT V. Claremboux vjclarem@mtu.edu Department of Chemical Engineering, Michigan Technological University, Houghton, MI, USA
© 2019 Taylor & Francis Group, LLC
2 X. ZHANG ET AL.
2. Flotation routes for iron ore
The flotation of iron ore was first investigated in America
starting in 1931 (Iwasaki 1983, 1999; Uwadiale 1992). Over
time, several different flotation routes have been devised.
These routes can be divided into 3 categories: direct flotation,
reverse anionic flotation, and reverse cationic flotation. Direct
flotation refers to processes which float the iron ore into the
froth product, whereas reverse flotation processes float the
gangue materials into the froth to be discarded.
Direct flotation and reverse anionic flotation were initially
developed by Hanna Mining and American Cyanamid in the
1930s and 1940s. These methods were implemented in
Minnesota and Michigan concentrators by the 1950s (Filippov,
Severov and Filippova 2014). Cationic reverse flotation was
simultaneously being developed by the U.S. Bureau of Mines,
which eventually became the primary flotation route for the
United States and other countries in the west (Filippov,
Severov and Filippova 2014). Meanwhile, anionic reverse flota-
tion became popular in China.
2.1. Direct flotation of iron ore
Several flotation media have been used for direct flotation
processes with iron ore, including alkaline media, acidic
media, dispersing media, selectively flocculating media, and
most combinations of the previous either in series or (where
possible) simultaneously. Direct flotation is not well-suited for
some gangue materials – in particular, sulfur, phosphorous,
fluorine, and carbonate gangue materials behave too similarly
to iron ore in direct flotation to achieve good separations (Rao
2004; Uwadiale 1992).
The first flotation route used in industry was direct flotation
in an alkaline medium. Soda ash was used to adjust the pH value
to between 9–10, and fatty acids were used as collectors. This
process was used starting in the 1950s by the Humbolt concen-
trator in America and the Donganshan concentrator in China
Figure 1. Overview of the Republic Mine beneficiation process using direct flotation (based on Houot 1983).
(Houot 1983; Iwasaki 1983). This flotation route is quite simple
and can be made effective without desliming. At high pH values
however, the surfaces of the common gangue minerals and the
iron ore behave quite similarly, limiting separation power.
A characteristic example of direct flotation in alkaline media
can be found in the Republic Mine. Republic Mine’s ore is
a specular hematite with small amounts of magnetite and martite.
The gangue is a recrystallized chert containing sericite, grunerite,
cummingtonite, and chlorite. Figure 1 outlines the refining pro-
cess at Republic Mine. Key highlights of this flowsheet are:
(1) Two stages of desliming involving two cyclones, the
underflow of which is treated with tall oil in a series
of conditioners.
(2) Regrinding to liberate residual quartz and silicates
from the iron minerals.
(3) Steam injection into the pulp conditioner, which is
used to progressively raise the temperature to boiling.
This process can upgrade the specular hematite from an iron
grade of 36.5% to 65.4% while maintaining an 82.5% iron
recovery. The flotation collector consists of approximately
91% oleic and linoleic acids, 6% rosin acids, remainder unsa-
ponifiable (Houot 1983).
In the 1960s, investigations began to understand direct
flotation in weakly acidic media. The advantage of an acidic
medium is that in acidic conditions the surface charges of iron
minerals and many common gangues can be more distinct
than in alkaline flotation. This yields a greater difference in
flotability, allowing for better separations (Bunge, Morrow
and Trainor 1977). One example of the acidic medium
approach would be Groveland Mine in the United States,
shown in Figure 2, which achieved a final iron grade of
64.3% with a silica content of 6.5% (Houot 1983).
Another direct flotation concentrator is the Qidashan concen-
trator in China, put into production in the early 1980s (Yong
2005). This process is shown in Figure 3, built to concentrate
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 3

Figure 2. Overview of the Groveland Mine iron ore beneficiation process, utilizing direct flotation in acidic conditions (based on Houot 1983).

Figure 3. Overview of the iron ore beneficiation process in the Qidashan concentrator (based on Yong 2005).

from an iron grade of 28.94% to 63.6% in a weakly acidic medium
(Fan, Jing and Zhu 2011; Zhang and Dai 2012). The flotation
collector was sodium petroleum sulfonate, with sulfuric acid
used as a pH regulator. Interestingly, the Qidashan concentrator
had previously run alkaline medium direct flotation, but could
only achieve grades of 59.5% (Fan, Jing and Zhu 2011; Zhang and
Dai 2012).
Unlike alkaline medium flotation, weak acidic media are highly
sensitive to the presence of slimes. This is because under acidic
conditions the opposing surface charges allow the ultra-fine par-
ticles of the slimes to coat the other materials, causing them to
behave like the slimes in flotation. Thus, desliming is required
to achieve high degrees of separation with direct flotation in
weakly acidic media. Due to the fine particle size of slimes most
traditional separation methods are ineffective, including high-
intensity magnetic separation, gravity separation, and cyclones.
In China, a lot of work going into designing efficient desliming
methodologies started in the 1980s (Sun 2006). Perhaps the com-
mon approach for desliming is selective flocculation and
dispersion.
Comparative studies of direct flotation in alkaline and weakly
acidic media have been carried out by the Maanshan Mine
Research Institute in China. In general, the final iron grade was
found to be 2–4 percentage points higher at the same recovery
using weakly acidic media. Additionally, filtration of the mildly
acidic concentrate is simple. However, due to the requirement
for desliming and the high collector usage, direct flotation in
weakly acidic media ends up having a higher overall cost.
In summary, direct flotation, whether alkaline or acidic, is
attractive due to the simplicity of the cost and reagent systems. It
4 X. ZHANG ET AL.
is suitable for the separation of low-grade and weakly-magnetic
iron ores with relatively coarse liberation sizes. However, direct
flotation has difficulty reaching iron grades above 64%, and the
simplicity of the reagent system is somewhat offset by the high
quantity of reagent necessary compared to alternative flotation
processes. Direct flotation processes around the world have
largely been replaced by reverse flotation processes. Direct flota-
tion in acidic conditions is capable of achieving more effective
separations but is also much more sensitive to slimes, while
direct flotation in alkaline conditions is limited by the similarity
of the surface charges on both the gangue and valuable minerals.
2.2. Reverse flotation of iron ore
Reverse flotation is presently the most popular methodology
for concentrating iron ore. In reverse flotation the goal is to
cause the gangue materials to move up and into the froth,
which is precisely the opposite of direct flotation (Ma 2012;
Filippov, Severov and Filippova 2014). Reverse flotation is
broadly divided into two categories depending on the choice
of collector: cationic reverse flotation and anionic reverse
flotation.
2.2.1. Cationic reverse flotation
Cationic reverse flotation utilizes a cationic collector to float
and reject negatively charged silica. Silica surfaces hold nega-
tive charges at all but exceedingly acidic pH values, so theo-
retically cationic reverse flotation can be performed at a wide
range of pH values. In practice, alkaline pH values are often
used to disperse valuable minerals and silica from each other
Figure 4. Overview of the Tilden Mine iron ore beneficiation process, utilizing cationic reverse flotation (based on Houot 1983).
and improve separation, but in the case of hematite ores this
also tends to require the addition of a depressant to prevent
the flotation of hematite.
Cationic reverse flotation was initially developed by the
U.S. Bureau of Mines branch in Minnesota, and is by far the
most widely used in the iron ore industry (Filippov, Severov
and Filippova 2014; Houot 1983; Iwasaki 1983). This process
floats silica gangue minerals such as quartz under alkaline
conditions (pH 9.5–10.5) using amine collectors and starch
depressants (Peres and Correa 1996; Papini, Brandao and
Peres 2001; Filippov, Filippova and Severov 2010). This pro-
cess primarily sees use while processing hematite and goethite
ores – some magnetite ores are floatable without a depressant
at lower pH values (around 8). The starch depressants prevent
the collector from attaching to the iron oxides, allowing for
a high degree of separation. Cationic reverse flotation has
been applied widely in the United States, Brazil, Canada,
India, Russia, and Chile (Lima, Valadão and Peres 2013;
Peres et al. 2009). Research in cationic reverse flotation for
iron ore continues to be an active field.
A characteristic example of the reverse cationic flotation
route is shown in Figure 4, which outlines the process of
Tilden Mine in the United States. Tilden Mine utilizes selec-
tive flocculation and dispersion followed by flotation to sepa-
rate a low-grade hematite ore (Villar and Dawe 1975). The ore
is initially ground to a passing size of 80% passing 25 μm and
dispersed using sodium hydroxide along with a dedicated
dispersant: originally sodium silicate, but more recently
sodium polyphosphates and since 2015 sodium polyacrylates.
Corn starch is used to flocculate the iron-bearing minerals in

the deslime thickener, and the overflow is removed as slimes.
Deslime overflow at Tilden accounts for 15–30% of the total
material loss and the loss of 5% of the iron-bearing minerals.
The deslime underflow typically has a grade around 44%, but
can vary widely based on the water quality. The deslime
underflow feeds the flotation stage, consisting of 1 rougher
and 4 scavengers. Each scavenger recycles its concentrate back
to the initial flotation feed, while passing its froth product to
the next scavenger (DeVaney 1985). The fourth scavenger’s
froth product is considered the final tailing product. The
flotation collector is an unneutralized primary ether amine,
and corn starch is again added as a depressant. The final
product has an iron grade of 64–67%, contains 5% silica,
while recovering approximately 75% of the iron.
Another example of reverse cationic flotation is the Empire
Mine in the United States. In Empire Mine, the flotation feed
is a magnetite concentrate prepared with 2-stages of low-
intensity magnetic separation with an iron grade of 63%.
While additional stages could be used to increase the grade
further, 3-stage low-intensity magnetic separation had been
tried in Griffith Iron Mine in Canada to achieve 66.5% iron
grade in magnetite from a 29% iron grade iron chert.
However, the final product still contained more than 6.5%
silica. Thus, instead of adding more stages to magnetic separa-
tion, Empire Mine chose to use reverse cationic flotation to
remove the problematic silica directly. This choice allowed for
a final concentrate iron grade of 69% with less than 3.5%
silica. The flotation step had a 96% recovery, using an amine
salt (ADMAG-83) collector. Similar results were found by
Samarco Mine which processed a 53% iron grade hematite
ore, which was ground to 92% passing 0.15 mm and floated
using mechanical flotation cells and column flotation.
Samarco Mine’s product is about 15.5 million tons per year
of crude concentrate at an iron grade of 67.17% and contain-
ing only 1.1% silica.
In Canada, iron mining operations started in 1954 in
Schefferville, Quebec, Canada. At that time, no particular
ore beneficiation was required, but by the end of the 1950s
research began on upgrading an iron deposit with an iron
grade of 51% and a silica content of 15%. In 1973, the first
pellets were produced after beneficiation with reverse cationic
flotation. In 1981 the Sept-Iles concentrator flotation circuit
consisted of 8 rougher cells, 3 cleaner cells, 4 first stage
scavenger cells, and 4 second stage scavenger cells. It operated
at a pH of 10.5 and produced a final concentrate with an iron
grade of 64% and containing 4.5% silica at a 93.5% iron
recovery (Gagnon 1981).
In Brazil, 10 different concentrators in the Iron Quadrangle
utilize reverse cationic flotation to upgrade a banded hematite
quartz ore. Some plants use only flotation to separate the ore,
while other plants use a combination of high intensity magnetic
separation followed by flotation. Slimes are usually treated with
separate flotation circuits to be reclassified (Peres et al. 2009).
In Chile, Candelaria’s mine is a copper beneficiation plant
that produces tailings with a magnetic iron grade of 2–10%.
These tailings are processed by a nearby concentrator, Planta
Magnetite, which mixes them with a magnetite ore from Mina
de Los Colorados (a part of the CAO Valle del Huasco deposit,
iron grade around 40%). After comminution and classification,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 5
magnetic separation suffices to increase the iron grade of the
feed material to 35–40%, after which it undergoes another grind-
ing step to 85% passing 44 μm to liberate the iron ore. This
reground ore is then deslimed and floated via reverse cationic
flotation to produce a final concentrate with an iron grade of
66% (Oyarzun 2013).
In Russia, the Mikhailovsk plant (MMPP) processes an
unoxidized ferruginous quartzite. While most Russian iron
ore is processed from the Kursk Magnetic Anomaly (KMA)
and possesses significant magnetic properties making mag-
netic separation ideal, the MMPP ore does not readily sepa-
rate under magnetic separation. The MMPP has developed an
integrated magnetic separation-flotation process for its ore,
which utilizes wet magnetic separation followed by reverse
cationic flotation using an amino ester collector and
a causticized corn starch as an iron minerals depressant. The
final concentrate has an iron grade of approximately 69.7%
(Varicheva et al. 2017).
In India, most iron ores are only washed and classified
before sale. However, as alumina rejection and the processing
of slimes (in this case, particles smaller than 37 μm) or tailings
have become more important (Jain et al. 2013), focus has
returned to cationic reverse flotation, often in tandem with
hydrocyclones or magnetic separation (Kumar et al. 2010).
In China, research on cationic reverse flotation began in the
1970s. In the 1980s, it was successfully implemented at the
Donganshan Sintering Plant, resulting in a 4 percentage point
increase in iron grade – from 61.50% to 65.50% (Fan, Jing and
Zhu 2011). However, there are fewer varieties of cationic and
amine collectors available in China, and many of the available
collectors have considerable drawbacks: too much froth, too
sticky froth, poor liquidity of the froth, poor selectivity overall,
and a high sensitivity to slimes. As such, the reverse cationic
flotation route was not widely popular at the time. In more
recent years, China has been vigorously promoting saving
costs, limiting energy consumption, and environmentally-
friendly practices to intensify its economy, and as such cationic
collectors have undergone rapid development. “Study on new
technology and new reagent for iron-increasing and silica-
reduction by cationic reverse flotation” has been undertaken
and completed by the Anshan Iron and Steel Company in
accordance with the National “Tenth Five-Year Plan” in China
as one of the Science-Technology Projects (Song and Li 2008).
It is interesting that cationic reverse flotation has not been
so successful in China. Instead, research there has focused
more heavily on anionic reverse flotation. There is little con-
crete data to explain this discrepancy, but perhaps it is
explained by the availability of reagents or a difference in
mineralogy. For the United States in particular, many iron
ore deposits have extremely fine liberation sizes (below
38 μm), which necessitates desliming to avoid issues with
entrainment. Many desliming routes lead very naturally into
cationic reverse flotation, as cationic reverse flotation typically
benefits from the dispersing conditions established during
deslime. Thus cationic reverse flotation is typically preferred
in these cases (Colombo 1980, 1986; Bruckard, Smith and
Heyes 2015; Haselhuhn and Kawatra 2015a, 2015b).
To summarize, cationic reverse flotation has several advan-
tages when compared to direct flotation (Filippov, Filippova
6 X. ZHANG ET AL.
and Severov 2010; Ma, Marques and Gontijo 2011; Song and
Li 2008; Zhang and Dai 2012):
(1) Higher flotation rates and low-operating tempera-
tures, simplifying practical implementation. While
the reagent system is necessarily more complex than
direct alkaline flotation, it is not unduly so.
(2) The operation is typically simple and reliable. There
are only a few key reagents in the reverse cationic
flotation process, and as such the flotation process is
easy to operate and readily adaptable to varying oper-
ating conditions.
(3) Reverse flotation and gravity or magnetic separation
readily complement each other, taking advantage of
differing physical mechanisms to achieve better
separations than are possible with only one technique
or the other.
However, there are also some considerable drawbacks (Filippov,
Filippova and Severov 2010; Ma, Marques and Gontijo 2011;
Song and Li 2008; Zhang and Dai 2012):
(1) The amine collector can still adsorb to the mineral
surface by complex adsorption, meaning that selec-
tivity is often lower than comparable anionic reverse
flotation processes.
(2) Compared to other collectors, many commonly used
amine collectors have both collecting and frothing prop-
erties. This results in high viscosity and poor fluidity of
the froth during flotation. Etheramines in particular
have considerable frothing properties, and it may be
desirable to investigate non-frothing alternatives so
that entrainment can be more completely controlled.
This is discussed in more detail in section 4.3.
(3) The cationic amine collectors are toxic, and present
an environmental hazard if improperly disposed of.
2.2.2. Anionic reverse flotation
Anionic reverse flotation uses anionic collectors to float and
reject positively charged silica. While silica surfaces only
naturally hold a positive charge at highly acidic pH values,
calcium and magnesium cations can specifically adsorb to it.
These cations contribute the positive charge to the silica sur-
face and the reagents which provide these calcium or magne-
sium ions are termed activators as a result.
Anionic reverse flotation was initially developed in China
(Yuan, Han and Yin 2007). In practice anionic reverse flota-
tion floats silica gangues by activating the silica with lime and
then floating them with fatty acids as a collector at elevated
pH (11–12) while using starch to depress the iron-bearing
minerals. The primary advantages of anionic reverse flotation
are a decreased sensitivity to slimes, and a lower collector cost
as the fatty acids are a major waste product from the paper
industry (Forsmo et al. 2008; Zhao, Yahui and Yongdan
2012). In practice it has been found that the calcium ions
provided by lime both activate the siliceous minerals while
allowing for strong depression of the iron-bearing minerals in
highly alkaline conditions. This results in a large difference in
flotability, leading to a high degree of selectivity and separa-
tion. The anionic reverse flotation process has also shown
a good adaptability to mineral variations, especially for iron-
bearing silicate minerals.
55% of the iron ore in China is referred to as Anshan-type
iron ore. 40% of these Anshan-type ores are low-grade hema-
tite ores with uneven mineral dissemination sizes along with
complex mineral compositions (Han et al. 2006; Sun 2006;
Fan, Jing and Zhu). As a result of these factors, these ores are
difficult to upgrade. Over the past 50 years, investigations
have been undertaken by research institutes, universities,
and industries to develop effective processes to handle these
ores. The mineralogy of the Anshan ores has led to the
application of anionic reverse flotation techniques in several
concentrators throughout China.
One of the major processes resulting from these repeated
investigations is depicted in Figure 5, which utilizes multi-
stage grinding, gravity separation, magnetic separation, and
anionic reverse flotation to achieve economical processing
costs while producing a useable product. This process has
been implemented at multiple large-scale concentrators
within China, including the Qidashan concentrator,
Gongchangling concentrator, Sijiaying Mine, Yuanjiacun,
and other. During the flotation stage of this process the quartz
is activated using calcium oxide, an industrial modified fatty
acid (RA-715) is used as a collector, corn starch is used to
depress the iron oxide, and the pH is adjusted to 11.5 using
sodium hydroxide. The results of these concentrators are
presented in Table 1 below.
The largest concentrator in China is the Yuanjiacun con-
centrator, owned by Tai Steel, which processes 22 million
tons/year of raw ore. It is supplied by a reserve of approxi-
mately 1.2 billion tons of Anshan-type hematite ore. The
liberation size of this ore is approximately 90% passing
45 μm, making gravity separation ineffective. As such, the
process outlined in Figure 5 is poorly suited for handling
this ore. An alternative process was developed by the
Changsha Mining and Metallurgy Research Institute consist-
ing of: grinding, low-intensity magnetic separation, high-
intensity magnetic separation, followed by anionic reverse
flotation. This flowsheet is depicted in Figure 6, and has
achieved stable operation at Yuanjiacun. The reverse flotation
stage at Yuanjiacun utilizes a newly developed modified fatty
acid referred to as MH. Otherwise, it is similar to previous
processes: calcium oxide is used to activate the quartz, iron is
depressed using corn starch, and pH is adjusted to 11.5 with
sodium hydroxide. The final concentrate has an iron grade of
66.95% and a final iron recovery of 72.62% from a run-of-
mine hematite ore with an iron grade of 31.72% (Chen, Ge
and Yu 2005; Mao, Huang and Zhao 2005).
Another ultrafine Anshan-type hematite-based ore deposit
is present at Qidong Mine. This deposit is the largest iron ore
deposit in the Hunan Province in China, with 360 million
tons of reserve. The liberation size is 95% passing 37 μm. At
this liberation size again gravity separation is ineffective.
Additionally, flotation by itself is also insufficient to achieve
a quality separation. Instead, due to the considerable forma-
tion of ultrafine silica slimes which interfere with both catio-
nic and anionic reverse flotation methodologies, desliming is
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 7

Figure 5. Overview of the beneficiation process used for low-grade Anshan-type iron ores in China via anionic reverse flotation.

Table 1. Summary of concentrator input feeds and final product compositions Jing and Zhu 2011; Sis and Chander 2003). These taconites have
for selected concentrators utilizing anionic reverse flotation.
an iron grade of approximately 39% and are ground to 60%
Raw Ore Iron Concentrate passing 44 μm. This flotation was performed without de-slime,
Iron Grade Iron Grade Silica Iron Recovery using calcium chloride to activate the silica, and depressing the
Concentrator (wt%) (wt%) (wt%) (wt%)
iron oxides with dextrin (Gum 9072). The anionic collector in
Qidashan 29.16 67.67 3.85 71.65
Sijiaying 29.14 66.50 4.50 75.00 this process was Acintol FA2, which contains 97.8% tall oil, while
Gongchangling 28.78 67.79 4.10 81.99 the pH was maintained at 11.5 using sodium hydroxide. The
Yuanjiacun 31.72 66.95 NA 72.62
Qidong 30.32 Approx. 63–65% NA Approx. 65–70% resulting concentrate had an iron grade of 60.3%, silica content
NA: Not Available.
of 6.0%, and an iron recovery of 90.5%. However, despite these
fairly successful results, the process did not see widespread
application due to the high cost of reagents and difficulties
arising during concentrate filtration (Filippov, Severov and
necessary. Thus, a process consisting of multi-stage grinding Filippova 2014; Ge, Yu and Zhu 2009).
followed by selective flocculation was developed, as depicted Anionic reverse flotation can also be used to float apatite
in Figure 7. An iron ore concentrator has been built following gangue materials, to lower the phosphorous content of the
this scheme with a capacity of 3 million tons/year, with an resulting concentrate. For an apatite-bearing magnetite ore,
iron grade target of 63–65% while maintaining an iron recov- successful separation was achieved using a fatty acid mixture
ery of 65–70% (Hu, Zheng and Xiao 2010; Liu 2003). This (Altrac 1563) of 95–98% tall oil and 2–5% maleic anhydride as
development represents a major breakthrough in the handling a collector, and sodium silicate as a dispersant for the fine
of ultrafine hematite ores via anionic reverse flotation. particles and a depressant for the magnetite (Forsmo et al. 2008).
Since the 1960s anionic reverse flotation of low-grade hema-
tite ores has also been carried out in the United States, Canada,
and the Soviet Union (Filippov, Severov and Filippova 2014;
2.3. Stepped flotation
Sandvik and Larsen 2014). In the United States, the Hanna
Mining and U.S. Bureau of Mines laboratories jointly developed Stepped flotation processes have recently been proposed for
the anionic reverse flotation route to separate the taconites of the treating difficult carbonate-bearing iron ores (Shao 2013).
Lake Superior deposits (Bunge, Morrow and Trainor 1977; Fan, These are processes which combine multiple flotation routes
8 X. ZHANG ET AL.
Figure 6. Overview of the beneficiation process used by the Yuanjiacun iron ore concentrator, utilizing anionic reverse flotation (based on Chen, Ge and Yu 2005;
Mao, Huang and Zhao 2005).
into a single complementary methodology. Carbonate miner-
als, which in iron ore primarily refers to siderite, are present
in up to 5 billion tons of China’s iron ore reserves (Luo et al.
2013; Song, Yuan and Wei 2015). In practice it has been
found that these minerals have middling flotabilities and read-
ily generate slimes during grinding. These slimes then end up
coating the surfaces of both the hematite and the silica phases,
resulting in considerable difficulties achieving good separa-
tions with flotation. In particular, some of the silica would be
depressed by the siderite slimes, which can itself be depressed
partially by starch, while some of the hematite would fail to be
depressed due to the presence of the same slimes (Yin, Han
and Xie 2010; Yin et al., 2011). As such, carbonate-bearing
iron ores were considered too difficult to process, and were
stockpiled at the cost of increased land usage and the resulting
environmental pollution risks.
Stepped flotation processes were developed by the
Northeastern University in China to breakthrough this
barrier to utilization. For the siderite-bearing iron ores in
China, the process begins by floating the siderite in neutral
direct flotation using an anionic collector and depressing
the hematite using starch (Zhang et al. 2007; Song, Yuan
and Wei 2015). Afterward, the silica is separated by anionic
reverse flotation in strongly alkaline conditions using lime
as an activator (Zhang et al. 2007; Song, Yuan and Wei
2015). This process, depicted in Figure 8, was put into
practice at the Donganshan Concentrator in China yielding
a concentrate with an iron grade of 63.02% and an overall
iron recovery of 63.77%. This two-step process mitigates
the impact of the siderite on the reverse flotation, allowing
for the efficient utilization of these carbonate-bearing ores.
3. Desliming
Desliming is the separation of ultrafine particles, typically but not
always silica, from coarser particles in a slurry during mineral

Figure 7. The Qidong concentrator uses multiple deslime and regrinding stages to separate an ultra-fine iron ore with anionic reverse flotation (based on Hu, Zheng
and Xiao 2010; Liu 2003).
processing. Slimes interfere with many aspects of any beneficiation
process resulting in higher reagent consumption and reduced
separation efficiencies. As such, desliming is necessary when work-
ing with finely ground iron ores, especially before gravity separa-
tion, magnetic separation, and flotation (Tripathy, Banerjee and
Suresh 2015).
With regards to flotation, it has been found that flotation of iron
ores is most effective with particle sizes ranging from 10 μm to
100 μm. Within the context of reverse flotation particles smaller
than 10 μm may be referred to as fine slime (Krishnan and Iwasaki
1984). These particles may nonselectively and spontaneously aggre-
grate in the slurry, or they may coat coarser particles making
surface selective separations like flotation less efficient. Due to the
large surface areas presented by these ultrafine particles, they can
adsorb a disproportionately large quantity of reagents despite their
low mass. These fine particles can also adsorb to and monopolize
the surface of the air bubbles, preventing them from attaching to
other minerals (Edwards, Kipkie and Agar 1980; Iwasaki 2000).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 9
The presence of fine slimes also complicates the filtration steps after
flotation. Thus, a high content of fine slimes negatively impacts the
flotation rate and selectivity, while increasing reagent usage (Lima,
Peres and Marques 2012).
Industrially, desliming is typically accomplished using either
a thickener or a cyclone, and is primarily targeted at removing
particles primarily smaller than 20 μm (Thella, Mukherjee and
Srikakulapu 2012). The particle size cut for cyclones is defined by
the cyclone geometry, pressure, and material being separated,
with the 20 μm being typical for applications in iron ore. Deslime
thickeners can achieve finer cut sizes by carefully controlling the
rise rate against the terminal velocities of the particles.
3.1. Conventional desliming
The earliest report proclaiming the importance of desliming
was published in 1947 (Clemmer 1947) in the context of
cationic reverse flotation of iron ores. The theory behind the
10 X. ZHANG ET AL.
Figure 8. Flowsheet for the beneficiation of a carbonate-containing iron ore using stepped flotation in Donganshan concentrator, using both direct and reverse
flotation methods (based on Zhang et al. 2007; SoSong, Yuan and Wei 2015).
behavior of slimes has been well-established as primarily an
electrostatic phenomenon stemming from heterocoagulation
(Fuerstenau, Gaudin and Miaw 1958; Iwasaki et al. 1962a;
Usui 1972). When slimes have different surface charge sign
than the bulk material they are attracted to and coat the bulk
material, causing the bulk material to display the surface
character of the slime material during flotation.
Iwasaki (2000) illustrated the effects of slimes on cationic and
anionic reverse flotation. Goethite slimes were found to quickly
inhibit the flotation of quartz by an equilibrium concentration of
0.1 mM dodecylamine at pH 6, with concentrations as low as
0.05 g/L of slimes lowering quartz recovery below 15%. Kaolinite
and bentonite had no effect on quartz recovery in cationic
flotation up to slime concentrations of 1 g/L so long as the
equilibrium concentration was maintained. In anionic reverse
flotation focusing on floating the goethite using 0.1 mM sodium
dodecylsulfate at pH 3, the presence of goethite slimes had little
effect on the goethite recovery up to slime concentrations of
1 g/L. However, quartz, kaolinite, and bentonite clays had an
increasingly detrimental effect on goethite recovery, with even
a 0.05 g/L concentration of bentonite slimes reducing goethite
recovery below 10%. At 1 g/L, quartz is associated with an
approximately 55% goethite recovery and kaolinite with an
approximately 15% goethite recovery. In both cationic and
anionic flotation these drops in recovery are associated with
the slimes and the coarser particles having opposing charges,
and thus the slimes will coat the coarse particles. This is part of
the reason why anionic flotation typically takes place at such

alkaline pH values: under such conditions both the silica gangue
and goethite surfaces are negatively charged, limiting the
amount of slime coating which can occur (Chen and Peng
2018; Iwasaki 2000).
It has also been demonstrated that ultrafine particles smal-
ler than 10 μm have a negative impact on cationic reverse
flotation in general (Lima 2001). This is largely attributed to
the considerable surface area of such fine particles causing
high reagent usage.
One comparative example of the effects of desliming can
be found at the Mikhailovsky plant in Russia. Removing the
sub-10 μm particles from the wet magnetic separation tailings
resulted in a modest improvement in the selectivity for hema-
tite of the cationic reverse flotation step. Removing the sub-
20 μm particles increased the selectivity dramatically, but also
increased the hematite loss during desliming from 7.6% to
16.6% (Filippov, Filippova and Severov 2010).
Ma, Marques and Gontijo (2011) reports an example of the
effects of desliming on the particle size distribution, which
reduced the sub-10 μm particle fraction from 7% to 2%, the
sub-20 μm particle fraction from approximately 12% to approxi-
mately 6%, the sub-50 μm particle fraction from approximately
45% to approximately 38%, and the sub-100 μm particle fraction
from approximately 80% to approximately 72%. Ma, Marques
and Gontijo (2011) also demonstrates that anionic reverse flota-
tion achieves better separation over the ultrafine fraction than
cationic reverse flotation, whereas cationic reverse flotation
achieves better separations at coarser size ranges. At sub-10 μm
particle size ranges, cationic reverse flotation recovers only 3–7%
of the iron in the concentrate, but anionic reverse flotation
recovers between 20–60% of the same material. Both anionic
and cationic reverse flotations reject the majority of the silica
from the concentrate. The main advantage of anionic reverse
flotation then is maintaining a high recovery of iron while
rejecting almost all of the silica even at very fine particle sizes.
As anionic reverse flotation is less sensitive to the presence
of fine slimes, Houot (1983) has claimed that desliming is not
essential to the operation of anionic reverse flotation.
However, this claim has not yet been validated with experi-
mental evidence. Ma (2012) has also reported that anionic
reverse flotation has been successful in China’s iron ore
industry in recent years, as the omission of the deslime step
reduces costs but the lower sensitivity to fine slimes can allow
even a potential improvement in final product grade over
cationic reverse flotation. It should be recalled that Chinese
concentrators frequently use multiple stages of magnetic
separation which may be responsible for the removal of
a significant quantity of the slimes. As previously mentioned
however, a large enough quantity of slimes is ultimately detri-
mental to both flotation routes, as all slimes will increase
reagent consumption.
Wang (2009) has studied the impact of desliming operations
at the Karara concentrator in Australia. The Karara concentrator
processes a low-grade and high-silica magnetite ore with
a liberation size of 80% passing 35 μm via anionic reverse
flotation. Both pilot-scale and plant-scale investigations showed
that desliming positively impacted the overall flotation effi-
ciency. Wang (2009) showed that higher degrees of separation
are achieved more quickly after desliming. In particular, a silica
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 11
content of 4.75% requires a 4-minute residence time to achieve
without desliming, but only a 3-minute residence time with
desliming. Although in both cases the final concentrate iron
grade and silica content were the same (at 67.9% and 4.75%
respectively), the iron recovery increased from 81% to 84% due
to desliming. To achieve the same recovery without desliming
requires increasing the reagent dosage and would result in
a higher recovery of silica in the concentrate.
Mohanty and Das (2010) investigated the modeling of
hydrocyclone-based slime upgrading using sodium hexameta-
phosphate as a dispersant for iron slimes at Indian iron ore
mines. These slimes have a high iron content (approx. 58%
iron grade) and are primarily contaminated with finer silica
and alumina, along with some organics and water. They
predicted ideal parameters for the diameter of the hydrocy-
clone’s vortex finder, the inlet pressure, the amount of dis-
persant, and the solids concentration for use with the iron ore
slimes generated, with the goal of achieving 60% recovery and
65% grade from the hydrocyclone. Though this is not strictly
speaking the same goal as desliming, the challenges presented
by the extremely fine particle sizes (90% passing 20 μm feed)
remain significant.
Jena et al. (2015) performed an investigation on a similar
Indian iron ore slime using hydrocyclones to design
a flowsheet for the upgrading of these slimes to a usable
iron concentrate. In this case, the slime was found to have
a 57.1% starting iron grade, and a magnetic separation plus
hydrocyclone circuit was designed to upgrade it to 62.5% iron
grade at 77.3% recovery. Again, quartz and alumina were the
major gangue materials.
Kruger, Naik and Naudé (2018) performed another inves-
tigation along the same lines, taking an ultra-fine material
from a SLon (WHIMS) concentrator and processing it into
low-silica iron product using largely desliming unit opera-
tions. In this case, approximately half of the silica needed to
be removed from a typical African iron ore to meet the target
grade, which they managed to achieve using a combination of
hydrocyclones and flotation. Around 60% of the iron recovery
was immediately realized in the hydrocyclone circuit, and of
the remaining 40% another half of that was recovered using
cationic reverse flotation.
In summary, slimes have been shown to have a notable,
negative impact on the quality and efficiency of flotation.
Desliming, regardless of methodology, allows for the improve-
ment of many iron ore separations if there are ultra-fine
particles present.
3.2. Selective dispersion and flocculation desliming
Selective dispersion and flocculation desliming is a particular
deslime technique which relies on surface chemistry principles
to separate ultrafine particles. In particular, the components
which are to be removed are strongly dispersed into the
solution to prevent settling, while the components which are
to be retained are selectively flocculated to increase settling. In
the context of iron ore, the dispersion is typically accom-
plished using sodium hydroxide or other strong bases, while
the flocculation is typically performed using starch.
12 X. ZHANG ET AL.
It has been found that one of the key factors leading to
effective desliming is a high degree of dispersion among the
fine particles in the pulp (Huang et al. 2016). This state can be
achieved by operating at highly alkaline conditions, such as by
using sodium hydroxide, which results in all mineral surfaces
carrying negative surface charges.
The extent of alkalinity required was investigated by Peres,
Lima and Araújo (2003) and Lima, Peres and Marques (2012)
for nine samples collected at the CVRD (now Vale) mines of
Alegria and Fabrica Nova in the Iron Quadrangle, Brazil.
These results found that when the pH remained above 8,
dispersion was largely unaffected. The amount of slimes by-
passing the desliming typically had a significant effect on
flotation behavior, where a larger amount of slimes present
lowered the selectivity index for most samples. However, two
samples are unaffected by the increased slimes concentration.
For one sample, this may be attributed to an atypically high
degree of dispersion compared to the other samples.
As a consequence of this behavior, it is suggested that
dispersants such as sodium silicate or tripolyphosphate be
used during the cationic reverse flotation of iron ores.
However, conventional desliming would still result in exces-
sive iron loss for ores with very fine liberation sizes. Instead,
dispersion combined with selective flocculation is proposed to
treat these ores (Colombo 1980; Colombo and Frommer
1976). By adding a dispersant and starch flocculant to the
desliming step, the iron losses can be mitigated. This style of
desliming has been implemented at Tilden Mine, Michigan,
United States (Villar and Dawe 1975).
To achieve the best results, it is necessary that the ground
pulps be properly dispersed before the starch is added. The
mineralogy and water chemistry of the slurry have
a significant impact on the optimal reagent dosages for selec-
tive desliming. Heerema, Lipp and Iwasaki (1982) investigated
this sensitivity by testing flotation with a 1:1 goethite-quartz
mixture. An iron grade of 28.5% was found to be the lower
limit of separation available, due to the natural desliming
properties of the dispersed material. In the absence of calcium
ions (Ca2+) corn starch results in very good selectivity.
However, even the addition of a fairly small quantity
(0.001 M) of calcium ions results in greatly lowered selectivity:
the iron grades were reduced from up to 48.5% to at best 32%.
The conclusion is that controlling the calcium concentration
via complexation or precipitation can significantly improve
deslime selectivity.
This can be accomplished with chemicals such as ethyle-
nediaminetetraacetic acid (EDTA), sodium tripolyphosphate
(STPP), or sodium hexametaphosphate (SHMP) (Arol and
Iwasaki 1987; Manukonda and Iwasaki 1987). Heerema,
Lipp and Iwasaki (1982) found that fully complexing the
calcium with EDTA restores the selectivity of the separation,
but STPP is less effective and SHMP is actively detrimental to
the separation. It appears that SHMP indiscriminately dis-
perses the pulp, resulting in poor separations overall. As
such it can also be concluded that desliming remains sensitive
to some of these calcium complexes or other calcium com-
pounds which may be formed in the slurry. Iwasaki (2000)
reported that montmorillonite (the principle component of
bentonite), which has a high cation exchange capacity, shows
promise in controlling calcium concentrations in the pulp.
Iwasaki (2000) also reports that precipitating the calcium
with carbonate or ultrasonic treatments can also be effective
for controlling the calcium concentration.
Krishnan and Iwasaki (1984) have found that sodium
silicate is nonselective for dispersing goethite-quartz mixtures.
At low silicate levels corn starch selectively flocculates
goethite, but at high silicate levels it is ineffective.
Weissenborn, Warren and Dunn (1994) carried out labora-
tory scale selective flocculation on sub-10 μm iron ore tailings
containing a primarily kaolinite gangue. They tested a variety
of commercially available starches and polyacrylamides to
upgrade a 46.6% iron grade feed material. Wheat starch was
found to be the most selective for this material, achieving
a 57–58% iron grade and a 65–75% iron recovery.
It is worth emphasizing that the process water going into
selective flocculation is a complex system of ions and reagents.
Haselhuhn, Carlson and Kawatra (2012) investigated the
effects of water chemistry on the selective flocculation and
dispersion of a hematite ore in an industrial concentrator
plant. The pH was shown to have the greatest impact on
selectivity, which can be attributed to the pH value’s effect
on the surface charges of all the materials present. The pH
value in this facility is maintained above 10.5 during deslime
and flotation to ensure that the silica and hematite remain
dispersed. The pH is then adjusted toward neutral before
filtration, which causes a significant change in the water
chemistry as ion solubilities change and the dolomite and
limestone fluxes are added.
Huang et al. (2016) reports that the selective flocculation
and dispersion process using a humate-based flocculant was
applied to a Bayer process red mud in China. Bayer process
red mud typically has a relatively high iron grade, as its
characteristic red color primarily stems from the presence of
fine hematite. The humate-based flocculant was shown to
exhibit good selectivity under alkaline conditions: iron recov-
ery was 86.25 ± 1.31% and the concentrate iron grade was
61.12 ± 0.10%. This was achieved at 2% solids, a flocculant
dosage of 30 mg/L, a sodium silicate dosage of 200 mg/L,
a slurry pH of 10.0, and continuous mixing at 1000 rpm. It is
found that the humates selectively bridge the iron minerals,
resulting in large iron flocs which can settle comparatively
rapidly.
Multi-stage flocculation-desliming has also been imple-
mented at a small plant scale. The plant in question has
a capacity of 150,000 tons/year and produces an iron concen-
trate with an iron grade of 64.77% at a recovery of 78.65%
(Liu and Shi 2009).
4. Flotation reagents for iron ore
Flotation reagents are chemicals which can either change the
surface properties of minerals, making them more or less
susceptible to flotation, or the properties of the liquid such as
stabilizing the froth layer. The reagents form the critical back-
bone of providing flotation circuits the control and efficiency
required to separate various minerals from each other. The
most common reagent schemes typically involve a variety of
reagent roles including: collector, frother, depressant, activator,

dispersant, and flocculant (Nakhaei and Irannajad 2018). In
many cases one chemical may serve in multiple roles. For
example, starch is used as a depressant in flotation and
a flocculant in desliming. Additionally, many amine collectors
have significant frothing properties, often negating the need for
a dedicated frother. Due to the critical importance of these
reagents to the flotation process, a significant amount of prac-
tical work and theoretical research has gone into understanding
their roles in flotation.
4.1. Collectors
The role of the collector is to adsorb to the mineral surface
while increasing its hydrophobicity. The hydrophobized sur-
face can then attach to air bubbles, carrying the collected
mineral into the froth phase. Because most minerals are sig-
nificantly hydrophilic, many collectors are designed to have
very hydrophilic functional groups on one end of their mole-
cular structure, while presenting a hydrophobic tail end on
the other. Common hydrophilic functional groups include
carboxylic acids (-COOH), amines (-NH2), sulfonic acids (-
SO3H), hydroximic acids (-COH•NOH), and others (Fan, Jing
and Zhu 2011). Depending on the charge of the functional
groups after disassociation in water, the collectors can be
classified as anionic (e.g. most acids), cationic (e.g. amines),
nonionic (no groups contribute to a charge when dissolved in
water), or amphoteric (groups contribute a charge, but the
molecule retains a neutral net charge). Nonionic collectors
may be mixed with cationic or anionic collectors, though
this is only infrequently used in iron ore flotations.
Amphoteric collectors can be used to boost the performance
of cationic or anionic collectors.
Additionally, it is in some cases worthwhile to co-dose
both cationic and anionic collectors in the same process.
Though they cannot both be simultaneously active in solu-
tion, as the ionic interactions between the collectors will result
in the complete utilization of one of them, co-dosing yields
a practical solution for the separation of certain refractory
flotation feeds.
4.1.1. Cationic collectors
Cationic collectors dissociate in water to hold a net positive
charge, and are attracted to negatively charged surfaces. For
this reason, they are primarily used to float minerals that
Figure 9. Synthesis of M-302 (Weng et al. 2013).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 13
present a negative surface charge. Cationic collectors are
used primarily in cationic reverse flotation, which as pre-
viously mentioned is popular in the United States, Australia,
Canada, Brazil, and others. Most cationic collectors are
amines, and several types of amines have been used very
successfully in iron ore flotation (Araujo, Viana and Peres
2005; Liu et al. 2019a, 2019b).
The earliest amine collectors were fatty amines such as
dodecylamine, pioneered by their utilization in the U.S.
Bureau of Mines cationic flotation process. However, fatty
amines were ultimately supplanted due to their poor selectiv-
ity, cohesive bubble formation, and low collection power at
low temperatures. They were largely replaced with more solu-
ble amines, particularly ether amines (Ma 2012).
Papini, Brandao and Peres (2001) performed a large number
of bench-scale flotation tests using ore from the Iron
Quadrangle, Brazil based on the most common amine collectors.
In particular, the collectors tested were: Clariant’s Flotigam SA-
B, Flotigam T2A-B, Collector 075/94, HOE F2835-B, Flotigam
EDA-B, and Flotigam EDA-3B; Sherex’s MG-70-A5, MG-83-A,
and MG-98-A3; Pietschemicals’ ECAN 04D, Nb 104, and Nb
112; Quimikao’s Colmin C12; and Akzo’s Poliad A-3. The final
result found that ether monoamines (Flotigam EDA-B, EDA-
3B, MG-70-A5, MG-98-A3, Colmin C12, and Poliad A-3) typi-
cally performed very well, ether diamines (HOE F2835-B
and MG-83-A) were somewhat less effective, and fatty amines
(Flotigam SA-B, Flotigam T2A-B, and Collector 075/94) and
condensates (ECAN 04D, Nb 104, and Nb 112) showed overall
poor selectivity for cationic reverse flotation of silica from iron
ores. However, it is worth noting that the Iron Quadrangle
possesses a unique mineralogy – ether diamines are typically
more effective than monoamines on coarser ores (Nakhaei and
Irannajad 2018).
More recently, Weng et al. (2013) proposed a novel quaternary
ammonium surfactant called M-302. M-302 contains ester bonds
and hydrocarbon tails. The synthesis route is provided in Figure 9,
involving the reaction of adipic acid and N-(2,3-epoxypropyl)
dodecyldimethylammonium chloride, the latter of which can be
prepared by reacting a dodecyldimethylammonium salt with
epichlorohydrin. M-302 was initially used as a cationic collector
for floating silicates from a Chinese magnetite ore, and it demon-
strated a stronger collecting power, wider effective temperature
range, and a higher rate of foam collapse than dodecylamine
chloride.
14 X. ZHANG ET AL.
Huang et al. (2014) introduced a gemini surfactant, ethane-
1,2-bis(dimethyldodecylammonium bromide) (EBAB) for use in
the cationic reverse flotation of silica from a magnetic separation
concentrate supplied by Gongchangling Iron Mine of the
Anshan Steel Company in China. EBAB was synthesized from
N,N,N’,N’-tetramethylethylenediamine with 1-bromododecane.
The chemical structures of the surfactant and the conventional
monomeric surfactant dodecylammonium chloride (DAC) are
shown in Figure 10. The bench-top flotation experiments using
EBAB found that the concentrate iron grade could be increased
to 70.58% with a silica content of 1.79% at an iron recovery of
98.42%, while DAC could only achieve a concentrate iron grade
of 69.15% with a silica content of 2.65% at an iron recovery of
95.78% (Huang et al. 2014). In summary, EBAB presented
a higher collecting power and superior selectivity when com-
pared to DAC. One notable property of EBAB is its high charge
density stemming from the relative proximity of the two ammo-
nium groups. Nakhaei and Irannajad (2018) also reviewed this
result, going into far more detail on the specific mechanism of
adsorption. Nakhaei and Irannajad (2018) also note that there is
very little detailed literature on the use of gemini surfactants in
the flotation of iron ore. From the results with EBAB, it appears
to be a field worth pursuing further.
Wang and Ren (2005) compared three collectors for the
flotation of quartz from magnetite and specularite:
a combined quaternary ammonium salt (CS-22), dodecylamine
chloride, and cetyltrimethylammonium bromide (CTAB). CS-
22 was prepared by mixing dodecyldimethylbenzylammonium
chloride and dodecyltrimethylammonium chloride in a 2:1
ratio. Wang and Ren (2005) showed that CS-22 had superior
selectivity and collecting power compared to DDA or CTAB.
CTAB was largely unselective at pH values above 6, though
showed high selectivity at pH 2. DDA showed the best selec-
tivity between pH 8 and 10, but recovered approximately half
of the iron-bearing minerals in the froth. CS-22 recovered
almost all (>90%) of the quartz when the pH was above 6,
while recovering less than 8% of the magnetite. CS-22
Figure 10. Chemical structures of ethane-1,2-bis(dimethyldodecylammonium bromide) (EBAB) (a) and dodecylammonium chloride (DAC) (b) (Huang et al. 2014).
Figure 11. Chemical structures of (a) tributyltetradecyl-phosphonium chloride (TTPC) and (b) dodecyl triethyl ammonium chloride (DTAC) (Chen et al. 2017).
recovered approximately 40% of the specularite at pH 12,
suggesting that a depressant such as quebracho may be
required to achieve optimal specularite separation. This result
was reviewed by Nakhaei and Irannajad (2018), who came to
a similar analysis and concluded that the CS-22 was an appro-
priate collector for separations of magnetite and quartz.
Chen et al. (2017) reports a novel cationic surfactant, tribu-
tyltetradecylphosphonium chloride (TTPC), which was found
to have higher collection power and selectivity than dodecyl-
triethylammonium chloride (DTAC) for the flotation of silica
from magnetite. At equimolar dosages and at a pH of 8, TTPC
recovered over 95% of the quartz and less than 5% of the
magnetite, while DTAC recovered approximately 60% of the
quartz and approximately 8% of the magnetite. Figure 11
depicts the chemical structures of TTPC and DTAC. Both
TTPC and DTAC effectively attach to the silica surface due
to the silica’s negative surface charge, but the active portion of
TTPC (-P+(C4H9)3-) presents a stronger positive charge than
the ammonium group (-N+(CH3)3-) in DTAC.
Sahoo et al. (2015) investigated the use of Aliquat-336,
a quaternary ammonium salt used as a catalyst for phase
transfer and for the extraction of metals, as a cationic
collector. Aliquat-336 contains a mixture of C8 and C10
carbon chains, primarily C8, along with nitrogen functional
groups which allow it to act as a cationic collector. Sahoo
et al.’s (2015) investigations focused on the separation of
a 38% iron grade banded hematite quartzite collected from
the Hospet area, Kamataka, India. The final concentrate
was able to achieve 65% iron grade at a 60% iron recovery.
Sahoo et al. (2016) also investigated several ionic liquids
based on imidazolium, ammonium, and pyridinium chemis-
tries. Dodecylamine (DDA) and cetyltrimethylammonium
bromide (CTAB) were used as collectors while soluble starch
was used as a depressant in the ionic liquid solutions for
separating the banded hematite quartzite ores. Sahoo et al.
(2016) found that the ammonium and pyridium based collec-
tors showed higher iron grade and recovery than the

imadizolium collectors, which is attributed to the presence of
longer alkyl chains allowing for greater hydrophobicity.
Nakhaei and Irannajad (2018) report that some common
collectors in commercial usage in Western plants include:
Aerosurf MG 98, Aerosurf MG584, Aerosurf MG70A3,
Armac CES342, MG98A3, MG83A, Specialty FR, and FA2.
These compounds are largely ether amines used to float silica,
aside from Specialty FR and FA2 which are fatty acids which
were used to float iron in Republic mine.
There is continuing work to develop new cationic collec-
tors, although ether amines remain dominant in industry
despite comparatively low selectivity. These ether amines
often have significant frothing properties, which can make
independently controlling the froth properties difficult. This
is discussed further in section 4.3.
4.1.2. Anionic collectors
Anionic collectors dissociate in water to hold a net negative
charge, which is subsequently attracted to positive surfaces.
There are a large variety of anionic collectors available for use
with iron ore and can be broadly divided based on their
chemistries, the most common of which are listed below
(Zhang and Dai 2012):
(1) Carboxylic acids and their salts (-RCOOH, -RCOONa,
-RCOOK, etc.). Common examples are fatty acids, e.g.
oleic acids and sodium oleates.
(2) Alkyl sulfonates and their salts (-RSO3H, -RSO3Na,
-RSO3K, etc.), such as sodium petroleum sulfonate.
Sodium petroleum sulfonate is prepared by sulfonating and
subsequently saponifying petroleum byproducts. Sulfonation
can proceed by reacting a terminal methylene group with SO3.
Saponification occurs by the addition of NaOH.
The earliest iron ore flotations were direct flotation using
anionic collectors, typically fatty acids, petroleum sulfonates, or
much later hydroxamates (Zhu et al. 2016). These, along with
resin acids, soaps, alkyl sulfates, and alkyl sulfonates are often used
to float iron ores, especially hematite (Liu, Zhang and Liu 2007).
However, the depression of gangue minerals remains a difficult
problem in direct flotation, and in more recent years anionic
reverse flotation has become preferred in China’s major iron
mines.
Since the 1950s Chinese scientists and technicians have
studied anionic collectors, starting with fatty acids and fatty
Figure 12. Chemical structures of RA-715 and RA-915 (Luo et al. 2015).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 15
acid salts. Fatty acids are obtained from the saponification of
various vegetable or animal oils, which can be processed into
collectors suitable for iron ore flotation. The degree to which
the fatty acids are unsaturated plays an important role in iron
ore flotation. As a general trend, fatty acids containing longer
carbon chains tend to be more powerful collectors than those
containing shorter carbon chains, as they provide more
hydrophobicity to the surfaces they attach to. It had been
thought that fatty acids with a higher degree of unsaturation
tend to be overall stronger collectors, but beyond oleic acid
this trend does not continue (Uwadiale 1992).
Changsha Mining and Metallurgy Research Institute in
China recently developed the RA series of anionic collectors
(Luo et al. 2015). The RA series collectors are prepared by
chlorinating and oxidizing tar oil, forming a mixture of
chlorinated and unchlorinated fatty acids and oleic acid.
These collectors provide good performance, are simple to
produce, inexpensive, relatively nontoxic, and can be made
from comparatively ubiquitous raw materials. The first devel-
opment in the RA series was RA-315, which was applied to
the Qidashan concentrate of the Anshan Steel Company in
China to upgrade it to 65.33% iron grade at 80.72% iron
recovery. RA-315 has also been applied to Donganshan and
Gongchangling iron ores, which are comparatively difficult to
process, as well as to Tilden ore from the United States. In
general, RA-315 was found to be more economically efficient
than other anionic collectors for these ores. RA-515, RA-715,
and RA-915 were developed afterward, of which the latter two
are currently in industrial use for anionic reverse flotation.
RA-715 and RA-915 have consistently shown good collect-
ibility and selectivity, and their chemical structures are out-
lined in Figure 12. The chlorine present acts as an electron
absorbing group, which is believed to improve the chemical
adsorption of the collector to alkali metal ions. A chelate can
be formed with RA-915 by introducing a hydroxyl group,
which can in turn physically adsorb to alkali metal ions.
Sinosteel Maanshan Mining Research Institute in China
has developed a low-temperature resistant anionic collector,
namely MH-80, by modifying fatty acids (Zhou 2017). MH-80
was applied in the Jianshan Iron Mine of Taisteel, China to
upgrade a magnetite concentrate to over 69% iron grade.
Abaka-Wood, Addai-Mensah and Skinner (2017) reported
successful flotation of monazite and hematite with sodium
oleate (SO), sodium dodecylsulfate (SDS), and an alkyl hydro-
xamic acid (AH) for pH values above the isoelectric point.
16 X. ZHANG ET AL.
The monazite was typically more susceptible to flotation than
the hematite. The silica recovery in the flotation concentrate
depended on the collector used, with SO collecting virtually
none of the silica and the other two collecting only a small
quantity of silica. SO was found to reach the highest monazite
recovery, while SDS recovered the greatest amount of iron
overall. SDS required higher pH values to achieve lower
quartz recoveries, but above pH 10 monazite and hematite
recoveries dropped as well. For SO, optimal recovery was
achieved at a pH of 9, while AH achieved its optimal separa-
tions at slightly alkaline pH values of 7–9.
Luo et al. (2015) reports the synthesis of α-bromodecanoic
acid (CH3(CH2)7CHBrCOOH, α-BDA) for use as an anionic
collector with calcium chloride as an activator. The synthesis
was performed by treating decanoic acid with bromine in the
presence of a small quantity of phosphorous trichloride as
a catalyst at 80–90°C for 7 hours. Single mineral flotation tests
were performed using calcium chloride as an activator over
a range of pH values at a temperature of 16°C. α-BDA has
been shown to perform quite well at the relatively lower
temperature, but is dependent on the presence of calcium
ions to achieve a high quartz rejection in reverse flotation.
Without calcium the maximum silica rejection was only
11.9%, but at a calcium concentration of 0.4 mmol/L the
rejection increased to 99.5%.
Cao, Zhang and Cao (2013) investigated the effects of
modifying sodium oleate with sulfuric acid. The modified
sodium oleate (MSO) was compared to unmodified sodium
oleate (SO), and MSO was found to be more tolerant of
fluctuations in process pH, temperature, and reagent dosages.
Both reagents were tested at a 600 g/t dosage on a magnetite
concentrate from Qiucheng Iron Mine, with MSO achieving
a 64.79% iron grade with a silica content of 3.18% at 93.60%
recovery while unmodified SO achieves a 63.77% iron recov-
ery with a much higher silica content of 4.23% and lower iron
recovery of 92.77% (Cao, Zhang and Cao 2013). These trials
were laboratory closed-circuit trials.
Quast (2006) investigated the behavior of basic satu-
rated fatty acids as anionic collectors with carbon chain
lengths of 6 to 18. It was found that for the shorter chain
fatty acids the predominant surface interaction was
between the undissociated acid group and the mineral,
while at longer chain lengths the dissociated anionic acid
groups became more important. At longer chain lengths,
the fatty acids also became too insoluble to be effective
flotation reagents. At tetradecanoic acid the highest flota-
tion recovery was found to occur at the saturation point of
the acid, implying that the overall flotation is being
directly limited by the limited solubility of the acid. The
longer chain acids were generally effective at more alkaline
pH ranges than shorter chain acids, with for example
octanoic acid primarily being effective below pH 7 and
dodecanoic acid primarily being effective above pH 5
(except at pH 9, which showed an unusually low recov-
ery). Hexanoic, tetradecanoic, hexadecanoic, and octade-
canoic acids were comparatively ineffective collectors
when compared at 1.0 kg/t dosages, and were unable to
achieve flotation recoveries above 55%.
4.1.3. Mixed collectors
Mixed collectors are typically mixtures of anionic and cationic
collectors which can have increased selectivity when com-
pared to single collectors (Holland and Rubingh 1992; Rao
et al. 2011). Appropriately synergistic mixtures can reduce
collector consumption, which in turn reduces production
cost and environmental pollution.
Rao, Antti and Forssberg (1990) and Rao and Forssberg
(1993, 1997) reported that mixtures of cationic and anionic
collectors could achieve better selectivity for silicate flotations
than either alone. This phenomenon was attributed to the co-
adsorption of the anionic collector to the silicate surface by
attaching to the tail of the cationic collector, which leads to an
increase in overall hydrophobicity. Cationic reverse flotation
can similarly be improved by the addition of nonionic surfac-
tants, such as fatty alcohols.
According to Leal Filho and Rodrigues (1992) the mixture
of a primary ether monoamine with oxyethylated nonylphenol
at an approximately 4:1 ratio improved silica recovery in
cationic reverse flotation. The addition of the nonylphenol
also decreases the surface tension of the froth, reducing the
overall froth depth.
Vidyadhar et al. (2002, 2003) reports that nonionic surfac-
tants reduce electrostatic repulsion between dodecylamine
cations during adsorption. This reduction allows for a closer
packing of particles in the froth layer, reducing the required
dosage of dodecylamine.
Pereira et al. (2006) suggests diesel oil to ether amine at
a 4:1 ratio while using Tergitol TMN-10 as an emulsifier at
a 19:1 ratio of oil:emulsifier. When tested on a Brazilian iron
ore at a 49.1% iron grade and containing 28.5% silica, an iron
concentrate containing 0.7% silica was obtained at a 74.4%
total iron recovery.
With regards to magnetite concentrates, Filippov,
Filippova and Severov (2010) reports that mixtures of ether
amines with either primary monoamines or alcohols are
effective for cationic reverse flotation. The mixture of collec-
tors was found to form a hydrophobic layer on amphiboles
and magnetite-silicate aggregates even in the presence of
starch. This allows for a thorough separation of silicate con-
taining particles, allowing for concentrates containing up to
70.3% iron grade and less than 1.0% silica from a feed con-
taining approximately 3% silica.
Vidyadhar, Kumari and Bhagat (2012) investigated the
recovery of hematite using sodium oleate in the presence
and absence of dodecylamine at natural pH (6–7). This
involved conditioning the sample for 5 minutes in a prepared
solution of the reagent, and then transferring it to the float
cell. In the absence of dodecylamine, increasing the sodium
oleate concentration improved hematite recovery. In the pre-
sence of dodecylamine the same trend is seen until the
sodium oleate concentration exceeds the dodecylamine con-
centration at which point a sharp decrease in recovery is
observed. This can be attributed to interactions between the
two excess collectors forming a complex precipitate with
randomly oriented surface sites, which provides little to no
benefit to flotation. At concentrations lower than the dode-
cylamine however, the mixed collector has superior

performance, attributed to the incorporation of the oleate
between amine attachment sites which helps mitigate their
electrostatic repulsion from each other (Vidyadhar, Kumari
and Bhagat 2012).
Tian et al. (2017) investigated the separation of ilmenite
from titanaugite using the anionic collector sodium oleate
(NaOL), the cationic collector dodecylamine acetate (DAA),
and a mixture of the two (NaOL-DAA). The mixture was
prepared by adding the two reagents together and mixing
for 5 minutes before utilizing it as a collector. The order in
which the reagents were added was not found to impact the
flotation results. It was found that ilmenite and titanaugite
could be separated using the mixture within the pH range of
5–7. Reagent consumption using the mixture can be reduced
by up to half as compared to NaOL alone. This mixed collec-
tor combines the superb flotation performance of DAA with
the relatively high selectivity of NaOL.
Yang et al. (2019) demonstrated that cetyltrimethylammo-
nium bromide (CTAB) mixed with sodium oleate (NaOL) also
achieved better separations than either individually. The mixed
reagent was prepared by mixing the reagents separately before
addition. Once added to the flotation cell the slurry and the
reagents were mixed together for 5 minutes. In particular
0.2 mM concentration of a mole ratio of 2:1 CTAB:NaOL at
pH 5.5 achieved an iron grade of 57% at a recovery of 79%, while
neither collector individually at similar or even much higher
dosages could exceed a 65% recovery. CTAB achieved 53%
iron grade at 42% recovery at a 0.12 mM dosage, while NaOL
achieved a 46% grade at 60% recovery at a 3.0 mM dosage.
4.2. Regulators
4.2.1. Activators
Activators interact with the mineral surface to promote the
interaction of the mineral with the collector. While in some
cases the mineral surface will naturally interact with the collector,
several minerals require the addition of an activator for collec-
tion to proceed (Rao 2013). This is quite common in reverse
anionic flotation as, at the pH ranges involved, the anionic
collector and the mineral surfaces to be floated both tend to
hold negative charges. Silicates tend to require the presence of
polyvalent metal cations, often Ca2+, Mg2+, or Fe2+ to activate
them. The pH ranges for which flotation can take place is
dependent on the presence of soluble metal hydroxide cations:
too low of a pH and the bare metal cation does not appropriately
adsorb to the surface, too high of a pH and the metal hydroxide
precipitates instead of adsorbing. Fuerstenau and Palmer (1976)
report these values in the presence of 0.1 mM sulfonate activator
and 0.1 mM of metal salt: for iron (iii) the metal hydroxide
cation begins forming at pH 2.9 and ceases to allow sulfonate
adsorption at 3.8, for aluminum the metal hydroxide begins
forming at pH 3.8 and ceases to allow sulfonate adsorption at
8.4, for lead the metal hydroxide begins forming at 6.5 and
ceases to allow sulfonate adsorption at 12.0, for manganese (ii)
the metal hydroxide begins forming at 10.9 and ceases to allow
sulfonate adsorption at 11.7, and for calcium the metal hydro-
xide forms and allows adsorption at all pH values above 12.
Calcium oxide (CaO) is widely used to activate silica in iron ore
flotation. The activation effect of calcium oxide is believed to stem
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 17
from the formation of Ca(OH)+ from the calcium hydroxide that
forms from the reaction of calcium oxide and water. When the pH
is below 11, calcium cations primarily exist as Ca2+, and the
activation of quartz is comparatively weak. At higher pH values,
Ca(OH)+ becomes preferred, leading to a strong activation of the
quartz. This activation is key to the high selectivity of the anionic
reverse flotation process.
Note that most of these activators can interact with clay
materials such as bentonite and kaolinite (Chen and Peng
2018; Ma 2010; Ma and Bruckard 2010; Ma, Bruckard and
Holmes 2009). With regard to flotation, these interactions are
typically undesirable: the metal cations added by CaO or NaOH
tend to cause these clays to become more receptive to adsorbing
to the hematite, making separations more difficult (Chen and
Peng 2018). Though the highly alkaline pH of cationic reverse
flotation does much to mitigate this effect, if neutral or acidic
salts are added it should be kept in mind. Similarly, the water
chemistry can have a significant impact on the flotation of clay-
rich ores.
4.2.2. Depressants
Depressants either prevent the attachment of the collector or
decrease the hydrophobic nature of the minerals, preventing
them from being transported to the froth. In reverse flotation
focusing on floating silica, the iron ore needs to be depressed.
Common iron oxide depressants are starch, guar, dextrin, and
carboxymethylcellulose (CMC) (Nakhaei and Irannajad 2018).
Starches can be extracted from several vegetable species: corn,
cassava, potato, wheat, rice, arrowroot, and so on. These
starches are the primary depressants used for the depression
of iron ores (McDonald and Kawatra 2017; Nakhaei and
Irannajad 2018; Turrer and Peres 2010). Corn starch is per-
haps the most widely used of all of these, owing to its high
availability and good results in flotation. However, starch
choice has historically been primarily motivated by cost effi-
ciency (Nakhaei and Irannajad 2018), rather than any parti-
cular quality metric. Most starches will adequately depress
iron ore under some condition.
The primary selective binding mechanism of starch may be
due to the very similar spacing between the hydroxyls of the
amylose and amylopectin pyranose rings. In crystalline amy-
lose, which is likely strongly indicative of the structures of
both dissolved amylose and amylopectin, the spacing between
the nearest adjacent hydroxyl groups is approximately 293 pm
and the closest spacing between the oxygen of the pyranose
ring and a hydroxyl group is 283 pm (Takahashi, Kumano
and Nishikawa 2004). Meanwhile, in hematite, the spacing of
surface iron sites and correspondingly of surface hydroxyl
sites is 285 pm (Haselhuhn 2015; Pradip 1994; Ravishankar,
Pradip and Khosla 1995). This similar chemical spacing would
suggest that pyranose-like structures may be an important
functional group to consider when designing new hematite
depressants.
Typical industrial corn starches contain a starch fraction
consisting of amylose and amylopectin, along with proteins,
oils, fibers, mineral matter, and moisture. A typical industrial
corn starch contains 20–30% amylose, 70–80% amylopectin, and
less than 1% lipids and proteins. The active component of corn
starch when used as a depressant is the amylose and the
18 X. ZHANG ET AL.
amylopectin (Fuerstenau, Jameson and Yoon 2007). Iwasaki and
Lai (1965) observed that starches with higher amylopectin con-
tent adsorb more readily to hematite surfaces. Amylose also
adsorbs to hematite, but the effect of amylose on flotation and
flocculation is comparatively limited (Pinto, Araujo and Peres
1992).
Despite practical evidence showing that most starches are
effective for flotation, there was concern that proteins present
within the starch may interfere with the depression of iron
ores. However, Peres and Correa (1996) found that zein, the
most common protein found in corn starch, is an excellent
iron ore depressant on its own and outperforms pure amylose
or amylopectin in lowering quartz recovery. However, gluten,
which has a comparatively high protein content compared to
starch, is a significantly less effective depressant than corn
starch or zein.
Pavlovic and Brandao (2003) investigated the depressant
effects of corn starch, amylose, amylopectin, glucose, and
maltose on hematite and quartz. Pavlovic and Brandao
(2003) found that amylose, amylopectin, and corn starch all
effectively attach to the quartz surface, though amylose more
so. They further found that all of these compounds effectively
depress hematite. However, amylose is the least effective at
depressing quartz, and amylopectin and corn starch were far
more effective for that. This is attributed to amylose not being
a very effective flocculant as it is a linear sugar, whereas
amylopectin is a more effective flocculant because its branch-
ing structure allows for more effective bridging. Thus, despite
the considerably lower absorption of amylopectin, it was far
more effective at depressing the silica. However, in reverse
flotation the poor quartz depression of amylose may be desir-
able, as amylose is still effective in depressing hematite allow-
ing for the separation to proceed. Glucose and maltose, which
are also linear sugars, were found to have even less of an effect
on quartz flotation than amylose, suggesting that to depress
quartz the flocculation behavior may be more important than
the surface modification.
Ma and Bruckard (2010) investigated the depressant effect of
corn starch on kaolinite. They reported that at high pH values
starch has almost no affinity for kaolinite in distilled water,
which means that kaolinite does not inherently interfere with
selective flocculation or depression of hematite or magnetite any
more than any ultrafine slimes ordinarily would at these pH
values. Below a pH of 9, however, the surface charge of kaolinite
becomes more positive and starch adsorption increases. The
affinity between starch and kaolinite is also dependent on ionic
strength (Ma and Bruckard 2010; Ma, Bruckard and Holmes
2009). With a NaCl concentration of 1 mM at pH 10.5, the
adsorption of starch on kaolinite doubled over the adsorption
in distilled water. The presence of other metal cations is also
known to influence the structure and attachment properties of
kaolinite, modifying its affinity for hematite as well as starch
(Chen and Peng 2018). Thus, while it is theoretically possible to
separate kaolinite from hematite using starch as a depressant,
doing so on a plant-scale requires very careful control of the
water chemistry.
Kar et al. (2013) investigated the effects of different types of
starch on cationic reverse flotation using dodecylamine. Soluble
starch, corn starch, rice starch, and potato starch were compared,
and found that soluble starch was the most effective. Otherwise,
each starch was found to be similar. Potato starch achieved the
least hematite depression, then rice starch, corn starch, and
solubilized starch in turn showed increasing hematite depres-
sion. Rice and potato starch depressed less quartz than corn or
soluble starch, but the overall difference is at most 8 percentage
points with a dodecylamine collector. The key highlights are that
maximum adsorption of each starch occurs in the pH range of
5–9, and that despite having the minimum absorption soluble
starch consistently depressed more hematite. While the depres-
sion of hematite increased with increasing starch adsorption, no
trend was found correlating starch adsorption with quartz
depression.
Kar et al. (2013) also investigated the recovery of iron from
low-grade banded hematite quartzites from Karnataka in
India using these same four starches as depressants. Using
dodecylamine at 32 g/t as the collector, the iron grade of the
hematite concentrate product initially increases with increas-
ing starch dosage, but eventually the depression of the quartz
limits further separation. Soluble starch was found to give the
most effective flotation, reaching an iron grade of 63.8% with
an iron recovery of 89.6% with a starch dosage of 400 g/t.
Ma (2008) investigated the effect of Na+ and K+ ions on the
adsorption of starch to quartz. In general, it was found that at
low concentrations the actions of sodium and potassium did
not differ significantly. However, at concentrations above
10 mM, an elevated concentration of potassium ions greatly
increased the adsorption of starch onto quartz at pH 10.5. It
was determined that the solvation of starch onto quartz
required energy, and only proceeded once a certain amount
of starch was added. The addition of potassium cations reduced
that energy by disrupting the structure of the hydrogen bonds
in water, allowing starch to adsorb far more readily.
Lelis, Da Cruz and Lima (2019) investigated the effect of
Ca2+ and Cl− on the adsorption of starch to quartz and
hematite in an itabiritic iron ore. The addition of calcium
cations tended to increase the adsorption of starch to both
minerals, resulting in increased depression in both cases. This
is typically undesirable, as increased quartz depression is
synonymous with decreased quartz rejection. The addition
of ethylenediaminetetraacetic acid (EDTA) to precipitate the
calcium fully restored the flotability of the quartz. The pre-
sence of chloride however resulted in the formation of
a lasting complex with the hematite, hindering starch adsorp-
tion. Thus, after the addition of CaCl2, the adsorption of
starch to hematite was partially compromised, even with the
addition of EDTA to capture the calcium cations.
Zhang et al. (2017) reported a novel hematite depressant,
the macromolecule polymaleicanhydridetriethylenetetra-
mine (PMTA). The synthesis route of PMTA is shown in
Figure 13. Using dodecylamine as the collector at pH 11,
PMTA achieved a flotation grade of 65.24% and a recovery
of 98.29% while starch achieved a flotation grade of 64.93%
and a recovery of 95.35%.
Aside from starch, carboxymethylcellulose (CMC) has
shown potential as an iron ore depressant. Testing modified
CMCs with iron ore found that high iron grades (>68%) could
be achieved in the concentrate (Poperechnikova et al. 2017).
However, CMCs typically lead to greater iron losses to the

Figure 13. The synthesis route of polymaleicanhydridetriethylenetetramine (PMTA) (Zhang et al. 2017).
tailings as compared to starch alone. As CMC is also more
expensive than starch, the loss of iron makes it difficult to
recommend universally.
Turrer and Peres (2010) performed a comparative analysis of
several depressants, including 6 CMCs, 3 lignosulphonates, 1
guar gum, and 4 humic acids. However, only CMC and guar
gum were able to reach the same flotation performance as starch,
which is attributed to the presence of the glucopyranose ring.
However, blends of these polymers achieved promising results.
Humic acids (HA) have been found to preferentially adsorb
to certain iron-bearing minerals (Illés and Tombácz 2003; Lai
and Chen 2001; Ramos-Tejada et al. 2003; Tombacz et al. 2004).
This preferential adsorption can lead to a depressant effect on
these minerals. Humic acids are high molecular weight polymers
which are internally apolar but present several hydrophilic
groups (primarily carboxylic acids and phenolic groups) on
their exterior (Chi and Amy 2004; Terashima, Fukushima and
Tanaka 2004). Dos Santos and Oliveira (2007) studied the use of
humic acid as an iron ore depressant for a 1:3 quartz:hematite
mixture in flotation. The resulting concentrate was 86.0% hema-
tite at >90% hematite recovery.
4.2.3. Dispersants and flocculants
Increasing demand for iron ore has necessitated investiga-
tion into the processing of low-grade, very fine iron ores,
the extraction of iron from iron-bearing slimes, and the
extraction of iron from existing tailings. Selective dispersion
and flocculation is the primary process for separating these
fine materials. Selective flocculation depends on the prefer-
ential adsorption of organic flocculants onto specific
mineral particles. These flocculants cause the particles to
settle quickly, while dispersants are used to keep the
remaining material largely suspended. To maximize the
effectiveness of this process, the pulp needs to be fully
dispersed before any flocculant is added. This process has
been quite successful for the extraction of valuable minerals
from fine materials on both laboratory and commercial
scales (Dogu and Arol 2004).
The selective flocculation and dispersion process is the
only economically viable method of processing hematite ores
with iron grades less than 40% and liberation sizes smaller
than 25 μm. However, it is only scarcely used in industry as
the reagent costs are relatively high and the process is very
sensitive to surface chemistry changes (Haselhuhn, Carlson
and Kawatra 2012; Haselhuhn and Kawatra 2015c).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 19
There are several reagents that may be used in selective
flocculation and dispersion, depending on the mineralogy.
These reagents adsorb to the mineral surfaces and induce either
dispersion or flocculation in the ore particles (Haselhuhn and
Kawatra 2015a, 2015b). Figure 14 shows some example disper-
sants to mitigate the effects of slimes during this process – of
these, sodium silicate, sodium hydroxide, and sodium carbonate
are the most commonly used in industry (Haselhuhn 2015).
Ma (2011) investigated the dispersion of kaolinite gangue
materials in the context of the cationic reverse flotation of
iron ore. Ma found that while sodium silicate is widely used
for dispersing kaolinite, it is only effective at acidic pH values.
Since cationic reverse flotation often takes place at pH values
above 9.5, this is less than ideal. However, sodium polypho-
sphate and polyacrylic acid were able to disperse kaolinite at
pH values up to 10.5. The adsorption of polyacrylic acid to
kaolinite can be improved further by the addition of CaCl2 or
MgCl2 at high pH values.
For flocculants, the most commonly used are starch, poly-
acrylamide, and humate. Macromolecule flocculants have seen
greater interest in recent years, however. This is in part due to
the continued growth and development of the industry, and
in part due to the increasing demand for environmentally
sustainable processes.
Starch is a natural polymer consisting primarily of amylose
and amylopectin. Starches display a particular affinity toward
iron minerals, which plays a role in its use as a depressant as
discussed earlier, but also plays a key role in its action as
a flocculant. Starch’s affinity for iron ore stems from its ability
to form complexes and hydrogen bonds with the iron ore
surface, and as such it has been utilized in commercial flota-
tion and selective flocculation processes (Panda et al. 2013;
Weisseborn, Warren and Dunn 1995). The Tilden concentra-
tor in the United States has been very successful utilizing corn
starch for selective flocculation of iron ore.
Weissenborn (1996) investigated the roles of amylose and
amylopectin from starch in the selective flocculation process and
found that amylopectin is overwhelmingly responsible for the
flocculant action of the starch. Amylopectin behaved almost as
a bulk flocculant, providing very high recoveries of hematite,
goethite, and kaolinite. Amylose suppressed the flocculation of
all these minerals, but kaolinite more than the others. Thus, the
presence of amylose increased the overall quality of the separation
which could be achieved. The optimal amylose to amylopectin
ratio for selective flocculation was found to be around 1:3, which is
20 X. ZHANG ET AL.
Figure 14. Chemical names and structures of common iron ore dispersants (based on Haselhuhn 2015).
close to the natural composition of starch. Amylopectin’s floccula-
tion abilities are attributed to its high molecular weight and
branched molecular structure, while amylose’s ability to selectively
suppress amylopectin’s flocculation is thought to stem from co-
adsorption between the two molecules.
Tripathy, Bhagat and Singh (2001) developed and investi-
gated the flocculation characteristics of sodium alginate-g-poly-
acrylamide grade VI (SAG-VI). When compared to some other
commercially available flocculants in aqueous suspensions of
0.5wt% iron ore slimes, SAG-VI performed on par with or
somewhat better than the alternatives. It was concluded that
iron ore slimes containing mostly smaller particle sizes are better
flocculated by neutral flocculants than those with a larger parti-
cle size.
Ng et al. (2015) proposed a novel approach for recovering
valuable fines using temperature-sensitive polymers. One
such polymer is poly(N-isopropylacrylamide) (PNIPAM).
Below approximately 32°C, the lower critical solution tem-
perature (LCST), PNIPAM is water soluble, hydrophilic, and
strongly dispersing. Above 32°C, PNIPAM transitions into
a strongly hydrophobic configuration, precipitating out of
solution and forming hydrophobic aggregates. While poly-
acrylamide’s flocculation mechanism is irreversible,
PNIPAM’s hydrophobic flocculation can easily be reverse
by lowering the temperature. As such, PNIPAM can serve
as the collector, flocculant, and dispersant. When compared
with sodium oleate, PNIPAM performs significantly better at
concentrating hematite particles larger than 20 μm due to its
higher selectivity. PNIPAM is also found to be less sensitive
to the presence of fine materials.
Kemppainen et al. (2016) investigated the roles of two
types of anionic cellulose nanofibers when used in single-
oxide mineral flocculation, particularly hematite and quartz.
Dicarboxylic acid (DCC) and sulfonated (ADAC) cellulose
nanofibers are found to selectively flocculate hematite in the
pH range of 5–10, with little interaction observed between
the nanofibers and quartz. The tendency of DCC to form
strong flocs is found to depend on the pH of the suspension,
with the largest quantity and most resilient flocs formed near
pH 8–9 with a DCC dosage of 200–500ppm. DCC is capable

of rapidly agglomerating hematite under vigorous stirring,
but ACAG requires longer and less rapid stirring to achieve
similar results. At 500ppm dosages however ACAG was
found to be as effective as DCC while operating over
a wider pH range.
4.3. Frothers
It is common knowledge that frothers serve a prominent role in
controlling the bubble size, froth stability, and froth mobility in
flotation (Bulatovic 2007). For iron ore flotation, several different
frothers are commonly used including pine oil, aliphatic alco-
hols, propylene glycols, alkylethers of polypropylene, and cresylic
acids. Most alcohols containing 5 to 8 carbon atoms can be
utilized as frothers, including mixed amyl alcohol, methyl iso-
butyl carbinol, and sometimes heptanols or octanols (Nakhaei
and Irannajad 2018).
Although Houot (1983) reports that some specific alcohols
and propylene glycol have been used on occasion in the
United States, they are rarely used in cationic reverse flotation
of hematite in the U.S. This is primarily because the cationic
flotation collectors, often ether amines, demonstrate strong
frothing properties at the pH ranges that cationic reverse
flotation is performed at. This is sufficient for floating hema-
tite, but MIBC is often used during the flotation of magnetite
at a dosage of near 1% of the amine dosage, whether or not
the amine presents frothing properties.
Frothers are particularly important because there are two
major mechanisms of recovery in flotation: true flotation,
which consists of air bubbles attaching to hydrophobized mate-
rials and causing them to rise to the top; and entrainment,
wherein solid particles become trapped between the rising bub-
bles. In the reverse flotation of iron minerals, the collector is used
to hydrophobize the silica so that it can be floated. True flotation
is highly selective, but entrainment is not (Nykänen et al. 2018).
Entrainment depends on many factors, including froth stability,
Figure 15. Shown in the graph is a hypothetical recovery curve for reverse
flotation. As the amount of water recovered increases, the amount of nonselec-
tive recovery also increases. However, the rate at which silica is recovered grows
much faster, due to the presence of the collector. This means that the best
separations are achieved near the minimum possible water recoveries, and thus
the lowest dosages of frothers (Kawatra and Eisele 2001).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 21
gas flow rate, rate of agitation, the addition of wash water if any,
and the physical properties of the particles (Dobby 2002; Pita
2015). However, the amount of entrainment can be strongly
correlated with the amount of water recovered in the froth, as
shown in Figure 15. Since frothers control both the amount of
froth formed and the amount of water retained in the froth, an
excess of frother directly leads to an excessive amount of non-
selective recovery by entrainment. Two liquid flotation has been
used to determine whether material is being recovered by
entrainment or true flotation (due to a failure of the depressant,
for example) at two concentrators in Brazil (Nykänen et al. 2018).
Suardini (1994) investigated controlling the rate of water
recovery by separating the frothing behavior of the collector
from the frothing behavior of a non-collecting frother. These
results are shown in Figure 16, where it is observed that
a partial replacement of the etheramine of a cationic reverse
flotation circuit with methyl isobutyl carbinol (MIBC)
increased recovery by approximately 5 percentage points at
a constant grade of 63.8%.
Araujo, Viana and Peres (2005) reports the investigation of
partial replacement of an amine collector with some commer-
cial frothers at laboratory scale. These tests apparently pro-
vided promising results: the addition of a polyglycol frother
could improve both the recovery and selectivity in several
tests. Pine oil frothers also improved performance, but linear
and branched alcohols were less effective. Unfortunately, the
associated mineralogy is not directly reported.
Rodrigues Silva, Correa De Araujo and Farias De Oliveira
(2008) performed plant testing of this partial replacement
strategy, partially replacing the amine collector at the
Vargem Grande iron ore concentrator in Brazil with
a frother. The frother used in this test was a blend of alcohols,
esters, and aldehydes, while the collector was a 20%-30%
neutralized etheramine. The starch dosage, pulp pH, and
water chemistry were kept constant throughout these experi-
ments, while varying the quantity of collector replaced. These
trials found that a 10% replacement of the collector improved
the overall results: iron recovery was improved from 67.96%
to 80.78%, while iron grade was simultaneously improved
from 64.92% to 65.43%. This allowed for approximately an
extra $3 million/year in revenue. It was also found that less
neutralized etheramines allowed for a higher substitution of
frother before results declined.
Despite these significant results, it is still not clearly under-
stood as to which non-collecting frothers would provide the
best results. It may also be possible to further separate and
control the two reagent properties if a non-frothing collector
could be designed for cationic flotation.
Extensive research has been carried out to determine the
effect of frothers on bubble size and gas holdup in flotation.
Corona-Arroyo et al. (2015) characterized the impact of dode-
cylamine (DDA) along with methyl isobutyl carbinol (MIBC)
and polyglycol OREPREP™ F507. MIBC has a molecular
weight of 102 and a hydrophile-lipophile balance of 6.05,
while F507 has a molecular weight of 425 and a hydrophile-
lipophile balance of 8.63. The critical coalescence concentra-
tion (CCC), which is the concentration at which further
addition of reagent no longer decreases the bubble size, fol-
lowed the order of MIBC > DDA > F507 – that is to say that
22 X. ZHANG ET AL.
Figure 16. Batch reverse cationic flotation results wherein the etheramine collector was partially replaced with methyl isobutyl carbinol (Suardini 1994).
quantity of F507 required to achieve the maximum bubble
formation was the smallest of the three. While DDA is pri-
marily a collector, it is included in the comparison of frothers
due to its, in this case, non-negligible frothing properties.
When the frothers (MIBC and F507) were mixed with the
DDA collector, the frother CCC and the resulting bubble sizes
were observed to decrease.
Laskowski et al. (2003) reports that blending selective frothers
(such as MIBC) with very small quantity of strong frothers (such
as polyglycol) result in froth behaviors more similar to the
stronger frother. That is, the small addition of polyglycol results
in smaller bubble sizes both below and above the CCC of MIBC.
Tan et al. (2005) also found this behavior. Elmahdy and Finch
(2013) reported that this decrease bubble size only occurs below
the CCC of MIBC, and that above the CCC of MIBC the bubble
size only decreases if the additional frother also reaches its CCC.
5. Principle surface chemical factors affecting iron
ore flotation
The selectivity of flotation depends on the complex interac-
tion of mineralogical, chemical, physical, and engineering
parameters. In an attempt to understand the key principles
driving these interactions, a considerable amount of research
effort has gone toward unraveling the effects of the surface
chemistry of iron ores and quartz. There have been several
extensive reviews of both the industrial practices and basic
principles of iron ore flotation (Houot 1983; Iwasaki 1983;
Numella and Iwasaki 1986).
Most of the physics of iron ore flotation can be traced back to
interactions between the soluble ions in the process water and
the surfaces of the minerals. Understanding these interactions is
critical to predicting and controlling the behavior of the surface
chemical processes which lie at the heart of iron ore processing.
5.1. Effects of zeta potential
Surfaces in water, except at the isoelectric point, tend to
become charged by either dissociating protons at their surface
or adsorbing protons or other ions from the water (Uwadiale
1992). These charges subsequently are balanced out by the
movement of freely moving ions and polar compounds within
the solution. However, some ions and compounds will remain
strongly adsorbed to the surface, even as the surface moves
through the water. The boundary between the domain domi-
nated by the surface and the domain dominated by the bulk
fluid is known as the shear plane. The effective surface charge
presented by the surface at the shear plane after accounting
for both the charge and volume of these attached ions is
known as the zeta potential. The pH at which the true surface
is neutral is known as point of zero charge (PZC), while the
pH at which the zeta potential is neutral is known as the
isoelectric point (IEP). In absence of specifically adsorbed
ions or other chemisorbed species, the surface charge and
the zeta potential will tend to carry the same sign, and thus
the PZC and IEP are usually, though not necessarily, the same
value. Figure 17 presents the relation between the surface
charge and the presence of various sorts of adsorbing ions
with the zeta potential.
The surface charge and correspondingly the PZC are the pri-
mary factors determining the behavior of a surface in flotation. As
changing the pH changes the availability of hydronium cations
and hydroxide anions, the surface charge is subsequently shifted.
Figure 18 shows the typical behavior of silica and hematite surfaces
under varying pH values. At high pH values, surfaces will tend to
become negatively charged, and at low pH values surfaces will tend
to become positively charged. The zeta potential again typically
follows the sign of the surface charge, and largely determines the
interaction between two surfaces in the solution. Surfaces exhibit-
ing low zeta potentials are typically quick to flocculate, while
surfaces exhibiting large zeta potentials of the same sign will
typically remain dispersed. Surfaces with opposing zeta potentials
may undergo heteroflocculation if the particles are fine enough,
but this is also the condition wherein simple direct flotation is most
applicable. After all, surfaces with negative charges can be selec-
tively collected with cationic collectors, and surfaces with positive
charges can be selectively collected with anionic collectors.
This interaction between surface charge and collector
depends on the effective surface charge and the charge of
the collector. At pH values below hematite’s PZC of 6.7
dodecylsulfonate is an effective collector, while above the
PZC dodecylammonium is the effective collector (Iwasaki,
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 23

Figure 17. The surface charge is measured at the inner Helmholtz plane, which includes only the effects of the surface and the specifically adsorbed ions. The zeta
potential is measured at the stern plane, which additionally contains the effects of other strongly adsorbed species, such as chemisorbed molecules or cations/anions
which move with the surface. Beyond the stern plane, dissolved ions tend to follow the liquid instead of the surface (based on Haselhuhn 2015).

Figure 18. Expected response of zeta potential to pH changes for hematite and silica. The value at which the zeta potential crosses 0 is known as the isoelectric
point, where the surface presents no net-charge.

Cooke and Colombo 1960; Uwadiale 1992). Note that while
the PZC is typically a fundamental property of the surface, the
key to determining the adsorption of these chemicals is the
IEP which may differ from the PZC in the presence of speci-
fically adsorbed ions such as Ca2+ in the case of iron ores.
The PZC of quartz is pH 1.8. Below the PZC, anionic collec-
tors are not typically adsorbed sufficiently to float quartz directly,
as they must compete with the significant quantity of anions
already present in solution from the pH adjustment.
Additionally, at such acidic conditions some anionic collectors,
24 X. ZHANG ET AL.
particularly those based on weaker organic acids, may be forced
to collect the acidic protons in solution leaving them in an
uncharged form. Above the PZC, aminium (-RN+H3 groups)
readily adsorb to the quartz surface. Cases (1970) reports that
other silicates exhibit similar behavior.
The surfaces of oxides and silicate minerals are often
extensively hydrated, and can in turn form hydrogen bonds
with the water phase. As such the adsorption of collectors,
and in particular the formation of collector hemimicelles, is
often necessary to induce any form of hydrophobicity in these
compounds.
Note that while pure hematite has a PZC of 6.7 (Uwadiale
1992), natural hematite will often display vastly different IEPs.
Very often, the IEP of natural hematite will appear to be
similar to the IEP of silica, which is attributed to the attach-
ment of silica slimes to the hematite surface before desliming
or even before grinding (Carlson and Kawatra 2013).
It is also worth noting that the zeta potential plays a role in
every aspect of iron ore refining, not just in flotation and
desliming. It can be helpful to be mindful of the roles that
deslime and flotation reagents will play in later stages of the
beneficiation process. In particular, filtration is adversely
affected by strongly dispersing conditions, leading to slow
filtration rates and which can be mitigated by reducing the
pH of filtration feed (Claremboux and Kawatra 2019).
Additionally, pelletization is adversely affected by strongly
flocculating conditions – while the addition of flocculants
makes pellet growth more rapid the strength of pellets
decreases dramatically (Halt and Kawatra 2017). On the
other hand, dispersing conditions do not significantly slow
pellet growth rates, but lead to significantly stronger pellets
(Halt and Kawatra 2017).
5.2. Effects of water chemistry
The importance of water quality on desliming and flotation of
iron ore has long been recognized. Fresh water may contain
any number of soluble ions. Most commonly fresh water
contains some concentration of Na+, K+, Ca2+, and Mg2+.
Acidic fresh water may also contain Al3+, Fe2+, and Fe3+.
Common anions in fresh water include HCO3−, SiO32-, and
sometimes SO42- in locations where sulfides or gypsum occur.
Oxidized iron ores also typically contain some of these ions to
begin with, and may release these ions back into the water up
to concentrations of 0.1–1 mmol/L if the water is sufficiently
pure. These released ions may result in the accidental activa-
tion of silica in anionic reverse flotation and the accidental
depression of silica in cationic reverse flotation. Ca2+ may also
be intentionally added to activate silica in anionic reverse
flotation under highly alkaline conditions (Iwasaki 2000).
The attachment of starches and clays to quartz or hematite
is largely determined by the water chemistry as many of these
ions are activators, such as calcium, or deactivators, such as
chloride in the context of starch adsorption on hematite
(Lelis, Da Cruz and Lima 2019).
Iwasaki et al. (1980) reports that at neutral pH values
calcium typically adsorbs as a Ca2+ cation, while at alkaline
conditions (pH 11) it typically adsorbs as a Ca(OH)+ cation.
Ca(OH)+ is the necessary form for efficient activation in the
presence of anionic collectors such as fatty acids (Clark 1968).
In cationic reverse flotation, Ca2+ plays apparently little role
in the collection process, but Ca(OH)+ contributes to
a decrease in flotation recovery at pH >10.5. As previously
mentioned the adverse effects of Ca(OH)+ can be mitigated by
the use of an appropriate complexing agent such as STPP,
SHMP, or EDTA.
Magnesium also occurs in iron ore pulps. Under alkaline
conditions (pH >10), magnesium causes a sharp decrease in
quartz recovery due to the precipitation of Mg(OH)2 which
coagulates onto the quartz surface. Mg(OH)2 is highly hydro-
philic and thus does not float. This can also be remedied with
the use of complexing agents, but sodium silicate is ineffective
at restoring the floatability of the afflicted quartz.
The effect of magnesium on desliming and flotation can
be far more pronounced than most other divalent cations.
This is attributed to the small covalent diameter of the
magnesium cation, 274 pm (Haselhuhn 2015; Pyykkö and
Atsumi 2009). This is smaller than the spacing between
surface hydroxyl groups on hematite ore, which is approxi-
mately 285 pm (Haselhuhn 2015). This allows magnesium
to adsorb to and saturate every available surface site on
hematite while calcium, which has a larger diameter of
342 pm, can only adsorb to every other site (Haselhuhn
2015; Pyykkö and Atsumi 2009).
Iron cations, both Fe2+ and Fe3+, can be found in iron ore
pulps processed in acidic conditions. The adsorption of these
cations onto magnetite surfaces can have a tremendous impact
on the zeta potential (Sun et al. 1998). Even the addition of
0.2 mM of iron (ii) chlorate increases the isoelectric point of
magnetite from approximately 5 to over 7, and at alkaline pH
values causes the zeta potential to increase in magnitude from
approximately −20mV to −40mV (Sun et al. 1998). The addi-
tion of 0.02 mM iron (iii) chlorate does not increase the iso-
electric point as much, but does cause a comparable increase in
the magnitude of the zeta potential by a similar amount at all
pH values above neutral (Sun et al. 1998). Interestingly, how-
ever, at 2 mM concentrations iron (iii) chlorate no longer shifts
the zeta potential at alkaline pH values, but at acidic ones
instead (Sun et al. 1998). In general, larger concentrations of
iron cations shift the IEP of the magnetite further toward
higher pH values (Sun et al. 1998).
The surface reactions controlling zeta potential may be
represented by the equations below:
;FeðII; IIIÞOH þ Fe2þ or Fe3þ þ nOH
¼ ;FeðII; IIIÞOFeðOHÞn1 ðn2 or 3Þ þ H2 O
ðn increases with increasing pHÞ
Hþ Hþ
;FeðII; IIIÞOH2 þ ! ;FeðII; IIIÞOH ! ;FeðII; IIIÞO
It is important also to realize that the surface adsorption of
metal ions to the minerals in iron ore can result in extre-
mely different ion concentrations than in the bulk fluid.
Studies of an iron ore filter cake following filtration found
that the filter cake moisture had an almost 25 times higher
concentration of phosphate than the filter feed slurry did,
and a 10 times higher concentration of sulfate (Haselhuhn
and Kawatra 2015d). The effect on calcium can be even

more dramatic, with one plant having a calcium concentra-
tion in the filter cake that was 565 times higher than in the
filtrate water (Eisele, Kawatra and Ripke 2005). The ten-
dency for ions to concentrate near the surfaces means that
even if the water is comparatively clean and deionized there
may still be a significant concentration of trapped ions
within the ore itself, leading to changes in the zeta potential
and the activity of many reagents.
6. Conclusions and recommendations
From the preceding review of the direct and reverse flota-
tion routes, desliming as a necessary precursor to many
flotation routes, flotation reagents, and the primary sur-
face chemistry factors affecting flotation, the following
conclusions and recommendations are provided:
(1) Flotation has been considered to be the most pro-
mising method of obtaining useful, high-grade iron
from low-grade, finely disseminated iron ores.
Flotation can be used alone or to complement
other separation methods, such as gravity separation
and magnetic separation.
(2) Flotation is highly dependent on the surface chemistry
of minerals to be separated. It is necessary to have
a firm understanding of effects of not only the
reagents, but also the chemistry of the available plant
water and the impact of soluble ions in the ore.
Selective flocculation and deslime is also very sensitive
to these parameters.
(3) Reverse flotation is the most promising flotation route
for further development. The choice of cationic versus
anionic reverse flotation is dependent on mineralogy
and available reagents. Many facilities in China have
found that anionic reverse flotation is more suitable
for their ores, but most of the rest of the world has
chosen cationic reverse flotation instead.
(4) Cationic reverse flotation has the advantage of
higher flotation rates, simpler reagent systems, sim-
ple and reliable operation, and can be operated at
low temperatures. However, cationic collectors have
relatively poor selectivity, foaming properties and
higher toxicity, which can lead to product loss,
highly viscous and poorly fluid froth, and environ-
mental pollution respectively.
(5) Anionic reverse flotation requires the use of an
activator (usually lime) to float the quartz using an
anionic collector at elevated pH values while depres-
sing the iron with starch or another depressant. In
comparison to cationic reverse flotation, anionic
reverse flotation is less sensitive to slimes, has
a lower collector cost, and high selectivity due to
the calcium activator having a combined activation
effect on the quartz and depression effect on the
iron ore. However, reverse anionic flotation requires
a significant quantity of activator, along with higher
process temperatures and alkalinities.
(6) Stepped flotation is a combination of direct flotation
of siderite from other iron ores followed by reverse
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 25
flotation to remove silica. This avoids the difficulties
of applying reverse flotation to carbonate rich iron
ores, allowing for the practical utilization of
a massive reserve of previously stubborn iron ores.
(7) Desliming before flotation is an essential technology, as
regardless of flotation route or reagents, an abundance of
slimes will result in low selectivity, poor flotation rates,
and tremendous reagent usage. Anionic reverse flotation
is less sensitive than cationic reverse flotation, but is still
negatively impacted by the presence of large amounts of
fine particles. Selective flocculation and dispersion
remains the most common approach for desliming in
industry.
(8) The key to floating silica by reverse flotation is to
develop collector and depressant systems to effi-
ciently separate iron ore from silicates. Further
research into high-efficiency and nontoxic cationic
collectors is recommended. If possible, finding addi-
tional varieties and sources of cationic collectors
would be preferable. Several novel cationic collectors
such as M-302, EBAB, CS-22, TTPC, etc. have been
tested successfully at laboratory scale, but remain
expensive and untested at industrial scales. Further
research is recommended into starch alternatives.
PMTA, HA, and CMC may prove to be valuable
starting points to developing more effective iron ore
depressants. The characteristic spacing within the
pyranose ring of amylose and amylopectin which
closely matches the surface spacing of hematite’s
iron atoms may be valuable when designing new
depressants.
(9) For anionic reverse flotation, the development of
low-temperature anionic collectors is paramount.
The elevated temperature requirements of present
collectors result in complex dosing controls and
high energy consumption by the flotation pro-
cess. RA series collectors and MH-80 are cur-
rently popular in industry, but laboratory results
for SO, α-BDA, etc. have also been promising.
(10) Mixed collectors have shown considerable promise
in improving flotation results while using fewer
reagents. Further investigation is recommended, as
lower reagent usage directly correlates to lower col-
lector costs, lower production costs, and less poten-
tial for environmental pollution.
(11) For understanding flotation processes, the zeta
potential and the factors that go into determining
it remain paramount. Understanding the effects of
process water chemistry and adsorbed ions on the
zeta potential and the surface chemistry of miner-
als is one of the most important parts of under-
standing the theory of flotation. It is worth
repeating that the water chemistry can be con-
trolled by either adding salts or removing the
cations using complexing agents such as STPP,
SHMP, and EDTA.
(12) Researchers should continue to aim to connect
laboratory scale results with industrial scale results
to further optimize the flotation process.
26 X. ZHANG ET AL.
Disclosure statement
No potential conflict of interest was reported by the authors.
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