Effect of starch type on selectivity of cationic

flotation of iron ore

N. A. Abdel-Khalek*1, K. E. Yassin1, K. A. Selim1, K. H. Rao2 and A.-H. Kandel3
Cationic flotation is one of the most widely accepted technologies for upgrading siliceous iron ore
using polysaccharides (mainly starches) as depressing agents for iron bearing minerals while
floating silica with amines. In this paper, a group of starches are investigated as depressants for
haematite. These starches are wheat, corn, rice, potato and dextrin. The role of starch type on the
selectivity of the separation process has been studied through zeta potential, adsorption
measurements as well as flotation tests. The effects of type of starch and pH of the medium have
been studied. The results indicate that the selectivity of the separation process is strongly
affected by the type of starch used, where better results are obtained with corn starch or wheat
starch in comparison to the other types. Fourier transform infrared spectroscopy measurements
indicated that the interaction between starches and haematite surface is intermolecular
interaction.
Keywords: Flotation, Iron ore, Starches of wheat, corn, rice, potato and dextrin, Adsorption

Introduction is a linear molecule and has a low molecular weight (105)

During the last decades, with the depletion of high grade
iron ores, low grade finely disseminated iron ore deposits
have become the main sources of raw iron material in
many countries. Therefore, new technologies must be
developed to achieve good separation, especially when
treating very fine particles. These technologies must also
maintain or improve current standards in many
economic and environmentally attractive ways. In
general, selective adsorption and surface modification
of minerals by surfactant are the primary steps in the
process of separating certain minerals that have similar
physicochemical properties. Cationic flotation is a
widely accepted technology for upgrading fine ore
particles using polysaccharides as depressing agent for
haematite and amine as floating agent for silica.
Polysaccharides are a chain of monosaccharide (sugar)
units linked by glycosidic bonds. Although different
types of polysaccharides exist in nature, only a small
number of them have been used by the mineral
processing industry (Liu et al., 2000). Starch is one of
the most important polysaccharides that has applica-
tions in mineral processing, especially in flotation due to
its adsorption onto the minerals’ surfaces (Weissenborn
et al., 1995). Starch is a natural polysaccharide consist-
ing of two components, amylase and amylpectin. Both
are polymers of monosaccharide a-D-(z)- gluopyranose
(Weissenborn et al., 1995), as shown in Fig. 1. Amylase
1
Central Metallurgical Research and Development Institute (CMRDI), PO
Box 87, Helwan, Cairo, Egypt
2
Lulea University of Technology, Lulea, Sweden
3
Chemistry Department, Faculty of Science, Helwan University, Helwan,
Egypt
*Corresponding author, email naguialy@yahoo.com
containing alpha glucosidic linkages, from carbon atom
number (-C-1-) to carbon number C4 of the adjacent
gluopyranose unit. Amylpectin is of high molecular
weight (106–107); a branched molecule consists of several
hundred short amylase chains cross-linked to each other
by glucosidic linkages from C-1 to C-6 of the adjacent
gluopyranose unit (Whistler et al., 1984). In this paper,
the adsorption of starches onto the haematite surface as
a selective depressant for ultrafine iron ore was studied.
The factors affecting the adsorption process, such as pH
of the medium and types of starches, were investigated.
Experimental
Materials
Samples of single minerals of haematite and quartz were
received from ‘Wards’ Company, USA. Samples of
2200 mesh (74 mm) were used in the adsorption and
flotation studies. The purity (99?9%) of the samples was
confirmed using X-ray fluorescence analysis. An iron ore
from the north Aswan locality was kindly provided by
the Egyptian Iron and Steel Company. The ore sample
contains 70?16%Fe2O3 and 15?09%SiO2. X-ray diffrac-
tion of the iron ore sample indicated that its main iron
bearing mineral is haematite and quartz is the main
gangue mineral. Mineralogical analysis showed that
quartz and apatite are finely disseminated in the matrix
of the ore, requiring fine grinding to achieve a
considerable degree of liberation. Analytical grade HCl
and NaOH (from Aldrich) were used for pH regulations.
Cetyl trimethyl ammonium bromide (CTAB), used as
collector for silica flotation and starches and as
depressant for iron oxides, was supplied by Merck
Company. Five types of starches, i.e. corn, wheat,

ß 2012 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 23 November 2010; accepted 26 January 2012 Mineral Processing and Extractive
98 DOI 10.1179/1743285512Y.0000000001 Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2

1 Structure of starches
potato, rice and dextrin, were investigated. A fresh
solution of 1?0% (w/v) of each type was prepared daily.
Methods
Chemical analysis
A subsample of 0?5 g of fine grained sample (2200
mesh) was digested using 30 mL concentrated HCl and
15 mL HNO3, followed by boiling until evaporation,
addition of the previous amount of HCl and HNO3 and
completion to 100 mL using bidistilled water. The
mixture was boiled and filtered using ashless filter paper.
SiO2% was determined gravimetrically as an insoluble
residue, and Fe2O3% was determined using an atomic
absorption instrument model Analyst 200.
Zeta potential measurements
A laser zetameter ‘Malvern Instruments Model Zetasiser
2000’ was used for zeta potential measurements. In these
tests, 0?01 g of ground 274 mm sample was placed in
50 mL double distilled water with pH modifier, having
an ionic strength of 261022M NaCl. The suspension
was conditioned for 1 h during which the pH was
adjusted. After shaking, the equilibrium pH was
recorded. It was then allowed to settle for 3 min, and
,10 mL of the supernatant was transferred into a
standard cuvette for zeta potential measurement. The
solution temperature was maintained at 25uC. Five
measurements were taken, and the average was reported
as the measured zeta potential.
2 Zeta potential of haematite
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Abdel-Khalek et al. Starch type on selectivity of cationic flotation of iron ore
Adsorption measurements
In adsorption experiments, 1 g dry sample of haematite
or quartz was placed with the required concentration of
collector or starch solutions (50 cm3) in a 100 cm3
volumetric flask and shaken by a shaker (Janke &
Kunkel type Vx10). The pH was adjusted to the desired
values using HCl and NaOH. A potentiometer (Orion
Mod. 720A) equipped with a combined electrode was
used to monitor the pH. The potentiometer was
calibrated before each test using buffer solutions of
pH 4, 7 and 10. The solution was shaken for 1 h at the
controlled temperature of 25uC. Then, the samples were
centrifuged at 15000 rev min21 for 15 min to separate
the supernatant from the settled fraction. The total
content of organic carbon (residual concentration) in
40 mL of supernatant was determined using a ‘Phoenix
8000’ total carbon analyser instrument. The average of
three readings was taken as a measure for the residual
concentration of organic carbon.
Fourier transform infrared spectroscopy (FTIR)
measurements
Infrared absorption spectra were recorded using an
FTIR 6300 model spectrometer for minerals before and
after their treatment with starches. After interaction
with starches, the mineral samples were washed using
double distilled water and vacuum dried. KBr pellet
technique was used to record the spectra.
Flotation experiments
A series of bench scale flotation experiments were
conducted using a Hallimond flotation cell. An ore
3 Zeta potential of quartz in absence and presence of
CTAB
2012 VOL 121 NO 2 99
Abdel-Khalek et al. Starch type on selectivity of cationic flotation of iron ore
4 Effect of pH on adsorption of CTAB onto quartz
surface
sample or single mineral samples of haematite and
quartz was conditioned with both depressant and
collector at certain concentrations and at different pH
values on a horizontal shaker for standard conditioning
time and then transferred to the Hallimond flotation
unit; the air flowrate was adjusted at 30 cm3 min21.
Both float and sink fractions were collected, dried and
weighted.
Results and discussion
Surface properties of single minerals
Figures 2 and 3 show the zeta potential of haematite and
quartz, from which it can be seen that the isoelectric
points (iep) for haematite and quartz are at about pH 7
and 3 respectively. This is in agreement with the results
reported in the literature (Fuerstenau, 1976).
The results in Fig. 3 confirm the adsorption mechan-
ism due to electrostatic attraction for quartz in the
presence of CTAB collector. However, the results of zeta
potential in the presence of the collector indicated no
effect on the iep of haematite (results not shown). On the
other hand, CTAB has a great effect on the zeta
potential values of quartz, where it changed from
negative to positive values over the entire pH range,
indicating the great adsorption of CTAB onto quartz
surface rather than the haematite surface.
5 Effect of starch type on adsorption density and silica
removal
100 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
6 Flotation of binary mixture of haematite and silica at
different pH values using wheat starch
Adsorption isotherm of CTAB on single quartz
mineral
Figure 4 shows the adsorption density of CTAB onto
quartz surface at different pH values. These results show
that the adsorption density increases with increasing pH
values until about pH 8?0, above which a plateau is
noticed. These results are in agreement with that
mentioned above for zeta potential measurements. At
low pH, more protons will be available to protonate
quartz surface groups, thereby decreasing the electro-
static attraction of the collector molecules to the active
sites of quartz. This leads to the observed low collector
adsorption. However, the adsorption of collector at
higher pH values could be attributed to the electrostatic
interaction between the protonated amine group
(NH3z) of the collector and silanol groups (Si–OH2)
on the quartz surface (Rubio and Kitchener, 1976; Lima
et al., 2005; Montes and Atenas, 2005; Geraldo et al.,
2008; Mowla et al., 2008).
Role of starch adsorption
Figure 5 illustrates the adsorption density of different
starch types onto the single haematite surface. Figure 5
also shows the silica content of concentrates obtained
from the cationic flotation of a mixture containing
80%Fe2O3 and 20%SiO2 at about pH 8?0 using
1?5 kg t21 starch and 1?061023M CTAB. These data
illustrate that the haematite–starch interaction is strong.
However, it can be seen that the wheat and corn starches
exhibited higher affinity for adsorption onto the
haematite surface in comparison to the other types of
starches. This is accompanied also by the minimum
amount of SiO2 percentage in the concentrates obtained
from flotation of the binary mixture of Fe2O3 and SiO2.
This is also confirmed from the results of flotation of the
natural iron ore at the same operating conditions as
Table 1 Flotation of iron ore with different types of
starches
Starch type Fe2O3/% SiO2/%
Wheat starch 78.2 8.8
Corn starch 72.1 12.0
Potato starch 71.2 14.0
Feed 70.2 15.1
2012 VOL 121 NO 2

7 Effect of starch on iep of haematite
shown in Table 1. It seems that both corn and wheat
starches have better affinity and, in turn, higher
adsorption capability to haematite surfaces than the
other types of starches. It is clear that the minimum
silica contents can be obtained at pH 8 (from Fig. 6). It
follows that around the iep (about pH 7?0), the
haematite, the surfaces become fully hydroxylated. The
observed adsorption maximum of starches around the
iep of the iron bearing minerals (pHiep 5?5–8) is in line
with the postulation that the polysaccharides interact
with surface metal–hydroxylated species (Laskowski
et al., 1991, 2007; Liu et al., 2000).
Meanwhile, a series of zeta potential measurements in
the presence of wheat starch were performed, the results
of which are shown in Fig. 7. These results reveal that
the adsorption of starch molecules on the haematite
surface caused a displacement of the iep, indicating the
strength of the starch–iron oxide surface interaction
(Montes et al., 1998).
Fourier transform infrared spectroscopy results
Figure 8 shows the IR absorption spectra of haematite
powder as well as haematite coated with wheat and corn
starches, while the assignments of different absorption
bands in the spectra are listed in Table 2. The infrared
spectrum above 400 cm21 of the powdered haematite
sample has two major bands attributed to lattice
vibrations. Haematite produces an infrared spectrum
with bands at ,560 and 480 cm21 with the more intense
band at 560 cm21. Published values for the position of
these two bands differ by up to 30 cm21. Several reasons
for these vibrations have been suggested in the literature,
but it is generally accepted that variations among the
spectra are most often caused by differences in size and
more importantly the shape of the haematite particles
(Vieira and Peres, 2007).
The attachment of different types of starches to the
particle surface of haematite was confirmed by FTIR
spectroscopy. The spectrum of the latter colloidal iron
Table 2 Assignment of absorption bands in IR spectra
Wave length Assignments
3500–3200 H–O… H stretching vibration
2925 C–H of CH2 asymmetrical stretching
vibration
1455: 1370, 1277 H–C–OH deformation
1152 C–O–C– stretching vibration
800–1200 C–C– symmetrical stretching vibration
590 Fe–O
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Abdel-Khalek et al. Starch type on selectivity of cationic flotation of iron ore
8 Fourier transform infrared spectroscopy of haematite
in the absence and presence of different types of
starches
oxide contains characteristic OH stretching (n OH) and
HOH bending (d OH) vibrational bands at 3400 and
1600 cm21. The band observed at 620–580 cm21 corre-
sponds to the stretching vibration MTh–O–MOh, and
MTh–MOh (n3<350–400 cm21), where MTh and MOh
correspond to the metal occupying tetrahedral and
octahedral positions respectively (Barrod et al., 2002).
The stretching vibration n (Fe–O) at 590 cm21 corre-
sponds to tetrahedral iron atoms.
A typical IR spectrum of the starch presents bands at
3365 cm21 (O–H), 2851–2940 cm21 (CH) and 1040–
1110 cm21 (C–O) (Pavlovic and Brandao, 2003; Wang
and Chen, 2006). The spectra of the haematite coated
with starch exhibit few differences if compared to the
ones of wheat or corn solutions, which indicates that the
interactions between starch and haematite particles are
intermolecular interactions.
Conclusion
A group of starches were investigated as depressants for
haematite while floating quartz with CTAB. These
starches were wheat, corn, rice, potato and dextrin.
The selectivity of the separation process is strongly
affected by the type of starch used, with better results
obtained while using corn starch or wheat starch in
comparison to the other types.
The lowest SiO2 assay in concentrates obtained from
flotation of a binary mixture of Fe2O3 and SiO2 as well
as from flotation of natural iron ore was obtained while
using wheat or corn starches as depressant at about
pH 6–8.
Adsorption of starch molecules on the haematite
surface caused displacement of the iep, indicating
the strength of starch–iron oxide surface interaction.
Fourier transform infrared spectroscopy measurements
indicated that the interactions between starches and iron
oxide surface were intermolecular interaction.
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2012 VOL 121 NO 2
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