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Minerals Engineering 72 (2015) 19

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

Flotation behaviors of ilmenite, titanaugite, and forsterite using sodium


oleate as the collector
Weijun Liu a, Jie Zhang a, Weiqing Wang a,b,, Jie Deng c, Bingyan Chen c, Wu Yan c, Shuqing Xiong c,
Yang Huang a,b, Jing Liu a,b
a
b
c

School of Environment and Resource, Southwest University of Science and Technology, Mianyang, Sichuan 621010, PR China
Key Laboratory of Solid Waste Treatment and Resource Recycle Ministry of Education, Southwest University of Science and Technology, Mianyang, Sichuan 621010, PR China
Key Laboratory of Vanadium-titanium Magnetite Comprehensive Utilization, Ministry of Land and Resources, Chengdu, Sichuan 610000, PR China

a r t i c l e

i n f o

Article history:
Received 20 July 2014
Accepted 12 December 2014

Keywords:
Ilmenite
Titanaugite
Forsterite
Sodium oleate
Flotation

a b s t r a c t
The otation behaviors of ilmenite, titanaugite, and forsterite using sodium oleate as the collector were
investigated using microotation experiments, zeta-potential measurements, Fourier transform infrared
(FT-IR) analyses, X-ray photoelectron spectroscopy (XPS) analyses and the articially mixed minerals
otation experiments. The results of the microotation experiments indicate that ilmenite exhibits good
oatability when pH > 4.0. Titanaugite possesses a certain oatability at pH 4.06.0 and pH > 10.0, and
forsterite possesses certain oatability at pH 5.07.0 and pH > 9.0. The results of FT-IR and XPS analyses
indicate that sodium oleate mainly interacts with Fe, resulting in ilmenite otation; that the Ca and Mg
on the titanaugite surface chemically reacted with sodium oleate, and that the Mg on the forsterite surface chemically reacted with sodium oleate under acidic condition. However, sodium oleate mainly
reacted with the Ca and Mg on the titanaugite surface, whereas sodium oleate mainly reacted with the
Mg on the ilmenite and forsterite surfaces under alkaline conditions. The results of the articially mixed
minerals otation experiment demonstrate that the concentrate of TiO2 grade increases from 16.92% to
30.19% at pH 5.4, which represents the appropriate conditions for the otation separation of ilmenite
from titanaugite and forsterite under weak acidic conditions.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The Panzhihua (Sichuan province in China) area possesses the
largest deposits of vanadiumtitanium magnetite. The vanadiumtitanium magnetite reserves are more than 1.0  1010 t,
and the reserves of titanium are 8.7  108 t, as TiO2, occupying over
91% of the total reserve in China (Han et al., 2011; Hou et al., 2011;
Zhang et al., 2013). Titanium resources occur in two types. In one
type, the titanium in vanadiumtitanium magnetite is partially
substituted by iron, thus making it difcult to be recovered by
magnetic separation. In the other type, the titanium occurs as granular ilmenite in the iron tailings during magnetic separation (Chen
et al., 2013; Zhou et al., 2013).
The Hongge area possesses the largest deposits of vanadium
titanium magnetite in Panzhihua (Luan et al., 2014). With the
increase of the exploration depth of vanadiumtitanium
Corresponding author at: School of Environment and Resource, Southwest
University of Science and Technology, Mianyang 621010, PR China. Tel./fax: +86
816 2419569.
E-mail address: swustwwq@sohu.com (W. Wang).
http://dx.doi.org/10.1016/j.mineng.2014.12.021
0892-6875/ 2014 Elsevier Ltd. All rights reserved.

magnetite, the olivine content has increased and the gabbro ore
has been found to be converted to the onkilonite ore in the Hongge
area. The results of most research studies indicate that the main
silicon gangue mineral of gabbro ore is titanaugite; however, for
onkilonite ore, the main silicon gangue minerals are titanaugite
and olivine (Bai et al., 2012; Cheng et al., 2014; Zhao and Zhou,
2007). The physical separation methods for ilmenite and silicon
gangue minerals are based on gravity separation, high-intensity
magnetic separation, electrical separation, or a combination of
the above methods. Because of the similar physical properties, it
is difcult to achieve the effective separation of ilmenite from silicon gangue minerals using these physical separation methods.
Currently, otation is the most common separation method for
ilmenite and silicon gangue minerals (Zhang et al., 2011;
Bulatovic and Wyslouzil, 1999; Drzymala et al., 1983). Sodium oleate, a fatty acid collector, is widely used in the otation separation
of ilmenite from silicon gangue minerals (Bulatovic and Wyslouzil,
1999; Hanumantha Rao and Forssberg, 1991). However, ilmenite
exhibits certain oatability under conventional otation conditions
compared to silicon gangue minerals even when using a large
amount of collector. For this reason, the otation behaviors of

W. Liu et al. / Minerals Engineering 72 (2015) 19

100
Volume

80

d25=32.309 m

Volume (%)

d50=62.617 m
d75=85.724 m

60

d90=105.761 m

4
40
2
20

Cumulative Volume (%)

Cumulative volume

d10=7.271 m

Ilmenite

0
0.1

10

100

1000

Partical Size (m)


100
3.0

Volume

2.5

d10=0.294 m

80

d25=3.038 m
d50=17.318 m

2.0

60

d75=52.136 m
d90=94.256 m

1.5
40
1.0

Cumulative Volume (%)

Cumulative volume

Volume (%)

20

0.5
Titanaugite

0.0
0

50

100

150

200

250

300

350

0
400

Partical Size (m)


4

100
Volume
Cumulative volume

80

d10=2.070 m

d25=7.783 m
d50=26.982 m
d75=60.834 m

60

d90=106.156 m

2
40
1

Cumulative Volume (%)

ilmenite and titanaugite were investigated to improve the otation


recovery of ilmenite. Mehdi Irannajad used a pretreatment
method, microwave irradiation, to modify the surface properties
of ilmenite, thus improving its otation recovery in the presence
of different gangue minerals including olivine, gabbro, tremolite,
and quartz. The irradiation of the ilmenite surface converted Fe2+
to Fe3+, as characterized by XPS analysis, thus improving the otation recovery of ilmenite (Fan et al., 2009; Irannajad et al., 2014).
Fan and Rowson (2000) used Pb(NO3)2 as an activator to effectively
and selectively improve the oatability of ilmenite. The addition of
Pb(NO3)2 increased the zeta potential of ilmenite, probably
because of the adsorption of oleate ions into the Helmholtz layer
of the activated ilmenite. Moreover, the high content of ne ilmenite and silicon gangue minerals in the pulp clearly affected the otation behavior of ilmenite. Zhang et al. (2009) reported that
titanaugite with a grain size of <10 lm signicantly affected the
otation recovery of ilmenite; however, titanaugite with a grain
size between 10 and 100 lm slightly affected the otation recovery of ilmenite. With the increasing content of titanaugite, the otation recovery of ilmenite decreased.
To the best of our knowledge, the otation behaviors of ilmenite, titanaugite, and olivine using sodium oleate as the collector
have rarely been investigated. Because the collectors may react
with the Fe and Mg on the olivine surface and improve the otation
recovery of olivine, it is difcult to achieve the effective separation
of ilmenite and olivine. The studies on the beneciation of onkilonite ore demonstrated that only a 40% grade of titanium concentrate and 36% of the recovery were obtained in the conventional
methods (Jinhua et al., 2011). The result revealed a high MgO content in the iron concentrate in the product inspection, thus making
it difcult for effective separation. Therefore, the difference in the
surface properties between ilmenite and silicon gangue minerals
should be extensively investigated. The effects of the surface properties of titanaugite on its otation behavior were mainly studied
in silicon gangue minerals. Zhu et al. (2011) reported that it is benecial to increase the oatability difference between ilmenite and
titanaugite by surface dissolution. In a weak acidic solution, the
contents of Ti and Fe on the titanaugite surface are less than those
of Ca and Mg. Because sodium oleate interacts with Ca and Mg in a
weak acidic solution, the oatability of titanaugite decreases.
The effective separation of olivine is difcult to achieve using
physical separation methods. Therefore, the otation behaviors of
ilmenite, titanaugite, and olivine should be studied to improve
the otation recovery of ilmenite. The objective of this study is to
explore the otation behavior of ilmenite, titanaugite, and olivine
using sodium oleate as the collector through otation tests,
zeta-potential measurements, FT-IR analyses, XPS analyses and
the articially mixed minerals otation experiments.

Volume (%)

20
Forsterite

0
0

100

200

300

400

500

600

700

0
800

Partical Size (m)


Fig. 1. The particle size distribution results of the puried samples.

2. Experimental
2.1. Materials
The high grade ilmenite and titanaugite samples used in the
experiments were obtained from the magnetic separation tailings
of vanadiumtitanium magnetite in Panzhihua. The samples were
repeatedly puried using low-intensity magnetic separation, highintensity magnetic separation, and gravity separation. Because of
the similar physical properties, olivine is difcult to separate from
silicon gangue minerals. Therefore, the puried forsterite was
hand-picked from the coarse peridotite instead of olivine. The puried ilmenite, titanaugite, and forsterite samples were dry-ground
in a ball mill. Fig. 1 shows the particle size distribution results of
the puried ilmenite, titanaugite, and forsterite samples (detected
by a laser diffraction particle size analyzer, Beckman Coulter,

LS13320). This gure indicates that the puried ilmenite,


titanaugite, and forsterite samples possess broad size distributions
in the experiments. The chemical compositions of the samples are
listed in Table 1. The purities of titanaugite and forsterite were
90%, while that of ilmenite was above 95%, based on Table 1
and the chemical compositions of the samples in theory (Zhu
et al., 2011). Fig. 2 shows the X-ray diffraction (XRD) patterns of
the puried ilmenite, titanaugite, and forsterite samples. This
indicates that the diffraction peaks of ilmenite, titanaugite, and
forsterite matched well with the pattern of standard diffraction
peaks: ilmenite (No. 3-781), titanaugite (No. 24-203), and forsterite (No. 7-74), respectively. According to the result of the XRD
analysis, the purities of ilmenite, titanaugite, and forsterite were
very high.

W. Liu et al. / Minerals Engineering 72 (2015) 19


Table 1
Chemical compositions of the puried samples (mass fraction, %).
Sample

TFe

TiO2

SiO2

Al2O3

CaO

MgO

Others

Total

Ilmenite
Titanaugite
Forsterite

31.07
13.56
6.62

50.40
1.88
0.03

2.37
41.57
44.4

0.51
11.39
1.00

0.28
16.34
0.13

5.24
12.45
47.56

10.13
2.81
0.26

100.00
100.00
100.00

F
F

I-Ilmenite
T-Titanaugite
F-Forsterite

F
F

F
F

Forsterite

F F

F
F F
F

FF

T
T
T
T

T
Titanaugite

T
TT T

T T

I
I

Ilmenite

10

20

30

40

I I

50

60

70

2
Fig. 2. XRD patterns of the puried samples.

2.2. Reagents
Sodium oleate (CH3(CH2)7CH=CH(CH2)7COONa) was used as the
anionic collector for the microotation tests. H2SO4 or NaOH were
used for the pH adjustment of aqueous suspensions in the experiments. All of the chemicals were of analytical grade, and the water
used in all of the experiments was ultrapure water (18.25 MX cm).

the puried mineral particles to 50 mL of ultrapure water. The prepared suspension was conditioned by magnetically stirring for
5 min during which the pH of the suspension was measured. After
settling for 10 min, the supernatant of the dilute ne particle suspension was obtained for zeta-potential measurements. Three
measurements of zeta potentials were run, and their averages were
taken as the nal result.

2.3. Microotation experiments

2.5. FT-IR spectroscopy measurements

Microotation experiments were performed in a 40-mL hitch


groove otation cell. The puried mineral particles (2.0 g) were
placed in a Plexiglas cell, which was then lled with 35 mL of ultrapure water. The pH of the suspension was adjusted by H2SO4 or
NaOH for 3 min, the collector was added and agitated for 3 min,
and then, the pH of the suspension was measured before the otation. The otation was conducted for 4 min. The concentrates were
weighed after ltering and drying, and then, the recoveries were
calculated. Three measurements of the microotation experiments
were run, and their averages were taken as the nal result.

The FT-IR spectra were obtained using a Spectrum One (Version


BM) FT-IR (USA) spectrometer to characterize the nature of the
interaction between the collector and minerals. Approximately
10% (mass fraction) of the solid sample was mixed with spectroscopic grade KBr. The wave number range of the spectra was
4004000 cm 1. The spectra were recorded with 32 scans measured at 2 cm 1 resolution.
The puried mineral particles (2.0 g) were placed in a Plexiglas
cell with H2SO4 or NaOH as the pH regulating reagent. Next, the
puried samples were conditioned for another 3 min with sodium
oleate. Subsequently, the solid samples were washed three times
using the ultrapure water with the same pH. The washed samples
for FT-IR analysis were vacuum dried at 55 C.

2.4. Zeta-potential measurements


The zeta-potentials were measured using a Zetasizer Nano Zs90
(England). The conductivity and pH of the suspension were monitored continuously during the measurement, and the environmental temperature was maintained at 22 C.
The puried mineral particles were ground to 2 lm using an
agate mortar. The suspension was prepared by adding 30 mg of

2.6. XPS experiments


The XPS analyses were performed using a Kratos AXIS Ultra XPS
system equipped with a monochromatic Al X-ray source operated
at 150 W. Each analysis started with a survey scan from 0 to

W. Liu et al. / Minerals Engineering 72 (2015) 19

1350 eV with a dwell time of 8 s and band pass energy of 150 eV at


steps of 1 eV, with 1 sweep performed. For the high-resolution
analysis, the number of sweeps was increased, the band pass
energy was lowered to 30 eV at steps of 50 meV, and the dwell
time was changed to 0.5 s.
The puried mineral particles (2.0 g) were placed in a Plexiglas
cell with H2SO4 or NaOH as the pH regulating reagent. Subsequently, the puried samples were conditioned for another 3 min
with sodium oleate. Next, the solid samples were washed three
times using the ultrapure water with the same pH. The washed
samples for XPS analysis were vacuum dried at 55 C.

100

80

Recovery (%)

60

40

20

2.7. Articially mixed minerals otation experiments


The articially mixed minerals consist of 0.67 g of the puried
ilmenite, 0.67 g of the puried titanaugite, and 0.67 g of the puried forsterite. The articially mixed minerals otation experiment
was performed in a 40-mL hitch groove otation cell. The articially mixed mineral (2.01 g) was placed in a Plexiglas cell, which
was then lled with 35 mL of ultrapure water. The pH of the suspension was adjusted by H2SO4 or NaOH for 3 min, the collector
(2.0  10 4 M) was added and agitated for 3 min, and then the
pH of the suspension was measured before the otation. The otation was conducted for 4 min. The concentrates and the tailings
were weighed after ltering and drying, and then separately sampled to analyze the grade of TiO2 by the chemical analysis method.
The otation recoveries of the concentrates and the tailings were
calculated based on the yield and the grade of TiO2. The average
value in three otation experiments under the same condition
was used as the results of the articially mixed minerals otation.
3. Results and discussion
3.1. Microotation
Fig. 3 shows the otation recoveries of ilmenite, titanaugite, and
forsterite as a function of pH using sodium oleate (2.0  10-4 M).
The results indicate that the oatability of ilmenite is better than
that of titanaugite and forsterite. The oatability of ilmenite is
good at pH > 4.0. Titanaugite possesses certain oatability at pH
4.06.0 and pH > 10.0, and forsterite possesses certain oatability
at pH 5.07.0 and pH > 9.0.
Fig. 4 shows the effect of sodium oleate concentration on the
otation recoveries of ilmenite, titanaugite and forsterite at pH

100
Ilmenite
Titanaugite
Forsterite

80

Ilmenite
Titanaugite
Forsterite

10

-4

Concentration of sodium oleate (10 mol/L)


Fig. 4. Flotation recovery of the minerals as a function of the collector concentration (pH = 5.06.0).

5.06.0. Fig. 4 shows that the increase in sodium oleate concentration clearly increased the otation recoveries of ilmenite, titanaugite, and forsterite. However, the otation recoveries of ilmenite and
titanaugite increased slowly above 2.0  10 4 M sodium oleate.
Thus, this sodium oleate concentration (2.0  10 4 M) was used
in all of the microotation experiments.
3.2. Zeta-potential
Fig. 5 shows the zeta-potentials of ilmenite, titanaugite, and forsterite in the absence and presence of sodium oleate as a function
of pH. In the absence of sodium oleate, the results indicate that the
point of zero charges (PZCs) of ilmenite, titanaugite, and forsterite
are located at pH 5.8, 3.8, and 2.8, respectively. In the presence of
sodium oleate, the zeta-potentials of ilmenite, titanaugite, and forsterite are negative at pH 3.012.0. The large decrease in the zetapotentials of ilmenite, titanaugite, and forsterite can be attributed
to the adsorption of oleate ions onto the Helmholtz layer of their
surfaces (Mehdilo et al., 2013).
Fig. 5 also shows that the decrease in the zeta-potential of
ilmenite is greater than those for titanaugite and forsterite after
the addition of sodium oleate. This result indicates that the sodium
oleate absorbed on the ilmenite surface is greater than that
absorbed on the surface of silicon gangue minerals. Therefore,
the interaction between sodium oleate and ilmenite is stronger
than that between the sodium oleate and silicon gangue minerals.
The result is almost identical to the oatability of ilmenite, titanaugite, and forsterite.

Recovery (%)

3.3. FT-IR analysis


60

40

20

10

12

pH
Fig. 3. Flotation recovery of the minerals as a function of pH using sodium oleate
(c = 2.0  10 4 M).

Fig. 6 shows the FT-IR spectra of sodium oleate, ilmenite, titanaugite, and forsterite. In the FT-IR spectrum of sodium oleate, the
bands at 2922.5 cm1 and 2852.5 cm 1 can be attributed to the
CAH stretching vibration of the ACH2A and ACH3 groups, respectively. The bands at 1712.9 cm 1, 1562.2 cm 1, 1446.6 cm 1, and
1424.6 cm 1 can be attributed to the ACOOA vibration. Among
these bands, the band at 1712.9 cm 1 can be attributed to the
C@O stretching vibration, whereas the band at 1562.2 cm 1 can
be attributed to the ACOOCA asymmetric stretching vibration.
The bands at 1446.6 cm 1 and 1424.6 cm 1 can be attributed to
the ACOOCA symmetric stretching vibration. The band at
722.1 cm 1 can be attributed to the A(CH2)nA deformation
(Njera, 2007; Tandon et al., 2001). Several characteristic bands

W. Liu et al. / Minerals Engineering 72 (2015) 19

20
Ilmenite
Ilmenite+sodium oleate

924.3

609.3

1068.7
967.3
874.3
1318.2

1636.6

-50

1487.6
1318.2

Forsterite

-40

722.1
698.8

1712.9

Titanaugite

671.1
633.7

1102.0

-30

Ilmenite

990.8
890.1

-20

1635.7

-10

2922.5
2852.5

Transmittance

Zeta potential (mV)

1076.4

Sodium oleate

1562.2
1446.6
1424.6

10

-60
2

10

12

4000

3500

3000

pH

2500

2000

1500

1000

500

Wavenumbers (cm-1)

10
Titanaugite
Titanaugite+sodium oleate

Fig. 6. FT-IR spectra of sodium oleate, ilmenite, titanaugite, and forsterite.

-10

10

10
Forsterite
Forsterite+sodium oleate

4000

3500

3000

2500

2000

546.78

693.93

1089.5

534.34

1121.5

1384.5

1629.9

688.01

12

pH

685.30

1630.1

1630.8

2927.0
2856.0

-50

pH=11.3

2924.6

-40

pH=6.2
2926.4
2855.2

-30

1384.4

pH=2.3

-20

Transmittance

Zeta potential (mV)

1500

1000

500

Wavenumbers (cm-1)

Zeta potential (mV)

0
Fig. 7. FT-IR spectra of the puried ilmenite sample with sodium oleate at different
pH levels.

-10

-20

-30

-40
2

10

12

pH
Fig. 5. Zeta-potentials of the minerals a function of pH in the absence and presence
of sodium oleate (c = 2.0  10 4 M).

for ilmenite were observed at 700 cm 1, and some characteristic


bands for titanaugite and forsterite were also observed (Liu et al.,
2013).
Fig. 7 shows the FT-IR spectra of the puried ilmenite sample
with sodium oleate at different pH levels. Compared to the FT-IR
spectrum of the puried ilmenite shown in Fig. 6, the spectra in
Fig. 6 show additional CAH and ACOOA stretching intensities for

sodium oleate. At pH 2.3, the new bands at 2927.0 cm 1 and


2856.0 cm 1 were previously attributed to the CAH stretching
vibration; however, the band frequency did not change. This result
indicates that sodium oleate was adsorbed onto the mineral surface. The new band at 1630.8 cm 1 was previously attributed to
the ACOOA vibration. The band at 1562.2 cm 1 shifted to a higher
wave number by 68.6 cm 1 compared to that in the FT-IR spectrum
of sodium oleate (Fig. 6). This result indicates that oleate reacted
on the ilmenite surface. A similar situation was observed at pH
6.2 and pH 11.3.
Fig. 8 shows the FT-IR spectra of the puried titanaugite sample
with sodium oleate at different pH levels. At pH 2.4, the new bands
at 2924.9 cm 1 and 2853.6 cm 1 were previously attributed to the
CAH stretching vibration; however, the band frequency did not
change. The new band at 1630.5 cm 1 was previously attributed
to the ACOOA vibration. The band at 1562.2 cm 1 shifted to a
higher wave number by 68.3 cm 1, compared to the FT-IR spectrum of sodium oleate (Fig. 6). This result indicates that the sodium
oleate reacted on the titanaugite surface. A similar situation was
observed at pH 6.7 and pH 11.4.
Fig. 9 shows the FT-IR spectra of the puried forsterite sample
with sodium oleate at different pH levels. Similar to ilmenite and

W. Liu et al. / Minerals Engineering 72 (2015) 19

-2
RCOOH(l)

2-

(RCOO)2

-6
RCOOH (aq)

log C

1384.4

RCOO

-4
1072.2
970.7
875.35

1635.5
1636.6

pH=11.4

1382.6 1383.2

1630.5

pH=6.7
2923.1 2923.5
2853.2 2852.8

Transmittance

2924.9
2853.6

pH=2.4

RC

-8

OO
HR

1068.9
967.5
875.3

-10

CO
O

-12

1068.8

967.8
875.0

-14

4000

3500

3000

2500

2000

1500

1000

-16

500

Wavenumbers (cm )
Fig. 8. FT-IR spectra of the puried titanaugite sample with sodium oleate at
different pH levels.

609.3

1385.9

1630.1

2925.0
2854.2

pH=2.4

4000

3500

3000

2500

2000

8 8.4

10

12

14

1500

608.0

Fig. 10. Logarithmic diagram of oleate hydrolysis components with sodium oleate
(c = 2.0  10 4 M).

whereas titanaugite and forsterite exhibited poor oatability


(Fig. 3). Because the number of metal cations absorbed onto the
ilmenite surface is greater than the number absorbed onto
the titanaugite and forsterite surfaces, this condition resulted in
the improved oatability of ilmenite compared to titanaugite and
forsterite. This result is consistent with the results of zeta-potential
measurements and the FT-IR analyses.

607.96

838.5

3.4. XPS analysis

887.1

985.5

887.1 888.9

838.2

1384.6
1383.2

1635.2 1634.8

2924.3 2925.7
2852.7 2853.6

Transmittance

pH=6.5
pH=11.4

pH

-1

1000

500

Wavenumbers (cm-1)
Fig. 9. FT-IR spectra of the puried forsterite sample with sodium oleate at
different pH levels.

titanaugite, the new band attributed to the CAH stretching


vibration indicate that sodium oleate was adsorbed onto forsterite
surface. The new bands attributed to the ACOOA vibration that
shifted to higher wave numbers indicate that sodium oleate
reacted on the forsterite surface.
In the otation process, the pulp collectors exhibited different
forms in different pH environments. The existing forms of the
collectors affected the otation behaviors of the minerals. The
solution chemistry of sodium oleate can be calculated to generate
the concentration logarithmic diagram of each component at
different pH. Fig. 10 shows the log CpH of the oleate hydrolysis
components as a function of pH when the oleate concentration
was 2.0  10 4 M. The result indicates that sodium oleate formed
oleate ions and a dimer at pH = 6.0. When the total concentration
of oleate ions was 2.0  10 4 M, an ionmolecule association complex was formed at the maximum concentration and pH = 8.4.
When the pH was above 8.4, the main components of sodium oleate are RCOO and (RCOO)22 . These components interacted with
metal cations and absorbed onto ilmenite, titanaugite, and forsterite. The interactions resulted in the otation behaviors of these
minerals. Ilmenite exhibited good oatability within this pH range,

XPS analyses were outperformed to further conrm that sodium


oleate mainly interacts with ilmenite, titanaugite, and forsterite in
different pH solutions. Table 2 presents the binding energies of elements on the ilmenite surface before and after the interactions
with sodium oleate. After ilmenite was treated by sodium oleate,
the chemical shifts of Ca and Mg were not obvious, while that of
Fe reached +0.5 eV under acidic conditions, which indicated the
transformation of the chemical environment. This result indicates
that the sodium oleate reacted on the ilmenite surface (Jie et al.,
2014).
The relative contents of the elements on the surface of ilmenite
in the absence and presence of sodium oleate, as measured by XPS,
are listed in Table 3. After ilmenite was treated by sodium oleate
under acidic condition, the relative contents of Fe, Ca, and Mg
decreased to 5.0%, 0.4%, and 2.8%, respectively. This result indicates
that sodium oleate mainly interacted with Fe under acidic conditions. A similar situation was observed under alkaline conditions.
The relative content of Fe, Ca, and Mg decreased to 1.8%, 0.3%,
and 2.4%, respectively, under alkaline conditions. This result indicates that sodium oleate mainly interacted with Mg under alkaline
conditions.
Table 4 presents the binding energies of elements on the titanaugite surface before and after the interactions with sodium oleate.
After titanaugite was treated by sodium oleate, the chemical shifts
of the elements indicated that the sodium oleate reacted on the
titanaugite surface.
The relative contents of elements on the surface of titanaugite
in the absence and presence of sodium oleate, as measured by
XPS, are listed in Table 5. After titanaugite was treated by sodium
oleate, the relative contents of the reduction of Ca and Mg were larger than that of Fe in the entire range of pH. This result indicates
that sodium oleate mainly interacted with Ca and Mg.
Table 6 presents the binding energies of elements on the forsterite surface before and after the interactions with sodium oleate.

W. Liu et al. / Minerals Engineering 72 (2015) 19


Table 2
Binding energies of elements on the ilmenite surface.
Samples

Original ilmenite
Ilmenite + H2SO4 (pH = 5.1)
Ilmenite + H2SO4 + sodium oleate (pH = 5.1)
Ilmenite + NaOH (pH = 10.1)
Ilmenite + NaOH + sodium oleate (pH = 10.1)

Binding energy (eV)

Chemical shift (eV)

C1s

Ti2p

Fe2p

Ca2p

Mg1s

C1s

Ti2p

Fe2p

Ca2p

Mg1s

284.8

284.8

458.2
458.2
458.1
458.2
458.1

710.9
711.3
710.9
711.1
710.9

347.5
347.6
347.4
347.6
347.5

1303.6
1303.5
1303.5
1303.5
1303.4

0
-0.1
0
-0.1

+0.4
-0.4
+0.2
-0.2

+0.1
-0.2
+0.1
-0.1

-0.1
0
-0.1
-0.1

Table 3
Relative contents of elements on the ilmenite surface.
Samples

Surface Atomic Composition (%)

Original ilmenite
Ilmenite + H2SO4 (pH = 5.1)
Ilmenite + H2SO4 + sodium oleate (pH = 5.1)
Ilmenite + NaOH (pH = 10.1)
Ilmenite + NaOH + sodium oleate (pH = 10.1)

C1s

Ti2p

Fe2p

Ca2p

Mg1s

64.3

50.9

3.4
3.7
2.1
3.5
2.5

3.7
6.7
1.7
5.5
3.7

0.4
0.7
0.3
0.1
0.4

5.2
4.2
1.4
5.5
3.1

Table 4
Binding energies of elements on the titanaugite surface.
Sample

Original titanaugite
Titanaugite + H2SO4 (pH = 5.7)
Titanaugite + H2SO4 + sodium oleate (pH = 5.7)
Titanaugite + NaOH (pH = 10.7)
Titanaugite + NaOH + sodium oleate (pH = 10.7)

Binding energy (eV)

Chemical shift (eV)

C1s

Ca2p

Mg1s

Ti2p

Fe2p

C1s

Ca2p

Mg1s

Ti2p

Fe2p

284.7

284.7

347.4
347.5
347.5
347.5
347.3

1303.6
1303.5
1303.6
1303.5
1303.4

458.5
458.7
459.2
458.8
458.9

711.5
711.5
711.3
711.4
711.3

+0.1
0
+0.1
0.2

+0.2
+0.5
+0.3
+0.1

0.1
+0.1
0.1
0.1

0
0.2
0.1
0.1

Table 5
Relative contents of elements on the titanaugite surface.
Sample

Surface Atomic Composition (%)

Original titanaugite
Titanaugite + H2SO4 (pH = 5.7)
Titanaugite + H2SO4 + sodium oleate (pH = 5.7)
Titanaugite + NaOH (pH = 10.7)
Titanaugite + NaOH + sodium oleate (pH = 10.7)

C1s

Ca2p

Mg1s

Ti2p

Fe2p

15.1

15.6

4.6
5.0
3.7
5.3
3.8

8.6
8.2
6.8
9.2
7.3

0.5
0.5
0.3
0.1
0.4

3.4
3.4
3.1
3.3
2.6

Table 6
Binding energies of elements on the forsterite surface.
Sample

Original forsterite
Forsterite + H2SO4 (pH = 7.1)
Forsterite + H2SO4 + sodium oleate (pH = 7.1)
Forsterite + NaOH (pH = 11.3)
Forsterite + NaOH + sodium oleate (pH = 11.3)

Binding energy (eV)

Chemical shift (eV)

C1s

Mg1s

Ca2p

Fe2p

C1s

Mg1s

Ca2p

Fe2p

284.8

284.8

1303.6
1303.6
1303.7
1303.4
1303.6

347.5
347.5
347.6
347.5
347.8

711.3
711.2
711.4
711.5
711.7

0
+0.1
-0.2
+0.2

0
+0.2
0
+0.3

After forsterite was treated by sodium oleate, the chemical shifts of


the elements indicated that the sodium oleate reacted on the forsterite surface.
The relative contents of elements on the surface of forsterite in
the absence and presence of sodium oleate, as measured by XPS,
are listed in Table 7. After forsterite was treated by sodium oleate,
the relative content of the reduction of Mg was larger than those of
Ca and Fe in the entire range of pH. This result indicates that
sodium oleate mainly interacted with Mg.

0.1
+0.2
+0.2
+0.2

According to the results of the FT-IR and XPS analyses, sodium


oleate mainly interacts with Fe, resulting in ilmenite otation; also,
the Ca and Mg on the titanaugite surface chemically reacted with
sodium oleate and the Mg on forsterite surface chemically reacted
with sodium oleate under acidic conditions. However, sodium oleate mainly reacted with the Ca and Mg on the titanaugite surface,
whereas sodium oleate mainly reacted with the Mg on the ilmenite
and forsterite surfaces under alkaline conditions (Fig. 11). Fig. 11
shows sodium oleate reacted with the different elements on the

W. Liu et al. / Minerals Engineering 72 (2015) 19

Table 7
Relative contents of elements on the forsterite surface.
Sample

Surface Atomic Composition (%)

Original forsterite
Forsterite + H2SO4 (pH = 7.1)
Forsterite + H2SO4 + sodium oleate (pH = 7.1)
Forsterite + NaOH (pH = 11.3)
Forsterite + NaOH + sodium oleate (pH = 11.3)

C1s

Mg1s

Ca2p

Fe2p

30.5

29.2

12.4
12.5
10.7
15.3
14.9

0.7
0.6
0.9
0.7
0.9

1.1
1.8
3.0
1.2
1.1

Fig. 11. Schematic illustration of sodium oleate reacting with the different elements on the ilmenite, titanaugite, and forsterite surfaces in different pH solutions.

Table 8
Results of the articially mixed minerals otation experiments.
pH

Product

Yield (%)

Grade of TiO2 (%)

Recovery of TiO2 (%)

5.4

Concentrate
Tailing
Feed

32.64
67.36
100.00

30.19
10.49
16.92

58.24
41.76
100.00

8.4

Concentrate
Tailing
Feed

28.72
71.28
100.00

31.66
10.98
16.92

53.74
46.26
100.00

10.7

Concentrate
Tailing
Feed

40.51
59.49
100.00

21.43
13.85
16.92

51.31
48.69
100.00

(2) The large decrease in the zeta-potentials of ilmenite, titanaugite, and forsterite can be attributed to the adsorption of
oleate ions onto the Helmholtz layer of their surfaces.
(3) Under acidic conditions, sodium oleate mainly interacted
with Fe resulting in ilmenite otation; also, the Ca and Mg
on the titanaugite surface chemically reacted with sodium
oleate, and the Mg on the forsterite surface chemically
reacted with sodium oleate. However, under alkaline conditions, sodium oleate mainly reacted with the Ca and Mg on
the titanaugite surface, whereas odium oleate mainly
reacted with the Mg on the ilmenite and forsterite surfaces.
(4) The results of the articially mixed minerals otation experiment demonstrate that the concentrate of TiO2 grade
increases from 16.92% to 30.19% at pH 5.4 and a weakly
acidic solution is the appropriate condition for the otation
separation of ilmenite from titanaugite and forsterite.

ilmenite, titanaugite, and forsterite surfaces in different pH


solutions.
Acknowledgements
3.5. Articially mixed minerals otation
Based on the results of microotation experiments, zeta-potential measurements, and FT-IR and XPS analyses, the articially
mixed minerals otation experiments were investigated at pH levels of 5.4, 8.4, and 10.7. The results of the articially mixed minerals otation experiments are listed in Table 8. The results indicate
that the concentrate of TiO2 grade increases from 16.92% to 30.19%,
31.66%, and 21.43% for pH levels of 5.4, 8.4, and 10.7, respectively.
Meanwhile, the otation recovery of the articially mixed minerals
is decreased. Therefore, sodium oleate possesses some selectivity
under the articially mixed minerals otation condition, and a
weakly acidic solution is the appropriate condition for the otation
separation of ilmenite from titanaugite and forsterite. This result is
consistent with the results of microotation experiments.
4. Conclusions
(1) The results of microotation experiments indicate that
ilmenite exhibited good oatability at pH > 4.0. Titanaugite
possesses certain oatability at pH 4.06.0 and pH > 10.0,
and forsterite possesses certain oatability at pH 5.07.0
and pH > 9.0.

This study was nancially supported by the Postgraduate Innovation Fund Project of the Southwest University of Science and
Technology (14ycx042), the Opening Project of the Key Laboratory
of Vanadium-Titanium Magnetite Comprehensive Utilization, Ministry of Land and Resources (No. KLVMCU-2013-01), the Opening
Project of the Key Laboratory of Solid Waste Treatment and
Resource Recycle, Ministry of Education (13zxsk06), and the
Applied Basic Research Programs of Science and Technology
Department of Sichuan Province (2014JY0124). The authors appreciate the nancial support and thank the editor and reviewers for
their very useful suggestions and comments.
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