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Minerals Engineering
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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
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
d10=7.271 m
Ilmenite
0
0.1
10
100
1000
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
Volume (%)
20
0.5
Titanaugite
0.0
0
50
100
150
200
250
300
350
0
400
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
Volume (%)
20
Forsterite
0
0
100
200
300
400
500
600
700
0
800
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,
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.
100
80
Recovery (%)
60
40
20
100
Ilmenite
Titanaugite
Forsterite
80
Ilmenite
Titanaugite
Forsterite
10
-4
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 (%)
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
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
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
-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
1500
1000
500
Wavenumbers (cm-1)
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).
-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).
607.96
838.5
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.
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
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
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)
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
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)
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
0.1
+0.2
+0.2
+0.2
Table 7
Relative contents 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)
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 (%)
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.
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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