metals

Article
Preparation of Ferrotitanium Using Ilmenite with
Different Reduction Degrees
Zixian Gao 1 , Gongjin Cheng 1,2 , He Yang 1,2 , Xiangxin Xue 1,2, * and Jongchol Ri 1
1 School of Metallurgy, Northeastern University, Shenyang 110819, China
2 Liaoning Key Laboratory of Recycling Science for Metallurgical Resources, Shenyang 110819, China
* Correspondence: [email protected]; Tel.: +86-024-8368-7719; Fax: +86-024-2390-6316




Received: 2 August 2019; Accepted: 27 August 2019; Published: 2 September 2019


Abstract: The effect of ilmenite with different reduction degrees on the production of ferrotitanium,
using a self-propagation high-temperature synthesis method with aluminum as the reducing agent,
was investigated. Increasing the degree of reduction not only contributed to lower consumption of
aluminum, but also lowered the oxygen content and improved the grades of titanium and iron in the
ferrotitanium. The aluminum content of the ferrotitanium increased with an increase in the extent of
reduction of ilmenite, so the Al2 O3 content formed in the slag decreased with the constant addition
of CaO and CaF2 to the Al powder. This decreased relatively the content of high-melting-point
CaAl12 O19 and increased the contents of low-melting-point CaAl2 O4 and CaF2 in the slag, thereby
promoting the separation of ferrotitanium and slag. Improving the reduction degree of ilmenite is
beneficial to the preparation of ferrotitanium.

Keywords: ilmenite; reduction; self-propagation high-temperature synthesis; ferrotitanium; slag

1. Introduction
Ilmenite (FeTiO3 ), a titanium-bearing ore, is abundant and economical [1,2], and is essential for the
production of metallic titanium [3] and titanium-containing materials [2,4–17]. Ferrotitanium is used as
a steelmaking additive [18–20] and as a raw material for the production of ferrosilicotitanium [21,22].
There are three main methods for the production of ferrotitanium: re-melting, molten salt
electrolysis [4–6,19], and the aluminothermic method [12,16].
The aluminothermic method predominates for the production of ferrotitanium in China, owing
to the lack of titanium scrap and the low efficiency of molten salt electrolysis. Researchers have
reported the effect of the ratio of ilmenite to rutile, Al, and KClO4 on the preparation of ferrotitanium
by the aluminothermic method. With an increase in the ratio of ilmenite to rutile, the Ti content of
ferrotitanium and the density of slag increased, and metal inclusions in the slag decreased [16,23].
The titanium concentration in the ferrotitanium decreased as the ferrotitanium yield in the refining
process decreased [16]. The oxygen content was positively correlated with the titanium content.
It was possible to decrease the oxygen content to 4–5% in refined ferrotitanium containing 55–65%
Ti based on the main phase component, Ti4 Fe2 O. An investigation of the effects of Al and KClO4 in
the self-propagating high-temperature synthesis (SHS) of ferrotitanium found that coarse Al powders
were able to decrease burning velocity and material loss caused by sputtering and increase the yield
of the target material to ingot. An increase in Al and KClO4 contents increased material loss caused
by sputtering and decreased the yield of target material to ingot, when the Al and KClO4 contents
exceeded 20 mass% and 7 mass%, respectively. It was also reported that an increase of slag volume was
detrimental to the recovery of titanium and increased consumption of aluminum [24]. Thus, reducing
the slag volume is considered a target for future improved production of ferrotitanium.

Metals 2019, 9, 962; doi:10.3390/met9090962 www.mdpi.com/journal/metals

Metals 2019, 9, 962 2 of 10

Most research has focused on natural ilmenite as the raw material for the preparation of
ferrotitanium. Improving the degree of reduction of ilmenite not only decreases the aluminum
consumption, but also reduces the slag volume. In this work, the effect of the degree of ilmenite
reduction on the preparation of ferrotitanium was investigated by analysis of chemical compositions,
phase transitions, and morphologies of the ferrotitanium and slag.

2. Experimental

2.1. Materials
Ilmenite was obtained from Liaoning, China. It comprised 26.85 mass% FeO, 19.48 mass% Fe2 O3 ,
and 44.44 mass% TiO2 . Ilmenite pellets were prepared by mixing ilmenite and additional 2 mass%
bentonite as a binder in a disc pelletizer, and then roasted in a muffle furnace at 1200 ◦ C for 2 h in the
presence of 2.5 L/min air. Ilmenites of varying reduction degrees were obtained by combinations of
natural and reduced ilmenite. Reduced ilmenite was obtained by reducing the pellets for 0, 30, and
240 min at 1100 ◦ C in a carbon monoxide atmosphere, which was calculated on the basis of reduction
formula of iron oxides [25]. The reduction degrees was 0%, 43%, and 75%, respectively. The reduction
degree of natural ilmenite was 11%, calculated based on oxidized ilmenite. Natural ilmenite and
reduced pellets were crushed to a powder of less than 75 µm in diameter to provide the feed material
for SHS. TiO2 (99%, <75 µm), Al (98%, <75 µm), CaO (99%, <75 µm), CaF2 (99%, <75 µm), and NaClO3
(99%, <75 µm) were all of chemical-reagent grade.

2.2. Theoretical Calculation

The main reactions of the SHS process are the reduction of iron oxide and titanium dioxide by
aluminum powder to metal, as shown in Equations (1) to (3). NaClO3 is an exothermal agent that
reacts with the aluminum powder to provide heat of 2.86 kJ/g of the reacting substances to ensure that
the SHS reaction takes place spontaneously and that the ferrotitanium and slag are well separated,
as presented in Equation (4). The heat released per unit mass of reacting substance was calculated
by Equation (5).
3FeO + 2Al → 3Fe + Al2 O3 , → Q(1) = 3.13 kJ/g, (1)

3TiO2 + 4Al → 3Ti + 2Al2 O3 , → Q(2) = 1.43 kJ/g, (2)

Fe2 O3 + 2Al → 2Fe + Al2 O3 , → Q(3) = 3.93 kJ/g, (3)

NaClO3 + 2Al → Al2 O3 + NaCl, → Q(4) = 10.70 kJ/g, (4)

m1 Q ( 1 ) + m2 Q ( 2 ) + m3 Q ( 3 ) + m4 Q ( 4 )
Q(average) = . (5)
mtotal
In Equation (5), m1 to m4 are the combined masses of FeO, TiO2 , Fe2 O3 , and NaClO3 and aluminum
that participate in Equations (1) to (4), respectively.

2.3. Experimental Methods

Except for the aluminum powder, the raw materials were dried in an oven at 110 ◦ C for 12 h.
The materials ratios are presented in Table 1. In this work, element Fe originated from the ilmenite
and Ti from the ilmenite and TiO2 . CaO and CaF2 were added at 20 mass% and 10 mass% of the
aluminum powder, respectively. After burdening, the compositions were mixed for 2 h in a blender,
and then 750 g of the mixed material was placed in a graphite crucible lined with magnesia sand.
The SHS reactions were initiated by employing upper ignition. After cooling to room temperature,
a ferrotitanium block was obtained after removing the slag.
Metals 2019, 9, 962 3 of 10

Table 1. Materials ratios in the experiment.

Reduction
Metals 2019, Degree/%
9, x FOR Ilmenite/g
PEER REVIEW TiO2 /g Al/g NaClO3 /g CaO/g CaF2 /g 3 of 10
0 500 822 652 217 130 65
11 11 482 482 822 822 643643 229
229 129
129 64 64
43 471 822 633 244 127 63
75 43 450 471 822 822 619633 244
264 127
124 63 62
75 450 822 619 264 124 62

The composition
compositionofofthe theilmenite
ilmenite was
was measured
measured by chemical
by chemical analysis
analysis and X-ray
and X-ray fluorescence
fluorescence (XRF;
(XRF; ZSXPrimus-II,
ZSXPrimus-II, Rigaku,
Rigaku, Tokyo,Tokyo,
Japan).Japan).
After After
the SHSthereactions
SHS reactions
were were complete,
complete, the ferrotitanium
the ferrotitanium alloy
alloy was crushed
was crushed to a powder
to a powder of lessofthan
less 75
thanµm 75toμm to measure
measure theTi,Fe,
the Fe, andTi,Al
and Al contents.
contents. O content
O content was
was measured
measured usingusing two small
two small pieces pieces
of theofalloy
the alloy
with with
a mass a mass of about
of about 0.1 g.0.1
Fe,g.Ti,Fe,
Al,Ti,and
Al,Oand O contents
contents were
were analyzed
analyzed by inductively
by inductively coupled coupled
plasmaplasma
optical optical
emission emission spectrometry
spectrometry (ICP–OES; (ICP–OES; Optima
Optima 8300DV,
8300DV, PerkinElmer,
PerkinElmer, Waltham,Waltham,
MA, USA)MA, andUSA) and by oxygen/nitrogen/hydrogen
by oxygen/nitrogen/hydrogen elemental(ONH836,
elemental analysis analysis
(ONH836,
LECO, USA). LECO, USA). X-ray (XRD;
X-ray diffractometry diffractometry
X’Pert Pro,(XRD; X’PertAlmelo,
PANalytical, Pro, PANalytical,
The Netherlands) Almelo, The
was used
Netherlands)
to determine thewasphases
used present
to determinein the the phases present
ferrotitanium in the
and slag. ferrotitanium
Scanning electronand slag. Scanning
microscopy linked
electron microscopy linked
to energy-dispersive to energy-dispersive
spectroscopy (SEM–EDS; Ultra spectroscopy
Plus, Carl (SEM–EDS; Ultra Plus,
Zeiss, Oberkochen, Carl Zeiss,
Germany) was
Oberkochen, Germany)
applied to observe was appliedand
the microstructure to observe
determine thethemicrostructure and determine
chemical compositions the phases
of different chemicalof
compositions of different
ferrotitanium and phases
slag. Prior of ferrotitanium
to observation, and slag.ofPrior
a cross-section to observation,
ferrotitanium was etched a cross-section of
for 15 s using
ferrotitanium was etched
an aqueous solution for 15 s2using
containing vol.%an HFaqueous solution
and 4 vol.% HNO containing
3 . 2 vol.% HF and 4 vol.% HNO 3.

3. Results
3. Results

3.1. Chemical
3.1. Chemical Composition
Composition of
of Ferrotitanium
Ferrotitanium
The chemical
The chemical composition
composition of
of ferrotitanium
ferrotitanium is
is presented
presented in
in Figure
Figure 1.
1. The
The contents
contents of
of Fe
Fe and
and Ti
Ti
increase with increasing reduction degrees of ilmenite. The Al content has an increasing trend, while
increase with increasing reduction degrees of ilmenite. The Al content has an increasing trend, while O
shows the opposite outcome.
O shows the opposite outcome.

50 10
Ti

45
8
Al
Al, O content/%

40
Fe, Ti content/%

35
O
4

30

2
Fe
25

0
0 11 43 75
Reduction degree/%

Figure 1. Effect of reduction degrees of ilmenite on the chemical composition of ferrotitanium.

Figure 1. Effect of reduction degrees of ilmenite on the chemical composition of ferrotitanium.
3.2. Phase Transitions
3.2. Phase Transitions
From the XRD patterns, shown in Figure 2, it is found that the ferrotitanium slags comprise
CaAlFrom
12 O19 ,the
CaAl 2 O4patterns,
XRD , Al2 O3 , FeO,
shown CaTiO 3 , TiO,2,and
in Figure it isCaF 2 . FeO
found thatdiffraction peaks only
the ferrotitanium occur
slags in the
comprise
slags 12formed
CaAl from
O19, CaAl 2O4ilmenites
, Al2O3, FeO,withCaTiO
0% and 11%and
3, TiO, reduction, as shown
CaF2. FeO in Figure
diffraction peaks2a,b,
onlyrespectively.
occur in theWhen
slags
the extent
formed fromofilmenites
reductionwithof ilmenite
0% and 11% increases to 11%,
reduction, CaAl2 O
as shown and CaF
in4Figures peaks
2a2 and are found inWhen
b, respectively. XRD
analysis of the slag. Figure 3 shows the phases of ferrotitanium as a function
the extent of reduction of ilmenite increases to 11%, CaAl2O4 and CaF2 peaks are found in XRD of different reduction
degrees of
analysis of ilmenite.
the slag. Ti 4 Fe2 O,
Figure 3 Ti 2 O, and
shows theAl 2 O3 are
phases ofthe main oxygen-bearing
ferrotitanium as a functionphases. All XRD
of different patterns
reduction
degrees of ilmenite. Ti4Fe2O, Ti2O, and Al2O3 are the main oxygen-bearing phases. All XRD patterns
of ferrotitanium show the presence of Ti4Fe2O, AlTi3, Al3Ti0.75Fe0.25, Ti2O, and FeTi phases. Al2O3
diffraction peaks are found in ferrotitanium produced from unreduced ilmenite, while Al3Ti peaks
only occur in ferrotitanium produced from ilmenite with 75% reduction degree. Reduction of SiO2 is
Metals 2019, 9, 962 4 of 10

of ferrotitanium show the presence of Ti4 Fe2 O, AlTi3 , Al3 Ti0.75 Fe0.25 , Ti2 O, and FeTi phases. Al2 O3
Metals 2019, 9, x FOR PEER REVIEW
diffraction peaks are found in ferrotitanium produced from unreduced ilmenite, while Al3 Ti 4peaks of 10
Metals 2019, 9,in
only occur x FOR PEER REVIEW
ferrotitanium produced from ilmenite with 75% reduction degree. Reduction of SiO 4 of2 10
is
also enhanced by increasing the degree of reduction; hence, SiTi is found in ferrotitanium prepared
also enhanced by increasing the degree of reduction; hence, SiTi is found in ferrotitanium prepared
from
also ilmenites by with 43% and the
75% reduction degree, as shownSiTi in Figures 3cinand d, respectively.
fromenhanced
ilmenites with increasing
43% and 75%degree of reduction;
reduction degree, ashence, is found
shown in Figure 3c,d, ferrotitanium
respectively. prepared
from ilmenites with 43% and 75%
⊙-CaAl reduction
O ♣-CaAl O ♦-Aldegree,
O ♠-TiO as shown
⊗-FeO -CaFin Figures
12 19 ♥-CaTiO 3c and d, respectively.
2 4 2 3 2 3
♣
⊙-CaAl12O19 ♣-CaAl O ♦-Al2O♠ ♠-TiO ⊗-FeO -CaF2 ♥-CaTiO3
2 4 ♦3
♥ ♦ ♣ ⊙
♦⊙ ⊙ ♠ ♦
(d) ♦ ⊙♦
⊙
 ♥♣⊙ ♦
♠♦ ⊙ 
⊙ ♦ ⊙⊙
⊙
♣ ⊙♦
♦
⊙
♦⊙ ⊙ ♦⊙ ♠ ♦ ⊙ 
(d) ⊙ ♣⊙ ⊙
⊙
♣  ♠♦⊙ ♦ ⊙ ♦
⊙ ⊙  ⊙ ♠♦
⊙
⊙ 
♥ ♦
Intensity/(a.u.)

(c) ⊙ ⊙ ⊙⊙ ⊙ ⊙ ⊙ ♦
♣ ⊙ ⊙⊙
♣ ♥ ♦ ♠ ⊙
♠ ♦ 
Intensity/(a.u.)

(c) ⊙ ⊙⊙ ⊙ ⊙ ⊙  ♦ ⊙ 
⊙ ♣ ⊙ ⊙⊙ ♠
♣ ♦ ♠  ⊙
♥ ⊙♠  ⊙ ⊙

⊙ ⊙ ♦ ⊙ ⊗ ⊙⊗ ⊙⊗
♠
(b) ⊙ ♠ ♦
♣ ♣♥ ⊙ ♦ ⊙
 ♦ ⊙
⊙ ⊗ ⊙⊗♠ ♦
⊙
⊙⊗ ♠
⊙ ⊙ ⊙
(b) ⊙ ♦ ♦
♣ ♣ ⊙
 ♦ ♠
⊙
⊙
⊙ ⊙♦
⊙ ⊗
⊙ ⊙⊙ ⊗♠ ⊗ ♦
(a) ♥⊙ ♦⊙⊙⊙♦ ⊙⊙ ⊙
⊙ ⊗ ♦ ⊙
⊙ ⊙⊙ ⊗♠ ⊗ ♦
(a) ♥ ♦ ⊙⊙♦ ⊙⊙ ⊙
⊙
10 20 30 40 50 60 70 80 90
2-Theta/°
10 20 30 40 50 60 70 80 90
2-Theta/°
Figure 2. X-ray diffraction patterns of slags formed from ilmenites with different reduction degrees.
Figure
(a) 2. X-ray
0%, (b) diffraction
11%, diffraction
(c) 43%, andpatterns of slags formed from ilmenites with different reduction degrees.
(d) 75%.of
Figure 2. X-ray patterns slags formed from ilmenites with different reduction degrees.
(a) 0%, (b) 11%, (c) 43%, and (d) 75%.
(a) 0%, (b) 11%, (c) 43%, and (d) 75%.
⊙-Ti4Fe2O ♣-Al3Ti0.75Fe0.25 ●-FeTi ♦-Al2O3 ♠-Ti2O 0-SiTi -AlTi3
♣♥ ♥-Al3Ti
⊙-Ti4Fe2O ♣-Al Ti Fe ♠-FeTi
●⊙  ♦-Al2O3 ♠-Ti2O 0-SiTi -AlTi3
3 0.75 0.25
♣♥
♠ ⊙ ♥-Al3Ti
⊙ 00
♠  ♣ ♥
(d) ⊙● ⊙ ♠
00 ⊙
⊙
♠ 0 ♣ ♥
(d) ♣ 0 ● ⊙ ♠
⊙
 ⊙
Intensity/(a.u.)

0 ⊙ 0 ● ♣
 ♠
♣ 0 ⊙
(c) ♠  ♠
Intensity/(a.u.)

⊙
0 ⊙ ● ♣
 ♠ ⊙
(c) ♠ ⊙ ⊙ ♠

 ⊙
♣
⊙
♣
(b) ♠  ♠ ● ⊙
⊙

♣
⊙
♣
(b) ♠  ♠ ⊙
● ⊙
⊙


♠ ⊙
♠ ⊙♣ ♦ ⊙♣ ⊙
(a) ♠  ● ♠ ♦
♠
♠ ⊙♣ ♦ ⊙♣ ⊙
(a) ♠ ● ♠ ♦
20 30 40 50 60 70
2-Theta/°
20 30 40 50 60 70
2-Theta/
Figure 3. X-ray diffraction patterns of ferrotitanium °
produced from ilmenites with different reduction
Figure 3. X-ray diffraction patterns of ferrotitanium produced from ilmenites with different reduction
degrees. (a) 0%, (b) 11%, (c) 43%, and (d) 75%.
degrees.
Figure 3.(a) 0%,diffraction
X-ray (b) 11%, (c)patterns
43%, and (d) 75%.
of ferrotitanium produced from ilmenites with different reduction
3.3. Morphology of Ferrotitanium
degrees. (a) 0%, andand
(b) 11%, (c) 43%, Slag(d) 75%.
3.3. Morphology of Ferrotitanium and Slag
Figure 4 shows the macroscopic morphology of ferrotitanium produced by ilmenite with different
3.3. Morphology
Figuredegrees.of Ferrotitanium
4 shows and Slag morphology of ferrotitanium produced by ilmenite with
the macroscopic
reduction Ferrotitanium produced by ilmenite with a low extent of reduction is porous and
different
difficult reduction
Figure
to 4 shows
separate degrees.
thethe
from Ferrotitanium
macroscopic to produced
slag, owingmorphology by ferrotitanium
of ilmenite
the ferrotitanium withembedding
and slag a low extent
produced by ofilmenite
within reduction is
with
each other,
porous
differentand difficult
reduction to separate
degrees. from the
Ferrotitaniumslag, owing
produced to the
by ferrotitanium
ilmenite with aand
low slag embedding
extent
as shown in Figure 4a,b. Figure 4c,d show that the ferrotitanium (light-gold color) produced from more of within
reduction is
each
porous other, as shown
and difficult
highly reduced in Figure
to separate
ilmenite 4a,b.
is dense,from
and theFigure
slag,
there 4c,d show that
owing toseparation
is excellent the
the ferrotitaniumferrotitanium
betweenand theslag (light-gold
slagembedding color)
within
and ferrotitanium.
produced
each other, from more highly
as shown reduced
in Figure ilmenite
4a,b. Figureis4c,d
dense,
showandthat
therethe
is excellent separation
ferrotitanium between
(light-gold the
color)
slag and ferrotitanium.
produced from more highly reduced ilmenite is dense, and there is excellent separation between the
slag and ferrotitanium.
Metals 2019, 9, 962 5 of 10
Metals 2019, 9, x FOR PEER REVIEW 5 of 10

Figure
Figure4.4.Macroscopic
Macroscopicmorphology
morphologyofofferrotitanium
ferrotitaniumproduced
producedfrom
fromilmenites
ilmeniteswith
withdifferent
differentreduction
reduction
degrees.
degrees.(a)
(a)0%,
0%,(b)
(b)11%,
11%,(c)
(c)43%,
43%,and
and(d)
(d)75%.
75%.

Microstructures of
Microstructures of the
the slags, obtained from SEM–EDS
SEM–EDS analysis,
analysis, are
arepresented
presentedin inFigures
Figures55and and6.
6. Figure 6 is an enlargement of the white frames in Figure 5. From Table 2, there is no doubt thatA
Figure 6 is an enlargement of the white frames in Figure 5. From Table 2, there is no doubt that points
and J comprise
points complex phases
A and J comprise complex composed of Ca, Al, Ti,
phases composed O, and
of Ca, Al, F;
Ti,that points
O, and F andpoints
F; that G are Falloy
and phases
G are
of Ti–Si
alloy and of
phases Fe–Ti–Si,
Ti–Si andrespectively; and that B, D,
Fe–Ti–Si, respectively; andH,that
andB,I D,
areH,
TiO,
andCaAl O19 ,CaAl
I are12TiO, Al2 O123O
, and
19, AlCaAl 2 O4 ,
2O3, and

respectively. Points C and K assay as 2(Ca,Ti)O·Al O and point E comprises

CaAl2O4, respectively. Points C and K assay 2 as3 2(Ca,Ti)O·Al2O3 and point E comprises (Ca,Ti)O·6Al 2 3 The
O .
CaAl12 O19 phases
(Ca,Ti)O·6Al areCaAl
2O3. The acicular
12O19(Figure
phases5a)areand the TiO
acicular phases5a)
(Figure in and
the slag
the are
TiOapproximately
phases in the spherical
slag are
(Figure 6). The TiO phases are enriched
approximately spherical (Figure 6). The TiO phases in CaAl O
12 19 phases or their boundaries,
are enriched in CaAl12O19 phases or theiras shown in
Figure 5a,b. as
boundaries, Some alloyinphases
shown Figureare enclosed
5a,b. in slag,
Some alloy as presented
phases in Figure
are enclosed 5b,d.asConsidering
in slag, presented in theFigure
phase
transitions
5b,d. shownthe
Considering in Figure 2 and the microstructures
phase transitions shown in Figureof2 Figure
and the5,microstructures
it is concluded of that the acicular
Figure 5, it is
CaAl12 O19that
concluded content decreases
the acicular CaAland
12Othe Al2 O3 and
19 content CaAl2and
decreases O4 contents
the Al2O3increase
and CaAl with2O4 an increase
contents in the
increase
degree
with an of reduction
increase of degree
in the ilmenite. of reduction of ilmenite.
Metals2019,
Metals 2019,9,
9,962
x FOR PEER REVIEW 6 of 1010
6 of
Metals 2019, 9, x FOR PEER REVIEW 6 of 10

Figure 5. Microstructures of slag produced from ilmenites with different reduction degrees. (a) 0%,
Figure
Figure 5.(c)
5.
(b) 11%, Microstructures
Microstructures of
of slag
43%, and (d) 75%. slag produced
produced from
fromilmenites
ilmeniteswith
withdifferent
differentreduction
reductiondegrees.
degrees.(a)(a)0%,
0%,
(b)11%,
(b) 11%, (c)
(c) 43%,
43%, and
and (d) 75%.

Figure 6. Microstructures
Figure 6. of slag
Microstructures of slag produced
producedfromfromilmenites
ilmeniteswith
withdifferent
differentreduction
reductiondegrees,
degrees,shown
shownatat
higher
Figure magnification. (a)
6. Microstructures
higher magnification. 0%, (b)
of slag
(a) 0%, 11%, (c)
(b) produced 43%,
from
11%, (c) 43%, and (d) 75%.
ilmenites
and (d) 75%.with different reduction degrees, shown at
higher magnification. (a) 0%, (b) 11%, (c) 43%, and (d) 75%.
Metals2019,
Metals 9, x962
2019, 9, FOR PEER REVIEW 7 7ofof10
10

Table 2. The atomic proportions of phases in Figure 6, %.

Table 2. The atomic proportions of phases in Figure 6, %.
Point Fe Ti Al O Ca Si F Mg Na
Point Fe Ti Al O Ca Si F Mg Na
A 12.75 11.48 57.00 15.67 0.13 2.39 0.32 0.26
A B 12.75 41.4411.482.47 57.00
54.43 15.67
0.48 0.13 2.39
1.19 0.32 0.26
B 41.44 2.47 54.43 0.48 1.19
C
C 15.30
15.3020.45
20.45 57.46
57.46
5.88
5.88
0.91 0.91
D D 3.22 3.2236.5736.57 55.97
55.97 3.00
3.00 1.23 1.23
E E 3.04 3.0432.5132.51 60.75
60.75 0.31
0.31 2.76 0.65
2.76 0.65
F 4.12
F 55.26
4.12 55.26 11.54
11.54 28.60
28.60
G 30.60 38.36 1.28 10.84 13.57
G 30.60 38.36 1.28 10.84 13.57
H 0.88 43.69 55.43
I H 2.33 0.8828.4643.69 55.43
55.59 13.62
J I 15.26 2.33 6.7028.46 55.59
56.26 13.62
16.81 4.48 0.48
K J 13.66 15.2622.906.70 56.13
56.26 6.24
16.81 4.48 1.06 0.48
K 13.66 22.90 56.13 6.24 1.06
Microstructures of
Microstructures of ferrotitanium
ferrotitanium are
are presented
presented in in Figure
Figure 7.
7. Three
Three main
mainphases
phasesare
areapparent
apparentfrom
from
Figure 7a,b.
Figures Asb.
7a and given in Table
As given 3, the color
in Table 3, theof the phase
color of the changes from light
phase changes fromto light
dark to
gray with
dark an with
gray increase
an
increase of Ti content. From analysis of the relative atomic proportions, the light-gray phases Lfound
of Ti content. From analysis of the relative atomic proportions, the light-gray phases L and O are and
Oto are
be the oxygen-bearing
found phase Ti4 Fe2 O,phase
to be the oxygen-bearing the intermediate-gray phases N and Q
Ti4Fe2O, the intermediate-gray are oxygen-bearing
phases N and Q are
oxygen-bearing Ti-rich phases, and the dark-gray phases M and P are Ti2O. In Figure 7c, Ti
Ti-rich phases, and the dark-gray phases M and P are Ti2 O. In Figure 7c, point T comprises 4 Fe2 O,
point T
and R and S are oxygen-free alloy phases. In ferrotitanium, Ti 4 Fe 2 O is the matrix within
comprises Ti4Fe2O, and R and S are oxygen-free alloy phases. In ferrotitanium, Ti4Fe2O is the matrix which Ti-rich
alloy phases
within whichcontaining Ti2 O phases
Ti-rich alloy are distributed.
containing Ferrotitanium prepared from
Ti2O are distributed. unreduced ilmenite
Ferrotitanium preparedcontains
from
more Ti2 O than
unreduced thatcontains
ilmenite from 75% reduced
more Ti2O ilmenite.
than that from 75% reduced ilmenite.

Figure 7. Microstructures of ferrotitanium produced from ilmenites with different reduction degrees.
Figure 7. Microstructures of ferrotitanium produced from ilmenites with different reduction degrees.
(a) 0%, (b) 75%, and (c) 75%.
(a) 0%, (b) 75%, and (c) 75%.
Metals 2019, 9, 962 8 of 10

Table 3. The atomic proportions of phases in Figure 7, %.

Point Fe Ti Al O Si
L 21.34 46.83 17.84 11.29 2.70
M 64.17 35.64
N 12.31 55.35 5.62 22.87 3.85
O 24.53 46.77 8.08 15.35 4.82
P 62.48 37.52
Q 11.44 54.14 6.02 20.70 3.68
R 20.16 56.20 19.15 4.50
S 33.87 41.41 20.17 4.55
T 25.59 46.48 8.00 14.61 5.33

4. Discussion
As mentioned above, an increase in the extent of reduction of ilmenite is helpful to improve the
grades of iron and titanium in ferrotitanium and can also decrease its oxygen content. Although the
aluminum content shows an increasing trend with increasing ilmenite reduction, the product still
meets the Chinese specifications for FeTi50B (GB/T 3282-2012). With increasing the extent of reduction
of ilmenite, the amount of iron oxide in the SHS raw materials is lowered. The remaining iron oxide is
more easily reduced to metallic Fe with increasing the degree of reduction, so there is no evidence
of FeO in the slag when the reduction exceeds 43%. The iron grade of ferrotitanium increases with
the extent of reduction. TiO is an intermediate product in the reduction of titanium oxide. This is
a basic oxide and is able to combine with Al2 O3 to form composite compounds [26], which is the
main reason for the formation of TiO, 2(Ca,Ti)O·Al2 O3 , and (Ca,Ti)O·6Al2 O3 in the slag. Owing to
incomplete reduction of TiO2 , the Al present as a reductant for titanium oxide has a surplus in the SHS
process. With increasing ilmenite reduction degrees, the ratio of residual aluminum to aluminum as the
reductant for iron oxide and TiO2 gradually increases. Residual aluminum melts in the ferrotitanium
as an alloy element. The high Al content leads to the formation of Al3 Ti in ferrotitanium, as show
in Figure 3d. Furthermore, an increase of Al content enhances its activity in ferrotitanium, which
promotes the reduction of Ti2 O in ferrotitanium and TiO in slag. The fact that the Al and O contents
show opposing trends in the ferrotitanium with varying degrees of ilmenite reduction also proves this
point: thus, compared with Figure 7a, there is less unreduced Ti2 O in Figure 7b. This is the main reason
for the decrease of the O content in ferrotitanium. When the reduction degree is above 43%, the O
content increases slightly as a result of the increase of Ti4 Fe2 O with the increase of Ti content, as shown
in Figure 3d. In addition, the increase of the residual aluminum also can promote the reduction of
silica, hence the new phase, SiTi, is generated in the ferrotitanium produced by the high extent of
reduction of ilmenite, as revealed in Figure 3c,d.
Metallic Ti melted in metallic Fe during the reduction of TiO2 . This can reduce its volatilization
and facilitate the reduction of TiO2 because of the decrease in Ti activity [23]. Therefore, volatilization
of Ti decreased and reduction of TiO2 is enhanced with increasing iron grade in the ferrotitanium.
Its Ti content increased with increasing ilmenite reduction degree.
With an increase of Al content in the ferrotitanium, Al2 O3 formed in the SHS process decreases
with a constant addition ratio of CaO and CaF2 to Al. Thus, there is a relative increase in the CaF2 and
CaO contents in the slag with increasing ilmenite reduction. Owing to the use of the same ratio of CaO
to CaF2 , Figure 8 shows that point A moves away from the direction of Al2 O3 along the blue line in the
Al2 O3 –CaO–CaF2 ternary phase diagram drawn by FactSage 7.0; hence, the melting point of the slag
decreases with an increase in reduction. The same conclusion also can be obtained from slag phases.
An increase of CaO caused a decrease in the CaAl12 O19 content and increase in CaAl2 O4 , as shown in
Figures 2 and 5. As the contents of low-melting-point CaF2 and CaAl2 O4 increased, slag is more easily
separated from the ferrotitanium. An increase in the degree of reduction of ilmenite thus promotes the
separation of ferrotitanium and slag.
Metals 2019,2019,
Metals 9, x FOR
9, 962PEER REVIEW 9 of 910of 10

Figure 8. Ternary phase diagram of Al2 O3 –CaO–CaF2 .

5. Conclusions
Figure 8. Ternary phase diagram of Al2O3–CaO–CaF2.
This work investigated the effect of the reduction degree of ilmenite on the chemical and phase
5. Conclusions
characteristics of the resulting ferrotitanium and slag produced by the SHS aluminothermic process.
Improving the reduction not only decreases the consumption of aluminum and the amount of slag
This work investigated the effect of the reduction degree of ilmenite on the chemical and phase
generated in the preparation of ferrotitanium, but also reduces the oxygen content and improves the
characteristics of the resulting ferrotitanium and slag produced by the SHS aluminothermic process.
grades of titanium and iron. The aluminum content of the ferrotitanium increases with increasing
Improving the reduction not only decreases the consumption of aluminum and the amount of slag
ilmenite reduction degree, so the Al2 O3 content formed in the SHS process decreases with addition of
generated in the preparation of ferrotitanium, but also reduces the oxygen content and improves the
a constant ratio of CaO and CaF2 to Al in the raw materials. Relatively, the CaF2 and CaO contents
grades of titanium and iron. The aluminum content of the ferrotitanium increases with increasing
increases in the slag. This decreases the content of high-melting-point CaAl12 O19 in the slag and
ilmenite reduction degree, so the Al2O3 content formed in the SHS process decreases with addition of
increases the contents of low-melting-point CaAl2 O4 and CaF2 , thereby promoting the separation of
a constant ratio of CaO and CaF2 to Al in the raw materials. Relatively, the CaF2 and CaO contents
ferrotitanium and slag.
increases in the slag. This decreases the content of high-melting-point CaAl12O19 in the slag and
increases
Authorthe contents ofConceptualization,
Contributions: low-melting-point X.X.CaAl 2O4 and CaF2, thereby promoting the separation of
and Z.G.; validation, Z.G., G.C. and H.Y.; formal analysis, Z.G. and
ferrotitanium and slag.
G.C.; investigation, Z.G. and X.X.; resources, H.Y.; data curation, Z.G.; writing—original draft preparation, Z.G.;
writing—review and editing, X.X., Z.G., G.C. and J.R.; visualization, G.C., J.R. and H.Y.; supervision, X.X. and
Author
Z.G.;Contributions: Conceptualization,
project administration, X.X. X.X. and Z.G.; validation, Z.G., G.C. and H.Y.; formal analysis, Z.G.
and G.C.; investigation, Z.G. and X.X.; resources, H.Y.; data curation, Z.G.; writing—original draft preparation,
Funding: This research was funded by National Natural Science Foundation of China, grant number 51674084.
Z.G.; writing—review and editing, X.X., Z.G. G.C. and J.R.; visualization, G.C., J.R. and H.Y.; supervision, X.X.
andConflicts of Interest:
Z.G.; project The authors
administration, X.X. declare that they have no conflict of interest.

Funding: This research was funded by National Natural Science Foundation of China, grant number 51674084.
References
Conflicts of interest: The authors declare that they have no conflict of interest.
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