chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Application of Taguchi method for optimization of synthetic

rutile nano powder preparation from ilmenite concentrate
B.N. Akhgar a , M. Pazouki b, , M. Ranjbar c , A. Hosseinnia b , R. Salarian d
a

Mining Engineering Faculty, Sahand University of Technology, Tabriz, Iran

Materials and Energy Research Center, MeshkinDasht, Karaj, Iran
c Department of Mineral Processing, Engineering Faculty, Shahid Bahonar University, Kerman, Iran
d Maziyar University, School of Art and Engineering, Noor, Mazandaran, Iran
b

a b s t r a c t
In the present research work Taguchi method was applied to investigate the effect of reductive leaching parameters
and mechanical pretreatment of ilmenite on nano synthetic rutile synthesis. The parameters such as ilmenite to
acid mass ratio, ilmenite to iron powder mass ratio, milling time and initial leaching temperature were selected
for optimization of experimental conditions. Consequently, the milling time was the most effective parameter on
synthetic rutile preparation compared to the rest of the selected parameters. The optimum conditions obtained
were as follows: milling in Argon atmosphere 40 min, initial reaction temperature 100 C, ilmenite to hydrochloric
acid mass ratio 1:9.55 and ilmenite to iron powder mass ratio 1:0.075. The characterization of products indicated that
the prepared powder with milling time 40 min, temperature 100 C, ilmenite to hydrochloric acid mass ratio 1:12.8
and ilmenite to iron powder mass ratio 1:0.05 had particles size of less than 100 nm. The analysis further conrmed
that synthetic rutile nano powder had 91.1% TiO2 . The nano powder obtained under the optimized condition had a
BET surface area of 54.6 m2 /g.
2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Reductive leaching; Mechanical activation; Taguchi method; Synthetic rutile; Nanomaterials

1.

Introduction

The importance of titania (TiO2 ) is due to its application in the

manufacturing of paints, pigment, ceramics, papers, and in
other related chemical industry (Diebold, 2003). The production of titanium dioxide pigment has been conducted by two
main processes, the sulfate process and the dry chlorination
process. The ilmenite as a raw material is used in sulfate process which is lengthy, costly and the by product ferrous sulfate
is less marketable (Abdel-Aal et al., 2000). The second process
(chlorination process) which employs rutile as raw material is
more economical and has less waste material (Mackey, 1994).
The conversion of ilmenite concentrate into synthetic rutile
due to shortage of natural rutile is considered to be interesting
substitution. The production of synthetic rutile from ilmenite
concentrate can be achieved by several methods (Mahmoud
et al., 2004; Li et al., 2008).
Some researchers for performing the reductive leaching of
ilmenite concentrate used iron powder as a reductive agent to

promote the leaching of ilmenite concentrate in hydrochloric acid (Mahmoud et al., 2004; Lasheen, 2005; El-Hazek
et al., 2007). However, dissolution of mechanically activated
ilmenite concentrate in various leaching agent for preparation of synthetic rutile was investigated. The achieved results
demonstrated that the mechanical pretreatment enhanced
the dissolution of ilmenite concentrate due to the increasing
lattice strain and surface area of milled ilmenite concentrate
(Amer, 2002; Welham and Llewellyn, 1998; Li et al., 2006a,b,
2007, 2008; Sasikumar et al., 2007).
There are various parameters affecting the properties of
the produced synthetic rutile such as reaction temperature,
ilmenite to acid mass ratio, pulp density, and agitation, leaching agent concentrate, ilmenite particle size, leaching time and
also related parameters to kind of additive and mechanical
activation conditions (Mahmoud et al., 2004; Lasheen, 2005; ElHazek et al., 2007; Amer, 2002; Welham and Llewellyn, 1998; Li
et al., 2006a,b, 2007, 2008; Sasikumar et al., 2007). These parameters were investigated by using classical one parameter at a

Corresponding author. Tel.: +98 261 6280036; fax: +98 261 6280030.
E-mail addresses: mpazouki@merc.ac.ir (M. Pazouki), r.salarian@maziar.ac.ir (R. Salarian).
Received 18 December 2010; Received in revised form 19 June 2011; Accepted 13 July 2011
0263-8762/$ see front matter 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2011.07.008

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chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

time. However in previous investigations, the leaching mechanism and kinetic studies have been performed (Mahmoud
et al., 2004; Amer, 2002; Welham and Llewellyn, 1998; Li et al.,
2006a, 2006b; Sasikumar et al., 2007; Van Dyk et al., 2002; Liu
et al., 2006). In all of the above mentioned investigations one
variable at a series of experiments has been studied to appreciate the effectiveness of parameters on the preparation of
synthetic rutile from ilmenite concentrate.
In recent years, the statistical experimental designs have
been employed to efcient analysis of complex systems (Kim
et al., 2005). The application of statistical experimental design
provides maximum and reliable data which is used fewer possible experiments. The Taguchi method as an experimental
design method can achieve these tasks.
In Taguchi method, the experience and knowledge of
researcher has a main role in the proper selection of variables
and their levels. The main and interaction effect of factors can
be investigated by using Taguchi method. The optimum conditions can be dened regarding the desired target of response
such as smaller is better, larger is better or nominal is the
best. The Taguchi method applied simple tools such as signal
to noise ratio (S/N) and analysis of variance (ANOVA) to determine optimal conditions and effect of each factors on main
properties. The effect of each selected parameters can be estimated through ANOVA test. However, the maximum S/N ratio
values which are calculated regarding to test target for each
factor in its selected levels is applied to determine optimum
test conditions (Keles, 2009).
In the present study, the aim was to investigate the reductive leaching of mechanically activated ilmenite concentrate
by hydrochloric acid. With applying the Taguchi method, the
effect of four parameters such as ilmenite to acid mass ratio,
ilmenite to iron powder mass ratio, milling time and temperature was investigated and the used technique was optimized
according to the calculated S/N ratio of parameters. The developments of nano particles and structures synthesis routes
gave access to various nanomaterials with different structural
and physical properties according to their corresponding bulk
material (Djerdj et al., 2008). The recent investigation veried
possibility of synthetic rutile nano powder preparation as a
photocatalytic material by combination of reductive leaching
and mechanical activation (Akhgar et al., 2010).

2.

Experimental

2.1.

Materials and procedure

The Kahnoje ilmenite deposits are available in the southeast

province of Iran, which is called Kerman has an estimated
reserve about 43 million tonnes. The ilmenite concentrate
with particle size 75 m was selected from the above mentioned deposit for mechanical activation.
The mechanical activation was conducted in a planetary
ball mill under argon atmosphere. The milling operation was
performed with rotation speed of 250 rpm and spin rate of
480 rpm. The steel balls with 20 mm diameter were used to
ll milling cells by the ball to ore mass ratio of 20:1.
The leaching experiments were carried out according to
the Taguchi experimental design in a 500 ml glass reactor
equipped with a reuxed condenser. A certain amount of
20% HCl solution was heated to the desired temperature in
a thermo-statically controlled parafn bath. The experiments
started with addition of 20 g ilmenite and followed by addi-

Ilmenite

Sieving
- 75 m
Mechanical Activation

Reductive Leaching

Solid/ Liquid Separation

Leach liquor (HCl recycle)
Leach residual
Dehydration

Calcination

Nano Synthetic Rutile

Fig. 1 A schematic ow sheet of techniques used.
tion of iron powder with determinate amount after 20 min. A
magnetic stirrer with stirring speed of 400 rpm was applied
to mechanical agitation, keeping homogeneous suspension of
slurry. The leaching experiments carried out for 6 h and then
the slurry was allowed to precipitate and the leach liquor was
separated from the leach residual. The dehydration of products was carried out by using benzene isotropic distillation
technique (Hosseinnia et al., 2009) and the products calcined
at 400 C.
Fig. 1 shows a schematic route of the process. The large
consumption of HCl as a disadvantage of this method can be
neglected with recycling of used acid (Walpole, 1995; Newman
and Balderson, 1993).

2.2.

Taguchi method

In this study, the milling time, ilmenite to hydrochloric acid

mass ratio, ilmenite to iron powder mass ratio and the reaction
temperature were considered in three levels to optimize process. The milling times were selected as 0, 40 and 360 min and
the planned levels for temperature were 85, 100 and 110 C.
However, the ilmenite to hydrochloric acid and ilmenite to iron
powder mass ratio were in three levels of 1:7.3, 1:9.55 and 12.8
and 1:0.05, 1:0.075 and 1:0.1, respectively. The used parameters and levels are presented in Table 1. The numbers of 1, 2
and 3 represented the lowest, mid and highest levels, respectively. Four parameters in three levels mean that the L9 (34 )
orthogonal array of Taguchi design have to be considered for
performance of experiments in 9 runs. The orthogonal array
of L9 was randomly performed and its structure is given in
Table 2. The S/N ratio and ANOVA are utilized for designation
of optimum conditions.

2.3.

Characterization

The chemical composition of ilmenite concentrate and products of each experiments were indicated by X-ray uorescence

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chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

Table 1 Process parameters and their levels used in the experiments.

Parameters

Symbol

Level 1

Level 2

Level 3

Milling time (min)

Ilmenite/acid mass ratio
Ilmenite/iron powder mass ratio
Temperature ( C)

Mt
A
Ip
T

0
1:7.3
1:0.05
85

40
1:9.55
1:0.075
100

360
1:12.8
1:0.1
110

Table 2 L9 (34 ) orthogonal array of Taguchi and their S/N ratio value.
Exp. no.

Mt

Ip

y1

y2

y3

yi

1
2
3
4
5
6
7
8
9

1
1
1
2
2
2
3
3
3

1
2
3
1
2
3
1
2
3

1
2
3
2
3
1
3
1
2

1
2
3
3
1
2
2
3
1

34.57
42.76
37.29
88.74
84.12
89.95
78.66
90.77
78.20

37.41
42.22
36.21
88.26
89.19
90.96
80.28
88.81
80.83

33.65
45.19
35.68
92.70
82.39
92.39
81.82
88.32
80.67

35.2
43.4
36.4
89.9
85.2
91.1
80.2
89.3
79.9

S/Ni

T=

(XRF) spectrometry (ARL 8410 SEQUENTIAL). The products

were examined three times by XRF test and the mean of TiO2
amount (yi ) in the products was considered as a response
in Taguchi method. Measurement of the surface area was
performed through a standard BET surface area analyzer
(Micrometrics Gimini III 2375, USA).
The XRD analysis was applied for examination of ilmenite
concentrate, the milled samples and the products. The X-ray
diffraction test was performed by Philips DW3710 instrument
applying Cu K radiation at 50 kV and 250 mA in the range
of 1575. Investigation of transmission electron microscopy
(TEM) and scanning electron microscopy (SEM) were carried
out by Zeiss Em 10c and Stereoscan 5390 Cambridge 1990
instruments, respectively.

3.

Result and discussion

3.1.

Mechanical activation

Surface area (m2/g)

0
40

80

120

160

200

S/Ni

* *

a
20

30

40

50

60

70

2 Theta/degree

Fig. 3 XRD pattern of (a) unmilled ilmenite, (b) 40 min

milled ilmenite and (c) 360 min milled ilmenite.

Fig. 2 illustrates the changes in milled samples surface

area caused by increasing milling time. As it can be seen,
the BET surface area increased from 0.7 m2 /g in unmilled
ilmenite concentrate to 4.8 m2 /g in 40 min milled ilmenite and
then decreased to about 2.9 m2 /g in 360 min milled samples.
With longer milling time, the broken particles begin to form
agglomerates which cause the increase of particle size and
consequently decrease the surface area (Li et al., 2008; Welham

* = ilmenite

30.93
32.75
31.22
39.08
38.61
39.19
38.09
39.02
38.05
326.94

240

280

320

360

MIlling time (min)

Fig. 2 Variation of surface area with milling time.

400

and Llewellyn, 1998). As shown in Fig. 2, the surface area

increased with milling time and then peaked before reducing
as result of agglomeration.
In order to avoid probable phase changes, the milling operation carried out in the Argon atmosphere. The XRD patterns
of ilmenite concentrate and milled powders indicated that all
the peaks were matched with the standard XRD pattern of
hexagonal FeTiO3 and no phase changes occurred in milled
samples (Fig. 3).
The XRD patterns of ilmenite concentrate and milled powders demonstrated that the increasing of milling time caused
to the broadening and weakening of peaks (Fig. 3). However,
the broadening and weakening of peaks can be related to
decreasing of crystallinity during the milling leading to rapid
dissolution of milled powders (Welham and Llewellyn, 1998).
The XRD patterns and BET results veried the mechanical activation increased the surface area and decreased the
crystallinity of ilmenite concentrate which were responsible
for enhanced reaction between milled powder and leaching
agent. The cited results will be reconrmed with achieved
result from Taguchi method in next part of our study.

chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

Table 3 ANOVA analysis results for all parameters.

Factors

Df

Mt
A
Ip
T
Total

2
2
2
2
8

3.2.

SS
4581.96
30.3
35.79
48.98
4697.03

MS
2290.98
15.15
17.89
24.49

Analysis of experimental data

A Taguchi orthogonal array experimental design was applied

to optimize reductive leaching of mechanically activated
ilmenite concentrate producing highest quantity of TiO2 . The
ANOVA test conducted to estimate the effect of each parameter on the characteristic properties, i.e. TiO2 content in this
study. The result of ANOVA test indicated the mechanical activation was the most effective parameter than others (Table 3).
The signal to noise ratio (S/N) approach was used for analysis of TiO2 . Since the target of the study is preparation of
synthetic rutile with highest TiO2 content, the corresponding
S/N ratio calculation was performed through larger is better
approach of Taguchi method (Eq. (1)).


S/N = 10 log

1 1
n
y2
n

i=1


(1)

where yi is the data obtained from experiments and n is the

number of repetition. The TiO2 amount (yi ) and calculated S/N
ratio of each experiment are presented in Table 2. The mean
S/N ratios for each level of every parameter were computed to
realize optimum conditions by Eq. (2) as follows:
Mt1 =

Exp.1 + Exp.2 + Exp.3

3

(2)

For example:
Mt1 =

A2 =

Exp.1 + Exp.2 + Exp.3

30.93 + 32.75 + 31.22
=
= 31.63
3
3

Exp.2 + Exp.5 + Exp.8

32.75 + 38.61 + 39.02
=
= 36.79
3
3

Table 5 shows the arrangement of calculated S/N ratios

and mean of them in each level for a parameter. The corresponded S/N ratio to a parameter in each level was ordered in
each column to calculate the mean of S/N ratio of a parameter in related level. It is obvious that the difference between
the maximum and minimum S/N ratios of milling time (Mt) is
7.33, higher than 0.64, 0.65 and 0.81 for other parameters (A,
Ip and T, respectively) signifying the effectiveness of milling
time.
The mean S/N ratio for each level of parameters is shown
in Fig. 4. The highest value of mean S/N ratio for a parameter was considered as optimum level of relative parameter.
Therefore it is clear that the optimum condition was Mt2, A2,
Ip2 and T2. The achieved optimum conditions were discussed
Table 4 ANOVA analysis after pooling.
Factors

Df

Mt
T
Error
Total

2
2
4
8

SS
4581.96
48.98
66.09
4697.03

MS
2290.98
24.49
33.04

223

independently based on the proposed mechanism of ilmenite

concentrate leaching in previous investigations (Van Dyk et
al., 2002; Mahmoud et al., 2004). The interactions of selected
parameters were not studied in the designed Taguchi method.
There is no doubt that the mechanical activation must be considered as a most effective parameter when TiO2 content in
leaching products of unmilled ilmenite concentrates are at
least. The outcomes of Taguchi method also indicated that
40 min milling time in level 2 preferred to 360 min milling
time in level 3. According to BET surface area measures and
mentioned outcome in this study, the TiO2 amount of prepared powders depended on surface area which is in contrary
with recent investigation while TiO2 amount in their prepared
powders depended directly on milling time (Li et al., 2008).
The mechanical activation results in several changes in material structure accelerating leaching rate such as lattice strain,
lattice defects, structural disorder increment and amorphization of mineral particles (Balaz, 2000; Pourghahramani and
Forssberg, 2006b) that all of them increased with milling time
in ilmenite concentrate (Amer, 2002; Welham and Llewellyn,
1998; Li et al., 2006a, 2006b, 2007, 2008; Sasikumar et al., 2007).
In other hand, the surface area of milled ilmenite decreased
when the broken particle agglomerated (after reaching a maximum value in early stage of milling) in longer milling time
slowing down reactions rate. The competitive changes of
ilmenite structure and surface area are in contrast with each
other affecting the leachability of milled ilmenite concentrate
in longer milling time. The products in experiments of 46 with
40 min milling time as pretreatment contained more TiO2 in
their compositions than the products of experiments leached
after 360 min milling time (79). In addition to the XRF test
results (Table 2 and 6), a violet color of related leach liquor, i.e.
experiments 79 comparing with the yellow-red color of leach
liquor in the experiments 46 indicated more Ti loss in leaching of 360 min milled ilmenite concentrate. In spite of surface
area decreasing, the changes of ilmenite structure brought
more Ti from milled ilmenite concentrate to the leach liquor
in the leached samples with 360 min milling, the extracted Ti
remained in solution and were not hydrolyzed to TiO2 leading
to less TiO2 content in the products of 79 than the products
of 46.
In the case of optimum leaching temperature similar to
previous investigation 100 C in level 2 was selected by applying Taguchi method (Li et al., 2008). In the experiments
which were conducted with initial temperature of 110 C in
level 3, hard-controlled initial temperature inside the reactor
increased due to the exothermic reaction between ilmenite
concentrate and hydrochloric acid, which caused evaporation of HCl and then the effectiveness of leaching agent was
reduced on ilmenite concentrate in 110 C of level 2. As nal
point; the ilmenite to hydrochloric acid (20%) and ilmenite to
iron powder mass ratio optimal levels were taken in 1:9.55 and
1:0.075, respectively. These two parameters have lowest effectiveness on TiO2 production with compared to other variables
and can be pooled to error (Table 4).
The stoichiometry of HCl and Fe powder was increased in
the proposed reactions (Mahmoud et al., 2004) due to the variation of the ilmenite to hydrochloric acid (20%) and ilmenite to
iron powder mass ratio, from 1:7.3 to 1:12.8 and from 1:0.05 to
1:0.1, respectively. It was reported that a higher HCl stoichiometry increases the TiO2 loss in the leach liquor (Mahmoud
et al., 2004; Lasheen, 2005; Li et al., 2008), thus the selection of ilmenite to hydrochloric acid mass ratio in mid level
of A2 is not unreasonable as Taguchi method outcomes rec-

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chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

Mean of SN ratio

40

35

30
1

Mt

Levels

Mean of SN ratio

40

35

30
1

Levels

Mean of SN ratio

40

35

30
1

Ip

Levels

Mean of SN ratio

40

35

30

Levels

Fig. 4 Plots of process parameters effect (S/N ratio).

ommend it. The parameter of ilmenite to iron powder mass
ratio (Ip) was optimized in med level (Ip2) similar to other
parameters. The iron powder addition inuences the leaching of ilmenite concentrate through different ways. The HCl
concentrate decreased less with smaller amount of Fe powder

addition and as well not more Fe+3 would be remained in solution leading to product contamination by unconverted Fe+3 ,
while the Fe powder addition helps Ti+3 to stay longer in solution as a reductive agent to convert Fe+3 to Fe+2 , also the iron
powder creates new surfaces by breaking up ilmenite grain

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chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

Table 5 The arrangement of calculated S/N ratios and mean of S/N ratios in each level to compute optimum conditions.

S/N
S/N
S/N
Mean in each level
Max Min

Mt1

Mt2

Mt3

A1

A2

A3

Ip1

Ip2

Ip3

T1

T2

30.93
32.75
31.22
31.63

39.08
38.61
39.19
38.96
7.33

38.09
39.02
38.05
38.39

30.93
39.08
38.09
36.03

32.75
38.61
39.02
36.79
0.64

31.22
39.19
38.05
36.15

30.93
39.19
39.02
36.38

32.75
39.08
38.05
36.62
0.65

31.22
38.61
38.09
35.97

30.93
38.61
38.05
35.87

32.75
39.19
38.09
36.68
0.81

structure during the reductive leaching in favor of ilmenite

dissolution (Mahmoud et al., 2004; Lasheen, 2005). In low and
high level of the iron powder addition (lp1 and lp3) one of the
mentioned phenomenons is dominant with their side effects
reducing product quality.
Finally, the S/N ratio of optimized process was calculated
by using Eq. (3) to predict the amount of TiO2 in the product
for optimum condition by Eq. (3), where  represents optimum
value and T is referred to the total levels of each parameter in
S/N ratios. Due to the effectiveness of milling time and initial
reaction temperature, Mt2 and T2 were used to estimate the
amount of TiO2 in optimal experiment and the A2 and Ip2 were
excluded due to their less inuence.

 

 

T
T
T
T
+ Mt2
+ A2
+ Ip2
n
n
n
n
326.94
+ 38.96 + 36.68 = 39.31
=
9

=

 

+ T2

T
n


(3)

Using the achieved optimal level of parameters, the maximum TiO2 amount was predicted by Eq. (3) where, T value
was 326.93 and Mt2 and T2 were mean of S/N ratios in
level 2 for milling time (Mt2) and temperature (T2), respectively. The predicted TiO2 amount was 92.35% corresponded
to 39.31. The conrmation experiment was conducted under
optimum condition to verify the Taguchi results. The prepared powder under optimum condition contained 92.8% TiO2
as main compound. The conrmation test result and predicted TiO2 amount were close together revealing the results of
designed Taguchi method were valid and also, the inuence of
uncontrolled factors (noise factor) such as operator error was
ignorable due to the precised experimental runs.

3.3.

Characterizations

Although nanosized titania can be denoted as one of the most

valuable photocatalyst with wide application elds, the synthesis of new materials which have elements such as iron in
their composition are important due to inuence of iron on
reactivity of these catalysts (Javio et al., 1999). In addition, the
preparation of nanopowders such as synthetic rutile similar to
iron-doped TiO2 directly from raw material such as ilmenite
concentrate has economically attractive issues. Therefore, the
prepared products in all of the nine experiments were characterized to examine the formation of nanosized synthetic rutile
which composed from TiO2 as a main component with small
amount of Fe2 O3 .
The X-ray diffraction (XRD) patterns revealed that major
phase of ilmenite concentrate was hexagonal structure of
FeTiO3 (Fig. 3). Table 6 provides information about chemical
composition of ilmenite concentrate and products of experiments 4, 6 and 8. Comparing with other ilmenite concentrate
in the world, the used concentrates in this investigation have
low TiO2 content and high impurity contents such as Fe2 O3
and SiO2 .

T3
31.22
39.08
39.02
36.44

The chemical composition of products was analyzed

through XRF test after dehydration followed by calcination in
400 C. The XRF results indicated that the products had main
impurities such as Fe2 O3 , SiO2 and traces of other impurities
such as MgO, CaO and Al2 O3 . The SiO2 and Fe2 O3 amount
increased and decreased in leach residuals, respectively. The
compound with less than 0.1% was presented as blank tables.
The X-ray diffraction (XRD) patterns of calcined products are presented in Fig. 5. The XRD patterns indicated the
ilmenite phase remained in the products of experiments 13.
Therefore, most of ilmenite concentrate did not participate
in the occurred reactions between ilmenite and hydrochloric
acid. In the case of experiments 49 where the mechanical
activation was carried out as pretreatment, the XRD pattern
conrmed the formation of rutile phase without traces of
ilmenite phase. The results matched achievements of Taguchi
method that mechanical activations had most signicant
effect in compare with other selected parameters. The formation of rutile phase instead of anatase phase is related to the
small particle size of products. It is known that the stability of
rutile and anatase phases depends on the particle size and also
the stability of rutile phase is more noticeable in extremely
small particles (Li et al., 2008). The existence of ilmenite phase
in experiments 1 and 3 reveals that nanosized synthetic rutile
cannot be produced in the related conditions. Therefore, the
prepared powders in experiments 49 were chosen for further
investigation with SEM in next stage.
Fig. 6 depicts the SEM micrographs of prepared powders
in experiments 49. The SEM micrograph of experiments 5
and 6 indicated the nest particles were produced during
the relative condition. Although the prepared powder through
experiments 4 and 79 had nanosized particles but their SEM
micrographs exposed that some of their particles were more
than 100 nm in size. Therefore, the produced powder of experiments 5 and 6 are considered for TEM microscopy examination
in order to prove for nano size preparation of the synthetic
rutile.
The TEM images of these powders certify the formation of
nanosized synthetic rutile with particles size which were less
than 100 nm. The particles were formed in different crystalline
shape and morphology. In comparison with produced powder
in experiment 5, the prepared nanopowder through experiment 6 had smaller and more uniform morphology (Fig. 7).
The BET surface area of nanosized synthetic rutile prepared through experiment 6 was 54.6 m2 /g. The high surface
area of product 6 provided further evidence for formation
of nanoparticles. The nanoparticles were created because of
accelerated dissolution of the ilmenite concentrate followed
by rapid hydrolysis of dissolved titanium (Li et al., 2008). The
combination of mechanical activation pretreatment and iron
powder addition was responsible for increasing the reactivity
of ilmenite concentrate because of the creation new surface
and new crystal defect on the ilmenite particle and also due
to breaking up the grain structure by addition of iron powder

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Table 6 Chemical composition of Kahnoje ilmenite concentrate and product of experiments 4, 6 and 8.

Ilmenite concentrate
Experiment no. 4
Experiment no. 6
Experiment no. 8

*= ilmenite

Fe2 O3 %

TiO2 %

SiO2 %

MgO%

CaO%

Al2 O3 %

MnO%

44.6
2.1
1.4
2.7

32.9
89.9
91.1
89.3

5.9
6.5
6.7
6.3

3.6
0.1

0.1

2.2
0.2

0.3

2.5
0.2
0.3
0.2

2.1

0.1

*= ilmenite

Exp. 1

Exp. 2

*
*

*
*

10

20

30

40

50

60

10

70

20

30

2Theta/degree

40

50

60

70

2Theta/degree

= rutile

*= ilmenite

Exp. 3

Exp. 4

*
*
*

10

20

30

40

50

60

70

10

20

30

2Theta/degree

= rutile

20

30

40

50

60

70

10

20

30

40

50

60

70

50

60

70

10

Exp. 8

20

30

2Theta/degree

40

2Theta/degree

= rutile

10

40

= rutile

Exp. 7

30

70

2Theta/degree

= rutile

20

60

Exp. 6

2Theta/degree

10

50

= rutile

Exp. 5

10

40

2Theta/degree

Exp. 9

20

30

40

50

60

70

2Theta/degree

Fig. 5 XRD patterns of powders produced in experiments 19.

50

60

70

chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

Fig. 6 SEM micrographs of synthetic rutile produced powders in experiments 49.

Fig. 7 TEM image of nanosized synthetic rutile prepared in experiments 5 and 6.

227

228

chemical engineering research and design 9 0 ( 2 0 1 2 ) 220228

during the ilmenite reductive leaching (Mahmoud et al., 2004;

Li et al., 2008).
The nanosized synthetic rutile prepared in experiment
6 with main constituent of TiO2 can be considered as heterogeneous photocatalysis. Depending on circumstance of
iron impurities being in nanosized synthetic rutile crystalline
structure, new properties like iron-doped TiO2 nano particles were anticipated for nanosized synthetic rutile as new
nanopowder.

4.

Conclusion

In this research, the Taguchis L9 (34 ) experimental design was

applied to set the optimal conditions of mechanically activated ilmenite reductive leaching for preparation of synthetic
rutile with highest TiO2 content from ilmenite concentrate.
By ANOVA test results, the milling time was more effective parameter on quantity of TiO2 in synthetic rutile than
other selected parameters. In addition, the optimal conditions achieved by using S/N ratios were as follows; milling
in Argon atmosphere for 40 min, initial reaction temperature:
100 C, ilmenite to 20% hydrochloric acid mass ratio: 1:9.55
and ilmenite to iron powder mass ratio: 1:0.075. The obtained
result from Taguchi method was controlled by performance of
an experiment under achieved optimum conditions. The TiO2
amount in prepared synthetic rutile of conrmation experiment was 92.8% close to calculated prediction. Based on the
XRD and BET results of milled powders, it was veried that
mechanical activation accelerated the dissolution of milled
powder by increasing the surface area and decreasing the crystallinity of ilmenite concentrate in comparison with unmilled
ilmenite concentrate.
The XRD patterns of calcined products (prepared during the
designed experiments of Taguchi method) revealed without
mechanical activation pretreatment, parts of ilmenite concentrate did not participate in the occurred reactions between
ilmenite and hydrochloric acid. However, the XRD patterns
indicated rutile as major phase formed in prepared powders from mechanically activated ilmenite. The TEM and SEM
micrographs proved the nanosized synthetic rutile produced
in experiments 6. The prepared nanosize synthetic rutile has
91.1% TiO2 , 1.4% Fe2 O3 , 6.7% SiO2 and trace amounts of impurities such as CaO, MgO, and Al2 O3 . The TEM analysis of
experiments 6 product presented its particle sizes were less
than 100 nm. As nal result, the BET surface area of prepared
powder in Exp. 6 measured was about 54.6 m2 /g.
In present study, the nano synthetic rutile was prepared
among some of Taguchi experimental design products and
more investigation was suggested.
1. Since the physical and chemical properties of nanoparticles were differing from the corresponding bulk material,
the nanosized synthetic rutile was recommended for characterization of new physical and chemical properties.
2. Fe-doped TiO2 and other composition of titania nano particles has wide usage in industry. The investigation for
indicating of crystalline structure and composing phase of
synthetic rutile nanopowders will be worthy to attention.

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