Hydrometallurgy 71 (2004) 397 401

www.elsevier.com/locate/hydromet

Statistical modeling and optimization of ultrasound-assisted

sulfuric acid leaching of TiO2 from red mud
Enes Sayan a,*, Mahmut Bayramoglu b
a

Deparment of Chemical Engineering, Faculty of Engineering, Ataturk University, 25240 Erzurum, Turkey
b
Faculty of Engineering, Gebze Institute of Technology, 41400 Gebze, Kocaeli, Turkey
Received 6 March 2003; received in revised form 28 April 2003; accepted 29 April 2003

Abstract
Ultrasound has proven to be a very effective tool for enhancing reaction rates by inducing a number of chemical and mechanical
effects on the reaction medium. In this study, the effect of ultrasound power on the sulfuric acid leaching of Ti from red mud has
been investigated by statistically designed experiments. The effects of five parameters, ultrasound power, temperature, leaching
time, acid concentration and solid to liquid ratio, on the leaching of TiO2, Al2O3 and Fe2O3 have been investigated. First-order
models have been obtained by using 25
1 fractional factorial design. Auxiliary experiments for second-order models have been
conducted according to an orthogonal central composite design. These second-order models have been used in a constrained
optimization study which showed that both high and selective yields of TiO2 may be obtained under suitable process conditions.
The major factors influencing TiO2 leaching were acid concentration and temperature, the other variables had comparatively small
effects. The use of ultrasound resulted in a 20% increase in TiO2 leaching compared to identical conditions without ultrasound.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Red mud; Leaching; Statistical modeling; Ultrasound; Optimization

1. Introduction
Sonochemistry is the use of ultrasound to accelerate or initiate chemical reactions; it is mainly concerned with reactions within the liquid phase where
ultrasound produces chemical and mechanical effects
through cavitation (Mason, 1991). Recently, the
effects of ultrasound for improving chemical reactions
have been reviewed (Thompson and Doraiswamy,
1999). Polyukhin (1978) reviewed the application of
ultrasound in extractive metallurgy.
* Corresponding author. Tel.: +90-442-2314564; fax: +90-4422360957.
E-mail address: enessayan@yahoo.com (E. Sayan).
0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-386X(03)00113-0

Sonochemical extraction techniques together with

classical methods gave faster (Pesic and Zhou, 1992)
and more selective (Barrera-Godinez et al., 1992)
extraction of metals. Ultrasound has also been found
to increase the rate of dissolution in several solid
liquid systems and also has a positive effect on the rate
of leaching. These effects can be explained by cavitation leading to the appearance of microcracks on the
solid surfaces subjected to ultrasound. Ultrasound also
increases the diffusion coefficient of soluble species;
this effect enables the leaching agents to more rapidly
reach the bottom of capillaries (Thompson and Doraiswamy, 1999). Furthermore, if the solid reagent is in
the form of a powder, sonication can cause particle
rupture, with a consequent increase in the surface area

398

E. Sayan, M. Bayramoglu / Hydrometallurgy 71 (2004) 397401

available for reaction. One might expect that the

increase in surface area alone would be sufficient to
explain any enhanced reactivity due to ultrasound
(Mason, 1991).
Red mud is a by-product of the Bayer Process and
causes serious disposal problems for the environment
due to the high alkalinity and the large amount of waste.
Intensive research has been conducted on the recovery
of valuable substances from red mud (Patel et al.,
1992). The economically feasible processes for the
total evaluation of red mud are carbon lime soda
sintering and electric furnace smelting. The latter
process yields pig iron and a slag useful for the
recovery of TiO2, Al2O3, Zr, U, Th and rare earth
elements as well (Erc ag and Apak, 1997). Red mud
has also been proposed as an absorbent to remove H2S
from industrial emissions, a constituent of building
materials, a coagulant to remove phosphate in wastewater, a catalyst in coal hydrogenation, a pH modifier
in heap leaching of gold leaching ores and as a
neutralizing agent for acid wastes (Vachon et al., 1994).
This paper aims to model and optimize the effect of
ultrasound on the sulfuric acid leaching of TiO2 from
red mud. The leaching yields of the by-products Al2O3
and Fe2O3 are also estimated in order to calculate the
leaching selectivity of the main product TiO2. This
research is mainly concerned with the leaching step.
The selective extraction of Ti4 + from the leaching
solution and subsequent hydrolysis of Ti4 + to TiO2
are other important process steps (Biswas et al., 2002;
Jinhui et al., 2001). The pre-optimization results presented in this paper may provide background information for a detailed process development study.

2. Experimental
2.1. Design of experiments
Factorial designs are widely used in statistical planning of experiments to obtain empirical linear models
relating process response to process factors (Montgomery, 1976). 2n factorial design, where each variable runs
at two levels, is often used to obtain first-order models.
If the variance analysis indicates that overall curvature
is significant, auxiliary experiments are carried out to
develop a second-order model. Among various secondorder designs, the orthogonal central composite design

is widely used as it only requires 2n additional runs

(Myers, 1971). A previous paper (Sayan and Bayramoglu, 2000) has demonstrated the application of this
type of experimental design to the leaching of red
muds.
2.2. Material and methods
Red mud was supplied by Etibank Seydis ehir
aluminium plant, Turkey. The chemical analysis of
washed, air dried and homogenized sample with
particle size of
75 Am (
200 mesh ASTM) is as
follows (wt.%); Fe2O3: 37.72, Al2O3: 17.27, TiO2:
4.81, SiO2: 17.10, CaO: 4.54, MgO: 0.40, K2O: 0.29,
Na2O: 7.13, SO3: 0.18 and loss on ignition: 10.22.
The experimental set-up consisted of an ultrasonic
generator (Cole Parmer ultrasonic homogenizer, 400
W, 20 kHz) equipped with a probe with a stainless steel
tip (13 mm diameter), a jacketed glass reactor fitted
with a reflux condenser and a constant temperature circulator to maintain the desired temperature in the reactor. In all the experiments, a constant stirring speed of
600 min
1 was used to ensure suspension of the particles. Ultrasound power was adjusted by means of the
amplitude setting of the generator using the relationship between the amplitude setting and ultrasound power absorbed by the reaction medium, which was
measured by a calorimetric method (Kimura et al.,
1996).
Specified amounts of preheated sulfuric acid of
known concentration and red mud were loaded into
the reactor and the desired ultrasound power was
applied. At the end of the experiment, the contents of
the reactor were immediately filtered. The TiO2 content
of the leach solution was determined by the H2O2spectrophotometric method (Furman, 1962), whereas
the Al2O3 and Fe2O3 contents were determined by
standard complexometric methods (Gulensoy, 1984).

3. Results and discussion

3.1. Modeling results
Process factors considered in this study are: reaction
temperature (X1), sulfuric acid concentration (X2),
ultrasound power absorbed by the reaction medium
(X3), solid-to-liquid ratio (X4) and leaching time (X5).

E. Sayan, M. Bayramoglu / Hydrometallurgy 71 (2004) 397401

The same factors, except ultrasound power, were used

in our recent study about the conventional acid leaching
of the red mud (Sayan and Bayramoglu, 2000, 2001),
where mechanical stirring was applied to disperse solid
particles in the liquid medium and to enhance the
leaching rate. Factor levels, shown in Table 1, are also
similar to those previously used to easily compare the
performances of the two leaching techniques.
Initially, the 25
1 fractional factorial design was
used to develop first-order model with interaction
terms. As usual, the experiments were run in random
order to avoid systematic error. Furthermore, three
central replicates were also carried out to calculate
pure experimental error. The experimental design and
leaching yields are given in Table 2. The first-order
models obtained by variance analysis conducted at
95% confidence interval are as follows:
YTiO2 61:38
4:81X1 22:90X2 2:65X3

9:24X4 8:78X1 X2
2:53X1 X4
1:69X2 X3 2:92X3 X4

YFe2 O3 30:39 9:62X1 16:57X2 5:24X3

10:35X4 3:40X5 10:14X1 X2

4:77X1 X4
7:47X2 X4 2:63X2 X5

5:61X3 X5

YAl2 O3 78:03 8:36X1 6:68X3 3:82X5

The analysis of variance revealed that the overall

curvature effect was significant; therefore, the orthogonal central composite design was used to estimate
quadratic terms separately. New factor levels are given
in Table 3, where some variable levels were rounded,
Table 1
Factor levels used in the fractional factorial design
Factors
Temperature
(jC) (X1)
Acid concentration
(N) (X2)
Ultrasound power
(W) (X3)
Solid to liquid ratio
(g mL
1) (X4)
Leaching time
(h) (X5)

399

Table 2
Experimental design and leaching yields of TiO2, Al2O3 and Fe2O3
Experiment X1 X2 X3 X4 X5 Leaching Leaching Leaching
no.
yield of yield of yield of
TiO2
Fe2O3
Al2O3
7
9
8
3
11
4
10
1
13
6
15
2
12
5
16
14
1j
2j
3j

+ + + + +
+ +

+
+ +
+

+

+ +

+
+ +
+ + +


+
+ +



+ + +

+ +
+

+ + +

+
+
+
+





+







+



+



+


0 0 0 0 0
0 0 0 0 0
0 0 0 0 0

83
99
65
6
72
99
18
47
89
76
29
39
77
61
36
57
72
69
71

52
97
28
10
21
96
15
17
49
22
23
11
24
15
7
25
20
24
22

99
98
75
76
65
95
83
77
81
81
90
77
45
70
66
74
80
76
75

based on the sensitivity of the equipment used. The

design matrix and results of the auxiliary runs are
given in Table 4. Models tested at 90% confidence
level are as follows:
yTiO2 71:3658
5:279X1 22:8582X2 3:3992X3

9:124X4 1:3221X5
6:9795X12

5:7919X22 1:0665X32 8:7812X1 X2

2:5213X1 X4
1:5412X1 X5
1:7063X2 X3 2:1038X2 X5 2:9287X3 X4

1:3462X3 X5

yFe2 O3 21:0624 8:5774X1 16:6259X2

High
level (+)

Medium
level (0)

Low
level (
)

90

75

60

23

17

11

4:9171X3
10:4854X4 3:1683X5

6:5748X22 4:2357X42 10:1381X1 X2

4:7706X1 X4
7:4719X2 X4 2:6281X2 X5

5:6056X3 X5
5
yAl2 O3 74:8956 7:9273X1 2:1824X2 5:9309X3

0.08

0.06

0.04

4:0337X5 4:0303X12 3:5013X1 X2

2:9725X1 X4 2:3050X2 X3
2:2325X4 X5

6

400

E. Sayan, M. Bayramoglu / Hydrometallurgy 71 (2004) 397401

Table 3
Auxiliary factor levels used in the central composite design
Parameters

High
level ( + h)

Medium
level (0)

Low
level (
h)

Temperature
(jC) (X1)
Acid concentration
(N) (X2)
Ultrasound power
(W) (X3)
Solid to liquid ratio
(g mL
1) (X4)
Leaching time
(h) (X5)

100

75

50

4.66

3.00

25

1.34

17

0.093

0.060

0.027

4.66

3.00

1.34

The correlation coefficients of models in Eqs. (4)

(6) are 0.9930, 0.9583 and 0.8725, respectively.
3.2. Constrained optimization results
The primary objective of process development is to
determine the optimum process conditions from the
models obtained theoretically or experimentally. For
this goal, firstly, the objective of the optimization is
decided, which may be either economic or technical. In
this optimization study, the leaching yield of TiO2 was
chosen as the objective function. Leaching selectivity
is another criteria which can be used or considered as a
secondary objective function. Furthermore, optimum
conditions are often calculated in the presence of some
constraints which ensure them to be more realistic. If
the model used in the optimization study is an empirical one, high and low levels of the process factors in
the experimental design are considered as explicit

Fig. 1. The dependence of maximum leaching yield of TiO2 on the

restrictions imposed on the leaching yields of Al2O3 and Fe2O3.

constraints in order to avoid extrapolation. The aim

in this case is to maximise the yield of TiO2, with the
experimental variables bounded by the experimental
values and the leaching of Fe2O3 and Al2O3 below
fixed values to give some constraint on selectivity.
Leaching selectivity is also defined as follows:
Selectivity mol of leached TiO2
=mol of leached Fe2 O3
mol of leached Al2 O3
The optimization problem was solved using the
constrained optimization program supplied in the

Table 4
Experimental design for second-order model and leaching yields of TiO2, Al2O3 and Fe2O3
Experiment
no.

X1

X2

X3

X4

X5

Leaching
yield of
TiO2 (%)

Leaching
yield of
Fe2O3 (%)

Leaching
yield of
Al2O3 (%)

21
24
26
18
20
25
17
23
19
22

1.6644
1.6644
0
0
0
0
0
0
0
0

0
0

1.6644
1.6644
0
0
0
0
0
0

0
0
0
0

1.6644
1.6644
0
0
0
0

0
0
0
0
0
0

1.6644
1.6644
0
0

0
0
0
0
0
0
0
0

1.6644
1.6644

63
41
18
93
65
84
89
59
66
73

13
32
11
67
15
28
51
14
13
22

77
99
67
79
69
81
80
83
68
83

E. Sayan, M. Bayramoglu / Hydrometallurgy 71 (2004) 397401

Matlab optimization toolbox. A series of optimization

study has been performed by varying the maximum
Fe2O3 leached between 5 and 50 and Al2O3 leaching
between 15 and 50.
The results show that ultrasound power is effectively used at its lower bound, with a low solid liquid
ratio and short leaching times giving optimum TiO2
yields, temperature and acid concentration had the
greatest effect on the optimum yield. The dependence
of maximum leaching yield of TiO2 on leaching yields
of Al2O3 and Fe2O3 is shown in Fig. 1. Clearly, the
high leaching yield of TiO2 requires inevitably high
leaching yields of the side-products. Meanwhile, this
is not always true when selectivity is also taken into
account as secondary optimization criteria. The highest selectivity values, 0.418 and 0.400, correspond to
moderate TiO2 yields and to low values of Fe2O3,
especially. In conclusion, realistic optimum process
conditions have to be selected by considering both
leaching yield and selectivity.

4. Conclusions
The effects of relevant parameters, temperature,
acid concentration, ultrasound power, solid-to-liquid
ratio and leaching time on the leaching of TiO2 from
red mud, have been explored by statistically planned
experiments. Initially, 25
1 fractional factorial design
was used to obtain a first-order model. Based on the
results of variance analysis, it was necessary to conduct auxiliary experiments, using an orthogonal central composite design, to obtain second-order models
relating TiO2, Fe2O3 and Al2O3 leaching yields to the
experimental variables.
Constrained optimization studies showed that high
leaching yield and selectivity may be obtained under
suitable process conditions. This study indicated the
beneficial effect of ultrasound power on the leaching
yield of TiO2, typically, a 20% greater dissolution of
TiO2 was obtained in this study when compared with
the conventional method at similar process conditions
(Sayan and Bayramoglu, 2000, 2001). However,
detailed optimization studies along with economical
analysis are needed to decide on the profitability of
using ultrasound. Further, bench-scale experimenta-

401

tion using higher solid liquid ratios must be conducted to assess the applicability of the method at an
industrial scale.
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