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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch
Improvement of iron removal from silica sand using ultrasound-assisted oxalic acid
Feihu Du, Jingsheng Li *, Xiaoxia Li, Zhizhen Zhang
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China
a r t i c l e
i n f o
Article history:
Received 18 December 2009
Received in revised form 3 July 2010
Accepted 7 July 2010
Available online 15 July 2010
Keywords:
Silica sand
Iron removal
Oxalic acid
Ultrasound
Leaching
a b s t r a c t
This paper deals with the removal of iron from silica sand in aqueous oxalic acid, in the absence and presence of ultrasound. The parameters investigated were the reaction temperature, stirring speed, ultrasound power, acid concentration and reaction time. The optimum conditions for the maximum
removal of 75.4% of iron with ultrasound were determined as follows: reaction temperature, 95 C; stirring speed, 500 rpm; ultrasound power, 150 W; acid concentration, 4 g/l; reaction time 30 min. The
method induces a remarkable acceleration for the iron leaching process, the leach acid concentration
reducing dramatically and the removal efciency increasing considerably, compared to conventional stirring method. The advantages of ultrasound-assisted leaching were also conrmed by characterizing the
silica sand and the leached solid samples using particle size, SEM and color measurement analysis.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The presence of iron compounds in silica sand is prohibitive to
the production of optical bers, glass, ceramics and refractory
materials. Considerable efforts have been devoted to the problem
of removing iron contaminants by physical [1], chemical [25],
and biological methods [68]. Sometimes various combinations
of these methods are required to upgrade silica sand [9,10]. The
most appropriate method depends on the mineralogical forms
and distribution of iron in the particular ore.
Chemical methods involve upgrading of such minerals with
inorganic and organic acids. The most commonly used inorganic
acids are sulphuric [11] and hydrochloric [12,13], but these are
generally costly and the ensuing efuents are environmentally
unacceptable. Furthermore, inorganic acids such as sulphuric or
hydrochloric acids easily contaminate the minerals with SO2
4
and Cl. Thus there is considerable interest in the development
of alternative technological means such as organic acid leaching
which may be more effective and eco-friendly. Additionally, oxalic
acid is found to be the most promising because of its acid strength,
good complexing characteristics and high reducing power, compared to other organic acids [14]. Using oxalic acid, the dissolved
iron can be precipitated from the leach solution as iron(II) oxalate
dihydrate, which can be represented a useful potential feedstock
for added-value products [15,16].
The removal of iron from silica sand with oxalic acid has been
studied by several workers [24]. The chemical reactions can be
summarized as follows [2,4]:
* Corresponding author. Tel.: +86 13646101959.
E-mail address: jli5154@ujs.edu.cn (J. Li).
1350-4177/$ - see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2010.07.006
2FeC2 O4 3
3
2
3
They try their best to optimize the process parameters and reach a
high degree of iron removal at minimum operating cost. The reaction temperature is found to be critical as conrmed by many
researchers. As an example, it is found by Taxiarchou et al. [2] that
at temperatures varying between 90 and 100 C the maximum
iron extraction that can be achieved is approximately 40%. At temperatures lower than 80 C this extraction is decreased to 30%. One
more interesting feature has been agreed by several workers that
the optimum pH for leaching of iron from silica sand is pH 2.53.0,
outside which range the leaching rate drops dramatically. The
phenomenon has been explained by Lee et al. [17,18] that the
solution pH governs the distribution of various oxalate ions in
the leach system. Below pH 1.5, oxalic acid exists mainly as
H2C2O4, whereas HC2 O
4 is the most predominant species (mole
fraction >0.92) at pH 2.53.0. Above pH 4, C2 O2
is the predomi4
nant species.
Recently, ultrasound as an auxiliary energy has been successfully applied in the mining industry. It is found that the iron on
the silica sand surface can be eliminated more efciently by ultrasound than by mechanical scrubbing [19,20]. Furthermore, the iron
elimination rate can be raised when the ultrasound technology is
combined with chemicals (such as water glass, soda and sodium
pyrophosphate) in solution due to their synergistic action
[1921]. This work reports the use of ultrasound-assisted oxalic
acid leaching for removal of iron and its comparison with the
390
2. Experimental section
2.1. Materials and reagents
The silica sand comes from the Mingwang quarry located in the
north of Jiangsu Province, China. The silica sand has been pretreated by some physical methods. The chemical composition of
the dry silica sand is shown in Table 1. All chemicals used were
of guaranteed-reagents grade (Sinopharm Chemical Reagent Co.,
Ltd., China) and deionized water was used throughout the work.
2.2. Leaching tests
For the rst part of the experiment, the oxalate leachant was
prepared by dissolving known quantities of oxalic acid in deionized
water. Ammonium hydroxide was added slowly to adjust the pH
value to 2.5. For each run, 200 ml volume of the liquor was poured
into a 500 ml beaker in a constant temperature magnetic stirrer
(DF-101S, Yuhua, China). Water bath (2000 ml) and continuous circulation of cooling water were used to control the solution temperature. When the required temperature of the beaker contents was
reached, approximately 20.0 g of dry sand was added into the beaker while the contents of the beaker were being stirred at a certain
speed. The beaker was covered to prevent losses by evaporation.
From leaching solution, an amount of sample of the reaction mixture was taken out at the pre-determined time intervals, ltered
immediately and then dried for characterization.
The second part of the experiment performed by using ultrasound energy, ultrasound device (SC, Jiuzhou, China) which has a
probe with tip radius of 1 cm and an ultrasonic generator
(20 kHz and 0300 W) in addition to the mechanism used in leaching process was used. The contents of the beaker were simultaneously stirred at a 500 rpm and sonicated at a certain power. All
the other experimental processes and parameters were designed
identically with those in the rst part. A schematic diagram of
the experimental setup is shown in Fig. 1. All the experiments were
carried out in duplicate and sometimes repeated again, and the
mean values have been reported.
2.3. Analysis and characterization
The elemental analysis of the silica sand and the leached solid
samples was carried out by ICP-OES (Vista-MPX, Varian, USA).
The iron removal efciency of a process can be calculated using
the equation:
Table 1
Chemical analysis of the dry silica sand.
Element
SiO2
Al2O3
Na2O
K2O
CaO
Fe2O3
TiO2
MgOa
MnOa
Cr2O3a
99.391
0.249
0.081
0.073
0.069
0.060
0.014
73
16
1
Sum
99.937
Composition in g/t.
391
70
500 rpm + 50 C
o
500 rpm + 65 C
o
500 rpm + 80 C
o
500 rpm + 95 C
80
60
50
40
30
20
10
0
10
15
20
Reaction Time min
25
30
goethite where dissolution can take place via both reduction (solid
and aqueous species) and complexation, whereas oxides such as
hematite dissolve mainly via solid reduction [17,18]. At 95 C, iron
reaches its maximum removal of 59.1%. Therefore, 95 C can be
chosen as an optimal temperature for all subsequent experiments.
3.2. Effect of stirring speed
The inuence of magnetic stirring speed on the iron removal
was investigated at stirring speeds of 300, 500, 700 and 800 rpm
in solutions containing 4 g/l of oxalic acid, in the absence of ultrasound. According to Fig. 3, the leaching rate is nearly independent
of the stirring speed, which points to the fact that the reaction is
not controlled by lm diffusion. For this reason, all subsequent
experiments were carried out with a stirring rate of 500 rpm to
prevent particles subsiding in the beaker.
3.3. Effect of ultrasound power
The inuence of ultrasonic power on the iron removal was performed with ultrasound powers of 90, 120, 150 and 180 W in solu-
80
80
70
60
60
50
300 rpm
500 rpm
700 rpm
800 rpm
500 rpm + 90 W
500 rpm + 120 W
500 rpm + 150 W
500 rpm + 180 W
40
30
20
10
0
0
10
15
20
Reaction Time min
25
30
70
50
2 g/l + 500 rpm
4 g/l + 500 rpm
6 g/l + 500 rpm
8 g/l + 500 rpm
2 g/l + 150 W
4 g/l + 150 W
6 g/l + 150 W
8 g/l + 150 W
40
30
20
10
0
0
10
15
20
25
Reaction Time (min)
30
Fig. 4. Effect of H2C2O4 concentration on iron removal in the absence and presence
of ultrasound.
392
2.5
a
b
c
d
Volume (%)
2.0
1.5
1.0
0.5
0.0
10
100
Particle Size m
1000
Fig. 5. The particle size and size distribution of the silica sand (a) and the leached
solid samples (b and c) prepared with a 4 g/l H2C2O4 concentration at 95 C for
30 min under conventional stirring at a speed of 500 rpm and ultrasound at a power
of 150 W; and the leached solid sample (d) prepared with water as a leach solvent
at 95 C for 30 min under ultrasound at a power of 150 W.
Fig. 6. SEM photographs of the silica sand and the leached solid samples, conditions of samples are same as those described in Fig. 5.
Whiteness
L*
a*
b*
% Al2O3
% Fe2O3
% TiO2
a
b
c
52.74
66.60
70.46
88.40
90.19
90.89
0.69
0.57
0.48
4.19
2.08
1.50
0.249
0.181
0.166
0.06
0.024
0.014
0.014
0.008
0.006
L*, Brightness; a*, red-green index; b*, yellow-blue index. Conditions of samples are
same as those described in Figs. 5 and 6.
393
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