Ultrasonics Sonochemistry 18 (2011) 389393

Contents lists available at ScienceDirect

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

Fe2 O3 6H2 C2 O4 2FeC2 O4 3

3 6H 3H2 O

2FeC2 O4 3
3

6H 4H2 O 2FeC2 O4  2H2 O 3H2 C2 O4 2CO2

Fe2 O3 3H2 C2 O4 H2 O 2FeC2 O4  2H2 O 2CO2

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

F. Du et al. / Ultrasonics Sonochemistry 18 (2011) 389393

conventional magnetic stirring method. Optimization of different

operating parameters has also been investigated.

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.

Fig. 1. Schematic diagram of the experimental set-up.

Iron removal efficiency %



amount of iron in leached solid samples
 100
1
amount of iron in original mineral
4
The particle size and size distribution of the silica sand and the leached solid samples were determined by laser light scattering method (Mastersizer 2000, Malvern, UK), measurements were performed
in diluted aqueous dispersions. The morphologies of the silica sand
and the leached solid samples were observed using eld emission
scanning electron microscopy (S-4800, Hitachi, Japan). The optical
properties of the silica sand and the leached solid samples were
analyzed on a spectrophotometer (CM-2500d, Minolta, Japan) using
XL-30 and D65 illuminant.
3. Results and discussion
Although grinding of the untreated silica sand would have improved iron removal by increasing the surface area, it would consume energy and cause particulate pollution. Hence the silica
sand was subjected to our work without prior grinding. The inuence of pH of the initial solution, which has been conrmed by
many workers, would not be discussed in this paper.
3.1. Effect of temperature
The inuence of temperature on the iron removal was studied
for temperatures of 50, 65, 80 and 95 C in solutions containing
4 g/l of oxalic acid, in the absence of ultrasound. According to
Fig. 2, increasing of the temperature is effective in increasing the
leaching rate, which is attributed to the fact that increasing temperature will increase both the reaction and diffusion rate of reactants and reaction products. One interesting feature has been
observed from the leaching rates of the iron. Especially at a high
temperature of 95 C, there are two distinct regimes of leaching:
initially, the leaching rate is high up to a certain period (around
23 min) of the leaching operation and then gradually decreases
showing a little increase in the iron removal. The possible reason
for these two distinct rates is explained as follows: in the initial
phase of the leaching, iron hydroxyl-oxides which are possibly
on the surface of the silica sand have been leaching out, and then,
during the second phase of the leaching, iron oxides which are possibly on the surface of silica sand react with the oxalic acid slowly.
In other words, it is easier to dissolve hydroxyl-oxides such as

391

F. Du et al. / Ultrasonics Sonochemistry 18 (2011) 389393

70

Iron Removal (%)

tions containing 4 g/l of oxalic acid. According to Fig. 3, as the

ultrasonic power increases, the leaching rate increases. Also shown
in Fig. 3, after test time reaches 20 min there is no signicant
change of the removal efciency between 150 and 180 W. Therefore, 150 W can be chosen as an optimal power for all subsequent
experiments.

500 rpm + 50 C
o
500 rpm + 65 C
o
500 rpm + 80 C
o
500 rpm + 95 C

80

60
50

3.4. Effect of oxalic acid concentration

40
30
20
10
0

10
15
20
Reaction Time min

25

30

Fig. 2. Effect of temperature on iron removal in the absence of ultrasound.

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-

The inuence of H2C2O4 concentration on the iron removal was

carried out in solutions containing initial H2C2O4 concentrations of
2, 4, 6 and 8 g/l, in the absence and presence of ultrasound. According to Fig. 4, the leaching rate increases with increasing concentration of oxalic acid until 6 g/l, but only slightly increases with
further increase in acid concentration, in the absence of ultrasound. This behavior may be attributed to the formation of more
oxalates when the acid concentration is over 6 g/l. The precipitation of oxalates can form a product layer around the mineral coatings, which decreases the leaching rate. Therefore, 6 g/l can be
chosen as an optimal concentration to obtain the maximum leaching rate. The similar results obtained by using ultrasound are also
shown in Fig. 4. The leaching rate increases with increasing concentration of oxalic acid until 4 g/l, but only slightly increases with
further increase in acid concentration. A possible explanation for
the phenomenon is that oxalates have been largely formed when
the oxalate concentration is over 4 g/l under ultrasonic treatment.
The oxalates(s) around the mineral coatings are dispersed into the
liquid phase and then quickly absorbed on the mineral coatings
surface due to intermittent ultrasound. The repeated behavior of
oxalates(s) can also decrease the leaching rate. Therefore, 4 g/l
can be chosen as an optimal concentration to obtain the maximum
leaching rate.
3.5. Comparison of the results between conventional stirring and
ultrasound-assisted leaching process
It can be shown from Figs. 3 and 4 that the leaching rate of iron
is much higher under ultrasound than that obtained by conventional stirring. Furthermore, Fig. 4 shows that the maximum removal of 75.4% of iron with ultrasound, is increased by 16.3%, in
comparison with that without ultrasound when the acid concentration is 4 g/l for the same period of 30 min. The maximum

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

Fig. 3. Effect of stirring speed and ultrasound power on iron removal.

Iron Removal (%)

Iron Removal (%)

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

F. Du et al. / Ultrasonics Sonochemistry 18 (2011) 389393

removal of 65.8% of iron is achieved with the solutions containing

6 g/l of oxalic acid for 30 min under conventional stirring. However, the same removal efciency can be obtained when the acid
concentration is only 4 g/l within 15 min of the leaching operation
under ultrasound irradiation. Thus, it is clear that the application of
ultrasound can improve the iron removal efciency, reduce leach
acid concentration and accelerate the leaching rate, compared to
conventional stirring.

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.

3.6. Particle size analysis

Fig. 5 shows the particle size and size distribution of the silica
sand and the leached solid samples prepared at a reaction temperature of 95 C for 30 min. The silica sand has a broad particle size
distribution in the range of micron-sized particles. The volume
mean diameter of the silica sand is 71.541 lm (Fig. 5a). There is
marginal reduction of particle size after leaching by conventional
stirring speed of 500 rpm in solutions containing 4 g/l of oxalic
acid. The volume mean diameter of the leached solid sample is
69.415 lm (Fig. 5b). Additionally, the volume mean diameter of
the leached solid sample is 64.198 lm after leaching with water
as a leach solvent under ultrasound power of 150 W (Fig. 5d). That
is to say, neither conventional stirring using oxalic acid nor ultrasound with water as a leach solvent can effectively reduce the particle size. However, there is signicant particle size reduction after
leaching by ultrasound power of 150 W in solutions containing
4 g/l of oxalic acid. The volume mean diameter of the leached solid
sample is 55.368 lm (Fig. 5c). A possible explanation for this is that
the appearance of many micro-pittings on the silica sand surface is
due to the reaction of oxalic acid with impurities, which makes the
particles more porous, loose, and easier to break down under ultrasound irradiation. Therefore, particle breakage (fragmentation) of
the silica sand during the leaching is more due to ultrasound than
under conventional stirring conditions. Furthermore, particle
breakage can lead to high specic solidliquid interfacial area
and by increase the surface diffusional rate of the reactive species
[22]. This is one reason demonstrates that the leaching rate of iron
is much higher under ultrasound than that obtained by conventional stirring. Another reason is that ultrasound can intensify both
external and internal mass transfer created by the cavitation phenomena (high-speed micro-jets formation and high-pressure shock
wave propagation). This makes ultrasound much better than conventional stirring in intensifying the leaching process [22,23].

Fig. 6. SEM photographs of the silica sand and the leached solid samples, conditions of samples are same as those described in Fig. 5.

F. Du et al. / Ultrasonics Sonochemistry 18 (2011) 389393

Table 2
Optical properties and Al, Fe and Ti content in the silica sand and the leached solid
samples.
Samples

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

removal efciency increasing considerably when compared with

conventional stirring method. Sonobleaching of silica sand may
therefore be considered as a competing technology for industry.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (No. 50874087) and the Natural Science Funds (No. BK2006078) in Jiangsu Province of China.
References

3.7. Scanning electron microscopy (SEM) analysis

Fig. 6 shows the SEM images of the silica sand and the leached
solid samples prepared at a reaction temperature of 95 C for
30 min. The presence of mineral coatings (<1 lm) on the ne silica
sand particles (25 lm) is shown in Fig. 6a. The main iron impurities are bonded at the mineral coatings. The surface coatings of the
solid sample become less after leaching by conventional stirring
speed of 500 rpm in solutions containing 4 g/l of oxalic acid
(Fig. 6b). Additionally, some mineral coatings are still on the sand
particles after leaching with water as a leach solvent under ultrasound power of 150 W (Fig. 6d). However, the surface coatings of
the solid sample are almost completely removed after leaching
by ultrasound power of 150 W in solutions containing 4 g/l of oxalic acid (Fig. 6c). The phenomenon can be explained by the act of a
powerful impulse wave, which can peel off mineral coatings from
silica sand into the liquid phase and then iron impurities can react
with oxalic acid easily. This implies that combined ultrasoundaqueous oxalic acid can generate synergistic action. Thus, the iron
from the silica sand surface can be eliminated more efciently by
ultrasound than by conventional stirring. Furthermore, although
the cleaning surface of the leached solid sample is showed in
Fig. 6c, the maximum iron removal efciency is only 75.4%. This
means that the remaining iron impurities are in silica lattice and
are extremely difcult to remove.
3.8. Color measurement analysis
The optical properties and Al, Fe and Ti content in the silica sand
and the leached solid samples are given in Table 2. The silica sand
has a positive values for a and b indicating they are red and yellow. The redness and yellowness can be attributed to some oxide
impurities, such as iron and titanium minerals, which considerably
decrease the whiteness of silica sand. But the leaching treatments
increase the brightness and whiteness and decrease the color values giving an overall improvement in optical properties. Furthermore, the optical properties of the solid sample leached by
ultrasound power of 150 W are found to be superior to that of
the solid sample leached by conventional stirring speed of
500 rpm under a 4 g/l H2C2O4 concentration at 95 C for 30 min.
4. Conclusion
In conclusion, we have found the best conditions for the iron removal from the silica sand under ultrasound irradiation. The method induces a remarkable acceleration for the iron leaching process,
the leach acid concentration reducing dramatically and the

[1] K. Yildirim, H. Cho, L.G. Austin, The modeling of dry grinding of quartz in
tumbling media mills, Powder Technology 105 (1999) 210221.
[2] M. Taxiarchou, D. Panias, I. Douni, I. Paspaliaris, A. Kontopoulos, Removal of
iron from silica sand by leaching with oxalic acid, Hydrometallurgy 46 (1997)
215227.
[3] F. Vegli, B. Passariello, C. Abbruzzese, Iron removal process for high-purity
silica sands production by oxalic acid leaching, Industrial and Engineering
Chemistry Research 38 (1999) 44434448.
[4] S. Ubaldini, L. Piga, P. Fornari, R. Massidda, Removal of iron from quartz sands: a
study by column leaching using a complete factorial design, Hydrometallurgy 40
(1996) 369379.
[5] F. Vegli, B. Passariello, M. Barbaro, P. Plescia, A.M. Marabini, Drum leaching
tests in iron removal from quartz using oxalic and sulphuric acids,
International Journal of Mineral Processing 54 (1998) 183200.
[6] I. tyriakov, I. tyriak, P. Malachovsky, Z. Vecera, D. Kolouek, Bacterial clay
release and iron dissolution during the quality improvement of quartz sands,
Hydrometallurgy 89 (2007) 89106.
[7] I. tyriakov, I. tyriak, I. Kraus, D. Hradil, T. Grygar, P. Bezdicka, Biodestruction
and deferritization of quartz sands by Bacillus species, Minerals Engineering 16
(2003) 709713.
[8] I. tyriakov, I. tyriak, M.P. Nandakumar, B. Mattiasson, Bacterial destruction
of mica during bioleaching of kaolin and quartz sands by Bacillus cereus, World
Journal of Microbiology and Biotechnology 19 (2003) 583590.
[9] M.N.H. Al-Maghrabi, Improvement of low-grade silica sand deposits in Jeddah
Area, Engineering Science 15 (2004) 113128.
[10] A.N. Banza, J. Quindt, E. Gock, Improvement of the quartz sand processing at
Hohenbocka, International Journal of Mineral Processing 79 (2006) 7682.
[11] F. Vegli, Factorial experiments in the development of a kaolin bleaching
process using thiourea in sulphuric acid solutions, Hydrometallurgy 45 (1997)
181197.
[12] G. Patermarakis, Y. Paspaliaris, The leaching of iron oxides in boehmitic
bauxite by hydrochloric acid, Hydrometallurgy 23 (1989) 7790.
[13] M.R. Lanyon, T. Lwin, R.R. Merritt, The dissolution of iron in the hydrochloric
acid leach of an ilmenite concentrate, Hydrometallurgy 51 (1999) 299323.
[14] V.R. Ambikadevi, M. Lalithambika, Effect of organic acids on ferric iron removal
from iron-stained kaolinite, Applied Clay Science 16 (2000) 133145.
[15] A.W.L. Dudeney, I.I. Tarasova, Photochemical decomposition of trisoxalatoiron(III): a hydrometallurgical application of daylight, Hydrometallurgy 47
(1998) 243257.
[16] I.I. Tarasova, A.W.L. Dudeney, S. Pilurzu, Glass sand processing by oxalic acid
leaching and photocatalytic efuent treatment, Minerals Engineering 14
(2001) 639646.
[17] S.O. Lee, T. Tran, Y.Y. Park, S.J. Kim, M.J. Kim, Study on the kinetics of iron oxide
leaching by oxalic acid, International Journal of Mineral Processing 80 (2006)
144152.
[18] S.O. Lee, T. Tran, B.H. Jung, S.J. Kim, M.J. Kim, Dissolution of iron oxide using
oxalic acid, Hydrometallurgy 87 (2007) 9199.
[19] A.D. Farmer, A.F. Collings, G.J. Jameson, Effect of ultrasound on surface cleaning
of silica particles, International Journal of Mineral Processing 60 (2000) 101
113.
[20] H.L. Zhao, D.X. Wang, Y.X. Cai, F.C. Zhang, Removal of iron from silica sand by
surface cleaning using power ultrasound, Minerals Engineering 20 (2007)
816818.
[21] A.D. Farmer, A.F. Collings, G.J. Jameson, The application of power ultrasound to
the surface cleaning of silica and heavy mineral sands, Ultrasonics
Sonochemistry 7 (2000) 243247.
[22] B. Avvaru, S.B. Roy, S. Chowdhury, K.N. Hareendran, A.B. Pandit, Enhancement
of the leaching rate of uranium in the presence of ultrasound, Industrial and
Engineering Chemistry Research 45 (2006) 76397648.
[23] J.B. Ji, X.H. Lu, M.Q. Cai, Z.C. Xu, Improvement of leaching process of Geniposide
with ultrasound, Ultrasonics Sonochemistry 13 (2006) 455462.