Powder Technology 217 (2012) 497–501

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

A recyclable method for production of pure silica from rice hull ash
Xiaoyu Ma, Bing Zhou, Wei Gao, Yuning Qu, Lili Wang, Zichen Wang, Yanchao Zhu ⁎
College of Chemistry, Jilin University, Changchun 130012, China

a r t i c l e i n f o a b s t r a c t

Article history: A recyclable technology was proposed for preparation of silica powder using rice hull ash and NH4F. The silica
Received 29 March 2011 in rice hull ash was dissolved into NH4F solution to produce (NH4)2SiF6 and NH3. The silica powder was
Received in revised form 16 September 2011 precipitated when (NH4)2SiF6 solution was added to NH3·H2O. The microstructure and morphology analysis
Accepted 12 November 2011
of the precipitated silica powders were characterized using transmission electron microscopy (TEM). The
Available online 25 November 2011
preparation conditions and the recyclable process were explored experimentally. The yield of silica reached
Keywords:
up to 94.6% and the particles were spherical with the diameter of 50–60 nm. Most importantly, all the
Silica powder reactants and byproducts were recyclable in this process.
Rice hull ash © 2011 Elsevier B.V. All rights reserved.
Ammonium fluoride
Recyclable technology

1. Introduction
Rice hull ash (RHA), rich in silica at about 65% is one of the waste
products when burning rice hull to generate energy, but it can be used
as an economically viable raw material for production of silica gels and
powders [1]. Silica has been widely used in vegetable oil refining [2,3],
pharmaceutical products, detergents, adhesives, chromatograph column
packing and ceramics [4]. Various methods have been reported for pre-
paring silica materials in the literatures, such as plasma synthesis [5],
chemical vapor deposition [6], sol–gel processing [7,8], microemulsion
processing [9], combustion synthesis [10] and hydrothermal technique
[11]. Meanwhile, a series of methods have been investigated for recover-
ing amorphous silica from rice hull [12,13] and RHA [14–18].
The traditional industrial method of preparing silica is that sodium
carbonate powder reacts with quartz sand at high temperature to
form the sodium silicate, and then the obtained sodium silicate reacts
with sulfuric acid in order to precipitate silica. This method was
hazardous to the environment because that 0.23 ton of carbon dioxide
(CO2), 0.74 ton of sodium sulfate and 20 tons of wastewater have been
produced during the preparation of 1 ton of silica by using 0.51 ton of
sulfuric acid and 0.53 ton of sodium carbonate. In recent years, one of
the world's primary concerns is the “greenhouse” effect, especially
relating with CO2 [19]. The main disadvantages of the traditional tech-
niques bring the high energy consumption and heavy pollution. The
processes produce large quantities of CO2 and inorganic salts, which
have limited their large-scale commercial applications and violated
the principle of sustainable development. It is believed that a cheaper
and environmental-benign route to produce silica powder with desir-
able materials attracts much more attention.
⁎ Corresponding author. Tel.: + 86 431 85155358; fax: +86 431 85155358.
E-mail address: yanchao_zhu@jlu.edu.cn (Y. Zhu).
A new and recyclable technique for the formation of silica powder
is proposed in our present work. All the reactants and byproducts are
recyclable in this process, and no pollutants are released to the envi-
ronment. Therefore, the recyclable technology is propitious to reduce
polluting emission. It is believed that the silica powder is obtained by
the following reactions [22].
6NH4 F þ SiO2 →ðNH4Þ2 SiF6 þ 4NH3 þ 2H2 O ðaÞ
ðNH4Þ2 SiF6 þ 4NH3 þ ðn þ 2ÞH2 O→6NH4 F þ SiO2 ↓ þ nH2 O ðbÞ
The process of silica dissolution and precipitation is described by
the reaction (a) and (b), respectively.
2. Materials and methods
A flow diagram of the procedure is shown in Fig. 1. RHA and NH4F
solution were added to the reactor to produce (NH4)2SiF6 solution
and NH3. NH3 was recycled by receiver to produce NH3·H2O which
was used for the next step. And then, the solid RHA residue and liquid
were filtrated by solid–liquid separator. The solid RHA residue was
washed with deionized water and dried at 393 K. The filtrate was
added to NH3·H2O under stirring in mixer. After aging for a period
of time, silica was precipitated. The followed slurry was filtrated by
solid–liquid separator. The filtrate mainly contained NH4F solution,
which was then added to concentrator to adjust the concentration.
The water, produced from concentrator, was returned to the
receiver for absorbing NH3 and the NH4F solution was returned for
reactivation as the reactant. The precipitate was washed several
times by deionized water and then dried to obtain silica powders.

0032-5910/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2011.11.009
498 X. Ma et al. / Powder Technology 217 (2012) 497–501

and reactivated as the reactant. The yield of silica was calculated as

the following equation:

Weight of silica obtained

Yield of silica ðwt:% Þ ¼  100%
Weight of silica in RHA

2.4. Experimental design and statistical analyses

The main factors influencing the dissolution rate of silica are the con-
centration, cycle index of NH4F solution, reaction temperature and reac-
tion time [21]. The variables in the process were shown as below: the
content of NH4F solution was 2, 3, 4 and 5 mol/L; the cycle index of
NH4F solution was 1, 2, 3, and 4; temperature of reaction was 373, 383,
393, 403, 413 and 423 K; reaction time was 1, 2, 3, 4 and 5 h, respectively.

2.5. Characterizations

Mineral composition of the RHA was determined by atomic emis-

Fig. 1. Flow diagram of the procedure used to produce silica from RHA.
2.1. Materials
RHA was obtained from a power plant near Haerbin, China in the
autumn of 2009, and porphyrized to 60 meshes. The proximate and
ultimate analysis of RHA used in this study is given in Table 1.
2.2. Reagents
All chemicals used in the synthetic procedures of this work were
purchased from the Beijing Chemicals Co. Ltd, which were of analyti-
cal grade. Deionized water was applied for all synthesis and treat-
ment processes.
2.3. Preparation of pure silica powder
2.3.1. Acid washing
The acid washing step was used to remove the small quantities of
minerals prior to extract silica from RHA as the following method
[20]. 100 g of RHA samples was dispersed in superfluous hydrochloric
acid (HCl) with the mass fraction of 10%. The dispersion was boiled
with stirring for 2 h and filtered. The RHA residues were washed by
deionized water until pH = 7.0 and dried at 393 K for 12 h. The resi-
dues were used for silica extraction.
2.3.2. Silica extraction
An appropriate concentration of NH4F solution and 2 g of acid
washed RHA samples were added to a 250 ml reactor to dissolve
the silica by constantly stirring at certain temperature to produce
(NH4)2SiF6 solution. The dispersion was rapidly filtrated after reac-
tion for a period of time, and the carbon residues were washed by
50 ml deionized water and then dried at 393 K for 12 h. NH3 pro-
duced during the reaction was collected by 100 ml deionized water
to form the NH3·H2O.
The filtrate was added to NH3·H2O with an appropriate concentra-
tion under stirring at 333 K–363 K. After reaction for a period of time,
the resulting slurry was kept aging for 3 h at 333 K, and then filtered.
The precipitate was washed by deionized water several times and
then dried in vacuum at 353 K for 12 h. The filtrate was collected
sion measurements using ICP emission spectroscopy (Perkin-Elmer
Optima 3300 DV).
Fourier transform infrared (FT-IR) spectroscopy (Shimadzu FTIR
8400) was obtained with the KBr method.
X-ray diffractometer (XRD) measurements were carried out (SHI-
MADZU XRD-6000) employing Ni-filtered Cu-Kα radiation. The diffrac-
tion angle was scanned from 10° to 80°, 2θ, at a scanning rate of 5°/min.
Component of silica powder was investigated by EDAX (EDAX
Genesis 2000) attached to FE-SEM. Prior to analysis, a thin layer of
gold was sputtered on the samples to enhance conductivity.
The sizes of silica powder were tested by a transmission electron
microscope (TEM, Hitachi H-800).
3. Results and discussion
3.1. Silica dissolution
Factors, such as reaction temperature (heating temperature, the
same as below), time, concentration, and cycle index of NH4F solution
could influence the synthesis of pure silica. Therefore, those factors
were investigated, respectively.
3.1.1. Effect of reaction time
The reaction was performed at 393 K with the concentration of
NH4F 4 mol/L. The reaction time was varied at a range of 1–5 h. The
yield of silica increased with increasing the reaction time, and it
reached the maximum value between 2 and 3 h. However, slight
decrease of yield has been observed when the reaction time was
longer than 3 h, as seen in Fig. 2. The influence of reaction time

Table 1
Chemical composition of RHA.

Element Si C K Ca Na Mg Al Zn Fe Cu Mn
wt.% 65 28 0.81 0.42 0.29 0.13 0.16 0.12 0.15 0.00025 0.64
Fig. 2. Effect of reaction time on yield of silica.
 X. Ma et al. / Powder Technology 217 (2012) 497–501 499

Table 2
Effect of the cycle index of NH4F solution on yield of silica.

Cycle index of NH4F solution 1 2 3 4

Yield of silica (wt.%) 94.6 93.1 92.3 92.3

of NH4F solution. The reaction (a) and reaction (b) are reversible
reaction. The increase of the concentration of reactant (NH4F) was
propitious to reaction (a) and dissolution of silica. However, Fig. 4
shows that the yield of silica has no significant increase when the
concentration of NH4F solution is more than 4 mol/L, which was
because most of silica in RHA was dissolved in NH4F solution.

3.1.4. Effects of the cycle index of NH4F solution

Fig. 3. Effect of reaction temperature on yield of silica.
might be explained by the fact that the silica in RHA needed at least
2 h to dissolve away.
In order to investigate the effect of the cycle index of NH4F solu-
tion on the yield of silica, the reactions were performed repeatedly
with the NH4F solution of 4 mol/L at 393 K for 2 h varying the cycle
index of NH4F solution from 1 to 4. The yield of silica does not obvi-
ously decrease with increasing the cycle index of NH4F solution as
shown in Table 2, which confirms that the reactant is recyclable in
this process.

3.1.2. Effect of reaction temperature

In order to investigate the effect of reaction temperature on the
yield of silica, the NH4F solution with concentration of 4 mol/L and
2 g of acid washed RHA samples were added to a 250 ml reactor for
2 h with constantly stirring at different temperatures from 373 K to
423 K. Fig. 3 shows that the yield of silica increases obviously with in-
creasing reaction temperature from 373 K to 383 K, increases slowly
at 383 K–393 K and has no significant change at a higher reaction
temperature above 393 K. The influence of reaction temperature on
the yield of silica might be explained that reaction (a) is an endother-
mal reaction and reaction (b) is an exothermal reaction. Higher tem-
perature was propitious to reaction (a) and also propitious for NH3
escape from the reaction system, which promoted the production of
(NH4)2SiF6 solution, resulting in a high yield of silica. This is in confor-
mity with the principle of reaction kinetics.

3.1.3. Effect of the concentration of NH4F solution

In order to investigate the effect of the concentration of NH4F
solution on the yield of silica, the reaction was performed at 393 K
for 2 h varying the concentration of NH4F at a range of 2–5 mol/L. Fig. 5. Fourier transform infrared spectra of silica produced from RHA.
The yield of silica increased with the increase of the concentration

Fig. 4. Effect of amount-of-substance concentration of NH4F on yield of silica. Fig. 6. X-ray diffraction pattern of silica produced from RHA.
500 X. Ma et al. / Powder Technology 217 (2012) 497–501
Fig. 7. EDAX spectrometric data of silica produced from RHA.
3.2. FT–IR spectrum of the Silica produced from RHA
As shown in Fig. 5, the absorption bands at 467, 799, and
1059 cm − 1 are attributed to the consequence of stretching and bend-
ing vibrations of silica [23,24]. The peak at 937 cm − 1 is attributed to
silanol Si–OH stretching vibration group of silica [25,26]. Fig. 5 also
shows absorption bands at 3431 and 1639 cm − 1 that were due to
the H–O–H stretching and bending modes of the adsorbed water,
respectively. There were no other absorption bands. Therefore, the
FT-IR confirmed that the powders consisted of the pure silica
particles.
3.3. X-ray diffraction pattern of pure silica produced from RHA
The X-ray pattern in Fig. 6 shows a broad peak centered at 2θ
angle of 22°, which is typical amorphous solids, and confirms the
absence of any ordered crystalline structure.
3.4. EDAX spectrometric data of silica produced from RHA
EDAX could be used for the analysis of the element component of
powder. Fig. 7 shows a typical EDAX elemental analysis of silica
produced from RHA. The powder is consisted of Si element and O
element without any other impurity elements, which is reasonably
matched with FT-IR spectra in Fig. 5. The small quantities of minerals
in the RHA could be washed out easily due to the step of acid washing.
Fig. 7 confirms that the powders are consisted of silica with high
purity.
Fig. 8. TEM micrographs of the silica powders.
3.5. TEM micrograph of silica produced from RHA
Fig. 8 shows TEM micrograph of the silica powder. It had been
observed that the particles were spherical with the diameter of
50–60 nm.
4. Conclusion
Silica powder could be prepared at low cost using RHA and NH4F
by the above method. The optimum preparation conditions were
determined to obtain the silica powder with nanometer, narrow
size distribution, sphere in shape, and high purity without impurity.
It was found that the desired powder could be synthesized at reaction
temperature of 393 K for 3 h, with NH4F of 4 mol/L. The recyclability
of the process was confirmed experimentally. Meanwhile, the
obtained yield of silica reached up to 94.6%, and the particles were
spherical with the diameter of 50–60 nm.
Acknowledgements
This work was supported by the Key Project of the National
Eleventh Five-Year Research Program of China (2008BAE66B00) and
the Scientific and Technological Planning Project of Jilin Province
(20075009).
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