A simple non-conventional method to extract amorphous silica

from rice husk

C. B. Majumder a,*, Mandeep Sharma a, Gaurav Soni a
a
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, Uttrakhand, India
Received 2 October 2013; received in revised form 20 April 2014; accepted 28 April 2014

Abstract
The paper describes the treatment of rice husk with acid and base, namely, hydrochloric acid
and sodium hydroxide to yield precipitates of silica. As rice husk contains over 80-90% silica when
converted to ash, it becomes important to extract it. A simple non-conventional method for
extracting silica in the amorphous form is based on alkaline extraction followed by acid
precipitation. Rice husk ash was prepared and washed with acid to remove the mineral impurities.
Further, it was treated with sodium hydroxide to form sodium silicate solution. The silicate
solution formed was titrated with hydrochloric acid and precipitation (in the form of gel) formation
takes place below pH 10.

Keywords: Rice husk, Rice husk ash, Silica xerogels, Minerals, Sodium silicate, Sodium hydroxide,
Hydrochloric acid.

1. Introduction Table 1
Composition of Rice husk on dry basis
Current environmental and economic Element Mass Fraction
conditions encourage us to develop and (%)
improve technology to reduce or utilize the Carbon 41.44
agricultural waste in the best possible way. Hydrogen 4.94
One of these wastes is Rice husk. Asia is the Oxygen 37.32
biggest zone for rice production (around 90 Nitrogen 0.57
%) in the world. Silicon 14.66
Rice mills produce bulk amount of rice Potassium 0.59
husk as a by-product which is used as a fuel Sodium 0.035
by the industries to generate energy. Other Sulphur 0.3
than its fuel importance, researcher says that Phosphorous 0.07
rice husk contains high amount of silica in the Calcium 0.06
form of rice husk ash (RHA). Iron 0.006
The Table 1 and Table 2 gives Magnesium 0.003
composition of rice husk and rice husk ash on Zinc 0.006
dry basis.
 Table 2
Composition of Rice husk ash on dry
basis
Elements Mass Fraction
(%)
Alumina 1 2.5
Ferric oxide 0.5
Titanium dioxide Nil
Calcium oxide 12
Magnesium oxide 0.5 2.0
Sodium oxide 0.2 0.5
Potash 0.2
Loss on Ignition 10 20
Silica (SiO2) 80 90
The above composition clearly indicates
silica as a major constituent of the rice husk
ash. As soluble silicates from silica are
widely used in ceramics glass, as adhesives
agents in detergents industries etc., thus it
becomes very important to extract it. Many
experiments have been carried out to extract
silica from rice husk ash (RHA), thus
yielding not only a valuable product but also
solving the problem of large amount of ash
disposal.
Generally, silica is present in gel,
crystalline or amorphous form. Some of its
properties are high specific surface area
(SSA), large pore volume and high reactivity.
There are two types of methods to extract
silica from rice husk. One is Conventional,
which is used in the industries where silica is
produced by smelting quartz in a high
temperature furnace, to produce ultrapure
polycrystalline silicon. Another one is the
Non-conventional method which can be
performed in the lab with the help of some
chemicals. It is based on simple low energy
chemical method for producing pure
amorphous silica by using low temperature
alkali extraction. The concept behind this
method is the low solubility of amorphous
silica at pH below 10. This unique solubility
behavior gives precipitates of silica at a lower
pH. This low energy method could be more
cost effective than the other conventional
methods.
Several authors have reported different
methods for obtaining silica from rice husk.
This paper reports a simple non-conventional
method of extracting silica by carrying out
acid-base treatment followed by the process
of burning to form precipitates of silica. The
silica obtained from this low energy method
is in the form of gel, namely Xerogel which
is mainly used to prepare dense ceramics.
2. Methods
2.1 Raw materials
Rice Husk (RH), Phosphoric Acid
(H3PO4), Hydrochloric Acid (HCl), caustic
soda (NaOH).
2.2 Rice husk ash preparation
The collected rice husk from mill was first
sieved to free it from dust and foreign
material. Then rice husk were several times
(At least 5 times) washed with distilled water
to remove more impurities of soil and dust.
Washed rice husk were dried in a hot air oven
for 24 h at 60C.
Dried Rice husk were carbonized with
40% H3PO4 solution in muffle furnace
maintained at 450 C, for 15 minutes at
volume to weight ratio of 2:1. This leads to
ash formation.
The carbonized rice husk were washed
with distilled water and ringed. They were
dried in hot air oven for 24 h. Dried sample
was crushed to a mesh size of 300m. Thus
the sample we get is nothing but Rice husk
ash. Its completely ash now. The image of
Rice husk and Rice husk ash is shown in
figure 1(a) and 1(b).
2.3 Acid washing
An acid washing step was used to remove
mineral impurities. 10 g of rice husk ash
(RHA) was taken and washed with 100 ml of
2M HCl solution. The solution was shacked
in an Incubator shaker for 2 h.
Further, the solution was filtered through
Whatman No. 42 ashless filter paper and then
RHA residue were washed with 100 ml of
distilled water which dissolves remaining Na,
K, Ca, Mg, Fe and Mn contents present in the
ash. The residue were again dried in hot air
oven for 24 h at 60C. The dried residue were
used for alkaline solubilization.
Fig 1.Rice husk preparation, (a) Rice husk, (b) Rice
husk ash
2.4 Alkaline solubilization
The method of Kamath and Proctor (1998)
was used for extraction of silica from RHA.
100 ml of 1N NaOH solution was prepared to
wash RHA samples and was stirred in a water
bath for 2 h at 80C while being in a covered
250 ml flask. The water bath automatically
boils and rotates the sample at a constant
speed, see figure 2(a).
After constant stirring the solution was
filtered through Whatman No. 42 ashless
filter paper, the carbon residue were washed
with 100 ml distilled water. The filtrates and
washing were allowed to cool down to room
temperature. The filtrate formed in this
process is nothing but sodium silicate
solution, see figure 2(b). The reaction
occurred is as follows:
SiO2 + 2 NaOH ----> Na2SiO3 + H2O
(Ash) (Caustic (Sodium (Water)
soda) silicate)
Fig 2. Alkaline solubilization, (a) RHA+NaOH after
heating in water bath, (b) Sodium silicate solution
after filtration
2.5 Acid titration to form gel precipitates
The sodium silicate solution formed above
is now titrated with 2M HCl solution. As HCl
Concentration increases pH of the solution
decreases. At below 10 pH silica gel
precipitate formation started taking place
(see figure 4(a)) and no gel formation was
observed below 7 pH. The silica gel formed
were aged for 24 h.
The reaction of Sodium silicate solution
with HCl is as follows:
Na2SiO3 + HCl ---> SiO2 + NaCl + H2O
(Sodium (Hydro- (Silica) (Sodium- (Water)
silicate) chloric acid) Chloride)
100 ml deionized water was added to gels and
gels were broken to make a slurry type
solution. The slurry solution was centrifuged
for 15 min at 6000 rpm. The solid gel gets
separates out (see figure 4(b)) and were kept
in a hot air oven for 12 h at 80C to form
xerogels (see figure 4(c)).
A flow diagram of the above procedure is
shown below in figure 3.
2.6 Moisture content of silica gels
Moisture content of the silica gels was
determined using an air oven method. About
1 g of each sample were placed in hot air oven
at 80oC for 2 h. The samples were cooled in a
dessicator and weighed. The weight loss (%)
was recorded as the moisture content of Wash Rice husk with distilled water(5 times) and dry (24 hr)
sample.
Add 40% H3PO4 at 450C

Crush the Rice husk ash(RHA) (300m)

Disperse RHA (10 g) in 2M HCL(100 ml)

Stir (2 hr)

Filter (Whatman 42)

Figure 3: (a) Silica gel precipitate formation, (b) Silica
Wash residue with distilled water(100 ml) and dried (24 hr)
gel after centrifuge, (c) Silica xerogel after drying
Disperse residue in 1 N NaOH(100 ml)
2.7 XRD Analysis of silica gel
Boiled with stirring (1 hr)

X-ray diffraction patterns were obtained Filter (Whatman 42)

by a dual goniometer Xpert XRD system
Wash residue with boiling distilled water (100 ml)
(Institute Instrumentation Center, IIT
Roorkee) using an acceleration voltage of 40 Collect filtrate and allowed to cool (24 hr)
kV and current of 45 mA. The diffraction
Titrate filtrate with 2M HCL (pH 7)
angle was scanned from 10o to 90o 2h, at a
rate of 5o/ min. The X-ray diffraction patter is Allow the gel to age (24 hr)
shown in figure 5. The pattern shows pick at
Add water (100 ml) and make slurry
22o which is an indication of amorphous
silica. Centrifuge the slurry at 6000 rpm (15 min)

Dry at 80C
2.8 FTIR Analysis of silica gel
Xerogel
Fourier transform infrared (FTIR) data
Wash with water and dry at 80C
were obtained by adding 100 interferograms
using an Impact 410 Nicolet instrument Purified silica
(Chemical Engineering Department, IIT Figure 4: Flow diagram of the procedure used to
Roorkee). See figure 6 for FTIR pattern. extract silica from RHA.

3. Result and Discussion

Silica obtained from rice husk was white in

color, X ray diffraction analysis shows a peak
at an angle of 20-22o which shows that silica
is in amorphous form. Many times washing
with distilled water shows minimum amount
of contaminants of Ca, Mg, K, Sulphur etc.
The purity of extracted silica is above 85-
90% with some Sodium (Na) impurity
present inside. Figure 5: X-ray diffraction pattern of obtained silica.
 [3] Hui L., Hui-gang X., Jie Y., and Jinping O.,
Microstructure of cement mortar with nano
particles, Composites part B: engineering, 2003;
35: 185-189.

[4] Kalapathy U., Proctor A. and Shultz J.,

An Improved method for production of silica
from rice hull ash, Bioresource Technology,
2000; 85: 285-289.

[5] Qing Y., Zhang Z., Kong D., and Chen R.,
Influence of nano-SiO2 addition on properties of
hardened cement paste as compared with silica
Figure 6: Fourier transform infrared spectra of silica
produced from RHA
fume, Contruction and Building Materials, 2007;
21: 539-545.
4. Conclusions [6] Jal P K., Sudarshan M., Saha A., Sabita P.,
and Mishra B.K., Synthesis and characterization
This study revealed that silica xerogels of nanosilica prepared by precipitation method,
with more than 90% silica content and Colloidals and Surface, 2004; 240: 173-178.
minimal mineral contaminants can be
produced from RHA using a simple low
energy chemical method. The initial acid
washing of RHA resulted in a lower Ca
content in the silica xerogel. The final
washing of the xerogel led to a silica product
with lower Na, and K contents. Incorporation
of initial acid washing of RHA and final
washing of the xerogel resulted in a pure
silica with total Na, K, and Ca contents of
<0.1%.

Acknowledgements

We wish to thank shiv rice mill,

bahadrabad (Production manager) for
providing Rice husk.
References

[1] Della V.P., Kuhn I. and Hotza D., Rice husk

ash as an alternate source for active silica
production, Materials Letters, 2000; 57: 818-821.
[2] Kalapathy U., Proctor A. and Shultz J., A
Simple method for production of pure silica from
rice hull ash, Bioresource Technology, 2000;
73: 257-262.