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Producing Amorphous White Silica from Rice Husk

Article · January 2009

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MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009
Producing Amorphous White Silica from Rice
Husk
K.A. Matori, M.M. Haslinawati, Z.A. Wahab, H.A.A. Sidek, T.K. Ban, W.A.W.A.K. Ghani
Abstract—- The aim of this paper is to investigate the effects of
various acid treatments of the rice husk (RH) on removal of its
metallic ingredients and determine the percentage of silica and
metallic ingredients contained in the RH. Leaching of RH in
diluted HCl proved to be effective in substantially removing most
of the metallic ingredients. Pre-heat treatment of RH at 500 °C
for 1 hour and continue at 800 °C for 2 hours are required for
complete combustion of RH to white ash. Ash residues obtained
from acid-treated samples were completely white in colours. The
acid treatment of RH does not affect the amorphicity of the silica.
5% HF and 5% HNO3 are used to digest the rice husk ash (RHA).
Inductively coupled plasma was used to characterize the
percentage of the silica and metallic ingredients contained in the
RH.
Index Terms— Digestion, leaching, rice husk, silica.
I. INTRODUCTION
Rice husk (RH) is an agricultural residue abundantly
available in rice producing countries. The annual RH produced
in Malaysia amounts to more than 2 million tons. As an agro
waste material RH is a fibrous material with high silica
content. It is one of the largest readily available but most
under-utilized biomass resources, being an ideal fuel for
electricity generation which producing energy through direct
combustion and/or by gasification. The major constituents of
RH are cellulose, lignin and ash which is unusually high
compared to other biomass fuels. The actual composition is
variable, typically: ash, 20%; lignin, 22%; cellulose, 38%;
pentosans, 18%; and other organics, 2% [1,2]. RH contains
silica ash in the range of 20–25 wt% [3, 4].
This work was supported by Malaysian Ministry of Higher Education
(MOHE) through Research University Grant Scheme (91477).
K.A. Matori (corresponding author phone: 00603-89466653; fax: 00603-
89454454; e-mail: khamirul@science.upm.edu.my), M.M. Haslinawati (e-
mail: dzul_lina@yahoo.com), Z.A. Wahab (e-mail:
zaidan@science.upm.edu.my), and H.A.A. Sidek (e-mail:
sidekaa@science.upm.edu.my) are with Department of Physics, Faculty of
Science, University Putra Malaysia, 43400 UPM Serdang, Selangor,
Malaysia.
T.K.Ban (e-mail: kbtan@science.upm.edu.my), is with
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia,
43400 UPM Serdang, Selangor, Malaysia.
W.A.W.A.K. Ghani (e-mail: wanaz@eng.upm.edu.my) is with
Department of Chemical and Environmental Engineering, Faculty of
Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor,
Malaysia
512
The silica (SiO2) in the RH exists in the hydrated
amorphous form like silica gel. Thermal degradation and
pyrolysis of RH [5], followed by combustion of the char,
results in highly porous and amorphous silica with a varying
percentage of unburnt carbon [6]. Combusted at moderate
temperature, the white ash obtained from RH contains
approximately 92–97% of amorphous silica [7] and some
amount of metallic impurities that can be further removed by a
simple acid-leaching treatment. It has been reported that acid
leaching of the husk helps to obtain relatively pure silica with
high specific surface area [8].
Leaching is an extraction of certain materials from a
carrier into a liquid or removes the impurities of the materials
by dissolving them away from the solids. The chemical
process industries often used organic solvents for leaching
process. Leaching has a variety of commercial applications,
including separation of metal from ore using acid and sugar
from beets using hot water. Chloride can also be leached from
food. The main theory of leaching neglects mechanisms for
holding the material on the solid. Although adsorption and ion
exchange can bind materials tightly to solids, we will simplify
the analysis and consider only dissolving a soluble constituent
away from an insoluble solid such as removing salt from sand
by extraction with water.
Inductively coupled plasma (ICP) is one of the most
important techniques of instrumental elemental analysis. It can
be used for the determination of approximately 70 elements in
a variety of matrices. In this project, ICP- Optical Emission
Spectrometry (OES) machine will be used in order to trace the
elements that contain in RH. ICP-OES is a type of emission
spectrometry (same with ICP-AES) that uses plasma to
produce excited atom that emit electromagnetic radiation at a
wavelength characteristic of particular element [9]. The
intensity of this emission is indicative of the concentration of
the element within the sample.
The silica in the ash undergoes structural
transformations depending on the temperature regime it
undergoes during combustion. The analyses showed that the
highest amount of amorphous silica is present in RH char
combusted at a range of 500–700°C, and at greater
temperatures, crystalline silica is formed [10]. On thermal
treatment, amorphous silica can change to crystalline phase
which can be α-quartz at below 573ºC, β-quartz at 573-870ºC,
β-tridymite at 870-1470ºC and β-cristobalite at 1470-1710ºC
[11]. However, under controlled burning conditions of RH,
amorphous silica with high reactivity, ultra fine size and large
surface area is produced. This micro silica can be a source for
MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009
preparing advanced materials like SiC, Si3N4, elemental Si and
Mg2Si. Due to the high pozzolanic activity, this RH silica also
finds application in high strength concrete as a substitute for
silica fume. The possibility of using this silica as filler in
polymers has been mentioned by Chandrasekhar and co-
workers [2].
II. EXPERIMENTAL PROCEDURE
A. Sample Preparation
The RH was thoroughly washed by distilled water to
remove adhering soil and dust. After that, let it dried in an
oven at 106 °C for 16 h. One part of the RH was untreated and
used as control. Whereas, another part of RH is separated into
3 portions and leached with 1M of HCl, H2SO4 and HNO3
respectively. The leaching process was carried out by heating
the mixture on the hot plate at 70 °C for 2 h. After that, the
mixtures were filtered. The residues are dried in an oven at
120 °C for 24 h.
B. Controlled Combustion of RH
About 5g of the treated and untreated RH was
preheated at 500 °C for 1 h in an electric furnace followed by
further heating at 800 °C for 2 h.
C. Sample Digestion
In this project, the purpose of digestion is digesting
the sample into liquid form for further characterization by
using ICP. Hydrofluoric acid (HF) with HNO3 has been used
to digest RHA. 0.1 g RHA is put into plastic volumetric flask.
12.5 g of concentrated HF is added into the flask and followed
by added 5% HNO3 until 250 g. The concentrated HF will
become 5% and the concentrated of the mixture is 400 ppm.
After digestion, the mixtures are filter and continue by further
dilution. The 400 ppm mixture is diluted to 80 ppm by using
5% HNO3. The digestion steps are repeated by different
sample prepared.
D. Analysis of Chemical Composition in RHA
First, 1000 ppm (part per million) of standard of Si is
poured into sample bottle. Then, 1000 ppm of the standard are
diluted to 100 ppm by using the formula
M 1 V1 = M 2 V2 (1)
Where M1 is the original standard which is 1000 ppm, M2 is
how many part per million that we want to dilute, V1 is the
volume of the standard that need to be found, normally in ml
unit and V2 is the volume of Volumetric Flask, 100ml.
After that, the standard of different ppm (5, 10, 25
and 50ppm) was prepared by diluting the 100 ppm standard
solution with 5% HNO3. The standard for Si must be put into
the plastic container in order to avoid it reacting with the
surface of the glass of Volumetric Flask. 5% HNO3 was used
as a calibration standard when running the sample using the
ICP machine. The concentration of Si was determined with
preparation of standard solution while the other metallic
elements were determined by running multi-element scan by
ICP.
513
E. Sample Characterization and Analysis
For XRD, powdered form of sintered samples were
scanned from 2θ; 20 to 80°, at a scanning rate of 1°/s, using a
X-ray Diffractometer (PANAalytical (Philips) X’Pert Pro
PW3050/60) (with Cu Kα radiation, λ = 0.154 nm) at 40 kV
and 30 mA. The apparent porosity was determined according
to ASTM C 134/95, apparent density according to ASTM C
773/88.
III. RESULTS AND DISCUSSION
Table 1 shows the percentage elements for untreated
and acid-treated RH. Compare the acid-treated samples,
treatment of RH with acid proved to be effective in removing
some metals to a lower level. The percentage of the SiO2 in
untreated RH is 93.67 wt.%. Among the metallic element, the
percentage of K2O is highest which is 1.82 wt.%, follow by
1.45 wt.% Al2O3 and 1.30 wt.% CaO. The percentage of SiO2
obtained from RH treated with HCl is the highest (97.64 wt.%)
compared to untreated and other acid-treated RH. This result is
consistent with studies by Condradt and co-workers [12], who
found that the RH treated with HCl contained higest
percentage of SiO2 compared to other acid-treated samples. It
is also consistent to the results found by Chakraverty and co-
workers [13] who concluded that HCl is superior to removing
metallic elements in RH compared to other acids. This is
because chloride ion (Cl¯) from HCl will protonated the silicon
and formed silicon chloride (SiCl4) during the leaching
process. SiCl4 is insoluble therefore silicon was not removed
during leaching process. The percentage of Na is 0.13 wt.%.
This is because sodium chloride (NaCl), a soluble salt is
formed. While leaching process, the Cl¯ will react to the
metallic element to form salts, calls chlorides. The metallic
chloride will dissolve and remove by filtration.
Treating RH with H2SO4 resulted in the least (97.20
wt.%) amount of SiO2 compared to other acid-treated samples.
The total percentage of metallic elements is highest among the
acid-treated samples. Treatment with H2SO4 is not suitable for
removing some metallic elements present in RH. This is
because of the formation of metallic sulphates, some of which
are not easily soluble in water. This results is consistent with
Chakraverty and co-workers who found that formation of
metallic sulphates caused the percentage of metallic elements
contained in the sample is highest compared to other sample
[13].
For RH treated with HNO3, the percentage of SiO2 is
97.23 wt.% which is higher than H2SO4-treated husk but lower
than HCl-treated husk. The percentage of metallic elements
present in RH samples treated with HCl and HNO3 were found
to be comparable and consistent with studies by Chakraverty
and co-workers [13]. HNO3 however is not suitable for
leaching Fe. Although Fe readily dissolves in dilute nitric acid,
the concentrated acid forms a metal oxide layer that protects
the metal from further oxidation, which is called passivation.
Thus, Fe in this sample is higher than other acid-treated RH.
MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009 514

Table 1. The chemical composition of untreated and treated

RH with acid

treated treated treated

Oxide untreated with with with
Element HCl H2SO4 HNO3
(wt %)
SiO2 93.67 97.64 97.20 97.23
K2O 1.82 0.25 0.25 0.23
Al2O3 1.45 0.24 0.44 0.29
CaO 1.30 0.93 0.89 0.91
MgO 0.57 0.31 0.32 0.29
Fig 2. XRD result for samples after heat treatment at 800 ˚C
Na2O 0.54 0.13 0.40 0.52 for 2 h.
Fe2O3 0.47 0.42 0.43 0.45
Table 2 showed the physical properties of untreated RHA.
MnO 0.09 0.01 0.01 0.01 RHA had a high percentage of porosity and moisture content.
Porous refractory have air entrapped in their pores. The
CuO 0.05 0.05 0.05 0.05
amount of entrapped air increases with porosity of refractory.
ZnO 0.04 0.02 0.01 0.02
Table 2. The physical properties of untreated RHA
The heat treatment for treated and untreated RH to
produce RHA is 500 ˚C, which the RHA was black in colour Properties
(Fig 1(a)). This is caused by the ash contained carbon. After
Density (g/cm3) 0.61
800 ˚C for 2 h, the ash was undergoes completed combustion.
The ash of untreated RH after heat treatment is not complete Apparent porosity (wt %) 79.70
white-yellowish in colour. This indicated that certain metallic
Moisture content (wt %) 62.22
elements possibly will present in the RH. The ash residues
obtained from complete combustion of acid-treated husk Water absorption (wt %) 37.41
samples were white in colour (Fig 1(b)).

IV. CONCLUSIONS

In this study, the chemical contents of RH were

(a) Black ashes (b) White ashes
Fig 1. RHA after heat treated at (a) 500 ˚C and (b) 800 ˚C
Fig 2 shows XRD traces for untreated and acid-
treated RHA after heat treating at 800 ˚C for 2 h, revealed that
the acid treated samples are in amorphous form. This result
shows the acid does not affect the amorphicity of the silica. On
the other hand, the untreated sample is in crystalline form. The
crystal phase obtained from untreated husk is cristobalite.
determined by using ICP. Various types of acid were used in
the leaching process of the RH samples. ICP data shows that,
samples that have undergone acid leaching contained a lower
percentage of metallic elements compared to untreated sample.
HCl leaching of husk is superior to H2SO4 and HNO3 for
removing the metallic elements. It also contained more
percentage of SiO2 compared to other sample.
For heat treatment, the required combustion temperature is 500
˚C and above to produced white ash within a reasonable time
(~1h in this study). By heat treating RHA at 800 ˚C for 2h, all
the carbon contained in RHA (black ash) was removed and an
amorphous white ash is produced. From XRD traces, it is
shown that acid does not affect the amorphicity of the silica.
The peaks (cristobalite) obtained from untreated husk is
caused by the metallic elements that contained in the sample
which might effect the structure of SiO2.
MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009 515

ACKNOWLEDGMENT [12] R. Condradt, P. Pimkhaokham and U. Leela-Adisorn,

The author gratefully acknowledged the University Putra “Nano-structured silica from rice husk,” Journal of
Malausia for the fund provided under Research University Non-crystalline Solids, vol. 145, pp. 75-79, 1992.
grant Scheme (91477). Doi:10.1016/S0022-3093(05)80433-8
[13] A. Chakraverty, P. Mishra and H.D. Banerjee,
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