MASAUM Journal of Basic and Applied Sciences, Vol. 1, No.

3, October 2009 512

ducation (MOHE) through Research University Grant Scheme (91477).
K.A. Matori (corresponding author phone: 00603-89466653; fax:
0603- 89454454; e-mail: ​khamirul@science.upm.edu.my​), M.M.
aslinawati (e- mail: ​dzul_lina@yahoo.com​), Z.A. Wahab (e-mail:
aidan@science.upm.edu.my​), and H.A.A. Sidek (e-mail:
dekaa@science.upm.edu.my) are with Department of Physics, Faculty of
cience, University Putra Malaysia, 43400 UPM Serdang, Selangor,
alaysia.
T.K.Ban (e-mail: ​kbtan@science.upm.edu.my​), is with
epartment of Chemistry, Faculty of Science, Universiti Putra Malaysia,
3400 UPM Serdang, Selangor, Malaysia.
W.A.W.A.K. Ghani (e-mail: ​wanaz@eng.upm.edu.my​) is
ith Department of Chemical and Environmental Engineering, Faculty of
​ he aim of this paper is to investigate the effectsngineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor,
Abstract​—​- T
alaysia
of various acid treatments of the rice husk (RH) on removal of
its metallic ingredients and determine the percentage of silica The silica (SiO​2​) in the RH exists in the
and metallic ingredients contained in the RH. Leaching of RH
in diluted HCl proved to be effective in substantially removinghydrated amorphous
​ form like silica gel. Thermal
most of the metallic ingredients. Pre-heat treatment of RH atdegradation and pyrolysis of RH [5], followed by combustion
500 °C for 1 hour and continue at 800 °C for 2 hours are
of the char, results in highly porous and amorphous silica
required for complete combustion of RH to white ash. Ash
with a varying percentage of unburnt carbon [6]. Combusted
residues obtained from acid-treated samples were completely
white in colours. The acid treatment of RH does not affect theat moderate temperature, the white ash obtained from RH
contains approximately 92–97% of amorphous silica [7] and
amorphicity of the silica. 5% HF and 5% HNO​3 ​are used to
some amount of metallic impurities that can be further
digest the rice husk ash (RHA). Inductively
​ coupled plasmaremoved by a simple acid-leaching treatment. It has been
was used to characterize the percentage of the silica andreported that acid leaching of the husk helps to obtain
relatively pure silica with high specific surface area [8].
metallic ingredients contained in the RH. ​Index Terms​—
Leaching is an extraction of certain materials
Digestion, leaching, rice husk, silica. 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
I. I​NTRODUCTION eaching process. Leaching has a variety of commercial
applications, including separation of metal from ore using
Rice husk (RH) is an agricultural residueacid and sugar from beets using hot water. Chloride can also
abundantly available in rice producing countries. The annualbe leached from food. The main theory of leaching neglects
RH produced in Malaysia amounts to more than 2 millionmechanisms for holding the material on the solid. Although
tons. As an agro waste material RH is a fibrous material withadsorption and ion exchange can bind materials tightly to
high silica content. It is one of the largest readily availablesolids, we will simplify the analysis and consider only
but most under-utilized biomass resources, being an idealdissolving a soluble constituent away from an insoluble solid
fuel for electricity generation which producing energy throughsuch as removing salt from sand by extraction with water.
direct combustion and/or by gasification. The major Inductively coupled plasma (ICP) is one of the
constituents of RH are cellulose, lignin and ash which ismost important techniques of instrumental elemental
unusually high compared to other biomass fuels. The actualanalysis. It can be used for the determination of
composition is variable, typically: ash, 20%; lignin, 22%;approximately 70 elements in a variety of matrices. In this
cellulose, 38%; pentosans, 18%; and other organics, 2%project, ICP- Optical Emission Spectrometry (OES) machine
[1,2]. RH contains silica ash in the range of 20–25 wt% [3, 4].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
This work was supported by Malaysian Ministry of Higher emit electromagnetic radiation at a wavelength characteristic
 of particular element [9]. The intensity of this emission temperatures,
is crystalline silica is formed [10]. On thermal
indicative of the concentration of the element within the treatment, amorphous silica can change to crystalline phase
sample. which can be α-quartz at below 573oC, β-quartz at
The silica in the ash undergoes structural 573-870oC, β-tridymite at 870-1470oC and β-cristobalite at
transformations depending on the temperature regime 1470-1710oC
it [11]. However, under controlled burning
undergoes during combustion. The analyses showed that the conditions of RH, amorphous silica with high reactivity, ultra
highest amount of amorphous silica is present in RH char fine size and large surface area is produced. This micro
combusted at a range of 500–700°C, and at greater silica can be a source for

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
MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009 513
In this project, the purpose of digestion is
igesting the sample into liquid form for further
preparing advanced materials like SiC, Si​3​N​4​, elemental Siharacterization by using ICP. Hydrofluoric acid (HF) with
NO​3 ​has been used to​ digest RHA. 0.1 g RHA is put into
and Mg​
​ 2​Si. Due to the high pozzolanic activity, this RH silica
lastic volumetric flask. 12.5 g of concentrated HF is added
also ​ finds application in high strength concrete as a
nto the flask and followed by added 5% HNO​3 ​until 250 g.
substitute for silica fume. The possibility of using this silica
as filler in polymers has been mentioned by Chandrasekharhe concentrated HF will become ​ 5% and the concentrated
and co- workers [2]. f the mixture is 400 ppm. After digestion, the mixtures are
ter and continue by further dilution. The 400 ppm mixture is
II. EXPERIMENTAL PROCEDURE
iluted to 80 ppm by using 5% HNO​3​. The digestion steps
A. Sample Preparation
re repeated by different sample
​ prepared.
The RH was thoroughly washed by distilled
water to remove adhering soil and dust. After that, let it dried
. Analysis of Chemical Composition in RHA
in an oven at 106 °C for 16 h. One part of the RH was
First, 1000 ppm (part per million) of standard
untreated and used as control. Whereas, another part of RH
f Si is poured into sample bottle. Then, 1000 ppm of the
is separated into 3 portions and leached with 1M of HCl,
tandard are diluted to 100 ppm by using the formula
H​2​SO​4 ​and HNO​3 respectively. The leaching process was
​
VMVM ​ = ​ (1) ​
carried out by heating the mixture on the hot plate at 70 °C 11 ​ 22 ​ Where M​1 ​is the original
for 2 h. After that, the mixtures were filtered. The residues
are dried in an oven at 120 °C for 24 h. tandard which is 1000 ppm, M​2 ​is how
​ many part per million

hat we want to dilute, V​1 ​is the volume

​ of the standard that
B. Controlled Combustion of RH
About 5g of the treated and untreated RH waseed to be found, normally in ml unit and V​2 ​is the volume of
preheated at 500 °C for 1 h in an electric furnace followed by
further heating at 800 °C for 2 h. olumetric Flask, 100ml.
After that, the standard of different ppm (5, 10,
C. Sample Digestion 5 and 50ppm) was prepared by diluting the 100 ppm
 n RH compared to other acids. This is because chloride ion
standard solution with 5% HNO​3​. The standard for Si must
(Cl ̄) from HCl will protonated the silicon and formed silicon

be put into the

​ plastic container in order to avoid it reactingchloride (SiCl​
4​) during the leaching process.
​ SiCl​4 ​is insoluble
with the surface of the glass of Volumetric Flask. 5% HNO​3
therefore silicon was not removed during ​ leaching process.
was used as
​ a calibration standard when running the sampleThe percentage of Na is 0.13 wt.%. This is because sodium
using the ICP machine. The concentration of Si waschloride (NaCl), a soluble salt is formed. While leaching
determined with preparation of standard solution while theprocess, the Cl ̄ will react to the metallic element to form
other metallic elements were determined by runningsalts, calls chlorides. The metallic chloride will dissolve and
multi-element scan by ICP. remove by filtration.
E. Sample Characterization and Analysis
For XRD, powdered form of sintered samples Treating RH with H​2​SO​4 ​resulted in the least
were scanned from 2θ; 20 to 80°, at a scanning rate of 1°/s,
using a X-ray Diffractometer (PANAalytical (Philips) X’Pert (97.20 wt.%)
​ amount of SiO​2 ​compared to other acid-treated

Pro PW3050/60) (with Cu Kα radiation, λ = 0.154 nm) at 40

samples. The ​ total percentage of metallic elements is
kV and 30 mA. The apparent porosity was determined highest among the acid-treated samples. Treatment with
according to ASTM C 134/95, apparent density according to
ASTM C 773/88. H​2​SO​4 ​is not suitable for removing
​ some metallic elements
present in RH. This is because of the formation of metallic
III. RESULTS AND DISCUSSION sulphates, some of which are not easily soluble in water.
This results is consistent with Chakraverty and co-workers
Table 1 shows the percentage elements for who found that formation of metallic sulphates caused the
untreated and acid-treated RH. Compare the acid-treated percentage of metallic elements contained in the sample is
samples, treatment of RH with acid proved to be effective highest in compared to other sample [13].
removing some metals to a lower level. The percentage of
For RH treated with HNO​3​, the percentage of
the SiO​2 ​in untreated
​ RH is 93.67 wt.%. Among the metallic
SiO​2 ​is 97.23
​ wt.% which is higher than H​2​SO​4​-treated husk
element, the percentage of K​2​O is highest which is 1.82
but lower than ​ HCl-treated husk. The percentage of metallic
wt.%, follow by ​ 1.45 wt.% Al​ 2​O​3 ​and 1.30 wt.% CaO. The elements present in RH samples treated with HCl and HNO​3

were found to
percentage of SiO​2 ​obtained from RH treated with HCl is the ​ be comparable and consistent with studies by

highest (97.64 wt.%) ​compared to untreated and other Chakraverty and co-workers [13]. HNO​3 ​however is not
acid-treated RH. This result is consistent with studies by
Condradt and co-workers [12], who found that the RH suitable for leaching
​ Fe. Although Fe readily dissolves in
treated with HCl contained higest percentage of SiO​dilute 2
nitric acid, the concentrated acid forms a metal oxide
ayer that protects the metal from further oxidation, which is
compared to other acid-treated samples. It is
​ also consistent
called passivation. Thus, Fe in this sample is higher than
to the results found by Chakraverty and co- workers [13] whoother acid-treated RH.
concluded that HCl is superior to removing metallic elements
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
untreated
treated with HCl

treated with H​2​SO​4

treated Oxide Element
 with HNO​3 (wt
​ %)

SiO​2 ​93.67 97.64 97.20 97.23 K​

​ 2​O 1.82 0.25 0.25 0.23
Al​2​O​3 ​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

Na​2​O 0.54 0.13 0.40 0.52

Fe​2​O​3 ​0.47 0.42 0.43 0.45

MnO 0.09 0.01 0.01 0.01
CuO 0.05 0.05 0.05 0.05 ZnO 0.04 0.02 0.01 0.02
The heat treatment for treated and untreated RH to produce RHA is 500 ̊C, which the RHA was black in
colour (Fig 1(a)). This is caused by the ash contained carbon. After 800 ̊C for 2 h, the ash was undergoes
completed combustion. The ash of untreated RH after heat treatment is not complete white-yellowish in
colour. This indicated that certain metallic elements possibly will present in the RH. The ash residues
obtained from complete combustion of acid-treated husk samples were white in colour (Fig 1(b)).
(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.
Fig 2. XRD result for samples after heat treatment at 800 ̊C
for 2 h.
Table 2 showed the physical properties of untreated RHA. RHA had a high percentage of porosity and
moisture content. Porous refractory have air entrapped in their pores. The amount of entrapped air increases
with porosity of refractory.
Table 2. The physical properties of untreated RHA
Properties
Density (g/cm​3​) 0.61
Apparent porosity (wt %) 79.70
Moisture content (wt %) 62.22
Water absorption (wt %) 37.41
IV. CONCLUSIONS
In this study, the chemical contents of RH were 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 H​2​SO​4 ​and HNO​3 ​for removing

​ the metallic elements. It also contained more percentage of SiO​2

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 SiO​2​.
MASAUM Journal of Basic and Applied Sciences, Vol. 1, No. 3, October 2009 515
 Non-crystalline Solids, ​vol. 145, pp. 75-79, 1992.
Doi:10.1016/S0022-3093(05)80433-8 [13] A. Chakraverty, P.
A​CKNOWLEDGMENT ​The author Mishra and H.D. Banerjee, “Investigation of combustion of
gratefully acknowledged the University Putra Malausia for raw and acid-leached rice husk for production of pure
the fund provided under Research University grant Scheme amorphous white silica,” ​Journal of Materials Science, ​vol.
(91477). 23, pp. 21- 24, 1988. Doi:10.1007/BF01174029

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