Carbon 42 (2004) 785794

www.elsevier.com/locate/carbon

Evolution of chemistry and morphology during the carbonization

and combustion of rice husk
Tzong-Horng Liou *

Department of Chemical Engineering, Hsiuping Institute of Technology, 11 Gungye Road, Dali City, Taichung 412, Taiwan, ROC
Received 21 June 2003; accepted 14 January 2004

Abstract
Both ne carbon/silica and pure silica powders can be obtained by carbonization and combustion of rice husk under non-iso-
thermal conditions, and the products can be used for preparation of high-quality ceramic materials. Studies on the morphology,
chemical and physical characteristics of products were carried out by N2 -adsorptionmeter, SEM, XRD, FTIR, ICP-MS and EA.
Results indicate that decreasing the heating rate increased the specic surface area, pore volume and pore diameter. At a heating rate
of 5 C/min, the specic surface areas of both the carbon/silica and pure silica powders were 261 and 235 m2 /g, and the average pore
diameters were 2.2 and 5.4 nm, respectively. The products obtained from various heating rates were all amorphous. Thermo-
gravimetric analysis was employed to study the reaction characteristics during carbonization or combustion, indicating that
decomposition process of rice husk could be divided into three temperature zones. This results of the study can also provide the
important information on the recovery of biomass material from rice husk.
2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon precursor; B. Carbonization, Combustion; C. Thermal analysis; D. Microstructure

1. Introduction addition, by burning the rice husk in air, a ultrane

Fine and porous carbon/silica (C/SiO2 ) powder has
attracted much attention as a starting material for
preparation of high-quality ceramic powders, such as
silicon nitride (Si3 N4 ) and silicon carbide (SiC) [14],
which are good for application in high temperature
material engineering, especially for turbine engines. In
addition, small scale of pure silica (SiO2 ) powder can be
widely used in electronics, ceramic and polymer indus-
tries, such as thixotropic agents, thermal insulators,
composite llers, etc. [57]. Generally, these two pow-
ders can be prepared by the solgel method [811].
However, this preparation method has high raw mate-
rials costs. In contrast, rice husk, a form of agricultural
biomass, is a potential source of energy and value-added
byproducts. Its major constituents are organic materials
and silica. After carbonization of the rice husk in a
nitrogen atmosphere, uniformly mixed carbon/silica
powder with very high surface area can be obtained. In
*
Tel.: +886-4-24961198; fax: +886-4-24961187.
E-mail address: liouth@mail.hit.edu.tw (T.-H. Liou).
0008-6223/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.01.050
silica powder of high purity can also be prepared. These
can be used as good raw materials for the production of
ne ceramic powders [1217]. Apart from these appli-
cations, rice husk can be used as a renewable source of
thermal energy [1820]. This process has the benet not
only of producing valuable ceramic materials but also
for recovering energy and reducing pollution problems.
The major constituents in rice husk are cellulose,
hemicellulose, lignin and silica (
20 wt.%). However,
the reported compositions of rice husk dier widely, as
aected by the type of paddy and climate [21]. There
have been several reports on the carbonization (or
pyrolysis) of rice husk [2224] or its combustion [2527].
The selected parameters include the various rice husk
sources, grain sizes, acid-leaching process, caking or
burning temperature and time, etc. Conventional prac-
tice on the carbonization of rice husk is performed in a
ow stream of nitrogen at a temperature ranging be-
tween 300 and 900 C. However, the combustion of rice
husk is performed in either air or O2 at a temperature
ranging between 300 and 700 C. Real et al. [28] found
that leaching of rice husks with an acid solution before
their combustion would yield silica powder of high
786 T.-H. Liou / Carbon 42 (2004) 785794
specic surface area. However, if the acid-leaching was
performed after combustion, the specic surface area of
silica would be poor. Sharma and Rao [19] studied the
carbonization of rice husk in both grain and powder,
carried out under isothermal and non-isothermal con-
ditions. They found that carbonization proceeded in two
distinct temperature zones with a transition at 350 C.
Conradt et al. [16] reported that nanostructured silica
could be obtained by chemical pre-treatment of rice
husk with enzyme. Hanna et al. [20] found that addition
of iron to the rice husk could increase the volatile matter
evolved during the carbonization process. Moreover, the
iron could also act as an inhibitor for the crystallization
of silica and carbon, leading to an increase in the rate
of silicon carbide formation at higher temperatures.
The operating variables of carbonization or com-
bustion of rice husk have been investigated in previous
studies. However, the thermal characteristics of decom-
posed rice husk including pore structure analysis under
non-isothermal condition have not received much atten-
tion. In the present investigation, rice husk is treated
with an optimum acidic solution, and then heated in
both nitrogen and air to produce porous materials with
high specic surface area. The eect of heating rates (5,
10, 15, 20 C/min) on the pore structure and thermal
characteristics of products is extensively discussed. The
thermal degradation of rice husk in both nitrogen and
air was investigated using a technique of thermogravi-
metric analysis (TGA).
These results of this study describe a potentially
attractive method to produce valuable silicon nitride,
silicon carbide and silica powders, as well as the man-
ufacture of supported-metal catalyst, zeolite and acti-
vated carbon with high value of specic surface area
[2931]. This method also helps to solve the disposal and
pollution problems of the rice milling industry.
2. Experimental
2.1. Material used and sample preparation
Rice husk obtained from a rice mill, was thoroughly
washed with distilled water to remove dust and dried in
an air oven. Hydrochloric acid used as the acid treat-
ment to remove metal impurities was chemically pure
quality (Merck & Co.). The water-rinsed rice husk was
impregnated with hydrochloric acid solution and boiled
at 100 C for 1 h, and then was washed with distilled
water to remove acid, and the pH level rose to about 7.
It was nally dried at 100 C.
For the carbonization process, carbon/silica powder
was prepared by coking the rice husk under nitrogen
atmosphere. A weighed amount of acid-leached husk
was placed in a xed bed reactor, which was made of
quartz with an inner diameter of 2.5 cm. The reaction
temperature ranged between ambient temperature and
900 C, using heating rates of 5, 10, 15, 20 C/min. For
the combustion process, pure silica powder was obtained
by burning the rice husk in air. The acid-leached husk
was placed in the quartz reactor at room temperature.
The temperature was increased to 700 C with heating
rates of 520 C/min. All gases were purchased from
San-Fu Chem. Co., and had a high purity of 99.999%.
2.2. Analysis of physical and chemical properties
The samples were characterized by Brunuer, Emmett
and Teller (BET) surface area, pore volume and pore
diameter. The measurement of pore characteristics was
carried out at 77 K using the adsorption of nitrogen
gas (Micrometric, model ASAP 2010).
The crystalline structures of reactant and product
were examined by X-ray diractometer (Siemens, model
D-500) using Cu-Ka ray and a scan speed of 2.5/min.
Fourier infrared spectrometer (Shimadzu, model FTIR-
8300) was used to further examine the composition of
samples. Morphological features of reactant and prod-
uct were obtained with a scanning-electron microscope
(Topcon, model ABT-150S).
The amounts of metallic impurities in the rice husk
samples were estimated by an inductively coupled plas-
ma-mass spectrometer (Kontron Plasmakon, model
S-35). A Heraeus elemental analyzer was used on the
rice husk samples to determine the amounts of funda-
mental organic element and ash.
2.3. Thermal analysis
Results for the thermal characteristics of the rice husk
were obtained using a PerkinElmer TGA 7 thermo-
gravimetric analyzer [32]. To ensure that the reaction
was free from interparticle heat and mass transfer
resistances, the initial sample weights were retained
within 6 0.2 mg and the acid-leached husk was ground
to pass through a 325 mesh ASTM standard sieve. The
weight of the sample was recorded against temperature
as the sample was heated a rate below 20 C/min. The
ow rate of N2 and air was xed at 60 ml/min. The
remaining amount of rice husk decomposed in N2 or air
is dened here as W =W0 , the W0 and W represent initial
and instantaneous mass of sample, respectively. The
TG and DTG curves were recorded simultaneously
along with temperature rise.
3. Results and discussion
3.1. Analysis of metallic impurities and organic elements
In our previous study [33], it was shown that the rice
husk leached with 3 M HCl had higher purity. In this
 T.-H. Liou / Carbon 42 (2004) 785794 787

Table 1
Amount of metallic ingredients as oxides (ppm) in rice husk for both before and after thermal decomposition of samples
Water Acid C/SiO2 (C/min)c SiO2 (C/min)d
rinseda leachedb 5 10 15 20 5 10 15 20
Mg 4680 110 378 496 508 797 84 222 86 65
Ca 15,460 5600 2050 2260 2280 2305 1810 1480 2000 1630
Fe 750 210 <10 <10 116 137 <10 <10 45 84
Na 3550 40 48 174 500 593 <10 <10 <10 345
K 8970 40 310 322 348 395 <10 122 <10 37
P 5430 260 359 544 669 746 30 256 151 514
Mn 1800 20 <10 <10 <10 <10 <10 <10 <10 <10
Zn 200 <10 <10 <10 <10 <10 <10 <10 <10 <10
Total 40,840 6290 3175 3826 4441 4993 1974 2120 2322 2695
a
Sample was water-rinsed and un-heated.
b
Sample was acid-leached and un-heated.
c
Samples were acid-leached and heated in N2 at various heating rates.
d
Samples were acid-leached and heated in air at various heating rates.

report, the HCl was used as acid-leaching agent. Table 1
illustrates the eect of heating rate on the residual
amounts of metallic ingredients in both carbonization
and combustion of rice husk samples. For all the ash
samples, the concentration of calcium is greatest. As
expected, the impurity content in acid-leached sample is
much lower than that in water-rinsed sample, indicating
that acid-leaching of the rice husk helps to remove most
of the metallic impurities. This decrease in impurities
can be attributed to the dissolution of metals in acid,
after which the metals are removed by ltration. Addi-
tionally, after heating the rice husk in N2 or air, the
impurity content is lower than that in acid-leached
sample, indicating that the metals are also probably
carried out from the volatiles during thermal decom-
position. For the carbonization process, the total resid-
ual amount of metallic ingredients from a low heating
rate is smaller than that from a high one. The same trend
is also observed for the combustion process. By com-
paring the purity of the two products, the silica samples
have higher purity than that of carbon/silica sam-
ples. The resulting purity is better than 99.7% for silica,
and 99.5% for carbon/silica. These are the important
renewable sources for producing good-quality ceramic
powders, and similar results have also been reported by
the other researchers [16,28,34].
Elemental analysis was used to investigate the ele-
ment change before and after thermal decomposition of
rice husk. Table 2 indicates that the percentage com-
positions of H and O elements in the carbonized or
burnt husk were lower than those in un-heated husks.
Hamad [35] reported that the decrease in the oxygen and
hydrogen contents may be attributed to the formation of
water vapor, carbon dioxide, formic and acetic acid.
However, the ash content clearly increased after car-
bonization or combustion process due to the decline in
the oxygen and hydrogen contents of the rice husk. In
the carbon/silica samples, it is observed that the carbon
content slightly increased, while the ash content de-
creased with increasing heating rate.
By comparing the carbon/silica molar ratio in the
carbonized husk, it was found that the carbon/silica
molar ratio increased with increasing the heating rate.
During carbothermal reduction reaction, excess carbon
is commonly required to increase the formation rate of
Si3 N4 or SiC [36,37]. The theoretical molar ratio of
carbon to silica is 2 for the formation of Si3 N4 and 3 for
SiC. When rice husk was carbonized at 520 C/min in

Table 2
Elemental composition (wt.%) of rice husk for both before and after thermal decomposition of samples
Water rinseda Acid leachedb C/SiO2 (C/min)c SiO2 (C/min)d
5 10 15 20 5
C 42.95 38.01 44.94 46.17 47.55 47.77 <0.10
H 6.01 5.28 1.41 1.42 1.75 1.15 <0.10
O 40.62 36.10 0.92 3.94 4.22 5.67 <0.20
N 2.68 1.94 1.28 0.87 1.60 0.83 <0.01
Ash 7.74 18.67 51.45 47.60 44.88 44.58 99.59
C/SiO2 (molar ratio) 27.74 10.18 4.37 4.85 5.30 5.36 0
a
Sample was water-rinsed and un-heated.
b
Sample was acid-leached and un-heated.
c
Samples were acid-leached and heated in N2 at various heating rates.
d
Sample was acid-leached and heated in air at 5 C/min heating rate.
788 T.-H. Liou / Carbon 42 (2004) 785794
N2 , a mixture of carbon and silica in a proportion of
4.45.4 was obtained, which is suitable for use as a
starting material in the preparation of Si3 N4 or SiC
powder. These ndings are in agreement with the pre-
vious observation for the preparation of Si3 N4 from
acid-leached and carbonized rice husk in a nitrogen
atmosphere by Liou and Chang [38]. The role of carbon
in the formation of Si3 N4 is to act as a reducing agent to
promote the nitridation reaction, and also to provide a
source of active sites at which the Si3 N4 can nucleate.
3.2. Analysis of pore structures
The nitrogen adsorptiondesorption isotherms of
samples obtained both before and after heating the rice
husk in N2 or air are shown in Fig. 1. For water-rinsed
and acid-leached samples, Fig. 1(a) and (b) shows lower
nitrogen adsorption capacity and no apparent desorp-
tion hysteresis, indicating that the porosity of the two
raw materials is relatively lower than that of heat-trea-
ted husk samples. For carbonized and burnt husk
samples, Fig. 1(c) and (d) shows that the isotherms are
of type I according to the IUPAC classication. The
hysteresis loops (associated with capillary condensation)
found in both samples are of various shapes. The car-
bon/silica isotherm displays a sharp knee and a narrow
loop, while the silica sample reveals a broad knee and a
more obvious loop. In the low-pressure region, the silica
isotherm follows the same path as the silica/carbon
isotherm, but at a certain point the silica isotherm begins
to deviate upward while the carbon/silica isotherm is
Fig. 1. Adsorptiondesorption isotherms before and after thermal
decomposition of specimens. (a) Water-rinsed husk, (b) acid-leached
husk, (c) carbonized husk in N2 at 5 C/min heating rate, (d) burnt
husk in air at 5 C/min heating rate.
nearly horizontal. When the saturation vapor pressure is
approached, the amount adsorbed show an upward
turn. According to these observations, the carbon/silica
sample is mainly microporous with narrow pore size
distribution, and the silica sample contains both mi-
cropores and mesopores [39,40]. It can also be seen that
the carbon/silica sample has lower nitrogen adsorption
capacity than the silica sample, indicating a decrease in
pore volume. These can be explained by the evolution of
volatiles and the decomposition of organic matter dur-
ing carbonization, thus leaving a highly microporous
structure. However, for combustion process, the gasi-
cation reaction occurs much more drastically than that
of carbonization process. In addition, the widening or
collapsing micropores during the removal of carbon
matter results in an increase in mesopores as well as
adsorptive volume. The same adsorption behavior was
also observed by James and Rao [41] for isothermal
heating of rice husk at various temperatures in the range
of 300900 C. They proposed that pore opening of
rice husk takes place probably due to the conversion of
silanol groups to siloxane bridge.
Fig. 2 shows a plot of pore size distribution calculated
using the BarrettJoynerHalenda (BJH) method. The
water-rinsed husk sample shows a narrow peak at the
pore diameter of about 3 nm, slightly smaller than that
of acid-leached husk sample, which has a value of 3.5
nm. The carbon/silica sample has a peak at about 4.0
nm. However, a double peak is observed in the silica
sample at about 2.5 and 4.0 nm, which is similar to the
results reported by Real et al. [28]. The increment of
pore volume (dVp =dDp ) in the water-rinsed and acid-
leached samples is much smaller than that of the carbon/
silica and pure silica samples. These pores are mainly
developed within the particles by the thermal decom-
position procedure.
The specic surface area, pore volume and average
pore diameter on rice husk samples before and after
thermal treatment are illustrated in Table 3. The water-
rinsed husk has a specic surface area of only 1.45 m2 /g,
whereas that of the acid-leached husk is increased to
10.39 m2 /g. The result indicates that the acid can help to
decompose the organic matter in the rice husk. Com-
paring the specic surface area before and after thermal
decomposition shows an obvious increase. The carbon/
silica and pure silica samples are highly porous materials
which have a larger internal surface area. When rice
husk was carbonized in N2 , the specic surface area of
carbon/silica powder decreased with heating rate
increasing from 5 to 20 C/min. The same trend is also
observed in the silica samples. This decrease in specic
surface area can be attributed to the portion of the pores
that were destroyed, and also to the variation in pore
structure. For the carbonization process, the maximum
surface area of carbon/silica samples is 261 m2 /g, which
occurs at a heating rate of 5 C/min. Comparatively, the
 T.-H. Liou / Carbon 42 (2004) 785794 789

Fig. 2. Dierential pore size and cumulative pore volume distribution before and after thermal decomposition of specimens. (a) Water-rinsed husk,
(b) acid-leached husk, (c) carbonized husk in N2 at 5 C/min heating rate, (d) burnt husk in air at 5 C/min heating rate.

Table 3
Surface area and pore characteristics of rice husk for both before and after thermal decomposition of samples
Water Acid C/SiO2 (C/min)c SiO2 (C/min)d
rinseda leachedb 5 10 15 20 5 10 15 20
BET surface area (m2 /g) 1.45 10.39 261 247 238 231 235 233 229 185
Total pore volume (ml/g) 0.005 0.025 0.146 0.135 0.129 0.115 0.318 0.313 0.307 0.248
Micropore volume (ml/g) 0.000 0.000 0.100 0.096 0.094 0.095 0.104 0.101 0.086 0.072
Mesopore volume (ml/g) 0.000 0.007 0.018 0.016 0.011 0.003 0.167 0.164 0.175 0.137
Macropore volume (ml/g) 0.005 0.018 0.028 0.023 0.024 0.017 0.047 0.048 0.046 0.039
Average pore diameter (nm) 11.10 9.56 2.23 2.18 2.15 1.98 5.42 5.47 5.27 5.36
a
Sample was water-rinsed and un-heated.
b
Sample was acid-leached and un-heated.
c
Samples were acid-leached and heated in N2 at various heating rates.
d
Samples were acid-leached and heated in air at various heating rates.

acid-leached rice husk carbonized in N2 atmosphere
kept under isothermal condition (900 C) had a surface
area of 261 m2 /g [38], which is the same as the present
observation. However, for the combustion process, the
maximum surface area of silica samples is 235 m2 /g. As
shown in Table 3, the total pore volume of the water-
rinsed sample is much smaller than that of the acid-
leached husk sample. However, the pore volume
increases steeply when rice husk is heated in N2 or air.
In the carbonized and burnt husk samples, the micro-
pore, mesopore and total pore volume decrease with
increasing heating rate. The decrease in pore volume is
probably due to a severe gasication reaction. In addi-
tion, the micropores are predominantly formed in car-
bon/silica samples, while the mesopores and micropores
are well mixed in the silica samples. The water-rinsed or
acid-leached sample has a larger average pore diameter
(by BET method) than the carbon/silica and pure silica
samples. The average pore diameters of carbon/silica
and pure silica samples range from 1.98 to 2.23 and 5.27
to 5.47 nm, respectively, both increasing with decrease
in heating rate. A comparison of the results of pore
790 T.-H. Liou / Carbon 42 (2004) 785794
structure analysis shows that the pore volume and
average pore diameter of silica samples are clearly
higher than those of carbon/silica samples. Conversely,
the carbon/silica sample has higher BET surface area
values. This is because the removal of carbon atoms
during combustion results in the elimination of pore
walls, leading to a increase in mesopore volume and
pore diameter. However, the increase in BET surface
area in the carbon/silica samples is mainly due to the
remarkable increase in micropores. This conclusion is
also supported by Fig. 1.
3.3. Analysis of physical properties
Fig. 3 shows X-ray diraction analysis on rice husk
before and after thermal decomposition in N2 or air. All
samples are amorphous, although a broad peak centered
at 2h 22:5 is typical of silica. These results agree
with those obtained in other studies [20,42]. However,
Hamad and Khattab [43] mentioned that cristobalite
was detected at 800 C when rice husk was burnt in air.
At 1150 C, both cristobalite and tridymite were present.
Fig. 4 shows IR patterns of both coked and burnt
husk samples after ring in N2 and air at a heating rate
of 5 C/min. As can be seen, the two samples have the
same absorption peaks at
475,
805 and 1115 cm1 .
The positions of this feature are the same as those from
silica in a commercial grade. The results are probably
because the silicon atom initially attaches to the oxygen
atom in rice husk [17]. After the rice husk has been
thermal decomposed, the combination of silicon and
oxygen atoms then leads to the formation of amorphous
Fig. 3. X-ray diractogram of rice husk. (a) Water-rinsed husk, (b)
acid-leached husk, (c) carbonized husk in N2 at 5 C/min heating rate,
(d) burnt husk in air at 5 C/min heating rate.
Fig. 4. FTIR spectrogram of rice husk. (a) Carbon/silica sample ob-
tained from carbonization of rice husk in N2 at 5 C/min heating rate,
(b) silica sample obtained from combustion of rice husk in air at 5 C/
min heating rate.
silica. In addition, it can be also observed that the silica
sample has a sharper peak than that of the carbon/silica
sample, indicating that the percentage of silica content
is increased when the rice husk is burnt in air. This
observation is consistent with the result of element
analysis, as indicated in Table 2.
Fig. 5 shows SEM photomicrographs of thermal
decomposed rice husk and nitrided specimen. From Fig.
5(a) and (b), it can be observed that the corrugated outer
epidermis and thin lamellar inner epidermis cracked
when rice husk was decomposed under nitrogen atmo-
sphere. This phenomenon may be due to the fact that
silica deposited in the husk is most highly concentrated
in the inner and outer surfaces of the epidermal tissue
[44]. Patel et al. [17] further pointed that rice husk has a
fairly rigid structural backbone formed by silicon, to
which the monosaccharides are bonded. Furthermore,
Fig. 5(c) shows that many ne pores were created in the
interior structure of the thermally decomposed husk,
which appears to be consistent with the pore charac-
teristic analysis (Fig. 1) showing a highly pore structure.
Fig. 5(d) shows the lamellar structure of the silica de-
posit obtained from combustion of rice husk in air. The
silica skeleton is not damaged by controlling thermal
decomposition of rice husk at relatively low heating rate.
Similar microstructural features have also been reported
[45], leading to the conclusion that the distribution of
silica in the husk is not haphazard, but follows a set
pattern. The carbon/silica obtained from carbonization
of rice husk in N2 is black, whereas the silica obtained
from combustion of rice husk in air is white. The two
materials are both highly brittle and easily converted
 T.-H. Liou / Carbon 42 (2004) 785794 791

Fig. 5. Scanning-electron micrographs of rice husk. (a) Outer epidermis of carbonized rice husk, (b) inner epidermis of carbonized rice husk,
(c) powder of thermal decomposed specimen, (d) cross-section of specimen obtained from combustion of rice husk in air, (e) crystalline silica
observed at a nearby crucible, (f) nitrided products at a heating rate 5 C/min from 1200 to 1450 C.

into an ultrane powder with very soft grinding in an
agate mortar [16,28,32]. After heating the husk in N2
beyond 1100 C, Fig. 5(e) shows that small amounts of
ne needle shape and crystalline silica are observed at a
nearby crucible. The formation indicates that an inter-
mediate (SiO) is probably generated by reaction of
carbon and silica, then further reacting with trace O2
(perhaps from N2 ) to form the crystalline silica [46]. Fig.
5(f) shows that ne gray silicon nitride whiskers are
formed when carbonized husk reacts with N2 at a
heating rate of 5 C/min from 1200 to 1450 C. The
width ranges between 50 and 100 nm. X-ray analysis
reveals that the nitrided-husk sample was mainly an a-
type silicon nitride powder. It is generally believed that
the formation of silicon nitride from carbon/silica is
completed in two stages. In the rst stage, the SiO
792 T.-H. Liou / Carbon 42 (2004) 785794
intermediate was generated from the carbon/silica solid.
In the second stage, the SiO further reacts with excess
carbon or carbon monoxide to form silicon nitride
powder [47].
3.4. Analysis of reaction characteristics
The TG curves in Fig. 6 show the remaining weight
(W =W0 ) from the carbonization of rice husk at 50900
C for dierent heating rates. The results indicate that
the mass loss of rice husk carbonized in N2 occurs in
three temperature zones. The curves show an initial
slight weight loss up to
150 C, followed by thermal
decomposition. This could be due to the elimination of
physically absorbed water in the rice husk. The mass
loss occurring in the range of 150375 C may be
associated with the removal of volatile matter. The
volatiles generated in this zone were attributed to the
decomposition of organic materials. The mass loss in
the range of 375800 C corresponds to the carboniza-
tion process, which may be attributed to further reac-
tions involving the intermediate. The eects of heating
rate on the derivative of weight (dW =dt) of rice husk
carbonized in N2 are also shown in Fig. 6 (DTG curves).
Comparing the results shows that the peak height and
position depend markedly on the heating rate. Increas-
ing the heating rate is accompanied with increase in
peak height, implying that the carbonization rate of rice
husk at higher heating rate is faster than that at a lower
one. These results are in close agreement with those
reported by the other workers [19,48].
The TGA plots of rice husk combustion obtained
from various heating rates are shown in Fig. 7. The
thermal decomposition eect is evident in the samples
heated at 50600 C. Same as the carbonization process,
Fig. 6. Eect of heating rate on the carbonization of the specimen: N2
ow rate, 60 ml/min; sample loading, 6 mg; initial grain size, 3845 lm.
Fig. 7. Eect of heating rate on the combustion of the specimen: air
ow rate, 60 ml/min; sample loading, 6 mg; initial grain size, 3845 lm.
the mass loss of rice husk combusted in air occurs also in
three temperature zones, namely 50150, 150325 and
325600 C. These results are similar to those previously
reported [49], where the decomposition of rice husk in
static air was divided into four zones, including a tran-
sition stage in the range 150250 C. The DTG curves in
Fig. 7 show that the peak height and position are very
sensitive to the heating rate, and there is an overlap
of two peaks in each heating rate.
By comparing Figs. 6 and 7, it can be observed that
the carbonized husk samples have a longer reaction
temperature range and lower reaction rate, compared to
burnt husk samples. With increases in heating rate, the
peak temperatures (which correspond to the maximum
rate of mass loss) for the carbonized husk samples are
higher than those of burnt husk samples. Fig. 8 illus-
trates the change in the amounts of volatile matter
(DW =W0 ) as a function of heating time at a heating rate
of 5 C/min for rice husk decomposing in N2 or air
environment. It can be seen that the amount of volatile
matter evolved from the burnt husk sample is greater
than that from the carbonized husk sample. The weight
loss of both carbonized and burnt husk samples at about
70 min is almost the same. However, the dierence is
clearly increased when the reaction is proceeded beyond
70 min, indicating that the decomposition mechanism of
rice husk during carbonization at the initial stage is
similar to that during combustion. The mechanism in
the initial stage is probably the decomposition of or-
ganic materials into smaller molecules, and then the
release of the gaseous volatiles. When the reaction has
been proceeded for a period, the carbonization or
combustion reaction begins to occur, so dierent weight
loss is observed at the later stage, probably due to car-
bon being removed when the rice husk is burnt in air.
 T.-H. Liou / Carbon 42 (2004) 785794
Fig. 8. The change in the amounts of volatile matter as a function
of heating time for carbonization and combustion of rice husk at
5 C/min heating rate.
The overall decomposition behavior of rice husk was
reported to be due to decomposition of hemicellulose,
cellulose and lignin [50,51]. Mansaray and Ghaly [48]
reported that the hemicellulose and cellulose compo-
nents of the rice husk were the main contributors to the
evolution of the volatile compounds, while lignin is
mainly responsible for the char portion of the product.
In this present study on the carbonization or combus-
tion behavior of rice husk, it can be deduced from these
observations that decomposition of hemicellulose starts
rst, followed by the cellulose and nally by the lignin.
The gaseous volatiles were released from organic mate-
rials (hemicellulose, cellulose and lignin) during thermal
decomposition. The nal solid product (or char) for the
carbonization process is composed of a mixture of car-
bon and silica, and for the combustion process it is
a pure silica powder.
4. Conclusions
The carbonization and combustion of acid-leaching
ground rice husk under non-isothermal conditions was
investigated to obtain ne and high purity carbon/silica
and silica powders. The eect of heating rate on the
thermal characteristics of products was studied. The
surface area, pore volume and pore diameter of heat-
treated husk were increased with decreases in heating
rate. The micropore fraction of carbon/silica sample was
higher than that of silica sample. The carbonization and
combustion nature of rice husk was examined using ther-
mogravimetry, indicating that thermal decomposition
793
proceeds in three temperature zones. The carbonized
husk samples have longer reaction temperature range
and lower reaction rate compared to burnt husk samples.
The results of this study are useful for the preparation of
valuable ceramic materials, and also provide a funda-
mental knowledge on the recovery of biomass material
from rice husk.
Acknowledgements
The author expresses thanks to the National Science
Council of Taiwan for its nancial support under Pro-
ject no. NSC 89-2214-E164-001.
References
[1] Meng GW, Cui Z, Zhang LD, Phillipp F. Growth and charac-
terization of nanostructured b-SiC via carbothermal reduction of
SiO2 xerogels containing carbon nanoparticles. J Cryst Growth
2000;209:80116.
[2] Sternitzke M. Review: structural ceramic nanocomposites. J Eur
Ceram Soc 1997;17:106182.
[3] Han W, Fan S, Li Q, Gu B, Zhang X, Yu D. Synthesis of silicon
nitride nanorods using carbon nanotube as a template. Appl Phys
Lett 1997;71:22713.
[4] Weimer AW, Nilsen KJ, Cochran GA, Roach RP. Kinetics of
carbothermal reduction synthesis of beta silicon carbide. AIChE J
1993;39:493503.
[5] Wu G, Wang J, Shen J, Yang T, Zhang Q, Zhou B, et al.
Properties of solgel derived scratch-resistant nano-porous silica
lms by a mixed atmosphere treatment. J Non-Cryst Solids
2000;275:16974.
[6] Tanner PA, Yan B, Zhang H. Preparation and luminescence
properties of solgel hybrid materials incorporated with europium
complexes. J Mater Sci 2000;35:43258.
[7] Sadasivan S, Rasmussen DH, Chen FP, Kannabiran RK.
Preparation and characterization of ultrane silica. Colloids Surf
A: Physicochem Eng Aspects 1998;132:4552.
[8] Tomozawa M, Kim DL, Lou V. Preparation of high purity, low
water content fused silica glass. J Non-Cryst Solids 2001;296:1026.
[9] Li J, Tian J, Dong L. Synthesis of SiC precursors by a two-step
solgel process and their conversion to SiC powders. J Eur Ceram
Soc 2000;77:18537.
[10] Preiss H, Berger LM, Braun M. Formation of black glasses and
silicon carbide from binary carbonaceous/silica hydrogels. Carbon
1995;33(12):173946.
[11] Russel-Floyd RS, Harris B, Cooke RG, Laurie J, Hammet FW,
Jones RW, et al. Application of solgel processing techniques for
the manufacture of ber-reinforced ceramics. J Am Ceram Soc
1993;76:263543.
[12] Sun L, Gong K. Silicon-based materials from rice husks and their
applications. Ind Eng Chem Res 2001;40:586177.
[13] Gorthy P, Pudukottah GM. Production of silicon carbide from
rice husks. J Am Ceram Soc 1999;82:1393400.
[14] Krishnarao RV, Mahajan YR, Kumar TJ. Conversion of raw rice
husks to SiC by pyrolysis in nitrogen atmosphere. J Eur Ceram
Soc 1998;18:14752.
[15] Weimer AW, Cassiday JR, Susnitzky DW, Black CK, Beaman
DR. Carbothermal nitridation synthesis of a-Si3 N4 powder from
pyrolyzed rice hulls. J Mater Sci 1996;31:600513.
794 T.-H. Liou / Carbon 42 (2004) 785794
[16] Conradt R, Pimkhaokham P, Leela-Adison U. Nano-structured
silica from rice husk. J Non-Cryst Solids 1992;145:759.
[17] Patel M, Karere A, Prasanna P. Eect of thermal and chemical
treatments on carbon and silica contents in rice husk. J Mater Sci
1987;22:245764.
[18] Williams PT, Nugranad N. Comparison of products from the
pyrolysis and catalytic carbonization of rice husks. Energy
2000;25:493513.
[19] Sharma A, Rao TR. Kinetics of pyrolysis of rice husk. Bioresour
Technol 1999;67:539.
[20] Hanna SB, Farag LM, Mansour NAL. Pyrolysis and combustion of
treated and untreated rice hulls. Thermochim Acta 1984;81:7786.
[21] Govindarao VMH. Utilization of rice huska preliminary
analysis. J Sci Ind Res 1980;39:495515.
[22] Teng H, Wei YC. Thermogravimetric studies on the kinetics of
rice hull pyrolysis and the inuence of water treatment. Ind Eng
Chem Res 1998;37:380611.
[23] Wang N, Low MJD. Spectroscopic studies of carbons. The
charring of rice hulls XVIII. Mater Chem Phys 1990;26:11730.
[24] Patel M, Prasanna P. Scanning electron microscopic studies
of heat-treated rice husk. X-ray Spectrom 1989;18:2679.
[25] Della VP, Kuhn I, Hotza D. Rice husk ash as an alternate source
for active silica production. Mater Lett 2002;57:81821.
[26] Kalapathy U, Proctor A, Shultz J. A simple method for
production of pure silica from rice hull ash. Bioresour Technol
2000;73:25762.
[27] Luan TC, Chou TC. Recovery of silica from the gasication of
rice husks/coal in the presence of a pilot ame in a modied
uidized bed. Ind Eng Chem Res 1990;29:19227.
[28] Real C, Alcala MD, Criado JM. Preparation of silica from rice
husks. J Am Ceram Soc 1996;79:20126.
[29] Chang FW, Tsay MT, Kuo MS, Yang CM. Characterization of
nickel catalysts on RHA-Al2 O3 composite oxides prepared by ion
exchange. Appl Catal A 2002;226:21324.
[30] Hamdan H, Muhid MNM, Endud S, Listiorini E, Ramli Z. Si
MAS NMR, XRD and FESEM studies of rice husk silica for the
synthesis of zeolites. J Non-Cryst Solids 1997;211:12631.
[31] Yalcin N, Sevinc V. Studies of the surface area and porosity of
activated carbons prepared from rice husks. Carbon
2000;38:19435.
[32] Liou TH. Preparation and characterization of nano-structured
silica from rice husk. Mater Sci Eng A 2004;364:31323.
[33] Liou TH, Chang FW, Lo JJ. Pyrolysis kinetics of acid-leached rice
husk. Ind Eng Chem Res 1997;36:56873.
[34] Chakraverty A, Mishra P, Banerjee HD. Investigation of
combustion of raw and acid-leached rice husk for production of
pure amorphous white silica. J Mater Sci 1988;23:214.
[35] Hamad MA. Thermal characteristics of rice hulls. J Chem
Technol Biotechnol 1981;31:6246.
[36] Durham STP, Shanker K, Drew RAL. Carbothermal synthesis of
silicon nitride: eect of reaction conditions. J Am Ceram Soc
1991;74:317.
[37] Chen CY, Lin CI, Chen SH. Kinetics of synthesis of silicon
carbide by carbothermal reduction of silicon dioxide. Br Ceram
Trans 2000;99(2):5762.
[38] Liou TH, Chang FW. The nitridation kinetics of pyrolyzed rice
husk. Ind Eng Chem Res 1996;35:337583.
[39] Park SJ, Jung WY. Preparation of activated carbons derived from
KOH-impregnated resin. Carbon 2002;40:20212.
[40] Oh GH, Park CR. Preparation and characteristics of rice-straw-
based porous carbons with high adsorption capacity. Fuel
2002;81:32736.
[41] James J, Rao MS. Characterization of silica in rice husk ash.
Am Ceram Soc Bull 1986;65:117780.
[42] Proctor A. X-ray diraction and scanning electron microscope
studies of processed rice hull silica. J Am Oil Chem Soc
1990;67:57684.
[43] Hamad MA, Khattab IA. Eect of the combustion process on the
structure of rice hull silica. Thermochim Acta 1981;48:3439.
[44] Sharma NK, Williams WS, Zangvil A. Formation and structure
of silicon carbide whiskers from rice hulls. J Am Ceram Soc
1984;67:71520.
[45] James J, Rao MS. Silica from rice husk through thermal
decomposition. Thermochim Acta 1986;97:32936.
[46] Chen SH, Lin CI. Eect of contact area on synthesis of silicon
carbide through carbothermal reduction of silicon dioxide.
J Mater Sci Lett 1997;16:7024.
[47] Liou TH, Chang FW. Kinetics of carbothermal reduction and
nitridation of silicon dioxide/carbon mixture. Ind Eng Chem Res
1995;34:11827.
[48] Mansaray KG, Ghaly AE. Thermal degradation of rice husks in
nitrogen atmosphere. Bioresour Technol 1998;65:1320.
[49] Chakraverty A, Mishra P, Banerjee HD. Investigation of thermal
decomposition of rice husk. Thermochim Acta 1985;94:26775.
[50] Williams PT, Besler S. The pyrolysis of rice husk in a thermo-
gravimetric analyzer and ststic batch reactor. Fuel 1993;72:1519.
[51] Antal MJ. Biomass pyrolysis: a review of the literature. Part
1carbohydrate pyrolysis. Adv Solar Energy 1983;11:61111.