Industrial Crops and Products 43 (2013) 291–296

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Industrial Crops and Products

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Nanosilica from rice husk: Extraction and characterization

V.B. Carmona a,b , R.M. Oliveira b , W.T.L. Silva b , L.H.C. Mattoso a,b , J.M. Marconcini a,b,∗
a
Departamento de Engenharia dos Materiais, Universidade Federal de São Carlos, São Carlos, SP, Brazil
b
Laboratório Nacional de Nanotecnologia aplicada ao Agronegócio (LNNA), EMBRAPA Instrumentação (CNPDIA), São Carlos, SP, Brazil

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

Article history: Rice husk are generated from the rice cultivation. Silica is the major inorganic constituent of the rice
Received 15 December 2011 husk, and by carrying out an acid chemical treatment followed by the process of burning, it is possible
Received in revised form 20 June 2012 to extract high-surface area amorphous silica. This paper reports the extraction and characterization of
Accepted 21 June 2012
nanosilica from two types of rice husk, namely agulhinha and cateto, using milder acid solutions. Thermo-
gravimetry was used to characterize the burning behavior and to determine the activation energies. FT-IR
Keywords:
results showed a good peak correlation between the commercial silica and burnt rice husk residue. There
Rice husk
were found both nano- and microparticles with a large particle size distribution. The results showed the
Nanosilica
Thermogravimetry
potential of silica extraction from rice husk, and additionally exhibited lower levels of corrosion damage
Activation energy to the reactor that generated weak acid residues due to the use of milder acid solutions.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Rice culture stands by the production and cultivated area, play-
ing a strategic role in the world economy. In 2005, about 620 mi ton
of rice was produced in an area of 160 mi hectares all around the
world. Nearly 90% of the entire rice culture is grown and consumed
in Asia. Brazil appears to be the world’s 9th producer, which means
13.1 mi ton of rice (http://sistemasdeproducao.cnptia.embrapa.
br/FontesHTML/Arroz/ArrozTerrasAltasMatoGrosso/index.htm),
resulting in about 2.5 mi ton of rice husk from the rice process-
ing.Rice husk is a by-product of the rice milling industry resulting
in problems associated with management of solid waste, which if
not handled adequately, should attract disease-carrying animals,
increasing the risk of fire, or even occupying large spaces in landfill
sites (Teng et al., 1997). Another common destination is the
disposal in rivers releasing methane during the decomposition,
which is a greenhouse gas. Rice husk studies are not recent and
have attracting attention of many researches, including patents
(Amick, 1982; Della et al., 2006; De Souza et al., 1999, 2002;
Hanna et al., 1984; Real et al., 1996). A preliminary leaching of rice
husk using boiled and concentrated acid solutions under pressure
before burning proved to be effective in removing most of the
metallic impurities and producing silica completely white in color
with a high specific surface area (Chakraverty et al., 1988; Della
et al., 2002; Hunt et al., 1984; James and Rao, 1985; Mishra et al.,
∗ Corresponding author at: Laboratório Nacional de Nanotecnologia aplicada ao
Agronegócio (LNNA), EMBRAPA Instrumentação (CNPDIA), São Carlos, SP, Brazil.
Tel.: +55 16 2107 2912; fax: +55 16 2107 2802.
E-mail address: marconcini@cnpdia.embrapa.br (J.M. Marconcini).
1985; Patel et al., 1987). Surprisingly, none of these studies have
investigated the use of milder acid solutions to extract silica.Rice
husk have a relatively high content of inorganic compounds,
representing approximately 20% of the dry weight of the husk.
Silica represents 94% of the total while the remaining 6% are K2 O,
CaO, MgO, Al2 O3 , and P2 O5 in decreasing concentrations (Houston,
1972; Gallo et al., 1974). The main organic components of the dry
weight of the husk are cellulose, hemicelluloses and lignin, repre-
senting more than 75% of the total, and the remainder consists of
oils, proteins, etc. The organic and inorganic composition depends
on many factors, such as variety, soil type, weather conditions, and
fertilizers (De Souza et al., 2002).
Silica (SiO2 ) is a basic raw material that is widely used in elec-
tronics, ceramic, and polymer material industries. Because of its
particles diameter, ultrafine silica powders have many techno-
logical applications, such as tixotropic agents, thermal insulators,
composite fillers, etc. (Liou, 2004). Refractory products based on
silica have great properties, like high strength under high temper-
atures, which are much better than argil products, having therefore
fantastic applications in furnaces (Shreve, 1980). The manufactur-
ing of insulating or refractory materials using rice husk ash is an
alternative for environmental subjects, as well as adding value to
the residue.
Some kinetics studies of biomass have attracted the atten-
tion of scientific community. Sonobe and Worasuwannarak (2008)
reported kinetics parameters of biomass pyrolisis (rice straw and
husk, corn cereal and cellulose activation energies 170, 174, 183
and 185 kJ mol−1 , respectively) using a simplified model known as
distributed activation energy model (DAEM). Mansaray and Ghaly
(1999) determined the existence of two distinct zones of reac-
tion during the thermal degradation of rice husk, and reported

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http://dx.doi.org/10.1016/j.indcrop.2012.06.050
292 V.B. Carmona et al. / Industrial Crops and Products 43 (2013) 291–296

kinetics parameters of thermochemical conversion of four vari-
eties of rice husk using thermogravimetric curves, with respective
activations energies from 142.7 to 188.5 kJ mol−1 and from 11.0
to 16.6 kJ mol−1 .In present work, the activation energies of the
thermal degradation of rice husk were determined by the Ozawa
method in accordance with Medeiros et al. (2003). This method
consists of a suggestion for a similar integral method, but more con-
venient than the method proposed by Doyle (1961). Moreover, it is
more applicable and can be used in the determination of kinetic
parameters of many polymers (Elmer and Nordberg, 1958).The
extraction of nanosilica and the burning behavior of the rice husk
were discussed using methodologies described in the literature
with proposed changes from the results of their characterizations.
The obtained materials from the burnt rice husk were characterized
by infrared spectroscopy and size particle analysis.
2. Methods
2.1. Materials
Two different types of rice husk were used for this work, named
agulhinha and cateto. Distilled water, solutions of citric acid (10%,
w/v), acetic acid (10%, v/v), and phosphoric acid 0.2 mol L−1 were
used in the chemical treatment process. Also, two available sili-
cas were used to compare with the obtained silica from this study,
Aldrich and Tixosil 333® (Rhodia).
2.2. Extraction of silica
the available silica Aldrich and Tixosil in saturated water solutions
prepared with distilled water after 48 h of rest period.
2.6. Thermogravimetric analysis (TGA)
Untreated and treated rice husk TGA analysis were performed in
a thermogravimetric equipment (TGA Q500, TA Instruments, USA)
to verify the mass loss behavior of rice husk and the effect of the
chemical treatments, as well as their activation energies from the
application of the Ozawa method.
TGA were carried out with 6 mg rice husk samples in platinum
pan in air atmosphere under 5, 10, 15 and 20 ◦ C min−1 heat rate pro-
viding the percentage composition of volatiles, organic compounds
and the residue created by the rice husk burning.
Three important process temperatures were determined from
TGA on the Universal Analysis software. T1 is the temperature
where the thermal degradation process of rice husk begins, at T2 the
initial characteristics of rice husk are already changed due to the
thermal degradation process, and T3 is the first temperature where
the material stops losing mass, remaining only the solid residue.
This means that, at temperatures smaller than T3 , the burning pro-
cess of rice husk will be uncompleted.
The activation energies were determined using the Ozawa
method for all types of dry rice husk. Because there are 2 distinct
zones of degradation and the 1st one is the determinant for the
rice husk burning, values from 5% to 45% of degradation of the
dry weight were used to report results of activation energies using
descriptive statistics.

For the extraction of silica from rice husk 25 g of each type of 3. Theoretical
rice husk for 150 ml of each acid solution were used and submitted
to high pressure (2 kgf cm−2 ) and temperature (150 ◦ C) for a period The kinetics of thermal transformation of a chemical reaction is
of 1 h. Rice husk treated with distilled water was submitted to high generally described for a single step reaction according to Eq. (1)
pressure and temperatures 4 times. The aim of this procedure is to (Brown et al., 1980)
remove flux materials that are present in the rice husk, like alkaline d˛
and alkaline-earth oxides (Della et al., 2002). Then, rice husk were r= = k(T )f (˛) (1)
dt
washed with distilled water, dried for 18 h at 60 ◦ C. Unlike previous
studies, cited in Section 1, in this study slighter acid solutions were where f(˛) is the reaction model, ˛ the extent of reaction, k(T) the
used taking into account its characteristics to exhibit lower levels temperature dependent rate constant, T the absolute temperature
of corrosion damage to the reactor while generating less aggressive and r the rate of degradation. k(T) is normally assumed to obey the
residue. Arrhenius equation:
Finally, the dry rice husk were calcined under a 10 ◦ C min−1 heat  −E 
rate up to 650 ◦ C, where it was submitted to a isotherm for 1 h to k(T ) = A exp (2)
RT
ensure the removal of the organic compounds according to previous
TGA analysis. where E is the activation energy of the kinetic process, A is the pre-
exponential factor and R the universal gas constant. Integration of
Eq. (1) yields:
2.3. Infrared spectroscopy (FT-IR)
 ˛  t
d˛
The obtained materials from the burnt rice husk were char- f (˛) = =k dt (3)
0
f (˛) 0
acterized in a Perkin Elmer Spectrum 1000 Spectrometer. All IR
spectra were recorded at 2 cm−1 resolution using 64 scans using where the temperature increases with time at a constant heating-
KBr powder as reference. rate, ˇ = dT/dt, Eqs. (2) and (3) may be represented as
 ˛ A t  −E 
d˛
2.4. Energy dispersive spectroscopy (EDS) f (˛) = = exp dT (4)
0
f (˛) ˇ 0
RT
Chemical compositions of obtained materials from the burnt By using Doyle’s approximation to the Arrhenius integral in Eq.
rice husk were investigated in scanning electron microscope JSM- (4), Ozawa (1965, 1970) derived a method for the determination
6510/JEOL accoupled to an EDS 6742A/Thermo Scientific, at 15 kV of activation energy based on:
using Proza correction method. All spectra were collected within
E
AE

300 s using the selected area mode and a 10 mm work distance. ln ˇ ∼
= −1.0516 + ln − ln f (˛) − 2.135 (5)
RT RT
2.5. Size particle analysis Eq. (5) can be used to calculate the activation energy of degrada-
tion from multiple constant heating-rate data. If the mechanism
The average size particle of the burnt material was determined of degradation is independent of the heating-rate, f(˛) is constant
in a High Resolution Malvern Zetasizer Nanoseries and compared to for constant ˛, and the activation energy can be obtained from the
 V.B. Carmona et al. / Industrial Crops and Products 43 (2013) 291–296 293

Table 1
Silicon, oxygen and metal impurities in rice husk ashes, in %atomic.

Rice husk Si O Mg Al K Ca Mn Cu Zn Total metal

Untreated 32.53 64.42 0.24 0.12 1.15 0.23 0.17 0.67 0.46 3.04
H2 O 33.03 64.97 0.22 0.10 0.22 0.26 0.10 0.65 0.44 1.99
Agulhinha Acetic acid 33.73 65.00 – 0.14 – – – 0.70 0.42 1.26
Citric acid 33.94 64.82 – 0.12 – – – 0.63 0.49 1.24
H3 PO4 33.75 65.09 – 0.08 – – – 0.62 0.45 1.15

Untreated 31.98 64.61 0.22 0.14 1.55 0.37 – 0.65 0.47 3.40
H2 O 32.79 65.83 – 0.13 – 0.16 – 0.62 0.47 1.38
Cateto Acetic acid 34.49 64.40 – 0.14 – – – 0.55 0.41 1.10
Citric acid 33.95 64.76 – 0.14 – – – 0.63 0.51 1.28
H3 PO4 32.72 66.61 – 0.11 – – – 0.55 – 0.66

slope of the straight-line by plotting (−ln ˇ) versus (1/T) for any
level of conversion.
4. Results and discussion
Silica was extracted from rice husk using acid leaching and a sub-
sequent burning. FT-IR spectrum results of the materials generated
from the rice husk burning at 650 ◦ C at heat rate of 10 ◦ C min−1 are
shown in Figs. 1 and 2. Can be observed a strong absorption peaks
correlation among the obtained materials FT-IR spectrum and com-
mercial silica Aldrich FT-IR spectrum (Pouchert, 1985) and Tixosil,
clearly indicating the presence of silica.
A large peak was observed between 2500 and 3800 cm−1 cor-
responding to the stretching vibrations of the surface silanols
(SiOH) groups perturbed by hydrogen bounds either intramolec-
ulary or with adsorbed water. FT-IR spectrum also exhibits bands
at 475, 900 and 1100 cm−1 , characteristic of symmetric and anti-
symmetric stretching of Si–O bonds (Kim et al., 2006; Mandejova,
2003).
De Souza et al. (1999) studied extraction of silica from rice husk
and its composition and structure. Excluding untreated rice husk,
all the other chemical treatments followed by burning generated
a white material, which is an indicative of pure silica. The acid
leaching generated amorphous and white silica, while the burn-
ing of untreated husk generated gray powder consisting of silica
and impurities.
Chemical compositions of burnt rice husk are showed in Table 1
with amounts of silicon, oxygen and metal impurities in atomic
percentage. Both agulhinha and cateto rice husk ashes present sim-
ilar compositions; with exception of manganese that is present
only in agulhinha rice husk ashes. Acid treatments were efficient
on removal of magnesium, potassium, calcium and manganese
from rice husk ashes. Water treatments could partially remove
potassium and manganese from agulhinha rice husk ashes and
completely removed potassium from cateto rice husk ashes. In
addition to it, only phosphoric acid could remove zinc from cateto
rice husk but not from agulhinha rice husk. These events indicate
that agulhinha rice husk and cateto rice husk can be assumed as dis-
tinct chemical systems that respond differently to same chemical
treatments.
Silica obtained from burnt rice husk varied from 181.2 nm to
294.7 nm and, in most cases, had a smaller average particle size
than the ordinary silica used for most commercial products. In
addition to it, the bimodal curves of size particle size uncovered
that there are present primary nanopartircles but also secondary
microparticles in powder due their agglomeration.
Thermal behaviors of rice husk were determined by thermo
gravimetric analysis (TGA) and are shown in Figs. 3 and 4. It is
observed an increase in the thermal stability of the leached rice
husk. Untreated agulhinha and cateto rice husk starts to thermally
degrade (T1 ) at 168 ◦ C and 173 ◦ C, respectively, while leached rice
husk have T1 in the range of 184–209 ◦ C, another parameter that
indicates the increase of thermal stability of the treated rice husk
is T2 , which increased about 10% or more for the treated rice husk
(Table 2). This occurred due to the removal of impurities with less
thermal stability. The increase in temperature from room tempera-
ture to about 200 ◦ C resulted in weight losses in a range of 5.4–8.6%,
depending of the rice husk variety and chemical treatment due
to the loss of water present in the samples and external water
bounded by surface tension.

Fig. 1. FT-IR spectrum of the burnt material from agulhinha rice husks. Fig. 2. FT-IR spectrum of the burnt material from cateto rice husks.
294 V.B. Carmona et al. / Industrial Crops and Products 43 (2013) 291–296

Fig. 3. TGA analysis of agulhinha rice husk in air atmosphere at 10 ◦ C min−1 . Fig. 5. The plots of logarithms of heat rate versus the reciprocal absolute tempera-
ture for the indicated conversions of decomposition of cateto rice husk treated with
acetic acid.

thermal decomposition behavior of its major organics constituents.

The first stage of the thermal decomposition is the loss of volatile
compounds, followed by the decomposition of cellulose and lignin
to the intermediate, which may be an organic material of smaller
molecular weight. In the second stage, there is no peak observed.
Hence the thermal decomposition mechanism of rice husk in that
stage is attributed to the further oxidation of carbon in the residual
intermediate to form other volatile species, tar and char. The final
char is composed of silica and others metal oxides in lower con-
centrations. Hemicelluloses decomposes between 200 and 260 ◦ C,
while the cellulose between 240 and 360 ◦ C, and lignin, from 280
to 360 ◦ C (Alvarez and Vázquez, 2004), it was not possible to sep-
arate the degradation process of the rice husk components due to
the complexity of the reactions and the superposition of the degra-
dation peaks.
To achieve a completed burning of untreated rice husk it is nec-
essary to achieve about 500 ◦ C. This temperature increased up to
Fig. 4. TGA analysis of cateto rice husk in air atmosphere at 10 ◦ C min−1 . 620 ◦ C when the rice husk became more thermally stable due to
the chemical treatment. The results found for T3 are smaller than
the result found in the literature, proving that it is possible to obtain
The organic compounds content was in the range of 74–84%
silica from rice husk in an economic way. Table 3 shows composi-
(depending on the rice husk variety and chemical treatment), which
tion of volatile, organic and inorganic compounds data, and also
is consistent with the literature. It is also observed that there is one
three important temperatures on the burning process of agulhinha
inflection point shown on the TGA curves, at about 350 ◦ C, indicat-
and cateto rice husk. The reported data was obtained by the mean
ing that the thermal decomposition of rice husk takes place in two
of each four heat rate TGA analysis using descriptive statistics. TGA
main stages. This phenomenon can be explained on the basis of the
was performed with all samples at constant heating rates of 5, 10,
15 and 20 ◦ C min−1 .
Table 2 Fig. 5 shows a typical (−ln ˇ) vs. (1/T) plot constructed at 5, 10,
Average size particle of the burnt material from agulhinha and cateto rice husk and 15, 20, 25, 30, 35, 40 and 45% of conversion of cateto rice husk
commercial silica.
treated with acetic acid. The parallel straight-line plots indicate
Sample Treatment d (nm) that there is a small change in the activation energy of degradation
Agulhinha rice husk Untreated 182.6 throughout this degradation process.
Water 190.6 Activation energies of degradation were calculated at differ-
Acetic acid 294.7 ent conversion levels using the Ozawa method for the agulhinha
Citric acid 250.4
and cateto rice husk, where it is observed that activation energy
Phosphoric acid 241.7
of degradation increases after the leaching. The determined acti-
Cateto rice husk Untreated 181.2 vation energies were in the range of (120.4 ± 8.9) kJ mol−1 to
Water 180.2
(163.3 ± 16.1) kJ mol−1 for untreated cateto rice husk and cateto
Acetic acid 273.8
Citric acid 249.9 rice husk treated with phosphoric acid, respectively, which are all
Phosphoric acid 239.8 in accordance with the literature. Tables 4 and 5 shows the acti-
Aldrich – 292.1
vation energies of degradation determined at different conversion
levels of agulhinha and cateto rice husk, respectively. These results
Tixosil 333 – 265.6
indicate that the activation energy of degradation is relatively
 V.B. Carmona et al. / Industrial Crops and Products 43 (2013) 291–296 295

Table 3
Volatile, organic and inorganic composition of agulhinha and cateto rice husk with their T1 , T2 and T3 .

Treatment %Volatile (25–200 ◦ C) %Organic (200–650 ◦ C) %Inorganic (650 ◦ C) T1 (◦ C) T2 (◦ C) T3 (◦ C)

Agulhinha Untreated 8.6 ± 0.3 82.7 ± 1.0 8.3 ± 1.2 168.1 ± 13.2 260 ± 8.9 501.5 ± 29.5
Water 5.4 ± 1.7 84.3 ± 2.3 10.2 ± 2.8 196.5 ± 9.9 285.7 ± 7.7 568.6 ± 37.6
Acetic acid 5.9 ± 0.6 83.3 ± 1.9 10.8 ± 1.6 188 ± 10.4 310.6 ± 12.3 620.6 ± 22.6
Citric acid 6.9 ± 0.6 82.3 ± 1.3 10.8 ± 1.7 189.5 ± 17.6 307 ± 10.4 613.0 ± 40.4
H3 PO4 5.5 ± 1.9 83.9 ± 3.1 10.4 ± 1.0 187.1 ± 7.9 309.7 ± 11.3 615.1 ± 21.1

Cateto Untreated 8.6 ± 0.5 74.7 ± 0.8 16.6 ± 1.2 173.1 ± 5.9 263.8 ± 10.7 496.0 ± 24.5
Water 5.9 ± 1.6 78.6 ± 3.7 15.5 ± 3.0 202.1 ± 18.4 287.8 ± 9.1 565.8 ± 27.7
Acetic acid 6.2 ± 0.6 76.6 ± 3.6 17.1 ± 4.3 184.4 ± 13.6 310.0 ± 10.6 620.3 ± 27.8
Citric acid 7.0 ± 0.4 75.9 ± 4.2 17.0 ± 4.1 191.3 ± 12.6 311.4 ± 11.4 619.6 ± 29.4
H3 PO3 7.0 ± 0.3 78.5 ± 2.8 14.4 ± 2.4 209.2 ± 8.8 308.7 ± 7.7 607.3 ± 35.9

constant throughout the degradation process for these 2 types of husk treated with water present higher T2 than untreated agul-
rice husk at 1st degradation zone. hinha rice husk, but there is no evidence of gain on its activation
It is possible to observe that activation energies of thermal energy. And finally, all acid treatments increased both activation
degradation of acid treated rice husk are higher than those from energy and T2 of untreated agulhinha rice husk from 127 kJ mol−1
untreated rice husk. Also, water treatment increased activation and 168 ◦ C, respectively, to values as high as 146.8 kJ mol−1 and
energy of only cateto rice husk. These results show that the pres- 310 ◦ C, respectively. In addition to the gain on activation energy
ence of alkaline and earth-alkaline metals interferes in activation caused by removal of metallic impurities, chemical treatment per-
energy of thermal degradation of biomaterials, such as rice husk. formed under pressure and temperature might have removed other
Sonobe and Worasuwannarak (2008) reported that alkali and more thermally unstable organic compounds from the rice husk.
alkaline-earth metals play an important role in the catalytic reac-
tions during the biomass pyrolysis. Therefore, from the activation 5. Conclusions
energy results reported in this work allied to chemical composition,
the acid treatments using either milder inorganic or organic acid Amorphous and white silica was successfully extracted from rice
solutions were effective at removing impurities like metal oxides, husk using mild acid solutions with the presence of both micro
except silica, and also water treatment was effective on cateto rice and nanometric particles. Cateto rice husk was found to contain
husk. higher percentage than agulhinha rice husk. Activation energies
Untreated rice husk showed a lower activation energy fol- were calculated up to 45% of conversion, proving the effective-
lowed by lower initial lower thermal degradation (T2 ) than those ness of the adopted method in removing impurities, such as metal
from treated rice husk (Tables 3–5). Cateto rice husk treated with oxides. From T1 and T2 it is possible to assign and optimize the pro-
water increased both activation energy and T2 , from 120.4 kJ mol−1 cess temperatures for the incorporation of rice husk into polymers
to 136.7 kJ mol−1 , and from 263 ◦ C to 268 ◦ C. Cateto rice husk and to the manufacturing of composites, and from T3 it is possible
treated with acid solutions present higher activation energy and to adjust the silica extraction under strictly controlled conditions.
T2 than those submitted under water treatment. Agulhinha rice
Acknowledgements
Table 4
Activation energies (kJ mol−1 ) of agulhinha rice husk for ˛ = 5, 10, 15, . . ., 45%.
The authors are grateful to PIBIC/CNPq, Project CNPq no 481999,
˛ Untreated Water Acetic acid Citric acid Phosphoric FINEP, MCT, CAPES, CNPq and Embrapa for their financial and tech-
acid nical supports.
5% 128.3 137.2 152.1 136.5 135.1
10% 132.5 135.1 152.8 139.4 150.0
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