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Ind. Eng. Chem. Res. 2008, 47, 47544757

Activated Carbons Obtained from Rice Husk: Influence of Leaching on Textural


Parameters
Cristina Deiana, Dolly Granados, Rosa Venturini, Alejandro Amaya, Marta Sergio, and
Nestor Tancredi*,
Instituto de Ingeniera Qumica, Facultad de Ingeniera, UniVersidad Nacional de San Juan, AV. Libertador
1109 oeste, CC 5400, San Juan, Argentina, and Laboratorio de Fisicoqumica de Superficies y Catedra de
Fisicoqumica, DETEMA, Facultad de Qumica, UniVersidad de la Republica Oriental del Uruguay,
General Flores 2124, CC 1157, MonteVideo, Uruguay

Activated carbons obtained from rice husk exhibit low specific surface areas when physical activation is
applied due to its high silica content. The purpose of this work was to improve textural parameters of powdered
activated carbons obtained from rice husk. To avoid the negative influence of the raw material ash content,
a leaching step was included in the preparation process. Hydrofluoric acid, in two concentrations (25 and 50
wt %), was used as leaching agent and applied in different stages of the process. Physical activation using
water vapor as activating agent was applied. Specific surface area and porosity were evaluated from nitrogen
adsorption data. When a leaching step was included, specific surface area values between 700 and 1200 m2/g
were obtained. These values are higher than that corresponding to the activated carbon prepared from rice
husk not treated with acid (290 m2/g). Pore size distribution depends on the step sequence of the preparation
process and on the HF concentration.
Introduction
Almost any carbonaceous material, with high carbon content
and low proportion of inorganic components, can be used as
precursors for the preparation of activated carbons.1 Many
agricultural solid wastes have traditionally been used as raw
materials for this purpose, among them coconut shell,2 olive
stones,3 eucalyptus wood,4 and corn cob.5 The increase of
agricultural activity produces large volumes of solid wastes that,
in many cases, become potential environmental contaminants.
Rice constitutes the base of diet for a great part of humanity.
Rice husk waste represents 20% of rice production and grows
up to many tons per year. Even though it has been used for
land filling and fuel or biogas production, new technical
applications have been explored in the last years.6,7
The major constituents of rice husk are cellulose, lignin, and
mineral components. The content of each of them depends on
rice variety, climatic conditions, and even the geographic
localization of the culture. When rice husk is subjected to
combustion at moderate temperature, an amorphous ash is
obtained; a 95% white silica powder could be produced after
calcination at 700 C for 6 h.6 Many authors have concluded
that rice husk is an excellent source of amorphous silica of high
purity appropriate to produce silicium, silicium nitride, silicium
carbide, or magnesium siliciure.8 As a consequence it constitutes
a non-traditional raw material for the ceramic industry.
As a result of its high cellulose and lignin content, rice husk
can be used as the raw material to prepare activated carbons,
which are known to be highly complex porous structures, with
high values of specific surface area (ssa) and porous sizes mainly
in the range of micropores. They are obtained by two different
processes: the physical or thermal activation and the
chemical activation. In the former carbonization is followed
by char activation; in the second one, carbonization and
* Author to whom correspondence should be addressed. E-mail:
nestor@fq.edu.uy. Tel: +598 2 9248352. Fax: +598 2 9241906.

Universidad Nacional de San Juan.

Universidad de la Republica Oriental del Uruguay.

activation are performed in a single step, using a chemical agent.


Activated carbons are very effective adsorbents due to their
textural parameters: ssa and microporous structure. Physical
activation of rice husk produces activated carbon that exhibits
very low ssas.9 This fact has been principally attributed to the
high ash content of the raw material.
Rice culture in Uruguay produces up to 160 to 200 thousands
of tons of rice husk per year. Nowadays, only a part of it finds
a profitable final disposal; used in the best cases as an energetic
source in different industrial processes or as chicken or horse
beds. Otherwise, and up to the half of the total production, it is
disposed as a solid residue in pourer spaces when not burned
in open sky.
The purpose of this work is to improve textural parameters
of powdered activated carbons obtained from rice husk. To avoid
the negative influence of the raw material ash content, leaching
steps are included in the preparation process, either before or
after the activation step. As ashes are mostly constituted by
silica, hydrofluoric acid is used as the leaching agent, whose
efficiency to dissolve silica is well-known.10 Textural parameters, ssa, and porosity are evaluated from nitrogen adsorption
data.
Materials and Methods
Rice husk provided by the Uruguayan firm Saman was used
as raw material. Elemental analysis was performed using Carlo
Erba equipment, EA 1108 CHNS-O model. C, H, N, S, and O
contents refer to dry mass. Oxygen content was determined by
difference and ash content by calcination of the sample at 900
C during 24 h.
Carbonization. A sample of 1500 g of rice husk was calcined
in a batch process using a retort-like stainless steel reactor, under
inert atmosphere of nitrogen, at a rate of 1.4 K/min from room
temperature up to 773 K and keeping the final temperature for
2 h.11 A K-type thermocouple and a digital temperature
controller were used to set and control the sample temperature.
The resulting solid was labeled as C, and the yield refers to the
mass of the starting dry raw material.

10.1021/ie071657x CCC: $40.75 2008 American Chemical Society


Published on Web 06/13/2008

Ind. Eng. Chem. Res., Vol. 47, No. 14, 2008 4755
Scheme 1. Experimental Scheme and Sample Identification

Table 1. Ultimate Analysis for Rice Husk and Derived Products (%,
Dry Basis, Ash Free) and Ash Content (%, Dry Basis)
sample

Oa

ash

rice husk
C
CA
CAL50
CAL25
CL50A
CL25A
CL50
CL25
L50CA

48.3
85.7
83.1
95.0
83.7
75.7
86.0
89.1
83.5
90.0

6.8
1.0
0.5
0.0
0.4
0.6
0.5
0.9
1.1
0.6

0.5
3.1
1.9
4.2
1.5
1.2
1.2
3.0
2.9
1.6

0
0
0
0
0
0
0
0
0
0

44.4
10.2
14.5
0.8
14.4
22.5
12.3
7.0
12.5
7.8

17.2
43.2
68.4
1.0
0.0
1.0
1.1
0.0
0.8
0.0

By difference.

Table 2. Textural Parameters and Yields for Activated Carbons


Obtained from Rice Husk
textural parameters

Activation. The sample in the form of powder was heated


in a 300 mm long stainless steel reactor with an internal diameter
of 30 mm, using an electric oven. The temperature was set and
controlled using a K-type thermocouple and a digital temperature
controller.12 The sample was heated at 5 K/min from room
temperature to 1123 K in nitrogen gas flowing at 300 mL/min.
When that temperature was reached, nitrogen was substituted
for water vapor as activating agent at a flowing rate of 1.7 g
per gram of carbonized matter per hour. This treatment last for
105 min. Samples subjected to this process were labeled as A.
Leaching. Hydrofluoric acid of analytic grade was used at
room temperature. The acid solution volume to solid mass ratio
was 2.5:1, and two different concentrations of acid (25% and
50%, w/w) were used. The slurry was magnetically stirred for
30 min. The solid was separated and washed with distilled water
until neutralization, and then oven-dried at 373 K during 16 h.
The corresponding samples were labeled as LX, where X (25
or 50) represents acid concentration. Leaching treatment was
performed before or after the activation one.
The carbonized rice husk was subjected to activation and
leaching following the experimental diagram shown in Scheme
1. Sample identifications are also shown in the scheme. For the
sake of comparison an additional sample was obtained by
leaching the rice husk with 50% HF and then carbonizing and
activating the solid as described previously. This sample was
labeled L50CA.
Characterization. Nitrogen adsorption-desorption isotherms
were performed using Autosorb-1 (Quantachrome) equipment.
Samples of about 0.100 g were oven-dried at 378 K during 24 h
and outgassed at room temperature, under vacuum, during other
24 h. The final pressure was less than 10-4 mbar. Textural
parameters were derived from adsorption data. The ssa was
determined based on the BET model.13 The specific total pore
volume (VT) was determined from the adsorption at the relative
pressure of 0.99, converted to liquid volume assuming a nitrogen
density of 0.808 g/cm3. The specific micropore volume (VDR)
was determined using the Dubinin-Radushkevich model.14 The
pore size distribution (PSD) was analyzed using the DFT
method.15,16
The total yield (YT) was calculated as
YT ) (obtained weight of the sample weight of the untreated
rice husk) 100
Results and Discussion
Results of rice husk and the derived products ultimate analysis
are listed in Table 1. Textural parameters determined after
adsorption data are shown in Table 2.

sample

YT (wt %)

ssa BET (m2/g)

VT (cm3/g)

VDR (cm3/g)

C
CL25
CL50
CA
CL25A
CL50A
CAL25
CAL50
L50CA

41.0
23.4
23.2
24.3
14.1
12.1
6.9
6.9
11.8

16
170
160
290
750
820
1030
1180
950

0.07
0.18
0.17
0.25
0.54
0.60
0.98
1.09
0.46

0.06
0.05
0.12
0.31
0.35
0.39
0.50
0.39

Ultimate analysis showed that for most of the processes the


chemical composition of the products did not change significantly. However, when lixiviation with 50% HF is involved,
some results are remarkable. The lixiviation with 50% HF seems
to increase the carbon percentage and to decrease the oxygen
percentage (see the series C, CL50 and CA, CAL50) perhaps
through the removal of surface oxygenated functions. On the
contrary, the activation of CL50 seems to increase the oxygen
content, and consequently a decrease in the carbon percentage
is observed (compare CL50A and CL50), probably as a result of
the inclusion of oxygenated groups through water vapor
activation.
Carbonization of the sample gave a solid (C) that presented
very low values of VT (0.07 cm3/g) and ssa (16 m2/g). These
results suggest that carbonization does not generate any porous
structure.
Leaching of the char C using hydrofluoric acid produced
solids (CLx) with higher ssa and VT; they were respectively 10fold and twice those of the char. At this stage, the concentration
of the acid did not cause any difference in these textural
parameters of the solids.
Activation of the char (CA) increased the ssa (18 times) and
the VT (3.5 times) and generated a VDR that represents half of
VT. It is well-known that physical activation generates the porous
network of activated carbon, widening the primary pores,
opening the secondary ones, and contributing to higher values
of textural parameters.1
Activation of leached solids (CLxA samples) had a more
drastic effect: the increase of the ssa was 4.4 times for CL25A
and 5.1 times for CL50A, referenced to the parent CLx sample.
The VT increase was 3 and 3.5 times and the VDR one was 5
and 7 times that of the CLx samples, using respectively, 25%
and 50% HF. In this case, when leaching was performed on
the char and before activation, some influence of the concentration of the acid was observed. The higher concentration
produced solids with ssa and VDR that are 2.8 times those of
CA. The results suggest that when the leaching step is performed
before the activation one, inorganic salts are removed, probably

4756 Ind. Eng. Chem. Res., Vol. 47, No. 14, 2008

Figure 1. Evolution of the ssa as a function of YT; sample C is not included.


Figure 3. PSD for samples CL25A and CL50A, DFT theory.

Figure 2. PSD for samples CL25 and CL50, DFT theory.


Figure 4. PSD for samples CAL25, CAL50, and CA, DFT theory.

allowing the bulk penetration of water vapor and generating a


more developed pore network.
Leaching of the activated samples (CALx samples) produced
solids that presented the highest values of textural parameters.
The leaching process increased the ssa of the activated samples
3.5 or 4 times, for concentration of the acid of 25% or 50%
respectively, referenced to CA. The VDR increased in the same
ratio. Possibly the porous network produced by the activation
process allows the hydrofluoric acid to penetrate deeply in the
sample, dissolving silica.
The leaching step (50% HF) performed before the carbonization-activation process to compare the results with those
previously described gave a solid (L50CA) with ssa and VDR
values that are, respectively, 16 and 11% higher than those of
CL50A. These results are discussed later.
From the point of view of the development of the ssa and
the VDR, the process sequence carbonization-activation-leaching
is more efficient than the sequence carbonization-leachingactivation.
Figure 1 shows the variation of the ssa as a function of YT:
a lineal correlation is observed between them. In fact, the
leaching process, as well as the activation one, generates the
porous structure by mass subtraction of the sample that is lost
in solution or as gas products, respectively.
Figures 25 show the PSD diagrams for the studied samples.
Only pore sizes over 10 are analyzed taking into account
literature reports on the artificial gap in the vicinity of 10 . 17
In all the cases, there are no peaks for pore sizes over 30 .
For samples CL25 and CL50 the PSDs are very similar (peaks
at 18 and 12 in Figure 2) according with the close values
for ssa, VT and VDR for both samples. The activation of these
samples increases pore volumes; the CL25A shows only a high
and wide peak at about 14 and a small one at 18 , and the

Figure 5. PSD for samples CA and L50CA, DFT theory.

CL50A shows two important peaks at 12 and 16 (Figure


3). The activation process of the CL25 widened the 12 pores
to 14 but seems not to have altered the 18 pores. For CL50
the activation process increased the 12 pore size volume and
generated 16 pores. The leaching process with higher acid
concentration removed mineral matter from the char in a higher
extension allowing the activation process to go deeply and to
widen the pores.
PSD for CA shows a peak at 16 with a shoulder at 13
(Figure 4). Leaching of this sample with HF splits this peak in
three: two small ones at 18 and 23 and a high and wide
one at 14 . Leaching seems to open pore mouths, from 13
to 14 and from 16 to 18 and 23 . The acid concentration

Ind. Eng. Chem. Res., Vol. 47, No. 14, 2008 4757

of the leaching step when performed after activation does not


seem to influence the PSD profile of the samples.
Leaching of rice husk previous to carbonization and activation
steps allows the formation of pores of 13 and 16 (Figure
5). These two values are coincident with the major peak and
the shoulder present in the PSD of the CA sample. The PSD
for L50CA (Figure 5) is coincident with that for CL50A (Figure
3), suggesting that when 50% HF is used, the sequence
leaching-carbonization-activation gives results similar to those
of the carbonization-leaching-activation one. The higher peak
areas for L50CA than for CL50A are a result of the higher VDR
of the former solid, as was already indicated.
Conclusions
Rice husk, a residue of the agricultural activity representing
high volumes of a potential contaminant, can be transformed
in powdered activated carbons with high ssa and developed
microporous structure. This is accomplished by the introduction
of a leaching step in the preparation process. The process
sequence carbonization-activation-leaching is more efficient
than the sequence carbonization-leaching-activation to improve the ssa and the VDR. Previous leaching of the rice husk
with 50% HF followed by carbonization and activation gives
solids with textural parameters similar to those obtained by the
sequence carbonization-activation-leaching. PSD is affected
in different extensions, not only by the step sequence of the
preparation process but also by the HF concentration.
Acknowledgment
The authors are grateful to Departamento Estrella Campos,
Facultad de Qumica, Universidad de la Republica, Uruguay,
for their assistance with ultimate chemical analysis, and to
Universidad Nacional de San Juan, Argentina, for financial
support.
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ReceiVed for reView December 4, 2007


ReVised manuscript receiVed April 17, 2008
Accepted April 30, 2008
IE071657X