Bioresource Technology 98 (2007) 16351641

0960-8524/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2006.05.049
Activated carbon briquettes from biomass materials
Alejandro Amaya
a,1
, Natalia Medero
a,1
, Nstor Tancredi
a,1
,
Hugo Silva
b,2
, Cristina Deiana
b,,2
a
Ctedra de Fisicoqumica y Laboratorio de Fisicoqumica de SuperWcies, DETEMA, Facultad de Qumica,
Universidad de la Repblica Oriental del Uruguay, Gral. Flores 2124, C.C. 1157, 11800 Montevideo, Uruguay
b
Instituto de Ingeniera Qumica, Facultad de Ingeniera, Universidad Nacional de San Juan, Av. Libertador 1109 (oeste), 5400 San Juan, Argentina
Received 27 June 2005; received in revised form 31 May 2006; accepted 31 May 2006
Available online 14 August 2006
Abstract
Disposal of biomass wastes, produced in diVerent agricultural activities, is frequently an environmental problem. A solution for such
situation is the recycling of these residues for the production of activated carbon, an adsorbent which has several applications, for
instance in the elimination of contaminants. For some uses, high mechanical strength and good adsorption characteristics are required.
To achieve this, carbonaceous materials are conformed as pellets or briquettes, in a process that involves mixing and pressing of char with
adhesive materials prior to activation. In this work, the inXuence of the operation conditions on the mechanical and surface properties of
briquettes was studied. Eucalyptus wood and rice husk from Uruguay were used as lignocellulosic raw materials, and concentrated grape
must from Cuyo RegionArgentina, as a binder. DiVerent wood:rice and solid:binder ratios were used to prepare briquettes in order to
study their inXuence on mechanical and surface properties of the Wnal products.
2006 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Rice husk; Eucalyptus wood; Briquettes
1. Introduction
The Wnal disposal of biomass wastes from agricultural
activities is usually an environmental problem. One solu-
tion for this situation is the reuse of these wastes to produce
activated carbon, which is one of the most widely used
materials because of its exceptional adsorbent properties.
It is applied in a variety of puriWcation and separation
processes, in the abatement of hazardous contaminants,
municipal and industrial wastewater treatments, as catalyst
or catalyst support, in medicine, in hydrometallurgy for the
recovery of gold and silver, etc.
Activated carbon has a large volume fraction of very
small pores, which results in a large speciWc surface area
(Bansal et al., 1988). Typical activated carbons have surface
areas from 600 to 1200m
2
/g, although products with values
higher than 2000m
2
/g have been reported (Otowa et al.,
1992; Nakagawa et al., 2003). Activated carbon has a prac-
tical advantage over other adsorbents because it may be
obtained from a variety of carbonaceous raw materials,
including byproducts or wastes from industrial processes
(Deiana et al., 1998; Rivera-Utrilla et al., 2001; Dastgheib
and Rockstraw, 2001; Hayashi et al., 2002; Milich et al.,
2002).
The reuse of solid wastes, as rice husk or wood sawdust,
could be important for regional economics. The prepara-
tion of activated carbon from wastes is an example of that,
because high value products are obtained from low cost
materials, and simultaneously, solutions to the problems of
disposal of wastes are a natural consequence.
Activated carbon can be prepared as a powder or
granular (Rodrguez-Reinoso et al., 2001), or shaped as
briquettes (Deiana et al., 2004), Wbers (Edie, 1998), cloth
(Pastor et al., 1999), depending on its speciWc applications
*
Corresponding author.
E-mail addresses: nestor@fq.edu.uy (N. Tancredi), cdeiana@unsj.edu.ar
(C. Deiana).
1
Tel.: +598 2 9248352; fax: +598 2 9241906.
2
Tel.: +54 264 4211700x228; fax: +54 264 4200289.
1636 A. Amaya et al. / Bioresource Technology 98 (2007) 16351641
(Rodrguez-Reinoso, 2002). Powder or granular forms can
be used with low Xow rates of Xuids (i.e. air or water) in
contact with the activated carbon, as in water puriWers.
However, the granules or grains of the activated carbon
may scatter around the container or Xow into the Xuid, in
cases where the rate of the Xuid Xow is relatively high, as in
a Wlter of an air conditioner. Thus, hard granules, pellets or
briquettes are used in continuous or cyclic processes, where
mechanical strength is an important property to be con-
sidered (Yan et al., 1996; Yamada and Tsumuki, 1997).
Activated carbons obtained from eucalyptus wood, in
previous studies, presented high speciWc surface areas but
low mechanical strength, even though the briquetting pro-
cess was applied to this material (Tancredi et al., 1996a,b,
1997; Deiana et al., 2004). Thus, its use in applications
where high mechanical strength is required should be
avoided. Preliminary studies on activation of rice husk
char with water vapour showed that the activated carbon
obtained presented a scarcely developed porous structure.
Furthermore, when this material was briquetted, the Wnal
product exhibited high mechanical strength.
The use of mixtures of carbonaceous materials, eucalyp-
tus wood and rice husk, to conform briquettes was consid-
ered as a potentially viable way to obtain Wnal products
with surface and mechanical properties similar to those of
the commercial products. Results of studies on the confor-
mation of activated carbon briquettes from those materials,
using concentrated grape must as binder, are presented. The
inXuence of the composition of the mixture and the opera-
tion conditions on the surface and mechanical properties of
the activated carbon were analyzed. The briquettes were
prepared from a single eucalyptus variety and rice husks
provided by a unique producer, to avoid quality control
problems of products due to variability in the precursors
composition.
2. Experimental
2.1. Materials
Rice husk and eucalyptus wood (Eucalyptus camaldulen-
sis Dehn) from Uruguay were used as carbonaceous precur-
sors, even though the latter is also a common wood source
in the region of Cuyo, Argentina. Rice husk was obtained
as the waste from SAMAN, a major rice producer of Uru-
guay.
Activated carbon briquettes were prepared from mix-
tures with diVerent proportions of those raw materials.
Concentrated grape must, a non-alcoholic byproduct of the
viticulture from Cuyo RegionArgentina, supplied by Mos-
tomat S.A., was used as a binder. This product is obtained
from the partial dehydration of grape juice. Although its
composition is complex, its main components are glucose
and fructose (around 860g total sugar/L). Small amounts of
organic acids, phenolic compounds, metals and vitamins
are also present. The analysis of concentrated grape must is
shown in Table 1.
2.2. Methods
The experimental program involved diVerent steps: car-
bonization of raw materials, conformation of briquettes,
and thermal activation. Furthermore, granular activated
carbons from rice husk and eucalyptus wood were prepared
in order to compare surface and mechanical properties.
The carbonization step was carried out in a retort-like
stainless steel batch reactor, which can process 2000 g of
raw materials. The reactor was heated from room tempera-
ture to 500 C at 1.4C/min, and kept at this temperature
for 2 h.
Chars of both raw materials were crushed and sieved.
The fraction that passed through the 80 mesh ASTM
(<0.18 mm) sieve was used to prepare the briquettes, which
were made by mixing in a mortar measured amounts of
char and binder and pressing 1 g of the resulting mixture
into a 10 mm I.D. cylindrical stainless steel mold held in a
hydraulic press. Binder:char ratios were 1:4 and 1:6. A pres-
sure of 140 MPa for 6min was applied. The resulting made
briquettes were measured, weighed, and stored.
The green briquettes were activated under a steam Xow
in a stainless steel tubular reactor, electrically heated, which
was described in Deiana et al. (1998). The heating from
room to activation temperatures was carried out in Xowing
nitrogen gas at 15 C/min. The activation tests were per-
formed at either 880 or 920 C, 1.7 or 2.5 g of steam/(g char
h), by 105 or 150 min. Once the activation step had taken
place, the activated briquettes were measured, weighed, and
stored. The operation conditions of the experimental tests
are summarized in Table 2.
The elemental analysis of the raw materials was carried
out in a Carlo Erba EA1108 equipment. The ash content
was determined from the thermogravimetric studies. In
order to evaluate the surface properties of the Wnal
products, adsorptiondesorption isotherms of nitrogen at
196 C were carried out in a Quantachrome, Autosorb-1
Model equipment, after a degasiWcation step at 25 C by
8 h. The microporous volume, obtained from the Dubinin
Radushkevich model, is reported.
The mechanical properties were evaluated by means of
the Impact Resistant Index (IRI), the Axial Compressive
Strength (ACS), and Tensile Strength by Diametrical Com-
pression (DCS). The IRI values were determined as a func-
tion of the number of drops and the number of pieces into
which each briquette breaks when it is repeatedly dropped
Table 1
Analysis of concentrated grape must
Refractive index (293 K) 1.4654
Density (293 K) 1.345 kg/L
Sugar (fructose +glucose) 860 g/L
Sucrose Below detection limit
Total acidity 0.4 meq/kg
Total cations 0.6 meq/kg
Chlorides 0.3 meq/kg
Sulfates 0.3 meq/kg
A. Amaya et al. / Bioresource Technology 98 (2007) 16351641 1637
from a stationary starting point at 2 m height onto a
concrete Xoor until it fractured (Richards, 1990). The ACS
and DCS were determined in a rigid-frame controlled
load equipment at a load rate of approximately 1 kgf
(cm
2
s)
1
. These tests were designed based on the standard
test methods for compressive and splitting tensile strengths
of concrete cylindrical specimens (ASTM C 3994 and
ASTM C 49696). Cylindrical briquettes were submitted
to uniformly distributed increasing axial or diametrical
compressive forces in a suitable testing machine until the
specimens were broken. The strength is expressed as the
maximum load sustained by the specimen divided by
appropriate geometrical factors, in kg/cm
2
(Popovics,
1998).
The raw materials, some briquettes and activated car-
bons were characterized by thermogravimetric analysis in a
Shimadzu TGA-50 equipment, under a heating rate of 5 C/
min and air Xow of 50 cm
3
/min. For this analysis, the frac-
tion that passed through the 80 mesh ASTM sieve was
used.
2.3. Statistical analysis methodology
In order to obtain the correlation between both, porous
structure and mechanical properties of adsorbents, stat-
istical analysis was carried out. MINITAB software was
applied. Variations of BET surface area (A
BET
) versus Axial
Compressive Strength (ACS) and Tensile Strength by Dia-
metrical Compression (DCS) were analyzed, and statistical
parameters were determined.
The experimental design was developed adopting a
base experiment as the starting point and generating the
remaining tests by changing the experimental conditions.
The base experiment was named as the REB-8 and included
the processing of a mixture of eucalyptus wood and rice
husk chars with a ratio of 10:90 wt, and a binder:char ratio
of 1:4 wt. The briquettes were obtained by applying a pres-
sure of 140MPa. The activation conditions corresponding
to base test were 880C, 1.7 g Xowing steam/(g char.h), and
105 min. These conditions were also applied to the granular
chars and concentrated grape must.
Each set of experimental conditions was duplicated. Tex-
tural properties were measured on two briquettes randomly
chosen from each sample and mechanical strengths on
three briquettes from each sample.
3. Results and discussion
3.1. Elemental analysis
The elemental analysis of the raw materials, some Wnal
products, and binder, all activated under the same opera-
tion conditions, are summarized in Table 3. An important
diVerence in the ash content between eucalyptus wood and
rice husk was observed. It has been attributed mainly to its
high silica content, though rice husk has also a higher con-
tent of other mineral matter than eucalyptus wood (Park
et al., 2003).
The carbonization and activation steps resulted in an
increment in the carbon content because of volatilization
processes that occur during the pyrolysis, and the reaction
between steam and carbon. Both processes lead to the elim-
ination of heteroatoms, and an increment in the relative
amount of ash. A similarity in the compositions of the acti-
vated carbons from eucalyptus wood (E-1) and from con-
centrated grape must (M-3) was observed. Therefore, the
activated briquettes from eucalyptus wood (EB-4) pre-
sented similar composition to the granular activated car-
bon (E-1) from this raw material. It is also observed that
activated husk rice briquettes (RB-5) exhibited minor ash
content compared to the activated rice husk (R-2), because
of the addition of concentrate grape must.
3.2. Textural and mechanical properties
The results of the nitrogen isotherms and mechanical
tests are shown in Table 4. The textural properties, BET
surface area (A
BET
) and microporous volume (V
micro
), are
Table 2
Operation conditions
E, eucalyptus wood; R, rice husk; M, concentrated grape must; B, bri-
quettes; L, binder; C, char mixture; T, temperature; t, time; F, steam Xow.
Test Agglomeration Activation
R:E L:C T (C) t (min) F (g/gh)
E-1 0:100 0:100 880 105 1.7
R-2 100:0 0:100 880 105 1.7
M-3 0:0 100:0 880 105 1.7
EB-4 0:100 1:4 880 105 1.7
RB-5 100:0 1:4 880 105 1.7
REB-6 30:70 1:4 880 105 1.7
REB-7 30:70 1:6 880 105 1.7
REB-8 10:90 1:4 880 105 1.7
REB-9 10:90 1:6 880 105 1.7
REB-10 10:90 1:4 880 150 1.7
REB-11 10:90 1:4 880 105 2.5
REB-12 10:90 1:4 880 150 2.5
REB-13 10:90 1:4 920 105 1.7
REB-14 10:90 1:4 920 150 1.7
REB-15 10:90 1:4 920 105 2.5
REB-16 10:90 1:4 920 150 2.5
REB-17 15:85 1:4 880 105 1.7
REB-18 50:50 1:4 880 105 1.7
Table 3
Elemental analysis of the materials (in %, db, af) and ash (db)
db: dry base; af: ash free.
a
Obtained by diVerence.
C N H S O
a
Ash
Eucalyptus wood 49.7 0.0 5.7 0.0 44.6 0.3
Activated eucalyptus (E-1) 91.8 0.0 1.0 0.0 7.3 6.3
Activated eucalyptus briquette (EB-4) 94.0 0.0 0.7 0.0 5.3 6.4
Rice husk 48.3 6.8 0.5 0.0 44.4 17.2
Activated rice husk (R-2) 100.0 0.0 0.0 0.0 0.0 81.6
Activated rice husk briquette (RB-5) 98.4 0.0 1.1 0.0 0.5 55.5
Carbonized grape must 59.0 0.1 5.1 0.0 35.8 1.7
Activated grape must (M-3) 93.5 0.0 0.9 0.0 5.6 5.0
1638 A. Amaya et al. / Bioresource Technology 98 (2007) 16351641
presented in columns 2 and 3, and mechanical properties
(IRI, ACS, and DCS) in columns 4, 5, and 6.
As an example, adsorption isotherms of the activated
products from the granular raw materials, binder, and bri-
quettes are shown in Figs. 1 and 2. In Fig. 1, the isotherms
corresponding to the granular activated carbon from euca-
lyptus (E-1), conformed activated carbon from eucalyptus
(EB-4), activated must (M-3), and briquettes with a 15:85
rice husk:eucalyptus ratio (REB-17) are compared. In
Fig. 2, graphics for granular activated carbon from rice
husk (R-2), conformed activated carbon from rice husk
(RB-5), and briquettes with 50:50 (REB-18) and 15:85
(REB-17) rice husk:eucalyptus ratio are presented. REB-17
isotherm appears in both graphics in order to have a
common reference for comparison.
From the isotherms analysis and the values of the BET
surface area and microporous volume summarized in Table
4, it can be conWrmed that activated carbon from rice husk
(R-2) presents an underdeveloped porous structure (BET
area <200 m
2
/g, V
micro
<0.10 cm
3
/g). On the contrary, the
activated carbon from eucalyptus wood (E-1) showed high
surface area and pore volume (1042 m
2
/g and 0.393 cm
3
/g).
The activated grape must (M-3) presents a similar micropo-
rous volume compared to the activated eucalyptus wood
(E-1). Although the isotherm corresponding to M-3 pre-
sents a hysteresis loop, which indicates mesoporosity, the
increase of the uptake at high relative pressures is low,
which reveals a low development of meso and macroporo-
sity (Gregg and Sing, 1982).
By comparing tests E-1 and EB-4, it can be observed a
decrease on the surface properties of the activated product
material after the briquetting process. This decrease has
been reported for diVerent binder and raw materials (Yam-
ada and Tsumuki, 1997; Rubio et al., 1999), and speciWcally
for eucalyptus wood and concentrated grape must by Dei-
ana et al. (2004). This behavior can be attributed to the
micro-intrusion of liquid binder into cracks and voids of
the char structure due to briquette conformation pressure,
according to the compaction and cementing model (Taylor,
1988). On the contrary, the activated briquettes from car-
bonized rice husk show a higher nitrogen uptake compared
to the activated product from the unbriquetted raw mate-
rial (compare tests R-2 and RB-5). This may be explained
by the fact that the surface area of the activated binder
is substantially higher than that of the rice husk. Conse-
quently, the surface properties of the Wnal products depend
on the eucalyptus:rice husk ratio in the solid mixture, and
the binder:char ratio used in the conformation step.
From Table 4, it can be observed that higher contents of
carbonized eucalyptus wood improve the textural properties
of the briquettes. Thus, higher rice husk contents produced
activated briquettes with lower surface area (compare tests
REB-6 and REB-7 with tests REB-8 and REB-9). Higher
binder contents also improve textural properties, though its
eVect on speciWc surface area is less pronounced (compare
test REB-6 with test REB-7 and test REB-8 with test REB-
9). The inXuence of the activation conditions (temperature,
Table 4
Porosity, surface properties and mechanical properties of the Wnal prod-
ucts
Test Textural properties Mechanical properties
A
BET
(m
2
/g)
V
micro
(cm
3
/g)
IRI ACS
(kg/cm
2
)
DCS
(kg/cm
2
)
E-1 1042 0.393 ND ND ND
R-2 194 0.072 ND ND ND
M-3 926 0.363 ND ND ND
EB-4 977 0.370 160 12.30 3.52
RB-5 386 0.148 >2000 124.21 25.25
REB-6 482 0.186 >2000 93.89 14.09
REB-7 454 0.162 >2000 55.17 12.30
REB-8 654 0.251 >2000 81.19 13.63
REB-9 611 0.235 >2000 38.19 8.82
REB-10 682 0.263 >2000 73.02 13.60
REB-11 710 0.272 >2000 63.89 18.61
REB-12 919 0.354 >2000 76.07 11.01
REB-13 895 0.348 >2000 53.53 15.45
REB-14 1022 0.396 >2000 50.51 8.97
REB-15 1001 0.388 >2000 72.87 8.13
REB-16 1122 0.434 1200 40.23 5.33
REB-17 528 0.331 >2000 86.15 12.90
REB-18 307 0.118 >2000 103.20 18.71
Fig. 1. N
2
adsorptiondesorption isotherms at 196 K for activated car-
bons prepared from eucalyptus wood, and REB 17 as reference. Open
symbols: adsorption; closed symbols: desorption. () E1; () EB-4; ()
M-3; () REB-17.
5
9
13
17
21
25
0.0 0.2 0.4 0.6 0.8 1.0
n

(
m
m
o
l
/
g
)

P/P
0
Fig. 2. N
2
adsorptiondesorption isotherms at 196 K for activated car-
bons prepared from rice husk, and REB 17 as reference. Open symbols:
adsorption; closed symbols: desorption. () REB-17; () RB-5; () RB-
18; () R-2.
0
2
4
6
8
10
12
0.0 0.2 0.4 0.6 0.8 1.0
P/P
0
n

(
m
m
o
l
/
g
)
A. Amaya et al. / Bioresource Technology 98 (2007) 16351641 1639
time and water vapor Xow) on surface properties of the bri-
quettes can be deduced from the results presented in Table
4. Weight ratios rice:woodD10:90 and binder:carbonizate
1:4 were used. Results for activation at 880 C and 920C
are presented, for two levels of activation time (150 and
105min) and water vapor Xow (2.5 and 1.7g/gh). BET sur-
face area and porous volume corresponding to these tests
are shown in Table 4. As it was expected, more severe activa-
tion conditions (higher temperatures, times and Xows) led to
higher speciWc surface areas but slightly diminish mechani-
cal toughness.
The inXuence of time and Xow on porous structure is
more important at the low temperature end than at the high
one (in Table 4 compare tests REB-8, 10, 11, 12 with REB-
13, 14, 15, 16). It can also be observed that the operation
variables can be adjusted in order to obtain briquettes with
surface properties similar to granular activated carbon
from eucalyptus wood.
From the results shown in Table 4 it may be seen that
the rice husk briquettes present high mechanical resistance
values (RB-5), particularly if they are compared with those
prepared from eucalyptus wood without rice husk (EB-4).
When rice husk is present in the mixture of raw materials to
prepare the briquettes, the mechanical resistance is notably
enhanced (compare test EB-4 with REB-616). These are
even higher than those reported previously (Rubio et al.,
1999 and Deiana et al., 2004), where an IRI value of 50 was
considered to be an acceptable limit.
From the results obtained in this work, it can be con-
cluded that briquettes conformed from mixtures with 10%
of carbonized rice husk and 90% of carbonized eucalyptus
wood, present mechanical strength and surface properties
that fall within ranges of commercially accepted.
3.3. Statistical analysis
Variations of BET surface area (A
BET
) versus Axial
Compressive Strength (ACS) and Tensile Strength by Dia-
metrical Compression (DCS) were analyzed. Tables 5 and 6
show the results of the corresponding lineal regression ana-
lysis. The Wrst one exhibited the results of Wtting a linear
model to describe the relationship between A
BET
and ACS.
The equation of the Wtted model is: A
BET
D1131.1
6.088 ACS. Since the P-value in the ANOVA table is less
than 0.01, there is a statistically signiWcant relationship
between A
BET
and Axial Compression Strength, at the 99%
conWdence level. The R-squared statistic indicates that the
model as Wtted explains 44% of the variability in A
BET
. The
correlation coeYcient equals 0.663324, indicating a mod-
erately strong relationship between the variables. The stan-
dard error of the estimate shows the standard deviation of
the residuals to be 200.3. The regression plot corresponding
to this analysis is exhibited in Fig. 3.
In accordance with the results of Table 6, the equation of
the Wtted model that describes A
BET
and DCS relationship
is: A
BET
D1136.2 33.062 DCS. Since the P-value is less
than 0.01, there is a statistically signiWcant relationship
between A
BET
and DCS at the 99% conWdence level. The R-
squared statistic indicates that the model as Wtted explains
50.6% of the variability in A
BET
. The correlation coeYcient
equals 0.71134, indicating a moderately strong relation-
ship between the variables. The standard error of the esti-
mate shows the standard deviation of the residuals to be
188.3. Fig. 4 shows the regression plot corresponding to this
analysis.
3.4. Thermogravimetric analysis
Results from thermogravimetric analysis (TGA) for car-
bonized and activated must are shown in Fig. 5. For car-
bonized grape must there are two reaction peaks, at about
250 C and 430 C; for activated must there is not reaction
Table 5
Relationship between A
BET
versus ACS
Statistical parameters.
Correlation coeYcient D0.663324; R-squared D44%; standard error of
estimate D200.3.
Parameter Estimate Standard deviation T statistic P-value
Intercept 1131.1 145.832 8.11 0.0000
Slope 6.088 1.98223 3.20 0.007
Source Sum of squares DF Mean square F-ratio P-value
Analysis of variance
Model 410303.0 1 410303.0 10.22 0.007
Residual 521744.0 13 40134.0
Total (corr.) 932047.0 14
Table 6
Relationship between A
BET
versus DCS
Statistical parameters.
Correlation coeYcient D0.71134; R-squared D50.6%; standard error of
estimate D188.3.
Parameter Estimate Standard deviation T statistic P-value
Intercept 1136.2 124.9 9.10 0.0000
Slope 33.062 9.065 3.65 0.003
Source Sum of squares DF Mean square F-ratio P-value
Analysis of variance
Model 471350 1 471350 13.30 0.003
Residual 460697 13 35438
Total (corr.) 932047 14
Fig. 3. A
BET
versus ACS regression plot.
0
200
400
600
800
1000
1200
1400
0 25 50 75 100 125 150
ACS (kg/cm
2
)
A
B
E
T

(
m
2
/
g
)
1640 A. Amaya et al. / Bioresource Technology 98 (2007) 16351641
up to about 480 C, being placed the oxidation peak at
500C. This indicates that resistance to the oxidation of the
grape must increased after activation, as a consequence of
the operation conditions (high temperature, oxidant action
of water vapor).
The behavior of samples for the airsolid reaction is
shown in Fig. 6. Rice husk (R) reacts between 200 and
400C, with a maximum at 270 C; the activated carbon
prepared from carbonized rice husk (R-2) reacts in the
range of 350500 C, with a maximum at 420 C. An
increase in the resistance to oxidation, as a result of the
high activation temperature and the oxidative conditions of
the activation process, is then veriWed. As it was pointed out
by Beagle (1978), heating may produce several eVects on
rice husk that prevented combustion: formation of a silica
ash cocoon, formation of silicon carbide, strengthening of
the silicacarbon bond.
The rice husk carbonized briquette conformed with
grape must, and then activated at 880 C (RB-5), reacts
with air between 400 and 550 C with a maximum at 480C.
The reaction range and the maximum are rather higher
than the corresponding values for R-2 and correspond to
the overlapping of R-2 peak and activated grape must peak
(Fig. 5). The briquette then has an oxidation resistance
similar to activated rice husk. Mineral content for RB-5
is intermediate between R (not devolatilized rice husk) and
R-2 (carbonized and activated rice husk).
The activated briquette made from wood (EB-4) has
higher oxidation resistance (oxidation temperature) than
rice husk (R). The explanation for this behavior is the pre-
vious carbonization of wood, before the agglomeration and
the activation processes. Finally, the addition of carbonized
rice husk to the briquette (REB-8) increases the oxidation
temperature with respect to EB-4 to a value similar to RB-5
or R-2. In conclusion, the addition of rice husk to the bri-
quettes increases its chemical resistance to combustion.
4. Conclusions
The results of this work may allow to devise processes
for a proper utilization of agro-industrial solid wastes,
which is a very important issue for our regional economy.
The use of mixtures of eucalyptus wood and rice husk car-
bonized to prepare briquettes with grape must as binder is
an interesting alternative for the preparation of activated
carbon briquettes. SpeciWc areas in the acceptable range
for commercial activated carbons (5001500 m
2
/g) were
obtained. It was found that when harsher activation condi-
tions (higher temperatures, times and steam Xows) were
used, higher speciWc areas were obtained, but mechanical
resistance slightly diminished. The inXuence of time and
Xow on porous structure is more important in the low
temperature range than in the high temperature.
From the point of view of the mechanical strength, the
addition of low quantities of rice husk (10% by weight) to
the mixtures considerably improved the mechanical proper-
ties of the prepared briquettes: IRI values higher than 2000
were obtained, which implies a signiWcant improvement in
this property with respect to the briquettes made exclusively
from eucalyptus wood (Deiana et al., 2004) and with the
minimum value established for this property. Results from
the thermogravimetric analysis show that the addition of rice
husk to the briquettes also decreases their combustibility.
Acknowledgements
The UNSJ grant received for this research is acknow-
ledged. The authors are also grateful to Instituto de
Fig. 4. A
BET
versus DCS regression plot.
0
200
400
600
800
1000
1200
1400
0 5 10 15 20 25 30
DCS (kg/cm
2
)
A
B
E
T

(
m
2
/
g
)
Fig. 5. DTG in air for activated and carbonized grape must. () Activated
must; () carbonized must.
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
100 200 300 400 500 600 700
Temperature

C
D
T
G

%
/
d
e
g
r
e
e
Fig. 6. DTG in air for raw materials and materials activated at 880 C. ()
R (rice husk); () R-2; () RB-5; ()EB-4; () REB-8.
-3
-2.5
-2
-1.5
-1
-0.5
0
0.5
100 200 300 400 500 600 700
D
T
G

a
r
b
i
t
r
a
r
y

u
n
i
t
s

Temperature

C
A. Amaya et al. / Bioresource Technology 98 (2007) 16351641 1641
Materiales y Suelos-UNSJ for running the strength tests, to
Arenas Winery (Caucete-San Juan) for providing the con-
centrated grape must, to Departamento de Matemtica-
UNSJ for providing the statistical analysis software and to
Departamento Estrella Campos, Facultad de Qumica,
Universidad de la Repblica, Uruguay, for their assistance
with ultimate analyses.
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