Bioresource Technology 100 (2009) 21112117

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Guava seed as an adsorbent and as a precursor of carbon for the

adsorption of acid dyes
Mara P. Elizalde-Gonzlez *, Virginia Hernndez-Montoya
Centro de Qumica, Instituto de Ciencias, Universidad Autnoma de Puebla, Apdo. Postal J-55, Puebla Pue. 72570, Mexico

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

Article history: The guava seed (SEGUVE) was characterized by ultimate and proximate analysis. In SEGUVE the principal
Received 14 January 2008 thermal effect occurred at 363 C and this can be attributed to the cellulose degradation, which was the
Received in revised form 5 September 2008 main component (61%). The guava seed has an acidic character with a high content of bulk functional
Accepted 16 October 2008
groups (C@O) and these characteristics were affected by carbonization. Two samples of carbon were pre-
Available online 16 December 2008
pared from the seeds at 600 and 1000 C without chemical activation. Adsorption of eight acid dyes
belonging to the monoazo and anthraquinone class was studied at 25 C. The non-carbonized SEGUVE
Keywords:
adsorbed the acid dyes more efciently than SEGUVE-C600 and SEGUVE-C1000 although the specic sur-
Guava seed
Carbon
face of the raw material SEGUVE was low.
Adsorption 2008 Published by Elsevier Ltd.
Acid dyes

1. Introduction Water pollution by dyes is a world-wide problem. Particularly

The waste materials from agriculture and forestry, together
with renewable animal materials including microorganisms are
considered biomass. The use of agriculture biomass as precursor
material in the production of activated carbon has a double pur-
pose. First, it converts unwanted, surplus agricultural waste, of
which billions of kilograms are produced annually, to useful, value
added-adsorbents. Secondly, activated carbons can be obtained
from raw material with low cost. The development of carbon
adsorbents is a present topic in materials research and activated
carbon is increasingly being used for the removal of metals and or-
ganic chemicals like dyes of environmental or economic concern
(Daifullah et al., 2003).
Actually, some types of biomass have been used as precursor
materials of activated carbon. For example, carbon with a specic
surface between 524 and 1032 m2 g 1 was obtained from cotton
stalks activated with H3PO4 (Girgis and Ishak, 1999). Highly micro-
porous carbon was prepared from peach stones activated with
ZnCl2 and H3PO4 (Molina-Sabio and Rodrguez-Reinoso, 2004).
Wood mixed with either phosphoric acid or diammonium hydro-
gen phosphate was heated at temperatures between 300 and
500 C using a nitrogen atmosphere or a nitrogen/steam mixture.
As a result of these processes, activated carbons with various sur-
face properties (9501780 m2 g 1) were obtained by Benaddi et al.
(2000).
* Corresponding author. Tel.: +52 2222295500.
E-mail address: melizald@siu.buap.mx (M.P. Elizalde-Gonzlez).
in the textile industry, large quantities of aqueous wastes and
dye efuents are discharged from the dyeing process. They are aes-
thetically and environmentally unacceptable due to the strong per-
sistent colour and high BOD (biochemical oxygen demand) loading.
Most of these dye wastes are toxic and may be carcinogenic (Hu
et al., 2006). For this reason, studies on the adsorption of dyes by
carbon prepared from different sources of biomass can contribute
to wastewater treatment. Carbon prepared from almond shell,
apricot stones, hazelnut sell and walnut shell exhibited a maxi-
mum adsorption capacity of 1.33, 4.11, 8.82 and 3.53 mg g 1,
respectively (Aygn et al., 2003) upon the most explored dye,
methylene blue (basic blue 9). Carbon prepared from bamboo dust,
coconut shell, groundnut shell and rice husk served also to study
the adsorption of this dye (Kannan and Sundaram, 2001).
The adsorption of basic dyes on non-carbonized biomass such
as: Indian rosewood (Garg et al., 2004), maize waste (Dvila-
Jimnez et al., 2005; Elizalde-Gonzlez et al., 2006), mango seed
kernel (Kumar and Kumaran, 2005), rice husk (Gupta et al., 2006),
coconut waste (Elizalde-Gonzlez and Pelez-Cid, 2003) and avo-
cado kernel (Elizalde-Gonzlez et al., 2007) has been investigated
and reviewed by Elizalde-Gonzlez (2006). The adsorption of acid
dyes has been less studied. Some examples are acid blue 29 and acid
red 91 on peat (Ramakrishna and Viraraghavan, 1997), shells of bit-
tim (Pistacia khinjuk stocks) for acid red 183 and acid green 25
(Aydin and Baysal, 2006), peanut hull for amaranth yellow, sunset
yellow and fast green FCF (Gong et al., 2005), and wool ber for acid
red 1, acid blue 90 and acid violet 17 (Saleem et al., 2005).
In guava (Psidium guajava L.) fruits 4% weight corresponds to
the seeds. They are abundant and low cost agricultural waste

0960-8524/$ - see front matter 2008 Published by Elsevier Ltd.

doi:10.1016/j.biortech.2008.10.056
2112 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117

residue easily available in large quantities in Aguascalientes, Mex-
ico, which is after India, the second world leader with an estimated
annual production of 127  109 t (Salunkhe and Kadam, 1995). The
protein main components in guava seed were found to be glutelins
and globulins (Bernardino-Nicanor et al., 2006). Cellulose, hemicel-
lulose and lignin were also identied (Rahman and Saad, 2003;
Ouensanga et al., 2003). Articles reporting the preparation of car-
bon from guava seed are scarce (Rahman and Saad, 2003; Ouensan-
ga et al., 2003; Villegas-Aguilar et al., 2002; Collin et al., 2007),
whereby the authors studied exclusively the adsorption of methy-
lene blue from aqueous solution (Rahman and Saad, 2003; Collin
et al., 2007).
This study comprises the characterization of guava seeds (P.
guajava L.) which were gathered in 2005 from a guava farm in
Calvillo, Aguascalientes. Two samples of carbon were prepared
from SEGUVE at 600 C (SEGUVE-C600) and at 1000 C (SEG-
UVE-C1000). The purpose of this work was to test the adsorption
feasibility of selected acid dyes (monoazo and anthraquinone
class) from aqueous solution on raw and carbonized guava
seed.
2. Methods
2.1. Precursor material
The seed of the guava denoted as SEGUVE, was pretreated be-
fore use by washing with deionized water and drying at 70 C for
24 h. Sieved particles with size 2.4 mm were selected. The material
was characterized by ultimate and proximate analysis according to
the standard procedures. A CHN 1000 Leco elemental analyzer was
used. Cellulose, hemicellulose and lignin were quantied by the
CramptonMaynard, neutral detergent ber (NDF) and acid deter-
gent ber (ADF) methods; according to procedures recommended
for fruits (Crampton and Maynard, 1938; Van-Soest et al., 1991)
using analytical grade reagents. The tannic acid content was quan-
tied according to the tyrosine method using the extraction de-

Table 1
Code, formula, structure, wavelength of maximum absorbance, colour index and chemical class of the studied dyes, and pH of their aqueous solutions.

Generic name and code kmax (nm) pH C.I. Structure Class and molecular weight of the anion
Acid blue 80 (AB80) 627 6.4 61585 H3 C SO3Na Anthraquinone (disulfonic)
C32H28N2Na2O8S2 632.13
O NH CH3

H 3C
H3 C

O NH CH3

H3 C SO3Na
a O NH2
Acid blue 324 (AB324) 600 7.6 Unknown Anthraquinone (monosulfonic)
SO3H
C22H17N3O6S 450.08
NH COCH3

O NH
NaO3S
Acid green 25 (AG25) 642 6.8 61570 Anthraquinone (disulfonic)
O NH CH3
C28H20N2Na2O8S2 576.07

O NH CH3

NaO S
NaO3S 3
Acid Green 27 (AG27) 642 6.1 61580 Anthraquinone (disulfonic)
C34H32N2Na2O8S2 O NH CH2CH2CH2CH3 660.16

O NH CH2CH2CH2CH3

NaO3S
Acid orange 7 (AO7) 490 6.1 15510 OH Monoazo (monosulfonic)
C16H11N2NaO4S 327.04
N N SO3Na

Acid orange 8 (AO8) 490 6.3 15575 OH H 3C Monoazo (monosulfonic)

C17H13N2NaO4S 364.05
N N SO3Na

Acid orange 10 (AO10) 475 6.1 16230 OH Monoazo (disulfonic)

C16H10N2Na2O7S2 405.99
N N

SO3Na

NaO3S
Acid red 1 (AR1) 506 6.0 18050 NaO3S N N Monoazo (disulfonic)
C18H13N3Na2O8S2 463.02
OH

H
N C CH3
O
NaO3S
a
Patent EP 0 139 294 A2 (1984).
 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117 2113

scribed in the ADF method. An analytical balance Ohaus and a Table 2

spectrophotometer UVvis HACH DR 5000 was used. The thermal
behavior was studied by thermogravimetry using a TG 209 Netzsch
analyzer localized at room temperature (22 C) and atmospheric
pressure (760 mm Hg). The experimental conditions were as fol-
lows: initial temperature 25 C; nal temperature 750 C; heating
rate of 10 C min 1 and nitrogen ow of 25 cm3 min 1.
The acidity, basicity and the point of zero charge (pHpzc) were
determined for all samples by potentiometric titration using NaOH
and HCl 0.1 N Merck according to the methodology reported by
Faria et al. (2004). A pH meter Oakton was employed during con-
tinuous deaeration with nitrogen.
The optical micrographs were obtained with an Olympus SZX-
12 microscope with magnication 63. A Nicolet Magna FT-IR-
750 spectroscopy apparatus was employed to determine the pres-
ence of bulk functional groups at room temperature. The pellets
were prepared in each case with the same quantity of ground sam-
ple in KBr.
The specic surface of all samples was determined from the
adsorption isotherms of water vapor and nitrogen. A desiccator
method was employed to obtain adsorption isotherms of water va-
por at 25 C by using H2SO4 H2O solutions as hygrostat. An auto-
mated adsorption apparatus (Quantachrome/Autosorb-1) was
used for the determination of nitrogen adsorption isotherms at
196 C. The specic surface was calculated by the Brunauer, Em-
mett and Teller (BET) equation and the pore size distribution with
the BarretJoynerHalenda (BJH) equation.
2.2. Preparation of carbon
Two samples of carbon were prepared from 2.4 mm particles of
SEGUVE. A horizontal tubular furnace EUROTHERM with a quartz
reactor was used. Samples of SEGUVE (30 g) were heated from
room temperature to 600 (for SEGUVE-C600) or 1000 C (for SEG-
UVE-C1000) in the atmosphere of the products released as a result
of the carbonization. The temperature program comprised two
heating ramps: (1) from room temperature to 70 C with
8 C min 1 and (2) from 70 to 600 or 1000 C with 5 C min 1. Iso-
thermal time at maximum heat treatment temperature was 4 h.
2.3. Adsorption of dyes
SEGUVE, SEGUVE-C600 and SEGUVE-C1000 were ground and
sieved to obtain a particle size of 0.63 mm. Adsorption tests were
performed without pH adjustment (see pH of the solution in Table
1) employing the following dyes: acid blue 80, acid blue 324, acid
green 25, acid green 27, acid orange 7, acid orange 8, acid orange
10 and acid red 1, whose structures are depicted in Table 1. The
dyes were commercial products from Clariant and Aldrich and
were used without purication. The adsorption tests were mea-
sured at 25 C in batch experiments by using polycarbonate cylin-
drical cells with a lid, a denite amount of adsorbent and a xed
Proximate analysis and chemical characterization of the raw material after washing
and drying.
Parameter Weight (%) Parameter Weight (%)
Moisture 3.5 Cellulose 60.6
Volatile matter 69.8 Hemicellulose 9.2
Ashes 1.3 Lignin 7.6
Fixed carbon 25.4 Tannic acid 3.5
Carbon 52.4
Hydrogen 6.4
Nitrogen 1.5
Oxygen 39.8
with those reported in other studies (cellulose: 2831% and lignin:
4042% (Rahman and Saad, 2003; Ouensanga et al., 2003). This can
be attributed rstly, to the procedure used by the authors, which is
suitable for the analysis of paper, and secondly to the fact that the
determination was performed using the ground guava seed. How-
ever, the biopolymeric constitution integrated by cellulose, hemi-
cellulose and lignin reaches in our work 77% approaching the
reported value of 8586% (Rahman and Saad, 2003; Ouensanga
et al., 2003).
The thermal behavior of SEGUVE is shown in Fig. 1, where four
peaks appear in the DTG curves being the more intensive at 306
and 363 C. They can be attributed, as in the case of olive stones
(Caballero et al., 1997) to water and to the degradation of hemicel-
lulose, cellulose and lignin. However, judging by the average
temperature of maximum weight loss at 363 C, the degradation
behavior is similar to that reported for other celluloses analyzed
in nitrogen atmosphere (rfo et al., 1999). Lignin, whose thermal
degradation reaction occurs over a relative wide range of
temperatures (200600 C) (Garca-Prez et al., 2001) seems not
to be the most signicant component in this guava seed sample,
congruently with the chemical analysis, but contradictory to the
reported 40% content (Rahman and Saad, 2003). Finally, the ther-
mal degradation is practically completed at 500 C as in the case
of mango seed (Elizalde-Gonzlez and Hernndez-Montoya,
2007), indicating that the temperature required in the preparation
of carbon from SEGUVE can be established starting at 500 C.
In any bed adsorption process, the adsorbent particle size plays
an important role. For example, using smaller sizes in xed bed
creates problems like solid agglomeration, air binding and fouling.
Under this perspective, the guava seeds were ground selecting not
an extremely small particle size of 0.63 mm, in contrast with the
size used in other work 0.15 mm (Gong et al., 2005). Fig. 2a is a
photograph of the original size of the seeds, while Fig. 2bd are
optical micrographs of the seed and carbon with the particle size
used in the adsorption test (0.63 mm). The gures depict the stony
100 0
Derivative of mass (% C )
-1

volume of the aqueous dye solution (50 mg l 1). The solution that 80 -0.5
resulted from the adsorption equilibrium after 24 h was separated
Mass (%)

from the exhausted adsorbent and centrifuged (12,000 rpm), and

nally analyzed by spectrophotometry UVvis at the wavelength
60 (a) -1.0

of maximum absorbance (see Table 1). A spectrophotometer HACH

DR 5000 was employed. 40 -1.5

3. Results and discussion

(b)
20 -2.0

3.1. Characterization of the raw and carbonized seed 0 100 200 300 400 500 600 700
Temperature, C
Results of the chemical characterization of the guava seeds are
presented in Table 2. The cellulose and lignin values do not agree Fig. 1. TG (a) and DTG (b) curves of SEGUVE in nitrogen atmosphere.
2114 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117

Fig. 2. Photograph of the guava seeds in the original size (a) and optical micrographs with magnication 63 and particle size of 0.63 mm of SEGUVE (b), SEGUVE-C600 (c)
and SEGUVE-C1000 (d).

irregular form of the seed (Fig. 2a), and the heterogeneous, rough
surface of a particle after grounding and carbonization at 600
and 1000 C (Fig. 2bd). In the ground seed fraction (Fig. 2b) crys-
talline fragments are observed together with a thin yellow husk
and a white core. No differences in the surface of the two carbon
samples (see, Fig. 2c and d) can be observed.
As expected, various organic functionalities disappeared from
the seed with carbonization (see IR spectra of the samples in
Fig. 3). The principal bands for non-carbonized SEGUVE were the
following: The band around 3450 cm 1 can be assigned to stretch-
ing NH or OH vibrations, and the band at 2927 cm 1 to CH
stretching. The bands at 1743 cm 1 (C@O) and 1243, 1050 cm 1
(CO) can be assigned to ester groups. The enolized b-diketone
C@O stretching characteristic band is also observed at
1651 cm 1. A split band observed at 1515 cm 1 is known for the
aminoacid L-tyrosine cycle (Ramachandran and Natarajan, 2002)
c Results of the textural characterization presented in Table 4
and considering the glutelins amino acids content in guava seeds,
the assignation of this band is congruently assigned to an amino
acid (Bernardino-Nicanor et al., 2006). For carbonized SEGUVE-
C600 and SEGUVE-C1000 only the bands at 3450 and 1050 cm 1
prevail and no substantial differences can be observed among them
in the IR spectra. The density (see Table 3) is similar for the sam-
ples carbonized at two different temperatures and the ash content
in SEGUVE-C1000 decreases with regard to SEGUVE-C600, due
probably to carbonate decomposition. The same trend is observed
in the yield of the two carbons. While both carbonized samples
cannot be distinguished by their morphology and bulk properties,
the acidic properties of the surface draw a major distinction be-
tween raw and carbonized samples, and between two different
carbonization temperatures as demonstrated in Table 3. The raw
seed SEGUVE is mainly acidic and turned basic in the carbonized
samples as a result of the decomposition of functional groups
and the possible formation of basic groups as the pyrones (Faria
et al., 2004) showing IR bands at 1050 cm 1 and in the region
16501500 cm 1 (C@O and C@C). The temperature of carboniza-
tion used to produce SEGUVE-C600 and SEGUVE-C1000 affected
the basicity and the surface zero charge pHpzc as it can be observed
in Table 3.
demonstrated that both precursor and carbonized guava seeds
exhibited low specic surface values and were macroporous mate-
rials. An improvement of 42% in the specic surface value was ob-
tained when carbonization temperature was changed from 600 to
1000 C. The values were however, markedly low.

Table 3
b Yield, bulk density and surface properties of the raw and carbonized seeds.

Parameter SEGUVE SEGUVE-C600 SEGUVE-C1000

Transmittance (%)

Yield (%) 30.2 24.5

Ashes (%) 1.3 4.4 4.1
Bulk density (g ml 1) 0.7 0.5 0.6
Acidity (mmol g 1) 1.23 0.02 0
Basicity (mmol g 1) 0.04 0.16 0.12
pHpzc 5.5 8.8 9.6

a
Table 4
Adsorption parameters obtained by application of the BET model to the adsorption
isotherms of water vapor at 25 C and nitrogen at 196 C.
1456
Material with BET Ssp R2 Vtotal Average pore
1243 particle size parameters (m2 g 1
) (cm3 g 1
) diameter ()
2927 0.63 mm
1515 am C
1
1651 550 (mg g )
1050
3447 1743 SEGUVEa 41.0 26 136 0.986 0.163
SEGUVEb 0.004 62
SEGUVE-C600b 2.0 38 7 0.999 0.026 55
4000 3000 2000 1500 1000 500 SEGUVE-C1000b 3.6 4 12 0.949 0.039 50
-1
Wavenumber (cm )
a
Isotherms of water vapor at 25 C.
b
Fig. 3. FT-IR spectra of SEGUVE (a), SEGUVE-C600 (b) and SEGUVE-C1000 (c). Isotherms of nitrogen at 196 C.
 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117
3.2. Comparison of the adsorption properties
Adsorption of gases and vapors is generally used quantitatively
to characterize solid materials, but the form and particularities of
the adsorption isotherm involve valuable qualitative information
about the nature of the surface. Fig. 4a shows substantial differ-
ences in the interaction of nitrogen with the precursor SEGUVE
and with the carbonized samples SEGUVE-C600 and SEGUVE-
C1000. The type III isotherm, according to the IUPAC classication
(Sing, 1989), of the raw SEGUVE denotes weak adsorbentadsor-
bate interaction in comparison with the relative strong nitrogen
nitrogen interactions. However, the carbonized seeds indicated
no formation of a well dened monolayer and multilayer adsorp-
tion. The sample obtained at 600 C exhibited (not shown here)
type H3 hysteresis (Rouquerol et al., 1999) without plateau at high
relative pressure; belonging thus to type IIb isotherms (Rouquerol
et al., 1999) observed for macroporous solids with slit-shaped
pores. Though diminution of the constant C value for SEGUVE-
C1000 (C = 4) in comparison with SEGUVE-C600 (C = 38), as shown
in Table 4, the sample obtained at 1000 C still exhibited a
smoothed type II isotherm indicating an increase in the mobility
of the nitrogen molecules adsorbed on non-porous particles inter-
connected by macrocavities. The pore size distribution curves de-
picted in the insert of Fig. 4a showed vaguely a diminution of the
pore diameter with carbonization and with temperature (see shift-
ing of the line interconnecting the peak maxima in the insert in
Fig. 4a).
The adsorption isotherm of water vapor on the precursor SEG-
UVE should depend on the presence of polar sites on the surface
and water is supposed to be able to penetrate all small cavities
in the micropore range. As shown in Fig. 4b, the type II adsorption
isotherm did not develop smoothly, but stairwise reecting pri-
mary adsorption centers and multilayer formation by hydrogen
bonding. The adsorbed amount of water exceeded much the extent
of adsorbed nitrogen and yield for SEGUVE a specic surface of
Ssp = 136 m2 g 1, when from the nitrogen adsorption isotherm
the determination of Ssp was not feasible. The total volume of
water adsorbed by SEGUVE of 213 cm3 g 1 in contrast with the ad-
sorbed nitrogen (4 cm3 g 1) indicated either unhindered water
penetration, or partial rehydratation of the solid sample. Water
adsorption on the carbonized samples was not measured, since
as demonstrated in the IR study, the small content of polar groups
28
0.04
dV / d log(Dp )
24
0.02
20
16
Vads (cm g )
3 -1
12
8 70
0
0 0.2
Fig. 4. Adsorption isotherms of nitrogen on SEGUVE (1), SEGUVE-C600 (2) and SEGUVE-C1000 (3) at
size distribution calculated by the BJH method.
2115
should lead to low afnity of SEGUVE-C600 and SEGUVE-C1000 for
water.
As shown from the height of the bars in Fig. 5, the adsorption on
non-carbonized SEGUVE, thermally activated by carbonization at
600 (SEGUVE-C600) and 1000 C (SEGUVE-C1000) against eight
acid anionic dyes, was in general higher on the non-carbonized
guava seeds exhibiting an acidity similar to that of Pistacia stocks
(Aydin and Baysal, 2006). This pointed out the intermolecular
interaction caused between the negatively charged surface im-
mersed in solution and cationic species generated from the anionic
dyes. All the studied anthraquinone dyes were 1,4-diaminoanthr-
aquinones with secondary amine groups (except AB324), whose
substituents at the positions 1 and 4 were capable of forming intra-
molecular hydrogen-bond with the anthraquinone carbonyl. Fur-
thermore, protonation of aminoanthraquinone dyes can occur
either at the nitrogen atom or at oxygen to give a resonance stabi-
lized cation, but only one protonated site (Gordon and Gregory,
1983). In the case of the hydroxyazo dyes studied by us, the intra-
molecular hydrogen-bond dominates the recurring hydroxyazo
hydrazone tautomerism. Both in the 2-phenylazo-1-naphthol dye
(AR1), and in the 1-phenylazo-2-naphthol dyes (AO7, AO8 and
AO10), the hydrazone form predominates (Gordon and Gregory,
1983). Protonation occurring at the b-nitrogen atom of the azo
group gives the positively charged azonium tautomer most likely
responsible for the interaction.
The amounts removed were greater for the anthraquinone dyes
group than for the azo dyes. The largest removed amount was on
SEGUVE and corresponded to acid green 27, the largest molecule.
The low adsorption of the disulfonic dye acid orange 10 on SEGUVE
suggested absence of protonation, thus showing superior adsorp-
tion on SEGUVE-C1000. Both carbon samples exhibited comparable
basicity and practically no acidity, the main difference was a 40%
larger specic surface in the sample carbonized at 1000 C.
The guava seeds in its non-carbonized form, with particle diam-
eter 0.63 mm and adsorbent dosage of 30 mg ml 1 adsorbed for
example, 0.10 mg g 1 of AO10 at 25 C and pH 6 from a 50 mg l 1
dye solution, which corresponded to a 7% removal. For comparison,
peanut hull (Gong et al., 2005) with particle diameter 0.15
0.18 mm and adsorbent dosage of 5 mg ml 1 removed 10% of the
dye Sunset yellow, an isomer of AO10 at the same temperature
and pH. The shells of bittim (Aydin and Baysal, 2006) exhibited
similar acidity as the guava seeds SEGUVE. From a 50 mg l 1
280
a b
3
210
3
2
0 1
2
140
10 100 1000
Pore Diameter ()
1 0
0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
p / p0 p / p0
196 C (a) and of water vapor on SEGUVE at 25 C (b). Insert in (a): Pore
2116 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117
2.0
a b
AG27
AB324
AG25
AB80
AO8
1.5
AO7
a (mg g )
-1
1.0
AR1
A010
0.5
0 0
Fig. 5. Comparison of the adsorption capacity of SEGUVE (a), SEGUVE-C600 (b) and SEGUVE-C1000 (c) upon different acid dyes at 25 C and from an initial concentration of
50 mg l 1 and adsorbent dosage 30 mg ml 1.
AG25 dye solution the removal by these shells (dosage
20 mg ml 1) was 80% at 35 C and 77% by guava seeds (dosage
30 mg ml 1) at 25 C, using in both cases the same particle size.
On wool ber 49% of the dye AR1 was removed at 23 C from a
5 mg l 1 solution and adsorbent dosage of 6 mg ml 1 (Saleem
et al., 2005). The guava seeds removed in this work 20% AR1 from
a 50 mg l 1 solution and adsorbent dosage of 30 mg ml 1 at 25 C.
It is worth noting that the inuence of low pH values on the
adsorption of acid dyes has been established for Pistacia stocks (Ay-
din and Baysal, 2006), peanut hull (Gong et al., 2005) and wool
(Saleem et al., 2005) and that the comparisons described above
do not correspond to the maximal performance of the natural sor-
bents, but to values obtained at the same pH (6.0) in this report.
This work has focused on the characterization of the guava seeds as
a natural sorbent and as a precursor, and on their ability to adsorb
anionic dyes. The role of pH, particle size and temperature is being
explored at present in our laboratory.
4. Conclusion
The guava seed SEGUVE is a lignocellulosic material with a large
quantity of acidic groups, which can be totally degraded by ther-
mal treatment at 500 C. SEGUVE can be used as a precursor of car-
bon or as a potential adsorbent for the removal of acid dyes. The
specic surface of the carbon samples with particle size 0.63 mm,
prepared by thermal treatment without chemical activation at
600 and 1000 C was low (<20 m2 g 1). The adsorption efciency
of the raw material upon eight acid dyes was superior to that of
the carbon samples, but when the carbonization temperature in-
creased from 600 to 1000 C, the adsorbed amount increased.
Acknowledgements
This work was supported by CONACyT (Project SEP-2004-C01-
46377). VHM acknowledges the grant (196409) received from
the same organization.
References
Aydin, H., Baysal, G., 2006. Adsorption of acid dyes in aqueous solutions by shells of
bittim (Pistacia khinjuk stocks). Desalination 196, 248259.
Aygn, A., Yenisoy-Karakas, S., Duman, I., 2003. Production of granular activated
carbon from fruit stones and nutshells and evaluation of their physical,
chemical and adsorption properties. Micropor. Mesopor. Mater. 66, 189195.
Benaddi, H., Bandosz, T.J., Jagiello, J., Schwarz, J.A., Rouzaud, J.N., Legras, D., Bguin,
F., 2000. Surface functionality and porosity of activated carbons obtained from
chemical activation of wood. Carbon 38, 669674.
2.0 2.0
c
AG27
1.5 1.5
0.5 0.5
AB324
AB80
AO8
AO7
AG27
AR1
AG25
AO8
AR1
A010
AB324
AB80
AG25
AO7
A010
0
Acid dyes
Bernardino-Nicanor, A., Scilingo, A.A., Aon, M.C., Dvila-Ortiz, G., 2006. Guava seed
storage protein: fractionation and characterization. LWT Food Sci. Technol. 39,
902910.
Caballero, J.A., Marcilla, A., Conesa, J.A., 1997. Thermogravimetric analysis of olive
stones with sulphuric acid treatment. J. Anal. Appl. Pyrol. 44, 7588.
Collin, G.J., Awang, B., Duduku, K., Kok Onn, S., 2007. Sorption of methylene blue dye
in aqueous solution by optimized carbon prepared from guava seeds (Psidium
guajava L.). Mater. Sci. (MEDZIAGOTYRA) 13, 8387.
Crampton, E.W., Maynard, L.A., 1938. The relation of cellulose and lignin content to
the nutritive value animal feeds. J. Nutr. 15, 383395.
Daifullah, A.A.M., Girgis, B.S., Gad, H.M.H., 2003. Utilization of agro-residues (rice
husk) in small waste water treatment plants. Mater. Lett. 57, 17231731.
Dvila-Jimnez, M.M., Elizalde-Gonzlez, M.P., Pelez-Cid, A.A., 2005. Adsorption
interaction between natural adsorbents and textile dyes aqueous solution.
Colloid Surf. A 254, 107114.
Elizalde-Gonzlez, M.P., Pelez-Cid, A.A., 2003. Removal of textile dyes from
aqueous solutions by adsorption on biodegradable wastes. Environ. Technol.
24, 821829.
Elizalde-Gonzlez, M.P., 2006. Development of non-carbonized natural adsorbents
for removal of textile dyes. Trends Chem. Eng. 10, 5566.
Elizalde-Gonzlez, M.P., Geyer, W., Guevara-Villa, M.R.G., Mattusch, J., Pelez-Cid,
A.A., Wennrich, R., 2006. Characterization of an adsorbent prepared from maize
waste and adsorption of three classes of textile dyes. Colloid Surf. A 278, 8997.
Elizalde-Gonzlez, M.P., Hernndez-Montoya, V., 2007. Characterization of mango
pit as raw material in the preparation of activated carbon for waste water
treatment. Biochem. Eng. J. 36, 230238.
Elizalde-Gonzlez, M.P., Mattusch, J., Pelez-Cid, A.A., Wennrich, R., 2007.
Characterization of adsorbent materials prepared from avocado kernel seeds:
natural, activated and carbonized forms. J. Anal. Appl. Pyrol 78, 185193.
Faria, P.P.C., rfo, J.J.M., Pereira, M.F.R., 2004. Adsorption of anionic and cationic
dyes on activated carbons with different surface chemistries. Water Res. 38,
20432052.
Garca-Prez, M., Chaala, A., Yang, J., Roy, C., 2001. Co-pyrolysis of sugarcane
bagasse with petroleum residue. Part I: thermogravimetric analysis. Fuel 80,
12451258.
Garg, V.K., Amita, M., Kumar, R., Gupta, R., 2004. Basic dye (methylene blue)
removal from simulated wastewater by adsorption using Indian rosewood
sawdust: a timber industry waste. Dyes Pigments 63, 243250.
Girgis, B.S., Ishak, M.F., 1999. Activated carbon from cotton stalks by impregnation
with phosphoric acid. Mater. Lett. 39, 107114.
Gong, R., Ding, Y., Li, M., Yang, C., Lui, H., Sun, Y., 2005. Utilization of powdered
peanut hull as biosorbent for removal of anionic dyes from aqueous solution.
Dyes Pigments 64, 187192.
Gordon, P.F., Gregory, P., 1983. Organic Chemistry in Colour. Akademie-Verlag,
Berlin.
Gupta, V.K., Mittal, A., Jain, R., Mathur, M., Sikarwar, S., 2006. Adsorption of safranin-
T from wastewater using waste materials-activated carbon and activated rice
husks. J. Colloid Interf. Sci. 303, 8086.
Hu, Z.G., Zhang, J., Chan, W.L., Szeto, Y.S., 2006. The sorption of acid dye onto
chitosan nanoparticles. Polymer 47, 58385842.
Kannan, N., Sundaram, M.M., 2001. Kinetics and mechanism of removal of
methylene blue by adsorption on various carbons a comparative study.
Dyes Pigments 51, 2540.
Kumar, K.V., Kumaran, A., 2005. Removal of methylene blue by mango seed kernel
powder. Biochem. Eng. J. 27, 8393.
Molina-Sabio, M., Rodrguez-Reinoso, F., 2004. Role of chemical activation in the
development of carbon porosity. Colloids Surf. A 241, 1525.
rfo, J.J.M., Antunes, F.J.A., Figueiredo, J.L., 1999. Pyrolysis kinetics of ligno-
cellulosic materials three independent reactions model. Fuel 78, 349358.
 M.P. Elizalde-Gonzlez, V. Hernndez-Montoya / Bioresource Technology 100 (2009) 21112117
Ouensanga, A., Largitte, L., Arsene, M.A., 2003. The dependence of char yield on the
amounts of components in precursors for pyrolysed tropical fruit stones and
seeds. Micropor. Mesopor. Mater. 59, 8591.
Rahman, I.A., Saad, B., 2003. Utilization of guava seeds as a source of activated
carbon for removal of methylene blue from aqueous solution. Malays J. Chem. 5,
814.
Ramachandran, E., Natarajan, S., 2002. Crystal growth of some urinary stone
constituents: I. In-vitro crystallization of L-tyrosine and its characterization.
Cryst. Res. Technol. 37, 11601164.
Ramakrishna, K.R., Viraraghavan, T., 1997. Dye removal using low cost adsorbents.
Water Sci. Technol. 36, 189196.
Rouquerol, F., Rouquerol, J., Sing, K., 1999. Adsorption by Powders and Porous Solid.
Academic Press, New York.
2117
Saleem, M., Pirzada, T., Qadeer, R., 2005. Sorption of some azo-dyes on wool ber
from aqueous solutions. Colloids Surf. A. 260, 183188.
Salunkhe, D.K., Kadam, S.S., 1995. Handbook of Fruit Science and Technology:
Production, Composition Storage and Processing. Marcel Dekker, New York.
Sing, K.S.W., 1989. The use of gas adsorption for the characterization of porous
solids. Colloids Surf. 38, 113124.
Van-Soest, P.J., Robertson, J.B., Lewis, B.A., 1991. Methods for dietary ber, neutral
detergent ber, and nonstarch polysaccharides in relation to animal nutrition. J.
Dairy Sci. 74, 35833597.
Villegas-Aguilar, P.J., Medina-Alvarez, B.F., Bucki-Wasserman, B., 2002. Incremento
de la capacidad de adsorcin de carbones activados obtenidos a partir de
fuentes renovables mediante lavado con soluciones de NaOH. Avances en
Energas renovables y medio ambiente 6, 06.07-06.10.