Fuel Processing Technology 92 (2011) 266–270

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Preparation of activated carbons from olive-tree wood revisited.

II. Physical activation with air
A. Ould-Idriss a, M. Stitou b, E.M. Cuerda-Correa a, C. Fernández-González a, A. Macías-García c,⁎,
M.F. Alexandre-Franco a, V. Gómez-Serrano a
a
Department of Organic and Inorganic Chemistry, Faculty of Sciences, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain
b
Departement de Chimie, Université Abdelmalek Esaadi, Tetouan, Morocco
c
Department of Mechanical, Energetic and Materials Engineering, School of Industrial Engineering, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain

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

Article history: Olive-tree has been grown in the Mediterranean countries for centuries. For an adequate development of the
Received 7 December 2009 tree it must be subjected to different treatments such as trimming, large amounts of a woody residue being
Accepted 17 May 2010 produced. Such a residue has been traditionally used as a domestic fuel or simply burnt in the landfield. In
both cases greenhouse gases are generated to a large extent. Thus, the preparation of activated carbons from
Keywords:
olive-tree wood appears as an attractive alternative to valorize this by-product. Commonly, two activation
Activated carbon
strategies are used with such an aim, namely chemical and physical activation. In this study, the optimization
Olive-tree wood
Physical activation
of the physical activation method with air for the production of activated carbon has been analyzed. The
Air results obtained clearly show that if the preparation conditions are adequately controlled, it is possible to
prepare activated carbons showing tailored properties in terms of micro- or mesoporous texture and surface
area.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction given temperature. The main advantage of physical activation over

Activated carbon is a carbonaceous material showing a well-
developed surface area and porous texture. As a consequence, it has
been widely used as adsorbent [1,2] and in catalysis [3,4] or separation
processes [5,6]. The physico-chemical properties of activated carbon
strongly influence its adsorptive behavior and determine its potential
applications. Thus, for the adsorption of molecules in gas phase the
adsorbent should exhibit large volumes of micro- and mesopores [7].
On the contrary, solutes commonly present in aqueous solution use
to be voluminous chemical species, their access to narrow pores being
handicapped due to capillarity effects. This may be avoided if the
adsorbent aimed to liquid-phase adsorption possesses a well-
developed mesoporous texture, since mesopores may act as channels
leading to micropores [8]. Furthermore, the surface functional groups
of activated carbons also play an important role not only in adsorption
processes but also in many other properties of this kind of materials
[9]. The physical activation method consists of two different steps. In
the first one – carbonization – the raw material is thermally treated
under nitrogen atmosphere and a carbonized material with an incipient
porosity is obtained. In the second step – activation – the carbonized
material previously prepared is subjected to thermal treatment in the
presence of a gasifying agent such as carbon dioxide, steam or air at a
⁎ Corresponding author. Tel.: +34 924 289300x86747.
E-mail address: amacias@materiales.unex.es (A. Macías-García).
chemical activation is that it avoids the incorporation of impurities
coming from the activating agent [10], which may affect the chemical
properties of the activated carbon. As a consequence of the activation
step, a certain mass of the carbonized material is lost due to the
formation of gaseous carbon oxides. The burn-off percent influences the
textural properties of the activated carbons although, in general, the
materials produced in this manner usually show a well-developed
surface area and porous texture.
Due to its versatility, activated carbon may be considered as a
virtually universal adsorbent. Namely, it has been successfully used in
drinking water treatment for the elimination of color, flavor, smell
and undesirable organic impurities [11]. Industrial and municipal
wastewaters have also been treated with this kind of adsorbents [12].
Another potential use of activated carbon is the removal of toxic metal
ions such as Pb(II), Cd(II), Cr(III), Cr(VI), etc., from aqueous solution.
Olive-tree (Olea europaea, L) has been grown for centuries in virtually
all the regions with a Mediterranean climate and high solar
exposition. This includes large areas of European countries such as
Spain, Greece and Italy, and other non-European countries such as the
Maghreb, Australia, Chile or Peru. In the olive grove conditioning
tasks, carried out yearly, a large amount of a woody residue is
generated which is usually burnt in the landfield, releasing green-
house gases. Owing to its ligneous character, abundance and low cost
such a residue is suitable to be used as a raw material for the
preparation of activated carbons. However, in spite of its potential use,
only a few studies have been performed previously on the preparation

0378-3820/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.05.018
 A. Ould-Idriss et al. / Fuel Processing Technology 92 (2011) 266–270
of activated carbon from olive wood [13–15]. This work aimed to
optimize the preparation procedure of activated carbons from olive-
tree wood by the physical activation method.
2. Materials and experimental procedure
2.1. Preparation of the activated carbons
The raw material as received was ground, dried and sieved, and
only the fraction of particle sizes comprised between 1 and 2 mm was
chosen as the precursor for the preparation of activated carbons. A
Termolab tubular furnace equipped with Eurotherm904 temperature
controllers and a 1 m long tubular ceramic insert was used for the
preparation of the activated carbons. The temperature within the
furnace was first calibrated and the length and position of the
constant temperature hot zone determined. Approximately 15 g of
the raw material was placed in a stainless steel boat with perforated
ends to facilitate gas flow and positioned in the center of the constant
temperature zone. The carbonization of the samples was carried out at
600 °C. The heating rate was 10 °C min− 1 under a constant N2 flow of
100 cm3 min− 1. The isothermal carbonization time was 2 h. The
activation temperature was, in all cases, 400 °C. A flow of activating
agent (air) equal to 100 cm3 min− 1 was used, the heating rate being
10 °C min− 1. The isothermal activation time was varied between 0.5
and 3 h. Once the isothermal activation time had finished the
activating agent flow was replaced by a N2 flow and the furnace
was cooled to a final temperature of 50 °C. Next, the sample was
removed from the oven and kept in a tightly closed container.
2.2. Characterization of the activated carbons
The sample morphology was observed using a scanning electron
microscope (SEM) model JEOL 5400. The specimens for SEM
observation were prepared by depositing the fibers onto specimen-
stubs with conductive doublesticky copper tapes, and then sputter-
coating (model Polaron SC7640, Quorum Technologies Ltd, UK) the
sample surface with Au–Pd to prevent electrical charging during
examination. Imaging was done in the high vacuum mode under an
accelerating voltage of 15 kV, using secondary electrons.
The samples were texturally characterized by gas adsorption (N2,
−196 °C), mercury porosimetry and mercury and helium density
measurements. The samples were always first oven dried at 120 °C for
24 h. The adsorption isotherms of N2 (purity N 99.998%) at −196 °C
were collected using an adsorption apparatus (Autosorb-1, Quanta-
chrome). Approximately 0.15 g of sample was used in each adsorption
experiment. Adsorbents were placed in a glass container and degassed
at 10− 3 Torr at 120 °C overnight prior to the adsorption measure-
ments. From such isotherms, the micropore volume (Vmi) was derived
by reading the volume adsorbed (Vad) at P / P0 = 0.10 and the
mesopore volume (Vme) by subtraction of (Vmi) from Vad at P / P0 =
0.95, all pore volumes being expressed as liquid volumes. The specific
surface area (SBET) was calculated by applying the BET equation also to
such isotherms [16]. The pore size distribution in the micropore range
was obtained using the Horvath–Kawazoe(HK) method [17]. Accord-
ing to this method, the cumulative pore volume distribution is first
calculated using points from the isotherm at relative pressures
corresponding to previously calculated pore sizes. Then, the cumula-
tive distribution is differentiated to give the pore size distributions
(PSDs).
A Quantachrome porosimeter, Autoscan-60, was used to obtain
the mercury intrusion curves. The values of surface tension and
contact angle used in the computational program of the porosimeter
were 0.480 N m− 1 and 140°, respectively. The mercury density was
determined when performing the mercury porosimetry. The volume
of the sample was obtained by knowing the calibration volume of the
sample holder and from the density of mercury at the working
267
temperature. The helium density was measured using a Quanta-
chrome stereopycnometer.
Finally, the surface chemistry was analyzed by determining the
experimental conditions when the electrical charge density on the
surface of the different adsorbents is zero (i.e., the so-called Point of
Zero Charge or pHPZC) following an experimental procedure analo-
gous to that described by Newcombe et al. [18].
3. Results and discussion
The preparation conditions, nomenclature and yield of the
different samples prepared by the method of physical activation
with air are summarized in Table 1.
The results obtained clearly show that, as expected, as the
isothermal time grows the total yield of the process decreases. Such
a decrease is particularly noticeable when this parameter rises from 2
up to 3 h. Consequently, and in order to avoid excessively large burn-
off percents, the maximum residence time tested was restricted to 3 h.
The SEM images of an only carbonized sample (left) as well as that
of sample activated in air for 1 h (right) are shown in Fig. 1. These
images suggest that the carbonization of the raw material results in a
scarcely altered product that maintains the original lignocellulosic
structure of the olive-tree wood. The activation treatment in air for 1 h
generates a more noticeable degradation of the cellulosic part of the
microstructure although most of the original lignine-like structure
remains only slightly modified. As a consequence, the mass loss in this
case is relatively small. The mass loss effect becomes more important
at larger treatment times (images not shown for brevity), which
results in a progressive decrease of the global yield of the process from
approximately 85% to 58%, as summarized in Table 1.
The N2 adsorption isotherms corresponding to these samples are
shown in Fig. 2 (left). From these isotherms it may be easily concluded
that two different effects are observed. Firstly, for samples treated
for 0.5 and 1 h the adsorption isotherms show an increase in the
adsorbed volume of nitrogen at low values of relative pressure (P / P0)
and a very long plateau which extends to P/P0 ≈ 1.0. This behavior
is characteristic of the type I isotherm of the BDDT classification
system [19] and it is commonly associated to essentially microporous
solids.
On the contrary, the N2 adsorption isotherms show that as the
treatment time increases up to 2–3 h a noticeable change in the
adsorbed volume of nitrogen at low values of relative pressure may be
observed for samples A2 and A3 as compared to samples A05 and A1.
This fact denotes the creation of a significant fraction of micropores
during the air activation process of the olive-tree char. Furthermore,
the isotherms lack of the type-I adsorption isotherm characteristic
horizontal plateau and, on the contrary, from a given value of relative
pressure, a continuously increasing slope tract is observed. Tradition-
ally, this isotherm feature has been associated with mesoporous
materials, the increase in the adsorption being connected with
capillary condensation phenomena occurring in mesopores. These
results indicate that a fraction of the micropores widen and become
larger pores such as mesopores, these pores being of different sizes.
Table 1
Nomenclature, preparation conditions and yields of the activation procedure.
Sample Carbonization Activation Isothermal Yield,
temperature, temperature, time, (%)
(°C) (°C) (h)
A05 600 400 0.5 90.1
A1 600 400 1 84.9
A2 600 400 2 72.5
A3 600 400 3 58.3
268 A. Ould-Idriss et al. / Fuel Processing Technology 92 (2011) 266–270

Fig. 1. SEM images of an only carbonized sample carbonized (left) and of sample A1 (right).

Fig. 2. N2 adsorption isotherms (left) and micropore size distributions (right) of the activated carbons.

It is worth noting that when the thermal treatment time increases mesopores (i.e., around 20 Å) is indicative of a noticeable develop-
from 2 up to 3 h the surface area and porosity scarcely change ment of the mesoporosity.
whereas the yield of the process decreases markedly. This, again, In order to corroborate this latter, mercury intrusion test of the air-
suggests that treatment times longer than 2–3 h should be avoided. activated samples have been performed. The intrusion curves are shown
All the above exposed is corroborated by the values of parameters in Fig. 3 (left). The pronounced slope of these curves in the region of pore
included in Table 2. On the other hand, the curves of pore size radii comprised between 100 and 500 Å is indicative of a noticeable
distribution for the air-activated samples are shown in Fig. 2 (right). development of wide mesopores and macropores. Furthermore, the
Such curves have been calculated by the Horvarth–Kawazoe (HK) pore size distributions derived from the mercury intrusion plots are
method [17] to the N2 adsorption data. The HK plots are in all cases shown in Fig. 3 (right). These plots suggest that the maximum pore
bimodal, with two maxima centered around 7.8 and 11.8 Å of pore volume corresponds, in all cases, to pores of radius approximately equal
diameter. The increase in the micropore volumes as the treatment to 125 Å, i.e., medium-size mesopores. The values of meso- and macro-
time becomes longer is corroborated from these plots. In fact, it may pore volumes calculated from mercury porosimetry (Vme − p and Vma − p,
be observed that the area under the HK curve is larger for samples A2 respectively) are summarized in Table 2. Notice that Vme–p increases for
and A3. The differences existing between samples activated for 0.5/1 h samples activated at larger activation times whereas Vma–p decreases.
and those treated for 2/3 h are also observed in these curves. The open This indicates that a more prolonged activation results in the
ending of the HK plots in the zone of the wider micropores close to the development of mesoporosity to the detriment of macroporosity.
To sum up, the textural characterization of the samples obtained
suggests that the physical activation procedure leads to activated
carbons showing a significant development in terms of specific
Table 2 surface area and porosity. If the preparation conditions are adequately
Textural characteristics of the simples prepared by physical activation with air.
controlled, it is possible to prepare activated carbons showing
Sample SBET Vmi Vme W0 Vme− p Vma− p different properties in terms of micro- or mesoporous texture and
(m2 g− 1) (cm3 g− 1) (cm3 g− 1) (cm3 g− 1) (cm3 g− 1) (cm3 g− 1) surface area. This fact is particularly interesting since the eventual
AA05 413 0.197 0.028 0.191 0.419 0.314 applications of the adsorbents may require specific pore sizes. Thus, in
AA1 413 0.197 0.030 0.195 0.519 0.270 the case of an adsorbent to be used in the liquid–solid interface, the
AA2 481 0.226 0.046 0.221 0.588 0.264 access of solutes to small pores of the adsorbent could be handicapped
AA3 474 0.222 0.048 0.219 0.593 0.233
due to capillarity effects and the adsorbent should possess a well-
 A. Ould-Idriss et al. / Fuel Processing Technology 92 (2011) 266–270
Fig. 3. Mercury intrusion curves (left) and meso- and macropore size distributions (right) of the activated carbons.
developed mesoporous texture because mesopores may act as channels
leading to micropores. On the contrary for the use of adsorbents in the
gas–solid interface large values of micropores are usually required.
Such characteristics markedly condition the potential uses of each
material. It is well-known that one of the most typical applications of
activated carbon is as adsorbent both, in the liquid and the gas phase.
The surface chemistry of a carbonaceous material is a very important
factor conditioning its potential use as an adsorbent. In this work, the
surface chemistry has been studied by determining the pH of the Point
of Zero Charge (pHPZC). Fig. 4 shows the final vs initial pH plots for the
different activated carbons here studied. The intersection of each of
these plots with the y = x function is considered to be the pHPZC. This
figure indicates that for samples treated for 0.5 and 1 h the pHPZC is
around 7.8, whereas for samples treated for 2 or 3 h such parameter
reaches values of 7.2 and 7.4, respectively. Thus, at pH values below 7–
8 the surface groups of the adsorbent will be protonated, i.e.,
positively charged. On the contrary, at pH in the close vicinity of the
pHPZC the net charge of the surface of the adsorbents will be equal to
zero. Finally, at pH values above 7–8 the surface groups will be
deprotonated to a large extent and, consequently, the surface will
exhibit a negative charge. Thus, at values of pH in the vicinity of
neutrality the adsorbents will tend to adsorb preferably non-charged
solutes. Consequently, the activated carbons prepared by physical
Fig. 4. Determination of the pH of the Point of Zero Charge of the different activated
carbons.
269
activation with air will be adequate candidates to be used as
adsorbents of non-polar organic pollutants in solution.
4. Conclusions
From the results obtained in this study on the preparation of
activated carbons by physical activation of olive-tree wood with air
the following conclusions may be drawn.
• Samples prepared show significant values of specific surface area
and micro-, meso- and macropore volumes.
• A remarkable difference between the SBET and pore volumes may
be observed depending on the treatment time for which the
activation process is performed.
• For samples activated for 0.5 or 1 h the development of surface and
texture is noticeable, although lower than that obtained when the
treatment time rises up to 2–3 h. This fact is attributable to the
progressive destruction of the more labile parts of the lignocellulosic
substratum, which is associated to a more remarkable presence of
micro- and mesoporosity in these samples.
• The samples here reported exhibit textural properties that could be
extremely useful for the removal of mainly non-charged organic
pollutants in aqueous solution.
It may be concluded that the physical activation method leads to
samples showing a well-developed porous texture. If the appropriate
conditions are used, it is possible to prepare activated carbons
showing tailored properties in terms of micro- or mesoporous texture
and surface area.
Acknowledgement
Financial support from the AECID through project A/018701/08 is
gratefully acknowledged.
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