ARTICLE IN PRESS

Journal of Environmental Management 85 (2007) 833846

www.elsevier.com/locate/jenvman

Review

Waste materials for activated carbon preparation and its use

in aqueous-phase treatment: A review
Joana M. Diasa,1, Maria C.M. Alvim-Ferraza,,1, Manuel F. Almeidaa,2,
Jose Rivera-Utrillab, Manuel Sanchez-Polob
a
LEPAE, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal
b
Departamento de Qumica Inorganica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain
Received 9 March 2007; received in revised form 6 July 2007; accepted 31 July 2007
Available online 19 September 2007

Abstract

Commercial activated carbon is a preferred adsorbent for the removal of micropollutants from the aqueous phase; however, its
widespread use is restricted due to high associated costs. To decrease treatment costs, attempts have been made to nd inexpensive
alternative activated carbon (AC) precursors, such as waste materials. Some reviews report the use of waste materials for the preparation
of AC; however, these studies are restricted to either type of wastes, preparation procedures, or specic aqueous-phase applications. The
present work reviews and evaluates literature dedicated both to the preparation of AC by recycling different types of waste materials and
also to its application in various aqueous-phase treatments. It is clear that conventional (from agriculture and wood industry) and non-
conventional (from municipal and industrial activities) wastes can be used to prepare AC, that can be applied in various aqueous
treatment processes, namely to remove organic pollutants, dyes, volatile organic compounds, and heavy metals. Moreover, high surface
areas can be obtained using either physical or chemical activation; however, combined treatments might enhance the surface properties of
the adsorbent, therefore increasing its adsorption capacity. It is evident from the revision made that AC prepared from both conventional
and non-conventional wastes might effectively compete with the commercial ones. This happens mostly when the activation procedures
are optimized considering both the raw material used to produce the carbons and the contaminants to be removed.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: Review; Activated carbon; Waste materials; Aqueous-phase treatments

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
2. AC for the removal of pollutants from aqueous phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
2.1. Adsorption of organic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
2.2. Adsorption of heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
3. Waste materials for the preparation of AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
3.1. Conventional wastes (from agriculture and wood industry) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
3.2. Non-conventional wastes (from municipal and industrial activities) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840

Abbreviations: AC, activated carbon/activated carbons; ACC, activated carbon cloths; ACF, activated carbon bbers; ChA, chemical activation; GAC,
granular activated carbon; PAC, powdered activated carbon; PET, polyethylene terephthalate; PhA, physical activation; PVC, polyvinyl chloride; VOC,
volatile organic compounds
Corresponding author. Tel.: +351 22 5081688; fax: +351 22 5081449.
E-mail address: aferraz@fe.up.pt (M.C.M. Alvim-Ferraz).
1
Departamento de Engenharia Qumica.
2
Departamento de Engenharia Metalurgica e de Materiais.

0301-4797/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2007.07.031
 ARTICLE IN PRESS
834 J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846
4.1. Conventional wastes as AC precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 841
4.2. Non-conventional wastes as AC precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 843
1. Introduction
Activated carbons (AC) are known as very effective
adsorbents due to their highly developed porosity, large
surface area (that can reach 3000 m2 g 1), variable char-
acteristics of surface chemistry, and high degree of surface
reactivity (Rodrgues-Reinoso, 1997; Bansal et al., 1988).
These unique characteristics make AC very versatile
materials, which have been studied not only as adsorbents,
but also as catalysts and catalyst supports used for
different purposes such as the removal of pollutants from
gaseous or liquid phases and the purication or recovery of
chemicals (Derbyshire et al., 2001). However, due to their
high production costs, these materials tend to be more
expensive than other adsorbents.
Currently, there are many studies on the development of
low-cost adsorbents, namely by using waste materials for
that purpose. Also, several reviews report a great deal of
work done on their application for the removal of specic
pollutants from aqueous phase, mainly heavy metals and
dyes (Crini, 2006; Chuah et al., 2005; Ramesh et al., 2005;
Babel and Kurniawan, 2003; Wang et al., 2003). Shukla
et al. (2002) presented a review on the use of sawdust for
the removal of contaminants from water and Brown et al.
(2000) reviewed the application of peat to remove metals
from waste streams. Despite the satisfactory results
obtained using some of these low-cost adsorbents, AC
are known to be more efcient in adsorbing a greater
amount of pollutants. AC production costs can be reduced
by either choosing a cheap raw material or by applying a
proper production method (La, 2001); nevertheless, it is
still a challenge to prepare AC with very specic
characteristics, such as a given pore size distribution, and
using low-cost raw materials processed at low temperature
(less energy costs) (Sudaryanto et al., 2006). Therefore, it is
of extreme relevance to nd suitable low-cost raw materials
that are economically attractive and at the same time
present similar or even better characteristics than the
conventional ones. The use of waste materials for the
preparation of AC is also very attractive from the point of
view of their contribution to decrease the costs of waste
disposal, therefore helping environmental protection.
There are some reviews reporting the use of waste
materials for the production of AC (Ioannidou and
Zabaniotou, 2007; Mohan and Pittman, 2006; Gupta and
Ali, 2002; Mohan et al., 2000; Pollard et al., 1992);
however, such studies are restricted to either type of waste,
preparation procedures, or specic aqueous-phase applica-
tions. The present work reviews and evaluates literature
dedicated both to the preparation of AC by recycling
different types of waste materials and also to its application
in various aqueous-phase treatments. To support the
revision, an overview on fundamental principles regarding
AC application in aqueous phase is also presented.
2. AC for the removal of pollutants from aqueous phase
The aqueous-phase adsorption of both organic and
inorganic compounds has been a very important applica-
tion of AC. In fact, it is known that around 80% of the
world production of AC is used in liquid-phase applica-
tions (Moreno-Castilla and Rivera-Utrilla, 2001). Also, the
treatment of wastewater and contaminated groundwater
using AC is increasing throughout the world as a result of
the limited sources of water supply (Meidl, 1997). In such
treatments, AC is normally used as a primary treatment,
preceding other purication processes, or as a nal tertiary
or advanced treatment.
When using AC, the adsorption process results from
interactions between the carbon surface and the adsorbate.
These interactions can be electrostatic or non-electrostatic.
When the adsorbate is an electrolyte that dissociates in
aqueous solution, electrostatic interactions occur; the
nature of these interactions, that can be attractive or
repulsive, depends on the: (i) charge density of the carbon
surface; (ii) chemical characteristics of the adsorbate; and
(iii) ionic strength of the solution. Non-electrostatic
interactions are always attractive and can include: (i) van
der Waals forces; (ii) hydrophobic interactions; and (iii)
hydrogen bonding.
According to Moreno-Castilla (2004), the properties of
the adsorbate that mainly inuence the adsorption process
in AC are: (1) molecular size; (2) solubility; (3) pKa; and (4)
nature of the substituents (in the case of aromatic
adsorbates). The molecular size determines the accessibility
of the adsorbate to the pores of the carbon, the solubility
determines the degree of hydrophobic interactions between
the adsorbate and the carbon surface and pKa controls the
dissociation of the adsorbate (if it is an electrolyte). When
the adsorbate is aromatic, the substituents of the aromatic
ring have the ability to withdraw or release electrons, which
therefore affects the non-electrostatic interactions between
the adsorbate and the AC surface.
When the AC is in contact with an aqueous solution, an
electric charge is generated. This charge results from either
the dissociation of the surface functional groups of the
carbon or the adsorption of ions from the solution, and
strongly depends on the solution pH and on the surface
characteristics of the adsorbent (Li et al., 2002). The central
issue for ion adsorption from an aqueous medium is the
understanding of the mechanisms by which ionic species
become attached to the carbon surface. There are three
 ARTICLE IN PRESS
J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846
different mechanisms by which metallic ions (or other ions)
are removed from an aqueous solution. The rst states that
the process is based on electrostatic adsorbateadsorbent
interactions being totally dependent on the existence of
carbon surfaces functionality, especially oxygen surfaces
complexes (ion-exchange process). The second one suggests
that enhanced adsorption potentials, as occurs in the
narrowest of microporosity, may be strong enough to
adsorb and retain ions. The third mechanism is based on
the hard and soft acids and bases concept, consequence of
the amphoteric nature of carbon surfaces.
Variable amounts of atoms, known as heteroatoms, can
be found in AC (e.g. oxygen, hydrogen, nitrogen and
sulphur). These atoms, which might have origin in the raw
material or could be introduced during preparation or
further treatments (Radovic et al., 2000), deeply inuence
the charge, hydrophobicity and electronic density of the
AC surface. The carbon surface chemistry is, therefore,
inuenced by the presence of heteroatoms (El-Sayed and
Bandosz, 2004) and has a great inuence on both,
electrostatic and non-electrostatic interactions. Additional
information regarding the surface characteristics of AC
which determine the removal of pollutants from the
aqueous phase can be found in a review by Moreno-
Castilla and Rivera-Utrilla (2001).
Based on numerous papers currently related with the
adsorption of organic pollutants and heavy metals in AC,
the fundamentals regarding the adsorption of these
micropollutants will be discussed from now on.
2.1. Adsorption of organic pollutants
The discharge of industrial wastes (generated in chemical
industry activities) and the leaching from agricultural and
forest land (when the application of chemical fertilizers and
pesticides is made) are the main sources of organic
pollution in several water streams.
The application of conventional biological treatments
for the removal of organic refractory contaminants from
aqueous solutions has proven to be very ineffective;
therefore, the satisfactory results obtained by using AC
led to their wide application for the removal and control of
synthetic and naturally occurring organic chemicals in
water (Gupta et al., 2006, 1997a; Li et al., 2002; Srivastava
et al., 1993).
Literature clearly shows a greater amount of studies on
the adsorption of organic compounds as compared with
the inorganic ones (Moreno-Castilla, 2004), probably due
to the greatest complexity associated with the mechanisms
regarding the adsorption of organic compounds. However,
the specic mechanism by which the adsorption of several
organic compounds takes place is still ambiguous and
controversial.
From the review by Radovic et al. (2000), the following
arguments appear to have solid experimental and theore-
tical support: (i) adsorption of aromatic compounds is
partly physical and partly chemical and future work should
835
carefully distinguish between the two; and (ii) pp
interactions might prevail under favourable conditions
and their strength can be modied by ring substitution on
both, the adsorbate and the adsorbent. Moreover, there are
different opinions about whether in the formation of
electron donoracceptor complexes it is the adsorbent or
the adsorbate that acts as the electron donor; and also to
what extent the molecular orbital theory, and the difference
between the HOMO and LUMO levels of the adsorbate
and the adsorbent can predict the degree and direction of
electron transfer that leads to the chemical adsorption
process.
The most important characteristics of AC in the
adsorption of organic compounds are pore size distribu-
tion, surface chemistry (functionality), and mineral matter
content. The adsorption capacity depends on the accessi-
bility of the organic molecules to the microporosity which
depends on their size. Thus, under appropriate experi-
mental conditions, small molecules such as phenol can
access micropores, natural organic matter can access
mesopores, and bacteria can only access macropores.
2.2. Adsorption of heavy metals
Industrial activities (e.g. mining, painting, car manufac-
turing, metal plating, and tanneries) and agricultural
activities (when fertilizers and fungicidal sprays are
intensively used) are the main sources of wastes containing
heavy metals. Heavy metals are considered to be one of the
most hazardous water contaminants. According to the
World Health Organization (WHO) (2004, 2006), among
the most toxic metals are cadmium, chromium, copper,
lead, mercury, and nickel.
Up to date, many studies report that the removal of
heavy metals by AC is economically favourable and
technically easy (Khezami and Capart, 2005); therefore,
AC are widely used to treat waters contaminated with
heavy metals. Additional information regarding the
adsorption of heavy metals such as cadmium, chromium,
mercury, iron, and copper can be found in a review by
Huang (1978).
A large number of researchers are still studying the use
of AC for removing heavy metals (Gupta et al., 1997b;
Srivastava et al., 1996). A compilation of some studies on
AC adsorption of different heavy metals is presented in
Table 1.
Adsorption of metallic ions from aqueous solution is far
from being a straightforward process. Metallic species have
small size, being frequently charged in solution; therefore,
the predominant interactions in their adsorption process on
AC are of electrostatic nature (Lopez-Ramon et al., 2002).
The factors that mainly control the extent of adsorption on
AC are: (i) the chemistry of the metal ion (speciation) or
metal ion complex; (ii) the solution pH and the point of
zero charge of the surface; (iii) the surface area and
porosity (narrow and wider microporosity); (iv) the surface
composition (oxygen functionality); and (v) the size of
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836 J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846

Table 1 Table 2
Removal of heavy metals using activated carbon Chemical activation using different activating agents

Heavy metal Reference Chemical agent Reference

Mercury (Hg) Zhang et al. (2005) Zinc chloride (ZnCl2) Mohanty et al. (2005)
Anoop Krishnan and Anirudhan (2002) Yue et al. (2002)
Olson et al. (2000) Phosphoric acid (H3PO4) Ichcho et al. (2005)
Copper (Ag) Chen and Wu (2004) Suarez-Garca et al. (2004)
Goyal et al. (2001) Daz-Dez et al. (2004)
Periasamy and Namasivayam (1996) Yue et al. (2003)
Lead (Pb) Issabayeva et al. (2006) Potassium hydroxide (KOH) Sudaryanto et al. (2006)
Nadeem et al. (2006) Lozano-Castello et al. (2001)
Goel et al. (2005) Guo and Lua (1999)
Chromium (Cr) Di Natale et al. (2007) Otowa et al. (1997)
Liu et al. (2007) Potassium carbonate (K2CO3) Erdogan et al. (2005)
Park et al. (2006) Hayashi et al. (2005)
Fahim et al. (2006) Hayashi et al. (2002)
Cadmium (Cd) Madhava Rao et al. (2006) Sodium hydroxide (NaOH) Rahman et al. (2005)
Youssef et al. (2004) Lillo-Rodenas et al. (2001)
Macias-Garcia et al. (2003) Sulphuric acid (H2SO4) Guo et al. (2005)
Rangel-Mendez and Streat (2002) Rio et al. (2005)
Nickel (Ni) Erdogan et al. (2005) Guo and Lua (1999)
Hasar (2003)
Kadirvelu et al. (2001)
Zinc (Zn) Dabek (2003)
activation (ChA) is a one-step method used for the
Galiatsatou et al. (2002)
Leyva Ramos et al. (2002) preparation of AC; different chemical activating agents
Lithium (Li) Alfarra et al. (2002) might be used and some examples and related recent
Frackowiak (1998) studies are presented in Table 2. The chemical agents help
Seron et al. (1996) to develop the AC porosity, by means of dehydratation
and degradation; the mixture of the chemical and the
carbon is then heated at a maximum of around 750 1C. The
adsorbing species (hydrated ions in the range 1.01.8 nm), use of a lower temperature, compared to PhA, is
mainly for carbons with signicant volumes of narrow compensated by the interaction between the chemicals
microporosity. and the carbon skeleton. Major advantages of ChA are the
Sanchez-Polo and Rivera-Utrilla (2002) studied the higher yield, lower temperature of activation (less energy
interactions adsorbent/adsorbate for Cd (II) and Hg (II) costs), less activation time and, generally, higher develop-
on ozonized AC, concluding that electrostatic forces were ment of porosity; among the disadvantages are the
dominant for the adsorption of Cd (II) and dispersive activating agents costs and the need to perform an
forces prevailed in the adsorption of Hg (II). The same additional washing stage to remove the chemical agent
authors also studied the adsorption of Cr (III) on ozonized (Macia-Agullo et al., 2004). To optimize preparation
carbon, concluding that although electrostatic and non- procedures, the parameters normally studied are time of
electrostatic forces both played an important role, electro- carbonization, temperature and CO2/steam ow rate
static forces dominated the adsorption process (Rivera- (PhA); and time of impregnation and impregnation ratio
Utrilla and Sanchez-Polo, 2003). of chemical agents (ChA). AC characteristics (namely its
surface area) strongly depend on both the raw material and
3. Waste materials for the preparation of AC the activation procedure. Consequently, it is not possible to
preview which is the activation procedure that yields a
AC texture includes a wide range of pores that can be product with the highest surface area.
classied according to their width in: micropores (o2 nm), There are different physical forms by which AC can be
mesopores (250 nm) and macropores (450 nm) (Moreno- found, including: (i) granular activated carbon (GAC);
Castilla, 2004). In order to increase its adsorption capacity, (ii) powdered activated carbon (PAC); (iii) activated
the pore network should be developed during AC carbon bbers (ACF); and (iv) activated carbon cloths
preparation by application of adequate physical or (ACC). GAC can be prepared from hard material, such as
chemical treatments. Physical activation (PhA) is normally coconut shells, and normally includes particles retained in
made by carbonization followed by activation using steam an 80-mesh sieve (0.177 mm); it is commonly used as
or CO2; during carbonization, the material is pyrolyzed to column ller for gas or liquid treatments and can be
remove non-carbon elements, then activation occurs, at regenerated after use. When small particles compose the
temperatures ranging from 700 to 1100 1C, using gases that raw material, like wood sawdust, PAC is obtained
open and develop the porosity of the carbonized material (includes particles o0.177 mm); PAC is normally mixed
(Rodrgues-Reinoso, 1997; Bansal et al., 1988). Chemical with the liquid to be treated and afterwards disposed of.
 ARTICLE IN PRESS
J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846
Due to its small particles, PAC adsorption is normally very
effective, however, and for the same reasons, settling and
removal tend to be slower than when using GAC. ACF can
be prepared from homogeneous polymeric raw materials
and, as opposed to GAC and PAC, show a monodispersed
pore size distribution (Kasaoka et al., 1989). Their thin
bber shape enhances intra-particle adsorption and there-
fore improved contact efciencies between the aqueous
media and the adsorbent can be achieved (Yu and Chou,
2000). ACC were initially developed in the early 1970s,
using as precursors phenolic or viscose rayon (Bailey et al.,
1971) and are considered to be excellent adsorbents due to
their low-pressure drop during process, high contact
efciency and exibility (Pastor et al., 1999). Although
many kinds of adsorbents were already prepared and tested
in aqueous-phase treatments, GAC and PAC are still the
most widely used.
AC can be prepared from a wide variety of raw materials
(Da browski, 2001), which should be abundant and cheap,
with high carbon content and low inorganic content; raw
materials should be easily activated and should have low
degradation by aging (Moreno-Castilla and Rivera-Utrilla,
2001). Coal is the most commonly used precursor, mainly
due to its low cost and large supply (Ahmadpour and Do,
1996). The adsorption properties of each type of coal
are determined by the nature of the vegetal material
and the extent of the physicalchemical changes occurring
during coal formation and after its deposition (Ahmedna
et al., 2000).
The preparation of AC from waste materials has several
advantages, mainly of economic and environmental nature.
A wide variety of AC have been prepared from different
waste materials; conventional wastes (from agriculture and
wood industry) as well as non-conventional wastes (from
municipal and industrial activities) have been used. The
preparation of AC from these waste materials as well as its
application in aqueous-phase treatments will be discussed
from now on.
3.1. Conventional wastes (from agriculture and wood
industry)
Due to their abundance, agricultural wastes have low
economic value; additionally, their current deposition
creates signicant environmental degradation. Agricultural
waste is a rich source for AC production due to its low ash
content and reasonable hardness (Ahmedna et al., 2000);
therefore, conversion of agricultural wastes into AC is a
promising alternative to solve environmental problems and
also to reduce the costs of AC preparation.
There are currently a large number of studies regarding
the use of several agricultural wastes to produce AC. Most
of them focus on the use of waste materials of considerable
rigidity, such as the shells and/or stones of fruits like nuts,
peanuts, olives, dates, almonds, apricots and cherries;
however, wastes resulting from the production of cereals
such as rice, coffee, soybean, maize and corn as well as
837
olive cakes, sugar cane and sugar beat bagasse, coirpith,
oil-palm shell (from oil-palm processing mills) and various
seed wastes were already used. The preparation of AC from
these materials has been made using both PhA and ChA. In
a study by Ioannidou and Zabaniotou (2007) an extensive
revision regarding AC preparation from agricultural
residues is made and the effects of different parameters
regarding activation procedures are presented. The struc-
ture of the raw material tends to strongly inuence the best
parameters needed to obtain a specic AC. It is possible to
obtain AC with different pore texture by varying the
activation conditions, therefore optimizing their produc-
tion for a specic purpose. High surface areas might be
obtained, with values over 2500 m2 g 1. Among the revised
studies, ChA was the most studied method, namely by
using H3PO4, KOH, and ZnCl as activating agents. From
the revision made considering recent studies on the
preparation of AC from agricultural wastes, some relevant
issues were summarized and are presented in Table 3.
AC prepared from different agricultural wastes have
been used for several treatment purposes. There is a
considerable amount of studies regarding the use of these
materials, (many of them considering ChA) to remove
contaminants from aqueous phase, namely different types
of dyes, herbicides, heavy metals and volatile organic
compounds (VOC). Kadirvelu et al. (2003) showed that AC
prepared from agricultural solid wastes removed very
signicant amounts of different types of dyes, Hg (II)
and Ni (II), in shorter time and with better adsorption rates
and removal capacities than when applying other methods.
Most of the revised studies show that these materials can
compete with the commercial AC, and some of them have
even better behaviour than the commercial ones. Some
relevant issues concerning different recent studies on the
application of these materials in aqueous phase were
summarized and are presented in Table 4.
Due to their particular porous characteristics, woody
materials are very relevant and challenging raw materials
to prepare AC, namely for the adsorption of solutes in the
liquid phase (Wu and Tseng, 2006). The wood industry is
responsible to produce great amounts of woody waste
materials that might be recycled to produce AC. Also,
several forest residues can be used, additionally contribut-
ing to a better forest management and conservation. Many
studies were made concerning the recycling of these
materials for the production of AC. Woody materials of
different types such as cedar, r, oak, as well as from
tropical trees have already been used. Activation by using
either PhA or ChA has been recently studied, namely the
use of PhA preceded by chemical treatment using for
instance H2O2 or H2SO4 as chemical agents. The use of
such pre-treatments mainly inuences the surface chemistry
of the AC, and lead to the preparation of enhanced
adsorbents. Also, compression treatment of sapwood
followed by carbonization was studied as a possible way
of producing AC, essentially microporous (Abe et al.,
2001). It was concluded that preparation procedures using
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838 J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846

Table 3
Preparation of activated carbons using agricultural wastes as raw material

Raw material Activation agent Relevant issues Reference

ChA PhA

Vineyard H3PO4 Well-developed pore structure. In general, AC were better when raw Corcho-Corral et al. (2006)
shoot material was impregnated and heated at intermediate temperatures.
Cassava peel KOH Activation time showed no signicant effect on the pore structure. Sudaryanto et al. (2006)
Maximum surface area and pore volume were obtained using:
impregnation ratio of 5:2 and carbonization temperature of 750 1C.
Olive pit KOH PAC adsorption capacity was the highest at 75% (w/w) KOH. Martnez et al. (2006)
Olive cake Steam The best AC was obtained activating for 68 min at 1095 K. Bac- aoui et al., (2001)
Date pit H3PO4 Iodine number increased with increasing activation temperature. Haimour and Emeish (2006)
Impregnation ratio increase caused an oscillation in the iodine number.
Iodine number varied in average 710% for all particle sizes used.
H3PO4, Raw material showed potential to prepare AC also used as catalytic Bouchenafa-Sab et al.
ZnCl2 supports. AC modications must be preformed when procedure and (2005)
starting material is well known.
H3PO4 Porosity and cellular structure of raw material inuenced acid Girgis and El-Hendawy
concentrations and/or temperatures. Best AC were obtained using 50 (2002)
and 60% (w/w) H3PO4. Excess acid reduced raw material activation.
The important effect of H3PO4 in porosity generation was
demonstrated.
Walnut shell KOH Macrocroporous texture with more homogeneous pore size distribution Martnez et al. (2006)
than the ones prepared from olive pits.
CO2 The best activation was at 800 1C, 2.5 h, and CO2 ow rate of Yang and Lua (2003a)
100 cm3 min 1. Surface area: 1064.2 m2 g 1.
KOH High-surface area (2259.4 m2 g 1) and pore volume (1.10 cm3 g 1) Yang and Lua (2003b)
where obtained using the following activation conditions: 0.5% (w/w)
KOH, 3 h at 800 1C.
Walnut shell H3PO4, Most important activation parameters: impregnation ratio and Ahmadpour and Do (1997)
ZnCl2 carbonization temperature. High surface areas were obtained.
Coffee bean H3PO4 Characteristics could be easily controlled by varying H3PO4 Baquero et al. (2003)
husk impregnation ratio. High impregnation ratios yielded essentially
mesoporous carbons with high surface areas and pore volumes.
Corn cob Steam, CO2 Microporosity was obtained using both agents. Surface areas of Chang et al. (2000)
1315 m2 g 1 could be reached.
ZnCl2 High-surface area (about 1400 m2 g 1) and microporosity was obtained Tsai et al. (1997)
using the following conditions: 175% (w/w) ZnCl2, 773 K for pyrolysis,
0.51.0 h for soaking time.
Cherry stone Steam, CO2 Steam activation more effective than CO2 activation. Surface area: Lussier et al. (1994)
1200 m2 g 1.

woody materials should be carefully optimized to produce
AC with very good porous texture and that can also be
used as catalyst supports. From the revision made
considering recent studies on the preparation of AC from
woody wastes, some relevant issues were summarized and
are presented in Table 5. The application of AC prepared
from woody materials has been made for the removal of
contaminants such as organic compounds, dyes, and heavy
metals, from aqueous phase. These materials seem to be
very effective in adsorbing heavy metals such as chromium
and copper, being considered potentially good substitutes
of the commercial ones. The adsorption rate is normally
inuenced by the proportion of AC used. On the other
hand, PAC obtained from sawdust might be used to
prepare GAC with the addition of a proper binder and a
reinforcer; such GAC seems to have a very good beha-
viour in adsorbing phenol, namely through physisorption
mechanisms (Tancredi et al., 2004). It was concluded that
woody materials lead to AC showing good adsorption
behaviour for adsorbates of various molecular forms.
Some relevant issues concerning different recent studies on
the application of these materials in aqueous phase were
summarized and are presented in Table 6.
3.2. Non-conventional wastes (from municipal and industrial
activities)
The economical activities in the modern society gradu-
ally created a pattern of mass production, mass consump-
tion as well as mass deposition (Gao et al., 2005). As a
consequence, there is an accumulation of several industrial
and post-consumer waste products, which by their nature
are difcult or poorly effective to be regenerated into other
materials and that more currently end up in incineration
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J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846 839

Table 4
Aqueous-phase application of activated carbon prepared using agricultural wastes as raw material

Raw material Contaminants Relevant issues Reference

removed

Olive-seed Dye (methylene blue) AC obtained trough chemical activation using KOH showed methylene Stavropoulos and
blue removal capacities comparable to commercial products and even Zabaniotou (2005)
higher at high degrees of activation.
Rice husk Dye (malachite green) AC treated with H3PO4 using a carbonization temperature of 500 1C Rahman et al. (2005)
showed adsorption capacities comparable to commercial ones.
Dye (acid yellow, acid AC showed the worst adsorption capacity for acid dyes among all the Mohamed (2004)
blue) tested adsorbents.
Humic acid The potential use of the AC was demonstrated. The amount uptaken was Daifullah et al. (2004)
directly related to the amount of phosphoric acid used at 500 1C.
Sugar cane Dye (acid blue 80) AC obtained from a precursor with high ash content presented high Valix et al. (2004)
bagasse surface areas (6141433 m2 g 1) and well developed microporous texture.
Low temperature chemical carbonization and gasication was effective.
Melanoidin (brown AC prepared by steam physical activation showed adsorption capacities Bernardo et al. (1997)
polymer) of melanoidin comparable to the commercial ones. Carbon regeneration
increased adsorption capacity and yield.
Almond shell VOC AC from almond shells showed the largest surface areas among all Bansode et al. (2003)
prepared adsorbents.
Pecan shell VOC Adsorption of benzene more effective than the other organics; Bansode et al. (2003)
commercial potential for volatile organic compounds removal.
Metal ions; organics GAC with surface areas equal or greater than commercial AC; Johns et al. (1999)
commercial potential for removal of metal ions and organics.
Olive cake Herbicides AC with large macropores and micropores, showing better adsorption Bac- aoui et al. (2002)
capacities than commercial carbons and ability to adsorb herbicides.
Coirpith Heavy metals The resulting carbon showed economic potential for the removal of toxic Kadirvelu et al. (2001)
heavy metals from industrial wastewaters.

Table 5
Preparation of activated carbon using wastes of wood industry as raw material

Raw material Activation agent Relevant issues Reference

ChA PhA

Cedar wood CO2 (H2O2 PT) Pre-treatment with H2O2 positively inuenced porous development, Lopez de Letona
and its probably due to the elimination of surface complexes produced during Sanchez et al. (2006)
shavings the activation step.
Cedar wood CO2 (H2SO4 PT) Dehydration of the raw material with H2SO4 improved the porous Cuerda-Correa et al.
texture and the adsorption capacity of the AC. (2006)
Teak sawdust Steam AC with a surface area of 1150 m2 g 1 and pore volume of 0.43 cm3 g 1 Ismadji et al. (2005)
was obtained.
Fir wood KOH Steam Highly porous AC with surface areas up to 1096 m2 g 1 were obtained. Wu et al. (2005)
Rate of external surface adsorption was higher using steam, but the rate
of intraparticle diffusion was much lower.
Pinewood CO2 (metal oxide AC was found to be suitable support for metal oxide catalyst. Adequate Alvim-Ferraz and
sawdust impregnation) porous texture could be induced by proceeding to the impregnation step Gaspar (2005)
before CO2 activation.
Oak wood CO2 The longer the duration of activation, the greater was the adsorption Zhang et al. (2004b)
capacity.
Chestnut, H3PO4 The best textural properties were obtained by chemical activation using Daz-Dez et al.
cedar, walnut 36% (w/w) H3PO4. (2004)
(shavings)
Coast live oak CO2 Porosity development seemed to be strongly inuenced by the kinetic Sanchez et al. (2001)
wood reaction stage and the reactant gas concentration.
Cedar wood Steam The formation of micropores by steam reaction was not affected by Abe et al. (2001)
(compression) macropore volume. AC of double density could be produced by
compression treatment.
Tropical tree H3PO4, CO2 Chemical activation was more effective than physical activation. The Lopez et al. (1996)
wood ZnCl2 choice of an appropriate wood was shown to be fundamental to obtain
AC with homogeneous porosity and high surface area.

PT, pre-treatment.
 ARTICLE IN PRESS
840 J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846

Table 6
Aqueous-phase application of activated carbon prepared using wastes of wood industry as raw material

Raw material Contaminants Relevant issues Reference

removed

Fir wood Dyes, phenols Surface areas from 1371 to 2821 m2 g 1 and pore volumes from 0.81 to Wu and Tseng (2006)
1.73 cm3 g 1. High adsorption capacities were obtained. CO2 gasication time
inuenced dye adsorption.
Chromium (VI) Adsorption of Cr(VI) was maximal at the lowest values of pH (3) increasing Khezami and Capart
with temperature. The KOH-AC showed higher adsorption capacity than the (2005)
commercial carbon.
Rubber wood Copper (II) AC prepared through chemical activation (H3PO4) were effective in adsorbing Kalavathy et al. (2005)
sawdust copper ions. Adsorption was pH dependent and maximum removals occurred
at pH 6.0.
Chromium (VI) Adsorption was shown to be chemical in nature and the process was Karthikeyan et al.
endothermic. Ruber wood sawdust might be effectively utilized to prepare AC (2005)
for removal of chromium (VI) from waste waters.
Eucalypt Phenol Phenol was adsorbed faster in PAC. Higher proportion of AC in the granule Tancredi et al. (2004)
sawdust increased adsorption rate and maximum uptake.
Mahogany Acid dyes AC showed an adsorption capacity of 138.8 mg g 1 and potential to replace Malik (2003)
sawdust commercial carbon for dye removal.
Pinus wood Organics AC showed similar organic removal efciency than electron beam process (if De Oliveira Sampa et al.
adequate irradiation dose was delivered to the organic pollutant). (2004)

plants or landlls. Due to the more restricted environ-
mental standards, limitations on the application of such
alternatives are remarkably increasing.
The discharge of plastic wastes, such as polyethylene
terephthalate (PET) and polyvinyl chloride (PVC), indus-
trial wastes, such as oil combustion residues and fabrics, as
well as the discharge of tires, sewage sludges, and fertilizers,
represents a serious challenge for waste management
strategies. It is therefore of main relevance to nd
alternatives by which such materials can be reused or
recycled according to environmentally acceptable proce-
dures (Hayashi et al., 2005).
The use of such non-conventional wastes as carbon
source for the production of AC might be an efcient
alternative for both, adoption of effective waste manage-
ment practices, and production of low-cost AC. A revision
of the literature showed that there are a considerable
amount of studies dedicated to the valorization of such
wastes, namely for the production of AC. Plastic wastes,
various industrial wastes like y ashes, pitch, and
polymeric residues from factories as well as other wastes
such as tires and sewage sludge have been used as raw
material for AC production. For instances, a waste
commercial ion-exchange resin might be used to prepare
AC with values of specic surface area and pore volume
suggesting its application in different purposes, that might
include aqueous-phase treatments (Gunko et al., 2005).
Also, AC can be successfully prepared from both old
newspaper and paper prepared from simulated paper
sludge by PhA and ChA (Okada et al., 2003a, b). A great
amount of the revised studies focus on the use of physical
treatment, sometimes preceded by a chemical treatment;
however, ChA was also made, and AC with high specic
surface areas could also be obtained. Due to the nature of
most of the raw materials, such as plastics and polymeric
materials, ACF are the physical form of AC more
commonly prepared. Naturally, studies show that raw
materials with higher carbon content lead to the achieve-
ment of a better AC. Generally, AC show good texture and
potential to compete with commercial ones. From the
revision made considering recent studies on the preparation
of AC from such non-conventional wastes, some relevant
issues were summarized and are presented in Table 7.
There is quite a great amount of recent studies on the
application of AC prepared from non-conventional waste
materials for the removal of pollutants from aqueous phase
(Gupta et al., 1997, 2000, 2004, 2005; Jain et al., 2003a, b).
Among the contaminants that might be removed using
these adsorbents are organic compounds of variable
nature namely phenol and its derivatives, and different
types of dyes and heavy metals such as mercury, nickel, and
copper. The use of industrial wastes loaded with chemicals
such as organometallics, could even be used to prepare AC
with antibacterial activity (Tamai et al., 2001). The
prepared AC are expected to be economically viable and
the adsorption mechanism is, in several studies, fundamen-
tally dependent on the solution pH. Generally, the
adsorbents present good development of both chemical
surface and porosity. Some relevant issues concerning
different recent studies on the application of these
materials in aqueous phase were summarized and are
presented in Table 8.
4. Conclusions
AC are powerful adsorbents that can efciently remove
several pollutants from the aqueous phase; however, their
large-scale application is limited by high production costs.
 ARTICLE IN PRESS
J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846 841

Table 7
Preparation of activated carbon using non conventional wastes as raw material

Raw material Activation agent Relevant issues Reference

ChA PhA

Plastics
PET Steam (H2SO4 PT) Combined treatment might replace physical activation. AC were Sych et al. (2006)
mainly micro- and mesoporous with surface areas up to
1030 m2 g 1.
KOH Nitrogen-enriched adsorbents could be obtained by co- Arenillas et al. (2005)
carbonization of PET waste and N-compounds.
PVC Steam PVC based ACF were mainly composed of micropores with surface Qiao et al. (2004)
areas between 1000 and 2000 m2 g 1.
Industrial wastes
Polymer K2CO3 High specic surface areas (2800 m2 g 1) where obtained mainly due Hayashi et al. (2005)
to the activating agent action. Optimal conditions were:
carbonization temperature of 1073 K, impregnation ratio of 1.0.
Fly ash CO2 AC showed low surface area. The mesoporous texture suggests their Caramuscio et al.
possible use in adsorption of large molecules. (2003)
CO2 AC with high surface area, high content of oxygen, and surface sites Davini (2003)
with prevalent basic characteristics were obtained.
Acrylic fabric Steam Activation at 900 1C for 5 min signicantly increased specic surface You et al. (2000)
waste area (to 2400 m2 g 1) and total pore volume (1.15 cm3 g 1). ACF
performance was superior to those of conventional carbons.
Pitch Steam (addition of Pitch-based spherical AC with high mesopore texture was obtained. Liu et al. (1999)
ferrocene) Catalytic activation reaction took place at the vicinity of iron
particles.
Others
Tire Steam, CO2 Surface areas were comparable with those of commercial carbons. Zabaniotou and
Stavropoulos (2003)
Sewage sludge ZnCl2 AC presented remarkable micropore and mesopore surface area Chen et al. (2002)
and distinct physical and chemical properties from commercial
carbons.
ZnCl2 The anaerobically undigested sludge had higher carbon content and Tay et al. (2001)
lower ash content than the digested one, therefore yielding a better
AC.

PT, pre-treatment.

Several low-cost adsorbents have been tested; however, AC
are known to have much better performances to treat
contaminated efuents.
The need for efcient and economic removal of
pollutants, namely from aqueous phase, resulted in the
development of research on the use of waste materials as
precursors for the preparation of less costly AC. The use of
such materials can be, therefore, an efcient alternative for
both, production of low-cost AC, and adoption of effective
waste management practices.
From the revision made, regarding the preparation of
AC from conventional (from agriculture and wood
industry) and non-conventional (from municipal and
industrial activities) wastes, the following conclusions have
been taken:
4.1. Conventional wastes as AC precursors
 With both conventional types of raw material (agricul-
tural and woody wastes), AC with high surface areas
might be obtained and adsorption behaviour might be
controlled by carefully manipulating preparation para-
meters. AC can compete with commercial ones, some of
them presenting even better behaviour.
 Studies on the production of AC from agricultural
wastes are mainly based on the use of waste materials of
considerable rigidity (e.g. nut and almond shells, olive
and cherry stones). There are also studies on the use of
wastes resulting from the production of cereals (e.g.
corn, soybean, and coffee) as well as other less rigid
materials such as sugar cane and sugar beat bagasse.
The use of ChA seems to be more frequent in the
preparation of AC from agricultural wastes and the
agents more frequently used are H3PO4, KOH, and
ZnCl. Such AC might be used to remove different types
of dyes, herbicides, heavy metals, and VOC from
aqueous solution.
 Research has also been made for the conversion of
woody materials, usually shavings, sawdust and pieces
resulting from different woods such as from cedar, r,
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842 J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846

Table 8
Aqueous-phase application of activated carbon prepared using non-conventional wastes as raw material

Raw material Contaminants removed Relevant issues Reference

Plastics
PET Dye (methylene blue) High adsorption capacity of methylene blue (reaching 1 mmol g 1). Sych et al. (2006)
Phenol, aniline Adsorption was pH dependent, stronger for aniline than for phenol. Laszlo (2005)
Aniline had low water solubility which did not affect adsorption
capacity. Adsorption interactions were mainly due to dispersion effect.
Phenol, 2,3,4- The adsorption capacities were comparable to commercial carbon. The + (2001)
Laszlo and Szucs
trichlorophenol adsorption mechanism depended fundamentally on the solution pH.
Industrial wastes
Sago waste Dye (rhodamine-B) Ion exchange was the predominant dye adsorption mechanism. 100% Kadirvelu et al. (2005)
removal was obtained when the pH increased to 7 (adsorbent dose of
275 mg/50 ml, 20 mg l 1 dye concentration).
Mercury (II) AC was effective and economically attractive for the removal of Hg (II). Kadirvelu et al. (2004)
Removal percentage increased with increasing pH from 2 to 10.
Heavy metal, dyes Adsorption of all dyes and metal ions required a very short time leading Kadirvelu et al. (2003)
to quantitative removal. AC are expected to be economically viable.
Coal tar pitch Bacteria (Bacillus subtilis) AC were prepared from pitch containing organometallics. The CaO, Tamai et al. (2001)
MgO, CoO, and ZnO dispersed AC exhibited antibacterial activity for
B. subtilis both in solutions and agar.
Furfural residue Caramel, dye PAC showed excellent adsorption capacities for caramel and Wang et al. (1999)
(chemical) (methylthionine chloride) methylthionine chloride. Optimal conditions were: H3PO4 impregnation
for 812 h, carbonization and activation at 450500 1C for 1.52 h
followed by soak washing (hot water) and drying.
Bufng dust Dye (acid brown) AC with adsorption capacities of 6.24 mg g 1 at pH 3.5 were obtained Sekaran et al. (1998)
(leather industries) The rate constant for removal of dye was 0.026 min 1. Adsorption
capacities where greater than for commercial AC.
Tires Dyes (methylene blue, Prepared adsorbents showed good development of the chemical surface. Rozada et al. (2005)
brilliant red) The processes were endothermic and spontaneous.
Phenol, dye (dye black 5) Comparing to the commercial, the prepared carbon had larger Ariyadejwanich et al.
micropore volume, slightly lower adsorption capacity for phenol and (2003)
higher for dye.
Sewage sludge Mercury (II) AC prepared by chemical activation (H2SO4, H3PO4 and ZnCl2) might Zhang et al. (2005)
be effective to remove mercury from industrial wastewaters.
Copper ion, Phenol, dyes AC allowed copper ion, phenol and dyes (Acid Red 18 and Basic Violet Rio et al. (2005)
4) to be removed from aqueous solution. The optimal preparation
conditions were: 1.5 g of H2SO4 per g of sludge, 700 1C and 145 min.
Mercury (II), Mercury (0) Combination of the AC and TiO2 (TiO2 modied sewage sludge carbon) Zhang et al. (2004a)
and under ultraviolet irradiation doubled the adsorption capacity of
mercury on the carbon (from 87 g kg 1 to151 g kg 1).
Anionic dyes Contrary to commercial carbons, for equilibrium pH values between 5 Martin et al. (2003)
and 9, the adsorption capacity of the AC for dyes was altered (due to the
presence of ionisable surface functional groups).
Dyes (methylene blue, The prepared adsorbents might be promising for dye removal from Rozada et al. (2003)
saphranine) aqueous streams.
Organics AC showed great porosity and high surface area. Adsorption of crystal Otero et al. (2003)
violet was higher and faster than indigo carmine or phenol. Prepared
AC can be promising materials to remove organic pollutants from
aqueous streams.
Fertilizer Mercury (II) Adsorption of Hg (II) increased with increasing pH and the process was Mohan et al. (2000)
exothermic. Adsorption occurred through a lm diffusion mechanism at
low concentrations, and particle diffusion mechanism at higher
concentrations.

oak, as well as tropical trees. The preparation of AC
from woody materials has been studied using both PhA
and ChA; also, PhA preceded by chemical treatments is
frequently used. AC might be used as catalyst supports
and also to remove contaminants such as organic
compounds, dyes and heavy metals (namely chromium
and copper).
4.2. Non-conventional wastes as AC precursors
 The prepared AC are expected to be economically viable
and have the potential to compete with the commercial
ones.
 Research has been made on the use of municipal wastes
(such as plastic wastes, tires, and sewage sludge) as well
 ARTICLE IN PRESS
J.M. Dias et al. / Journal of Environmental Management 85 (2007) 833846
as various industrial wastes (such as y ashes and
polymeric materials) as AC precursors.
 Due to the nature of most raw materials, such as plastics
and polymeric wastes, ACF are the physical form by
which AC are commonly prepared. Most of the studies
on the preparation of AC from non-conventional wastes
focus on the use of PhA, sometimes preceded by a
chemical treatment. Organic compounds of variable
nature namely phenol and its derivatives, dyes and
heavy metals (such as mercury, nickel, and copper)
might be removed from aqueous phase using these
adsorbents. AC generally show good texture and the
adsorption mechanism was, in several studies, funda-
mentally dependent on the solution pH.
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