Activated Carbon From Wood
Activated Carbon From Wood
Activated Carbon From Wood
Contents
5.1 Introduction 160
5.2 Activated Carbon from Lignocellulosic Biomass 162
5.3 Lignocellulosic Precursors for Activated Carbons Process 163
5.4 Characterization of Lignocellulosic Based Activated Carbons 165
5.5 Activated Carbon for Water Purification and Wastewater Treatment 169
5.5.1 Dyes Removal 170
5.5.2 Heavy Metals Removal 174
5.6 Conclusions 176
References 177
materials, apple pulp, potato peel – as activated carbon precursors. In this chapter,
special attention is given to activated carbons based on some of agricultural wastes
from the Mediterranean region, which can be characterized as green.
5.1 Introduction
With the growth of mankind, society, science, technology our world is reaching to
new high horizons but the cost which we are paying or will pay in near future is
surely going to be too high. Among the consequences of this rapid growth is envi-
ronmental disorder with a big pollution problem. Environmental pollution is the
contamination of the physical and biological components of the earth/atmosphere
system to such an extent that normal environmental processes are adversely affected.
The introduction of contaminants into the environment causes harm or discomfort
to humans or other living organisms damaging the environment. Environmental pol-
lution is categorised in three main groups; air, water and soil pollution. In general,
any human activity releases pollutants, with the most severe being sulphur dioxide,
nitrogen dioxide, carbon monoxide, ozone, volatile organic compounds, insecti-
cides and herbicides, food processing waste, pollutants from livestock operations,
heavy metals, chemical waste and others. With the rapid push of globalization, wide
application of new technologies and the increasing pressure from resource and envi-
ronment, it has been realized that the natural environment is irreversible and criti-
cally important for urban development, thus is the call for urban transition towards
greening (McGranahan 2015). Green technology, also referred to as environmental
technology or clean technology, is an encompassing term. It deals with using sci-
ence and technology in order to protect the environment. A lot of techniques fall
under this term such as the use of green chemistry, environmental monitoring, and
more. Specifically, Green Chemistry is defined as the design of chemical products
and processes to reduce or eliminate the use and generation of hazardous substances
(Sheldon 2008), governed by 12 principles. One of them is the usage of renewable
feedstock for material synthesis (Anastas and Eghbali 2010). The major renewable
feedstock on the planet both for material and energy is bio-mass, the material avail-
able from living organisms. This includes wood, crops, agricultural residues, food
(Kamm et al. 2000; Fornasiero and Graziani 2011). Research of the past two decades
have shown that bio-mass as feedstock has many applications including transport
fuel production (McKendry 2002), chemicals (Tong et al. 2010), electricity genera-
tion (Chaudhuri and Lovley 2003) as well as materials production for usage in many
industrial applications (Agbor et al. 2011).
According to Environmental and Energy Study Institute, a list of some of the
most “common” bio-mass feedstocks is comprised of (i) grains and starch crops
(sugar cane, corn, wheat, sugar beets, industrial sweet potatoes), (ii) agricultural
residues (corn stover, wheat straw, rice straw, orchard pruning), (iii) food waste
(waste produce, food processing waste), (iv) forestry materials (logging residues,
5 Activated Carbon from Food Waste 161
forest thinning), (v) animal byproducts (tallow, fish oil, manure), (vi) energy crops
(switchgrass, hybrid poplar, willow, algae) and (vii) urban and suburban wastes
(municipal solid wastes, lawn wastes, wastewater treatment sludge, urban wood
wastes, disaster debris, trap grease, yellow grease, waste cooking oil). Biomass
derived from plants, the so-called lignocellulosic bio-mass, is the most abundant
and bio-renewable bio-mass on earth (Isikgor and Becer 2015). The major
components of woody plants, as well as grasses and agricultural residues are three
structural polymers; lignin (10–25%), hemicellulose (20–30%) and cellulose (40–
50%) (Pérez et al. 2002). Apart of these three components, which vary regarding the
source, there are also some minor non-structural components such as proteins, chlo-
rophylls, ash, waxes, tannins (in the case of wood) and pectin (in most of fibers).
Among the three fractions of the lignocellulosic materials, lignin has been identified
as the main component in lignocellulosic bio-mass responsible for the adsorption
process (Mohamad Nor et al. 2013). Specifically, lignocellulosic wastes are a low
cost natural carbon source for the production of various materials including acti-
vated carbon. In addition, lignocellulosic precursors and biomass sources have
become important materials to produce activated carbon because their use creates
many benefits, mainly environmental. Nowadays, it is possible to find numerous
research papers devoted to the synthesis characterization and applications of novel
precursors to produce activated carbon. Except from the treatment conditions, the
biomass source determines many of the properties of the final material. In fact,
although the lignin is considered to be the major contributor for activated carbons
production, properties such as the mean pore size versus the specific porous volume
are effected by all precursor’s components whatever is its weight contribution
(Cagnon et al. 2009).
Activated carbon is a well-known material used in an increasing number of envi-
ronmental applications; namely water and waste water treatment, gas filters, green
gases capturing. High surface area, a microporous structure, and a high degree of
surface reactivity make activated carbons versatile adsorbents, particularly effective
in the adsorption of organic and inorganic pollutants from aqueous solutions ref. In
recent years, scientific interest on lignocellulosic precursors for activated carbon
production used as storage material of several gases as well as catalytic reactor has
been increased (Fiuza et al. 2015; Ruiz et al. 2017), leading to replacement of less
cost effective materials such as metal organic frameworks (Llewellyn et al. 2008;
Kuppler et al. 2009; Sumida et al. 2012) or less eco-friendly (in sense of production
of raw material or activation treatment) such as fly ash (Lu and Do 1991).
Activated carbon is the generic term used to describe a family of amorphous
carbonaceous adsorbents with a highly crystalline form and well developed internal
pore structure. Any organic material can be the starter material (precursor) of acti-
vated carbon production after being subjected to carbonization and activation of its
organic substances (Bansal and Goyal 2005). Traditionally, typical precursors for
activated carbon production were coal (Teng et al. 1998), peat (Veksha et al. 2009),
and lignite (Shrestha et al. 2013). Mainly due to economical as well as environmen-
tal issues, the replacement of those raw materials with low-cost and environmental
friendly precursors is mandatory. To this end, in recent years there has been a
162 R. Kosheleva et al.
g rowing interest in the production of activated carbons from agricultural and for-
estry wastes (Dias et al. 2007). In the context of the present chapter, as agricultural
wastes are considered residues of agricultural by products (not for consumption) i.e.
peels, stems and fruit core. The following sections describes the treatment and acti-
vation processes of carbonaceous materials of various precursors. Furthermore,
comparison of final properties regarding treatment conditions as well as the source
is provided too. Related industrial applications are discussed.
5.3 L
ignocellulosic Precursors for Activated Carbons
Process
Chemical activation on the other hand, prohibits the formation of tar; in this way
a carbonized product with a well-developed porosity may be obtained in a single
operation (Lozano-Castelló et al. 2001; Kalderis et al. 2008). Chemical activation
takes place prior to carbonization wherein the agricultural waste is impregnated
with certain chemicals, which is typically an acid such as H3PO4, a strong base such
as KOH, and NaOH or a salt such as ZnCl2. Then the agricultural precursor is car-
bonized at lower temperatures (450–900 °C). Number of studies conducted, indi-
cate that the carbonization/activation step proceeds simultaneously with the
chemical activation (Milenković et al. 2009; Ludwinowicz and Jaroniec 2015). It is
also believed that the chemical incorporated to the interior of the precursor particles
reacts with the products resulting from the thermal decomposition of the precursor,
reducing the evolution of volatile matter and inhibiting the shrinking of the particle;
in this way the conversion of the precursor to carbon is high, and once the chemical
is eliminated after heat treatment, a large amount of porosity is formed (Kumar and
Jena 2016; Shamsuddin et al. 2016). Chemical activation is preferred over physical
activation owing to the lower temperature and shorter time needed for activating the
material. The chemical activation method presents many advantages over the physi-
cal activation method and therefore it has been employed enormously in many stud-
ies when the preparation of activated carbon from agricultural wastes is concerned.
In addition, activated carbon obtained by chemical activation exhibits a larger sur-
face area and better developed mesoporosity than physical activation (Aygün et al.
2003; Valix et al. 2004). On the other hand, from the economical point of view,
chemical activation requires the use of agents that rise the total cost of the produc-
tion process (Zhang et al. 2004; Dias et al. 2008).
As it was mentioned in previous section, the suitability of an activated carbon for
different applications is matter of many parameters. Although carbonization/activa-
tion conditions play the most important role in adsorbent’s efficiency, they are not
the only major contribution towards porous structure of activated carbon; the origi-
nal nature and structure of the precursor also is significant. The proximate analysis
along with ultimate analysis of the precursor are common properties investigated in
the related literature. Proximate analysis involves the determination of moisture
content, volatile matter, fixed carbon and ash content of the raw material (Jin et al.
2012; Koay et al. 2013).
From the economical aspect, biomaterials are promising precursors for adsor-
bents because of their abundance. To preserve their cost effective treatment, espe-
cially regarding large scale applications, the source should be taken into account.
For instance, although some agricultural wastes (i.e. coconut shells (Shrestha et al.
2013; Nandeshwar et al. 2016), hazelnut husk (Imamoglu and Tekir 2008;
Milenković et al. 2009; Kwiatkowski and Broniek 2017), rice husk (Foo and
Hameed 2011; Menya et al. 2018; Rwiza et al. 2018) and others) are acknowledged
as highly efficient precursor, in many cases it has to be imported, resulting in an
increase of cost. Therefore, agricultural/household residuals, including fruit and
vegetable peels are considered as good alternatives. Moreover, regions such as
Mediterranean, can take advantage of residuals produced from regional commodi-
ties like olive or peach stones. Properties of such agricultural wastes are collected
5 Activated Carbon from Food Waste 165
form recent studies. Table 5.1 summarizes some of the most investigated agricul-
tural wastes as activated precursors; only obtained surface is presented because
properties such as pore size, contaminant uptake and are omitted because such
characteristics depend mainly on process conditions. Effect of process conditions
will be discussed in a following section.
5.4 C
haracterization of Lignocellulosic Based Activated
Carbons
Fig. 5.1 Scanning Electron Microscopy (SEM) micrograph of sun-dried apricot stone (a) prior
activation, (b) after activation; prior activation the sun-dried raw material presents almost no
porosity and a thick wall structure while after activation a wide porosity is observed. (Reprinted
with permission by Elsevier (Şentorun-Shalaby et al. 2006))
Fig. 5.2 Scanning Electron Microscopy (SEM) micrographs of SO2-dried apricot stone (a) prior
activation, (b) after activation; high ash and Sulphur content of the precursor leads to the appear-
ance of anon-porous cloudy surface (a) while activated material does not present a well-developed
porous network compared to sun-dried material (Fig. 5.1). (Reprinted with permission by Elsevier
(Şentorun-Shalaby et al. 2006))
Temperature during carbonization phase plays significant role in the final mate-
rial’s properties. Biochar yield increases with a decrease in pyrolysis temperature,
an increase in the residence time, and a preferable low heating rate (Tripathi et al.
2016). The highest treatment temperature is regarded to have the greatest effect on
the physical properties of biochar produced (Mukome et al. 2013). In a recent study,
Palanisamy et al. reported that biochar of C. vulgaris prepared at higher tempera-
tures (450–600 °C) contained a higher proportion of organic matter (C, H and N)
than those produced at lower temperatures.
Kyzas et al. (2016) conducted experiments involving potato peels for metal ion
removal. In this work, potato peels were cleaned and dried for 24 h for moisture
reduction. The activation agent used was H3PO4. All conditions kept same (amount
of dried material, activation agent) and three samples were produced at different
heating temperature (400, 600, 800 °C). Comparison of the samples regarding,
among others, the surface area of the material, revealed that the higher surface area
resulted for the sample treated at 600 °C, while at higher temperature the surface
area of the sample was less than 1 m2/g. Size distribution analysis confirms the
5 Activated Carbon from Food Waste 167
Fig. 5.3 Pore size distribution curves of potato peels (denoted as PoP in the graph) carbons acti-
vated at 400 °C, 600 °C and 800 °C. PoP400 is defined by micro-meso porosity while PoP600
curve shows a structure combined of all three groups of pores. (Reprinted with permission by
Elsevier (Kyzas et al. 2016))
Fig. 5.4 Scanning Electron Microscopy (SEM) micrographs of surface morphology of potato
peels samples; (a) potato peels treated at 400 °C, (b) potato peels treated at 600 °C. (Reprinted
with permission taken by Elsevier (Kyzas et al. 2016))
ent lignocellulosic materials and the influence of treatment conditions on the pro-
duced activated carbons.
Köseoğlu and Akmil-Başar (2015) reported the effect of treatment temperature
on orange peel activation. Chemical activation using zinc chloride (ZnCl2) and
potassium carbonate (K2CO3) was performed. The activation temperatures and
impregnation ratios were selected at the range of 500–1000 °C and 1:1, respectively.
The carbon content of activated carbons resulted 70% while BET surface area of
activated carbons prepared with K2CO3 and ZnCl2 activation is 1352 and 1215 m2/g,
respectively. An increase in the temperature for both K2CO3 and ZnCl2 led to a
decrease in the yields of the activated carbons. The overall yield of material, esti-
mated to be greater for activated carbons by ZnCl2 than those activated by K2CO3,
although it does not play any role in performance.
Besides, the activation temperature, the time and heating rate are important prep-
aration variables for obtaining activated carbon with specific characteristics (Yorgun
and Yıldız 2015). According to the literature review, chemically activated carbons
have developed surface areas ranging from very poor surface area to as high as
3000 m2/g, a broad range of pore size distribution from a few nm to a few microm-
eters and pore volume from 0.1 to 2.5 cm3/g. From released scientific reviews, it is
possible to note that activation with alkaline agents produces the highest surface
area values. Secondly, treatment with acids and acid salts supplies also high surface
areas; for instance, impregnation of Chinese fir using H3PO4 yields to 2518 m2/g,
impregnation of lignin with H2SO4 produces 1946 m2/g, the use of FePO4 on peach
stone provides 2160 m2/g, use of CaHPO4 on pistachio shell supplies 1919 m2/g, and
the use of K2CO3 on wasted tea yields 1722 m2/g. Finally, activation of coconut
shells with ZnCl2 and with a mixture ZnCl2/H2O2 yields to 2450 and 2050 m2/g,
respectively. Additionally, depending on the activation agent, the carbon surface
exhibits numerous functional groups, mainly acidic, which favor specific interac-
tions allowing it to act as an ionic interchanger (Toles et al. 2000; Bharathi and
Ramesh 2013). Physical activation of lignocellulosic chars with steam or CO2
causes different effects on the development of microporosity. In early stages of acti-
vation process, CO2 develops narrow micropores, while steam widens the initial
micropores of the char. At high degrees of burn-off, steam generates activated chars
which exhibit larger meso- and macropore volume than those prepared by CO2
(Liou 2010). As a result, CO2 creates activated chars with larger micropore volume
and narrower micropore size than those activated by steam. At this point is possible
to note that physically activated carbons have smaller surface area values than those
obtained from chemical (i.e H3PO4, KOH, NaOH and ZnCl2) activation. However,
there have been reported high surface area adsorbents from lignocellulosic precur-
sors activated physically (Maciá-Agulló et al. 2004). On the other hand, oxidizing
treatments using water steam and CO2 atmospheres, yield average surface area val-
ues, comparable with those obtained from the activation using acid salts; such as
K2CO3 or CaHPO4. In this sense, water steam of date pits yields surface area of
1467 m2/g and CO2 activation of olive stones yields 1355 m2/g (Román et al. 2008).
Other option to design activated carbons with controlled porosity and larger surface
areas is the combination of both, chemical and physical activations, simultaneously
5 Activated Carbon from Food Waste 169
5.5 A
ctivated Carbon for Water Purification
and Wastewater Treatment
60
55
% Removal
50
45
40
35
30
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Dose (g)
Fig. 5.5 Effect of adsorbent dose on dye removal efficiency. (Reprinted with permission by
Springer (AbdurRahman et al. 2013))
Dyes are widely used in industries such as textiles, rubber, plastics, printing, leather,
cosmetics, to color their products. As a result, they generate a considerable amount
of colored wastewater. Besides aesthetic issues, dyes can have acute and/or chronic
effects on exposed organisms depending on the exposure time and dye concentra-
tion. Among side-effects, there are allergic dermatitis, skin irritation, cancer,
mutation.
AbdurRahman et al. (2013), studied the removal of various dyes from textile
wastewater by adsorption on orange peels. Obtained results indicate that the adsorp-
tion of dyes onto orange peels is influenced by pH values, amount of adsorbents and
contact time. Also, the adsorption of dyes onto orange peels follows the Langmuir
isotherm model. Additionally, it is reported that for higher removal of dyes from
textile effluents adsorbent dose of 1.5 g was favorable (Fig. 5.5). The uptake of the
dye increased with increasing contact time and the optimum contact time was
obtained at 2 h. Also, the adsorption was found to be higher for pH 7 (Fig. 5.6).
Authors concluded that even though the removal efficiency of orange peels is not
much higher than other bio-adsorbents, it is preferred for its available.
Another work has been conducted for removal of methylene blue from an aque-
ous solution (Amela et al. 2012) by biosorption on banana and orange peels waste.
Kinetic study is also carried out to observe the effects of various process parame-
ters. The maximum values of adsorption capacities for activated banana peel was
19.671 and 18.647 mg/g for natural banana peel at pH 4–8, 20 °C. The results fol-
low kinetic of pseudo second-order rate equation (Fig. 5.7). The suitability of the
5 Activated Carbon from Food Waste 171
% Removal vs. pH
60
55
50
45
% Removal
40
35
30
25
20
4 5 6 7 8 9 10
pH
Fig. 5.6 Effect of pH on dye removal; the adsorbent dosage was 1.5 g (previously found) for
90 min of contact time. (Reprinted with permission by Springer (AbdurRahman et al. 2013))
Fig. 5.7 Kinetics of Methylene blue ions onto banana peels (activated and natural –ABP, NBP
respectively) test for pseudo second order equation. (Reprinted with permission by Elsevier
(Amela et al. 2012))
172 R. Kosheleva et al.
adsorbent was tested by fitting the adsorption data with four isotherms, namely
Freundlich, Langmuir and Temkin. The characteristic parameters for each isotherm
have been determined. The Freundlich equation represented the best fit of experi-
mental data for activated banana peel than the other isotherm equations, and
Langmuir equation described the adsorption of natural biosorbent.
Namasivayam et al. (1998), examined the adsorption of direct red and acid bril-
liant blue by waste banana pith. Varying the agitation time, dye concentration, adsor-
bent dose and pH results were obtained; adsorption capacity was 5·92 and 4·42 mg
dye per gram of the adsorbent for direct red and acid brilliant blue, respectively.
Adsorption of dye followed first-order kinetics. An acidic pH was favorable for the
adsorption of both dyes. An alkaline pH was favorable for desorption of the dyes.
Removal of ultramarine blue dye from aqueous solution using yam peels waste
was investigated in the study conducted by Owamah et al. (2013). The effect of
adsorbent concentration, dye concentration, time and pH were evaluated. Maximum
adsorption occurred at pH of 10. A general increase in adsorption with increase in
adsorbent concentration, dye concentration, time and temperature, respectively was
also reported. The pseudo second order model with R2 of 0.98 indicates that adsorp-
tion occurred mainly by intra-particle diffusion. The Freundlich and Langmuir iso-
therms were found suitable for describing the adsorption.
Valorization of olive stones as an agricultural waste into an efficient granular
activated carbon for the removal of Methylene blue in batch and fixed bed modes
from aqueous solutions was proposed by Benallou Benzekri et al. (2018) The acti-
vated carbon preparation was carried out in two steps: an impregnation with 50%
phosphoric acid at 170 °C for 2.5 h followed by physical activation using steam at
750 °C. Activated carbons resulted in specific surface areas of 1031.5 and
1029.2 m2/g, respectively. The Langmuir model was found to describe correctly the
isothermal adsorption of Methylene blue for both adsorbents and resulted in adsorp-
tion capacities of 107 and 121 mg/g for the commercial one.
Chemically modified olive stones investigated regarding the sorption efficiency
towards cadmium and safranine removal from their respective aqueous solutions.
Treated Olive stones material was prepared by treatment of olive stones with con-
centrated sulfuric acid at room temperature followed up by a subsequent neutraliza-
tion with 0.1 M NaOH aqueous solution. Results indicated that treated olive stones
exhibited efficiency in terms of sorption capacities toward the two pollutants (128.2
and 526.3 mg/g for cadmium and safranine, respectively).
In order to valorize olive stones and to show its potential use in the sorption of
two dispersed dyes, it was transformed in activate carbon and characterized by
Hemsas et al. (2014). The adsorption capacity of activated carbon for the dyes
removal was found to be affected by the solution’s pH. Acidic pH was found the
favour disperse dyes removal. Over 95% removal was achieved for both the dyes at
pH 3. The equilibrium time for both dyes was 30 min. Both Langmuir and Freundlich
5 Activated Carbon from Food Waste 173
isotherms could be used to describe the adsorption of the dyes. Freundlich adsorp-
tion model succeeded in fitting the adsorption isotherms of dyes on olive stones
activated carbon in single-solute systems, and prediction of the competitive
adsorption behavior of dyes with the Freundlich-based Sheindorf-Rebuhn-Sheintuch
model gave acceptable results.
Uğurlu et al. (2007) studied the removal of a reactive dye from aqueous solution
by adsorption onto activated carbon from olive stone. Different amounts of activat-
ing agent (ZnCl2) and adsorbent particle size were studied to optimize adsorbent
surface area. The adsorption experiments were conducted at different process
parameters such as adsorbent dose, temperature, equilibrium time and pH. The
experimental results showed that at equilibrium time 120 min, optimum pH ranged
between 3 and 4, and adsorbent dosage was 2.0 g per 200 mL. While the kinetic data
support pseudo-second order, a pseudo-first order model shows very poor fit. In
addition, the thermodynamic parameters such as isosteric enthalpy of adsorption
(ΔHads)y, isosteric entropy of adsorption (ΔSads)y and free energy of adsorption
ΔG0ads were calculated. BET surface area measurements were made to reveal the
adsorptive characteristics of the produced active carbon. The surface area of the
activated carbon produced with 20% w/w ZnCl2 solution was 790.25 m2/g.
Survey on the feasibility of the biosorption of two acid dyes (Acid blue 113 and
Acid black 1) from aqueous solution using biomass prepared from potato peel waste
was attempted by (Hoseinzadeh et al. 2014). Adsorption isotherms were constructed
and the kinetics of dye adsorption were studied. Langmuir and Freundlich iso-
therms, pseudo-first-order, and pseudo-second-order kinetic models were studied.
The maximum biosorption was observed at a pH of 2 and 3 for Acid blue 113 and
Acid black 1, respectively. The biosorption of two dyes increased with increasing
contact time and reached equilibrium after two hours, approximately. Pseudo-
second-order kinetic and the Langmuir isotherm model was shown to have better fit
for the adsorption of Acid blue 113 and Acid black 1 on used potato peel waste.
Interesting findings are also provided by Atttia et al. (2008), in their work of
activated carbon production from peach stones. The acid used for activation was
H3PO4 at constant temperature but at different concentrations. The obtained results
of the materials characteristics such as porosity, surface area reveal that impregna-
tion ratio effects positively the process. On the other hand, increase of temperature
conditions and post heat treatment effect negatively the same properties. Equilibrium
adsorption of methylene blue proved good uptake of the bulky dye, which improved
considerably with impregnation concentration that was related to enhanced poros-
ity. Increased impregnation ratio improved column performance, as well as forcing
N2 pyrolysis or extra heat-treatment. Activated carbon impregnated with 70% H3PO4
and carbonized at 500 °C exhibited the best properties which prevailed upon raising
treated dye concentration to 150 and 200 mg/L, although degraded its capacity due
to the limited mass of adsorbent and to the short contact time.
174 R. Kosheleva et al.
The release of heavy metals into our environment is still large. In certain areas of the
world it is even increasing. The pollution of water resources due to the disposal of
heavy metals has been an increasing worldwide concern for the last few decades. It
is well known that some metals can have poisonous or otherwise toxic to human
beings and ecological environments, include chromium, antimony, copper, lead,
mercury, cadmium, manganese. Studies on heavy metal adsorption by activated car-
bon from agricultural wastes have shown remarkable removal efficiency even com-
pered to commercial ones (Babel and Kurniawan 2004; Kołodyńska et al. 2017).
Among others, most common metals constituting in water pollution are arsenic
(As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), mercury
(Hg) and their ions. Related studies are presented for heavy metals adsorption by
activated carbons from various fruit and vegetable peels as well as stones that can
be found abundant in Mediterranean region.
According to Khalfaoui and Meniai (2012), orange peels can efficiently remove
copper ions from aqueous solutions. In fact the use of orange peels without any
pretreatment leads at the most a copper retention percentage of the order of 75%,
whereas percentages over 99% could be achieved by means of chemical activations
with sulfuric acid, caustic soda, methanol and acetic anhydride. Remarkably, results
showed that saturation was reached after 10 and 5 min, for the cases of no pretreat-
ment and the chemical activation of the orange peels, respectively. The pH study
indicated that a value between 4 and 6 seemed to be the most adequate. The results
did also show that the copper initial concentration value did have an influence on the
retention capacity for the natural solid support. The sorption kinetic study showed
that the process could be considered of a pseudo-second order, whereas the obtained
equilibrium data were best fitted to the Freundlich model.
Liu et al. (2013) have conducted experiments of cysteine-modified orange peel
for the removal of Cu(II) from aqueous solutions compared to diethylenetriamine-
modified orange peel. Both materials were systematically evaluated via their capa-
bilities for adsorbing Cu(II), including the key influential parameters such as initial
pH, contact time and initial Cu(II) concentration. This work suggests that the sorp-
tion of Cu(II) onto both materials fits well with the pseudo-second-order equation,
and the corresponding sorption isotherm can be classified to a Langmuir. The maxi-
mum capacities of both materaials for adsorbing Cu(II) were found to be 95.23 and
83.68 mg/g, respectively, about three times higher than that of unmodified orange
peels. The sorption efficiency of cysteine-modified orange peel drops by merely
about 3% after five cycles, implying a promising usage in the removal of Cu(II)
from wastewater in practice.
The performance of a microporous activated carbon prepared chemically from
olive stones for removing Cu(II), Cd(II) and Pb(II) from single and binary aqueous
solutions was investigated by Bohli et al. (2015). Adsorption kinetic rates were
found to be fast and kinetic experimental data fitted very well the pseudo-second-order
equation. The adsorption isotherms fit the Redlich–Peterson model very well and
maximum adsorption amounts of single metal ions solutions follow the trend
5 Activated Carbon from Food Waste 175
Ahmed et al. (2015) tested nanofibers for lead removal from wastewaters. Here,
activated carbon was used as substrate for nanofibers growth. Pb2+ was the target
pollutant of the study. After experiments of pH, contact time, adsorbent dosage and
agitation speed, optimal conditions for sorption were determined. Specifically, the
best performance was obtained when the dosage of adsorbent was 0.25 g/L at solu-
tion pH 5.5 and 200 rpm for 60 min of contact.
At this point, it will be good to just report some cases of organic components
removal. Organic compounds are another severe source of water pollution.
Polycyclic aromatic hydrocarbons (PAH) were efficiently removed from water sam-
ples by solid phase extraction. Razmi et al. (2016) proposed a new nanocomposite
of graphene quantum dots and eggshells for extract PAH. Effect of initial pH of the
solution, adsorbent amount within the column as well as the flow rate of the sample
on the total extraction efficiency was investigated. Characterization by SEM
revealed that although eggshells examined separately presented an irregular crystal
structure when mixed with graphene quantum dots a uniform distribution was
achieved resulting in an effective contact of the effluent. This study concluded that
taking into consideration both the ease of preparation and well adsorption desorp-
tion performance, graphene quantum dots-eggshell nanocomposite can be consid-
ered suitable for extraction of various aromatic hydrocarbons from water.
Also, in a review article for nitrogen and phosphorous containing pollutants
removal, several adsorbents are presented by Prashantha Kumar et al. (2017).
Among adsorbents such as zero-valent metal, metal oxides/metal hydroxides, there
is a reference to carbon based materials too. Specifically, carbon nanotubes and
chitosan based nanocomposite present high uptake values compared to other carbon
based materials including graphene (Prashantha Kumar et al. 2017). From all car-
bon based materials, carbon nanotubes have gained a great attention the past decade.
Due to their versatility, carbon nanotubes find many applications including water
desalination (Hebbar et al. 2017).
5.6 Conclusions
Activated carbons are considered to be the most successful adsorbent materials due
to their high adsorption capacity for the majority of pollutants (dyes, heavy metals,
pharmaceuticals, phenols). Their large surface area, and different surface functional
groups, which include carboxyl, carbonyl, phenol, quinone, lactone and other
groups bound to the edges of the graphite-like layers. Numerous agro-food wastes
as summarized in this Chapter regarding their adsorption potential to many pollut-
ants. The most important conclusion is that some basic characteristic of adsorption
as capacity and kinetics are directly influenced by the structural characteristics of
the prepared materials. It is mandatory to note that the system of adsorbent-adsor-
bate is unique and therefore to make a safe comparison, the adsorption conditions
must be exactly the same. Otherwise, the comparison is faulty.
5 Activated Carbon from Food Waste 177
References
AbdurRahman FB, Akter M, Zainal Abedin M (2013) Dyes removal from textile wastewater using
orange peels. Int J Sci Technol Res 2:47–50
Agbor VB, Cicek N, Sparling R, Berlin A, Levin DB (2011) Biomass pretreatment: fun-
damentals toward application. Biotechnol Adv 29:675–685. https://doi.org/10.1016/j.
biotechadv.2011.05.005
Ahmed YM, Al-Mamun A, Al Khatib MFR, Jameel AT, AlSaadi MAHAR (2015) Efficient lead
sorption from wastewater by carbon nanofibers. Environ Chem Lett 13:341–346. https://doi.
org/10.1007/s10311-015-0509-3
Aman T, Kazi AA, Sabri MU, Bano Q (2008) Potato peels as solid waste for the removal of heavy
metal copper(II) from waste water/industrial effluent. Colloids Surf B: Biointerfaces 63:116–
121. https://doi.org/10.1016/j.colsurfb.2007.11.013
Amela K, Hassen MA, Kerroum D (2012) Isotherm and kinetics study of biosorption of cationic dye
onto banana peel. Energy Procedia 19:286–295. https://doi.org/10.1016/j.egypro.2012.05.208
Anastas P, Eghbali N (2010) Green chemistry: principles and practice. Chem Soc Rev 39:301–312.
https://doi.org/10.1039/B918763B
Attia AA, Girgis BS, Fathy NA (2008) Removal of methylene blue by carbons derived from peach
stones by H3PO4 activation: batch and column studies. Dyes Pigments 76:282–289. https://doi.
org/10.1016/j.dyepig.2006.08.039
Aygün A, Yenisoy-Karakaş 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 66:189–195. https://doi.org/10.1016/j.micromeso.2003.08.028
Babel S, Kurniawan TA (2004) Cr(VI) removal from synthetic wastewater using coconut shell
charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan.
Chemosphere 54:951–967. https://doi.org/10.1016/j.chemosphere.2003.10.001
Balan V (2014) Current challenges in commercially producing biofuels from lignocellulosic bio-
mass. ISRN Biotechnol 2014:31. https://doi.org/10.1155/2014/463074
Bansal RC, Goyal M (2005) Activated carbon adsorption. CRC Press, Taylor & Francis, Boca
Raton
Benallou Benzekri M, Benderdouche N, Bestani B, Douara N, Duclaux L (2018) Valorization of
olive stones into a granular activated carbon for the removal of methylene blue in batch and
fixed bed modes. J Mater Environ Sci 9:272–284. https://doi.org/10.26872/jmes.2018.9.1.31
Bharathi KS, Ramesh ST (2013) Removal of dyes using agricultural waste as low-cost adsorbents:
a review. Appl Water Sci 3:773–790. https://doi.org/10.1007/s13201-013-0117-y
Blondeau P, Iordache V, Poupard O, Genin D, Allard F (2005) Relationship between out-
door and indoor air quality in eight French schools. Indoor Air 15:2–12. https://doi.
org/10.1111/j.1600-0668.2004.00263.x
Bohli T, Ouederni A (2016) Improvement of oxygen-containing functional groups on olive stones
activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.
Environ Sci Pollut Res 23:15852–15861. https://doi.org/10.1007/s11356-015-4330-0
Bohli T, Ouederni A, Fiol N, Villaescusa I (2015) Evaluation of an activated carbon from olive
stones used as an adsorbent for heavy metal removal from aqueous phases. C R Chim 18:88–
99. https://doi.org/10.1016/j.crci.2014.05.009
Cagnon B, Py X, Guillot A, Stoeckli F, Chambat G (2009) Contributions of hemicellulose, cellu-
lose and lignin to the mass and the porous properties of chars and steam activated carbons from
various lignocellulosic precursors. Bioresour Technol 100:292–298. https://doi.org/10.1016/j.
biortech.2008.06.009
Celik A, Demirbaş A (2005) Removal of heavy metal ions from aqueous solutions via adsorp-
tion onto modified lignin from pulping wastes. Energy Sources 27:1167–1177. https://doi.
org/10.1080/00908310490479583
Chaudhuri SK, Lovley DR (2003) Electricity generation by direct oxidation of glucose in media-
torless microbial fuel cells. Nat Biotechnol 21:1229. https://doi.org/10.1038/nbt867
178 R. Kosheleva et al.
Cooney DO (1998) Adsorption design for wastewater treatment. CRC Press, Taylor&Francis,
Boca Raton
Demirbas A (2008) Heavy metal adsorption onto agro-based waste materials: a review. J Hazard
Mater 157:220–229. https://doi.org/10.1016/j.jhazmat.2008.01.024
Dias JM, Alvim-Ferraz MCM, Almeida MF, Rivera-Utrilla J, Sánchez-Polo M (2007) Waste
materials for activated carbon preparation and its use in aqueous-phase treatment: a review.
J Environ Manag 85:833–846. https://doi.org/10.1016/j.jenvman.2007.07.031
Dias JM, Alvim-Ferraz MC, Almeida MF, Rivera-Utrilla J, Sánchez-Polo M (2008) Waste materi-
als for activated carbon preparation and its use in aqueous-phase treatment: a review. J Environ
Manag 85:833–846. https://doi.org/10.1016/j.jenvman.2007.07.031
Duranoğlu D, Trochimczuk AW, Beker Ü (2010) A comparison study of peach stone and
acrylonitrile-divinylbenzene copolymer based activated carbons as chromium(VI) sorbents.
Chem Eng J 165:56–63. https://doi.org/10.1016/j.cej.2010.08.054
Fernandez ME, Nunell GV, Bonelli PR, Cukierman AL (2014) Activated carbon developed from
orange peels: batch and dynamic competitive adsorption of basic dyes. Ind Crop Prod 62:437–
445. https://doi.org/10.1016/j.indcrop.2014.09.015
Fiuza RA, Medeiros de Jesus Neto R, Correia LB, Carvalho Andrade HM (2015) Preparation of
granular activated carbons from yellow mombin fruit stones for CO2 adsorption. J Environ
Manag 161:198–205. https://doi.org/10.1016/j.jenvman.2015.06.053
Foo KY, Hameed BH (2011) Utilization of rice husks as a feedstock for preparation of activated
carbon by microwave induced KOH and K2CO3 activation. Bioresour Technol 102:9814–9817.
https://doi.org/10.1016/j.biortech.2011.07.102
Fornasiero P, Graziani M (2011) Renewable resources and renewable energy: a global challenge,
2nd edn. CRC Press, Boca Raton
Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manag
92:407–418. https://doi.org/10.1016/j.jenvman.2010.11.011
Fu K, Yue Q, Gao B, Sun Y, Zhu L (2013) Preparation, characterization and application of lignin-
based activated carbon from black liquor lignin by steam activation. Chem Eng J 228:1074–
1082. https://doi.org/10.1016/j.cej.2013.05.028
Ghouma I et al (2017) The potential of activated carbon made of agro-industrial residues in NOx
immissions abatement. Energies 10:Article ID 1508. https://doi.org/10.3390/en10101508
González PG, Pliego-Cuervo YB (2013) Physicochemical and microtextural characterization of
activated carbons produced from water steam activation of three bamboo species. J Anal Appl
Pyrolysis 99:32–39. https://doi.org/10.1016/j.jaap.2012.11.004
Grigor’ev LN, Burenina TI, Sukhenko AM (2003) Adsorption of carbon monoxide on oxidized acti-
vated lignin carbon. Russ J Appl Chem 76:723–726. https://doi.org/10.1023/a:1026001018005
Hebbar RS, Isloor AM, Inamuddin I, Asiri AM (2017) Carbon nanotube- and graphene-based
advanced membrane materials for desalination. Environ Chem Lett 15:643–671. https://doi.
org/10.1007/s10311-017-0653-z
Hemsas S, Lounici H, Belbeki Z, Benrachedi K (2014) Removal of dispersed dyes from aqueous
solution using activated carbon prepared from olive stones. J Agric Sci Technol 4:414–421
Hoseinzadeh E, Samarghandi M-R, McKay G, Rahimi N, Jafari J (2014) Removal of acid dyes
from aqueous solution using potato peel waste biomass: a kinetic and equilibrium study.
Desalin Water Treat 52:4999–5006. https://doi.org/10.1080/19443994.2013.810355
Huggins DR, Karow RS, Collins HP, Ransom JK (2011) Introduction: evaluating long-term impacts
of harvesting crop residues on soil quality. Agron J 103:230–233. https://doi.org/10.2134/
agronj2010.0382s
Imamoglu M, Tekir O (2008) Removal of copper (II) and lead (II) ions from aqueous solutions by
adsorption on activated carbon from a new precursor hazelnut husks. Desalination 228:108–
113. https://doi.org/10.1016/j.desal.2007.08.011
Ince M (2014) Comparision of low-cost and eco-friendly adsorbent for adsorption of Ni(II). Atom
Spectrosc -Norwalk Connecticut 35:223–233
5 Activated Carbon from Food Waste 179
Isikgor FH, Becer CR (2015) Lignocellulosic biomass: a sustainable platform for the produc-
tion of bio-based chemicals and polymers. Polym Chem 6:4497–4559. https://doi.org/10.1039/
C5PY00263J
Jin X, Zhang T, She Y (2012) Preparation of activated carbon by KOH activation on straw lignin.
Cellul Chem Technol 46:79–85. https://doi.org/10.4028/www.scientific.net/MSF.704-705.517
Kalderis D, Bethanis S, Paraskeva P, Diamadopoulos E (2008) Production of activated carbon from
bagasse and rice husk by a single-stage chemical activation method at low retention times.
Bioresour Technol 99:6809–6816. https://doi.org/10.1016/j.biortech.2008.01.041
Kamm B, Gruber PR, Kamm M (2000) Biorefineries – industrial processes and products. In:
Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH Verlag GmbH & co. KGaA.
https://doi.org/10.1002/14356007.l04_l01
Khalfaoui A, Meniai AH (2012) Application of chemically modified orange peels for removal of
copper(II) from aqueous solutions. Theor Found Chem Eng 46:732–739
Koay YS, Ahamad IS, Nourouzi MM, Abdullah LC, Choong TSY (2013) Development of novel
low-cost quaternized adsorbent from palm oil agriculture waste for reactive dye removal.
Bioresources 9:66–85
Kołodyńska D, Krukowska J, Thomas P (2017) Comparison of sorption and desorption studies
of heavy metal ions from biochar and commercial active carbon. Chem Eng J 307:353–363.
https://doi.org/10.1016/j.cej.2016.08.088
Köseoğlu E, Akmil-Başar C (2015) Preparation, structural evaluation and adsorptive properties of
activated carbon from agricultural waste biomass. Adv Powder Technol 26:811–818. https://
doi.org/10.1016/j.apt.2015.02.006
Kula I, Uğurlu M, Karaoğlu H, Çelik A (2008) Adsorption of cd(II) ions from aqueous solu-
tions using activated carbon prepared from olive stone by ZnCl2 activation. Bioresour Technol
99:492–501. https://doi.org/10.1016/j.biortech.2007.01.015
Kumar A, Jena HM (2016) Preparation and characterization of high surface area activated carbon
from Fox nut (Euryale ferox) shell by chemical activation with H3PO4. Result Phys 6:651–658.
https://doi.org/10.1016/j.rinp.2016.09.012
Kuppler RJ et al (2009) Potential applications of metal-organic frameworks. Coord Chem Rev
253:3042–3066. https://doi.org/10.1016/j.ccr.2009.05.019
Kwiatkowski M, Broniek E (2017) An analysis of the porous structure of activated carbons
obtained from hazelnut shells by various physical and chemical methods of activation. Colloid
Surf A 529:443–453. https://doi.org/10.1016/j.colsurfa.2017.06.028
Kyzas GZ, Deliyanni EA, Matis KA (2016) Activated carbons produced by pyrolysis of waste
potato peels: cobalt ions removal by adsorption. Colloid Surf A 490:74–83. https://doi.
org/10.1016/j.colsurfa.2015.11.038
Libra JA et al (2011) Hydrothermal carbonization of biomass residuals: a comparative review of
the chemistry, processes and applications of wet and dry pyrolysis. Biofuels 2:71–106. https://
doi.org/10.4155/bfs.10.81
Liou T-H (2010) Development of mesoporous structure and high adsorption capacity of biomass-
based activated carbon by phosphoric acid and zinc chloride activation. Chem Eng J 158:129–
142. https://doi.org/10.1016/j.cej.2009.12.016
Liu M, Yuan Q, Jia H, Li S, Wang X, Wang C (2013) Cysteine-modified orange peel for removal
of cu(II) from aqueous solutions. Water Sci Technol 67:2444–2450. https://doi.org/10.2166/
wst.2013.136
Llewellyn PL et al (2008) High uptakes of CO2 and CH4 in mesoporous metal—organic frame-
works MIL-100 and MIL-101. Langmuir 24:7245–7250. https://doi.org/10.1021/la800227x
Lozano-Castelló D, Lillo-Ródenas MA, Cazorla-Amorós D, Linares-Solano A (2001) Preparation
of activated carbons from Spanish anthracite: I. Activation by KOH. Carbon 39:741–749.
https://doi.org/10.1016/S0008-6223(00)00185-8
Lu GQ, Do DD (1991) Adsorption properties of fly ash particles for NOx removal from flue gases.
Fuel Process Technol 27:95–107. https://doi.org/10.1016/0378-3820(91)90011-Z
180 R. Kosheleva et al.
Rwiza MJ, Oh S-Y, Kim K-W, Kim SD (2018) Comparative sorption isotherms and removal
studies for Pb(II) by physical and thermochemical modification of low-cost agro-wastes from
Tanzania. Chemosphere 195:135–145. https://doi.org/10.1016/j.chemosphere.2017.12.043
Şentorun-Shalaby Ç, Uçak-Astarlıogˇlu MG, Artok L, Sarıcı Ç (2006) Preparation and charac-
terization of activated carbons by one-step steam pyrolysis/activation from apricot stones.
Micropor Mesopor Mater 88:126–134. https://doi.org/10.1016/j.micromeso.2005.09.003
Shamsuddin MS, Yusoff NRN, Sulaiman MA (2016) Synthesis and characterization of activated
carbon produced from kenaf core fiber using H3PO4 activation. Proced Chem 19:558–565.
https://doi.org/10.1016/j.proche.2016.03.053
Sheldon RA (2008) E factors, green chemistry and catalysis: an odyssey. Chem Commun
(Cambridge UK):3352–3365. https://doi.org/10.1039/B803584A
Shrestha S, Son G, Lee SH, Lee TG (2013) Isotherm and thermodynamic studies of Zn(II) adsorp-
tion on lignite and coconut shell-based activated carbon fiber. Chemosphere 92:1053–1061.
https://doi.org/10.1016/j.chemosphere.2013.02.068
Sumida K et al (2012) Carbon dioxide capture in metal–organic frameworks. Chem Rev 112:724–
781. https://doi.org/10.1021/cr2003272
Teng H, Yeh T-S, Hsu L-Y (1998) Preparation of activated carbon from bituminous coal with phos-
phoric acid activation. Carbon 36:1387–1395. https://doi.org/10.1016/S0008-6223(98)00127-4
Thue PS et al (2016) Preparation, characterization and application of microwave-assisted activated
carbons from wood chips for removal of phenol from aqueous solution. J Mol Liq 223:1067–
1080. https://doi.org/10.1016/j.molliq.2016.09.032
Toles CA, Marshall WE, Johns MM, Wartelle LH, McAloon A (2000) Acid-activated carbons from
almond shells: physical, chemical and adsorptive properties and estimated cost of production.
Bioresour Technol 71:87–92. https://doi.org/10.1016/S0960-8524(99)00029-2
Tong X, Ma Y, Li Y (2010) Biomass into chemicals: conversion of sugars to furan derivatives by
catalytic processes. Appl Catal A 385:1–13. https://doi.org/10.1016/j.apcata.2010.06.049
Treviño-Cordero H, Juárez-Aguilar LG, Mendoza-Castillo DI, Hernández-Montoya V, Bonilla-
Petriciolet A, Montes-Morán MA (2013) Synthesis and adsorption properties of activated
carbons from biomass of Prunus domestica and Jacaranda mimosifolia for the removal of
heavy metals and dyes from water. Ind Crop Prod 42:315–323. https://doi.org/10.1016/j.
indcrop.2012.05.029
Tripathi M, Sahu JN, Ganesan P (2016) Effect of process parameters on production of biochar
from biomass waste through pyrolysis: a review. Renew Sust Energ Rev 55:467–481. https://
doi.org/10.1016/j.rser.2015.10.122
Uğurlu M, Gürses A, Doğar Ç (2007) Adsorption studies on the treatment of textile dyeing effluent
by activated carbon prepared from olive stone by ZnCl2 activation. Color Technol 123:106–
114. https://doi.org/10.1111/j.1478-4408.2007.00072.x
Valix M, Cheung WH, McKay G (2004) Preparation of activated carbon using low tempera-
ture carbonisation and physical activation of high ash raw bagasse for acid dye adsorption.
Chemosphere 56:493–501. https://doi.org/10.1016/j.chemosphere.2004.04.004
Veksha A, Sasaoka E, Uddin MA (2009) The influence of porosity and surface oxygen groups of
peat-based activated carbons on benzene adsorption from dry and humid air. Carbon 47:2371–
2378. https://doi.org/10.1016/j.carbon.2009.04.028
Vivo-Vilches JF, Carrasco-Marín F, Pérez-Cadenas AF, Maldonado-Hódar FJ (2015) Fitting
the porosity of carbon xerogel by CO2 activation to improve the TMP/n-octane separation.
Micropor Mesopor Mater 209:10–17. https://doi.org/10.1016/j.micromeso.2015.01.010
Wilkins CK et al (2001) Formation of strong airway irritants in mixtures of isoprene/ozone and
isoprene/ozone/nitrogen dioxide. Environ Health Perspect 109:937–941
Xie Z, Guan W, Ji F, Song Z, Zhao Y (2014) Production of biologically activated carbon from
orange peel and landfill leachate subsequent treatment technology. J Chem 2014:9. https://doi.
org/10.1155/2014/491912
Yorgun S, Yıldız D (2015) Preparation and characterization of activated carbons from Paulownia
wood by chemical activation with H3PO4. J Taiwan Inst Chem Eng 53:122–131. https://doi.
org/10.1016/j.jtice.2015.02.032
182 R. Kosheleva et al.
Yu B, Zhang Y, Shukla A, Shukla SS, Dorris KL (2000) The removal of heavy metal from aqueous
solutions by sawdust adsorption – removal of copper. J Hazard Mater 80:33–42. https://doi.
org/10.1016/S0304-3894(00)00278-8
Zhang T, Walawender WP, Fan LT, Fan M, Daugaard D, Brown RC (2004) Preparation of activated
carbon from forest and agricultural residues through CO2 activation. Chem Eng J 105:53–59.
https://doi.org/10.1016/j.cej.2004.06.011
Zhang Y-J, Xing Z-J, Duan Z-K, Meng L, Wang Y (2014) Effects of steam activation on the pore
structure and surface chemistry of activated carbon derived from bamboo waste. Appl Surf Sci
315:279–286. https://doi.org/10.1016/j.apsusc.2014.07.126