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Activated Carbon
Chapter April 2014
DOI: 10.1002/0471238961.0103200902011105.a01.pub3

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ACTIVATED CARBON
1. Introduction: Definition and History of Activated Carbon
Activated carbon is a material with a high degree of porosity and an extended
surface area (1). More than 90% of activated carbon consists of the carbon element.
Activated carbon is a very versatile adsorbent that finds wide use in the environmental, industrial and other fields for removal, recovery, separation and modification of a variety of species in liquid- and gas-phase applications.
Activated carbon, also called activated charcoal, is a more effective and
advanced form of charcoal whose use dates back to prehistoric age. Charcoal is the
oldest form of human-made carbon and was used since about 8000 B.C. in metal
production (2). At about 3750 B.C. charcoal was employed for various purposes
such as reduction of copper and other metals, zinc and tin ores in the manufacture
of bronze (3), adsorption of odorous vapors from putrefying wounds and the
intestinal tract (4). Charcoal was also used in food poisoning cases where its
effect depended on the adsorption of toxins emitted by bacteria. Hindu documents
reveal that sand and charcoal filters were used for the purification of drinking
water. At about 460 B.C. Phoenicians applied charcoal filters for purification of
drinking water (4). In the time of Hippocrates (ca. 460370 BC) and also later,
carbons were applied for the removal of taste and odor and prevention of many
diseases (3,5). Later, in the 17th century Dutch traders also noticed that people
who drank out of charred water barrels suffered less from infections and diarrhea.
Thus, they understood that charcoal played a role in water purification (6).
Beginning from the 18th century, the mechanisms leading to the beneficial
effects of carbon were recognized more clearly. The specific adsorptive properties
of charcoal were first observed by Scheele in 1773 in the treatment of gases,
whereas in 1786 Lowitz demonstrated the adsorptive abilities of charcoal for
decolorization of contaminated tartaric acid solutions (4). The need of the sugar
refining industry for a material to be used in decolorization of raw sugar syrups
paved the way for the development of wood charcoals. Later, bone char was
discovered in 1811 which proved to have a higher decolorizing ability than wood
chars. In 1822 Bussy heated blood with potash and recognized that the resulting
material was a much better adsorbent than the bone char. This is considered to be
the first recorded example of activated carbon production by a combination of
thermal and chemical processes (7,8). Later, Schatten in Germany carried out
systematic studies on the manufacture and regeneration of bone chars. In London
sewers Stenhouse applied charcoal air filters for removing vapors and gases (8). In
1862, Lipscombe prepared a carbon material to purify potable water. However,
despite these efforts it is remarkable that the term adsorption was introduced
much later, in 1881 by Kayser for describing the uptake of gases (8).
On industrial scale, activated carbon was produced at the beginning of the
20th century. Two patents were obtained by von Ostreijko at about 19001901, for
chemical and thermal (or physical) activation of carbon, respectively (2). In 1909,
the first powdered activated carbon (PAC) with the trade name Eponit was
industrially produced by gas activation of charcoal with steam and carbon dioxide
according to von Ostreijkos patent (2,9). Then, in 1911 the Dutch company Norit
started with PAC production by steam activation of peat (2). Chemical activation
with zinc chloride was introduced on industrial scale at about 1914 (4,10). In the
1

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

ACTIVATED CARBON

1st World War the use of poisonous gases paved the way for the development and
large-scale production of granular activated carbon (GAC) which was seen to be
effective in the adsorption of such gases. Then, a variety of raw materials and
production techniques came into use in the manufacture of activated carbon. As a
result of these advances, activated carbon found large application in water and
wastewater treatment, solvent recovery, air purification and in industrial processes. More information about the historical development of activated carbon can
be obtained in literature (2,4,8,11).

2. Production and Properties of Activated Carbon

2.1. Production of Activated Carbon. Theoretically, all natural
organic materials rich in carbon, usually denoted as carbonaceous materials,
can be converted into activated carbon. However, in reality only few can be used
commercially (12).
Activated carbon may be produced from materials of vegetable, animal or
petrochemical origin. The annual production of activated carbon is estimated
about 100000 t worldwide (13). The basic raw materials used for production of
activated carbon include coal (anthracite or brown coal), peat, lignite, wood, nut
shells, petroleum coke, coconut shell etc., sometimes also synthetic high polymers.
Nowadays, great efforts are spent to exploit wastes as a raw material (precursor)
in activated carbon production. Municipal and industrial wastewater treatment
plants produce large volumes of sludges. These sludges bear the potential for
activated carbon production since they are mainly composed of organic material
(14). Also attempts are made to utilize agricultural wastes such as olive stones,
biomass residues, rice husks, corn cobs, bagasse, hard shells of apricot stones,
almond, walnut and hazelnut shells (15) or others such as waste tires, phenol
formaldehyde resins, pulp-mill residues, bones, coffee beans (16).
Figure 1 illustrates the general scheme in activated carbon production. The
raw materials used in the production have to fulfill various requirements: They
should be low in inorganic matter, available and cheap. Their degradation should
be low upon storage. They should be easily activated (17). Nowadays, literature
contains numerous examples on the production of activated carbon from a
variety of natural or waste materials. Although production of activated carbon
from such materials is principally possible, in reality only few provide commercially attractive activated carbons (12). To be commercially available, the raw
material should first have a well-defined and reproducible property. Since mostly
natural materials are employed in production, it is very probable that the
character of the final product varies. In addition, for the production of activated
carbon collection, transportation, bulk availability and seasonal variations in the
quality and availability of the raw material have to be considered. If all these
factors are taken into regard, many natural materials prove to be not suitable for
this purpose (12,16).
The production of activated carbon involves basically two different steps:
carbonization and activation (18) (Figure 1). Depending on the type of starting
organic-rich raw material and carbonization and activation conditions, the properties of the final product vary.

3
THERMALLY ACTIVATED CARBON

optional ash removal

with acids

at 500900C

GAS-PHASE ACTIVATION

low temperature
carbonization at 600C

lignite low temperature coke

hard coal

Fossil-fuel sources

Fig. 1. Production of activated carbon (based on reference (18)).

CHEMICALLY ACTIVATED CARBON

multistage washing,
drying

CHEMICAL ACTIVATION at
400600C with phosphoric acid or
600700C with zinc chloride

mixing, forming

Addition of
phosphoric acid or
zinc chloride

Biomass sources: wood, sawdust, peat, nut shells

pulverisation, briquetting,
crushing

anthracite

ACTIVATED CARBON

Carbonization. Carbonization is defined as the heat treatment or pyrolytic

decomposition of a heterogeneous precursor material like coal or wood in the
absence of oxygen at temperatures lower than 1000
C, usually in the temperature
range of 400600
C (1).
In the carbonization step of activated carbon production, the raw material is
in the form of lumps, pre-sized material, briquettes or extrudates (19). Carbonization is carried out in furnaces like rotary kilns, multiple hearth furnaces, and to
a lesser extent in fluidized bed furnaces (12). Along with tars, oils and gases,
carbonization yields a carbonized material, simply called char. In this material
noncarbon impurities such as oxygen, hydrogen, nitrogen, and sulfur have been
largely removed by conversion into volatile gaseous products. Thus, the carbon
element predominates in the resulting char. The char exhibits considerable
disorder since residual carbon atoms have arranged themselves into flat aromatic
sheets that are cross-linked in a random manner (1,3). The interstices in these
irregularly aromatic sheets give rise to the porosity upon which the properties of
activated carbon mostly depend (12).
Oxidation/Activation. The char obtained after carbonization does not have
a high adsorption capacity yet because its pore structure is not fully pronounced.
Therefore, for most applications this pore structure needs to be further enhanced
by an oxidative treatment called activation (1,12). The idea in this process bases on
the destruction of the carbon structure by the oxidation of carbonized material,
leading to the development of a highly porous structure consisting largely of
micropores. Regarding the majority of uses, in activated carbon production the
development of pores having a width lower than 2 nm (micropores) is the most
crucial factor to be considered (20). Activation leads to a product with extended and
extremely high surface area which gives rise to an excellent adsorption capacity.
Activated carbons are divided into two types depending on the activation
procedure, namely thermal or chemical activation (Figure 1).
Thermally Activated Carbons. This type of activation, also denoted as
physical or gaseous activation, involves basically two steps which usually succeed
each other:
(a) Carbonization: The raw material with a relatively high carbon content is
pyrolyzed at temperatures in the range 600900
C, in the absence of oxygen
and the presence of inert gases.
(b) Thermal Activation: In this step, raw or already carbonized material is
exposed to an oxidizing atmosphere consisting of gases such as steam, air,
carbon dioxide or their combination in a wide temperature range from 500 to
1000
C (17,21,22). In activation the carbon will be partially combusted according to following reactions (18,22).

C H2 O
C 2 H2 O
C CO2

! CO H2

(1)

! CO2 2 H2

(2)

! 2 CO

(3)

ACTIVATED CARBON

The reactions of carbon with steam (H2O) and CO2 (Equations 1 to 3) are
endothermic and occur at moderate rates. On the other hand, the reactions of
carbon with oxygen are exothermic and proceed at a rapid rate (18). Therefore,
oxygen is added to the mixture to bring about an exothermic combustion of the
intermediate products H2 and CO whereby the reaction temperature is maintained above 800
C (18,12). These reactions of carbon with carbon dioxide and
steam lead to the development of a highly porous structure (18).
Generally, thermal activation is carried out with already carbonized feedstocks such as lignite low temperature coke, hard coal and anthracite that are
called fossil-fuel sources (18). However, also biomass sources such as peat and
wood can be employed (Figure 1). Feedstocks like lignite low temperature coke can
be directly activated by skipping the step of carbonization. However, for others the
carbonization step is usually unavoidable since this makes subsequent activation
much easier (18).
Chemically Activated Carbons. Chemical activation is generally applied
to raw materials that contain cellulose like wood, sawdust, or nutshells. These
materials are also called biomass sources. For chemical activation, the raw
material is first impregnated with strongly dehydrating and oxidizing chemicals.
Typical chemicals used nowadays are phosphoric acid and zinc chloride although
formerly also potassium hydroxide, sodium hydroxide, calcium chloride were
employed. After impregnation, the material is pyrolytically heated to temperatures of about 400800
C in order to bring about degradation of cellulose
(17,18,22,23). Depending on the type of the activating agent, the activation
temperature can vary. Finally, activated carbon as a product is obtained by
repeated washing of the resulting mixture. Another aim in this step is usually
also the recovery of the activating chemical.
Unlike thermal activation of carbon, in chemical activation carbonization
and activation proceed simultaneously. Thus, in contrast to thermal activation in
which carbonization and activation are normally achieved in two different kilns,
chemical activation can be conducted in a single kiln (3). The advantages of
chemical activation over physical activation are the operation at lower temperatures and shorter activation times.
Chemical activation normally yields a PAC (19). Usually, wood and sawdust
are favored for the manufacture of PAC by the chemical activation with phosphoric acid (12). However, also GAC can be produced by chemical activation. For
this purpose, granular raw materials are impregnated with activating agents in
the same way as in PAC production.
2.2. Types of Activated Carbon Products. Beginning from the 1920s
large-scale production of activated carbon gained importance. To satisfy the
different requirements in industrial, environmental and other fields, many types
of activated carbons are produced today that can take different shapes. The most
well-known types are in the form of Powdered Activated Carbon (PAC) and
Granular Activated Carbon (GAC) (Figure 2a and 2b (30)). GAC is obtained by
crushing and sieving of activated material. Milling of the material yields PAC.
The primary characteristic that differentiates GAC and PAC is the particle
size. PAC particles have typically a particle size less than 100 mm (24); the particle
size is commonly in the range of 1525 mm. GAC particles have a mean particle
size in the range of 15 mm (3).

ACTIVATED CARBON

Fig. 2. Different forms of activated carbon (a) granular activated carbon (GAC),
(b) powdered activated carbon (PAC), (c) extruded activated carbon (EAC) (permission
received from (30)).

In standards, PAC is defined as an activated carbon with a mean particle

diameter less than 45 mm or with particle sizes predominantly smaller than US
Mesh 80 (0.18 mm) whereby the mesh size indicates the range of particle sizes in
an activated carbon (25,26). Accordingly, GAC is an activated carbon with particle
sizes predominantly greater than US Mesh 80 (12,25). GAC is designated by mesh
sizes such as 8/20, 20/40, or 8/30 for liquid-phase applications and 4/6, 4/8, or 4/10
for vapor phase applications (5). Particle sizes in the range of 12/42 mesh are
advantageous for liquid-phase adsorption (27). While PAC is mainly used in
liquid-phase applications and for flue gas treatment, GAC is used in both liquidand gas-phase applications (28).
Activated carbon can be produced in other forms such as extruded activated
carbon (EAC) (Figure 2c), bead activated carbon, impregnated carbon, and
polymer coated carbon. Activated carbon cloths (ACCs) are used mainly for

ACTIVATED CARBON

medical, healthcare, defence and industrial purposes (29). Activated carbon cloths
and activated carbon fibers (ACFs) can be prepared from rayon, polyacrylonitrile
(PAN), phenolic resins, acetate, petroleum and coal tar pitch etc. (12).

2.3. Properties of Activated Carbon. Classification of Activated

Carbon in Carbon Materials. Carbon exists in five allotropic modifications
as carbine (chaoite), fullerenes and nanotubes, non-graphite carbon, graphite,
and diamond. The differences in these modifications arise from the arrangement
of the carbon atoms in their crystals (2).
Solid-phase pyrolysis of organic materials produces basically two types of
carbons as graphitizing and non-graphitizing carbons. A graphitizable carbon
is soft, non-porous and of high density; it can be readily transformed into graphite
by heating, whereas non-graphitizing carbons are hard and low-density materials
that cannot be transformed into graphite even at very high temperatures. In that
regard, activated carbon is a non-graphitizing or a non-graphite carbon; its low
density is the consequence of the highly porous structure. Its porous structure
gives this material a high internal surface area (31). In this non-graphitizing
material, carbon atoms are arranged in a two dimensional, planar hexagonal
network (2). Thus, activated carbon is not a truly amorphous material, but has
also a microcrystalline structure which, however, differs from that of graphite (1).
In activated carbon the orientation of the stacks of aromatic sheets is disordered
whereas a graphite has a highly ordered crystalline structure.
Porous Structure and Surface Area. Activated carbon is composed of
pores consisting of different sizes and shapes. According to the definition of
International Union of Pure and Applied Chemistry (IUPAC), micropores are
pores having a width lower than 2 nm, mesopores are defined as those having a
width between 2 and 50 nm, and macropores are those pores having a width larger
than 50 nm. Another classification also involves ultramicropores denoting micropores less than 0.7 nm (5). Figure 3 exemplifies the macro-, meso- and micropores
in an activated carbon. The scanning electron micrographs (SEM) in Figure 4
provide an idea on the porosity of activated carbon (22).
During the production of activated carbon, first macropores are formed by
the oxidation of edge groups on the external surface area of the raw material.
Then, mesopores are formed which are essentially secondary channels in the walls
of the macropore structure. Finally, the micropores are formed by attack of the
planes within the structure of the raw material (16).

Fig. 3. Macro-, meso- and micropores in an activated carbon.

ACTIVATED CARBON

Fig. 4. Porous structure of activated carbon (permission received from (22)).

Activated carbon has a very large surface area per unit weight, which makes
it an ideal absorptive material. The porous surface of activated carbon is responsible for the adsorption of a number of solutes and gases. All pores have walls and
will comprise two types of surfaces: an internal surface (microporous surface) and
an external surface. The former, reaching several thousands m2/g in many
activated carbons constitutes about 95 % of the total surface area of activated
carbon (1). The latter representing the walls of the meso- and macropores as well
as the edges of aromatic sheets in activated carbon is much smaller and may vary
between 10 and 200 m2/g in most activated carbons (1).
Depending on the raw material and carbonization/activation conditions, the
surface area and pore volumes of activated carbons vary in a wide range. The
amount of material adsorbed can be very large because of the great internal
surface of activated carbon. In that respect, the internal surface area, also called
the Brunauer-Emmett-Teller (BET) area, plays a more important role than the
external one. The BET area is determined by the measurement of gas adsorbed
(typically N2) at a given pressure. Activated carbons used in air- and gas
purification generally have a BET area ranging from 800 to 1500 m2/g, whereas
those employed in water treatment have usually a BET area of 5001500 m2/g
(22).
Since adsorption is the accumulation of molecules on the surface of an
adsorbent, the adsorbed mass is usually thought to be strongly dependent on
the size of surface area. This assumption is true, but incomplete because surface

ACTIVATED CARBON

area is only one of the criteria that determines adsorption. Moreover, in literature
it is also advised to use the concept surface area itself with caution since the
adsorbed amounts need not to be proportionally related to surface area. In
addition, the available surface area is not a fixed entity, but will change according
to the adsorbate (12).
Both the raw material and activation type have a great effect on the pore
structure of activated carbon. Since in chemical activation the temperatures are
lower, in chemically activated carbons micropores are not as pronounced as in
steam activated carbons. As a result chemically activated carbons generally
possess a very open pore structure (32). Besides the type of activation, the raw
material is also of importance. Although both carbons were subjected to activation
with steam, a wood-based carbon was reported to have a very regular network of
large pores whereas the coal-based one had a very irregular network of macropores (17). This dramatic difference in pores will also have an impact on the
diffusion of molecules to adsorption sites (17).
An important factor for adsorption is also the total pore volume and pore size
distribution (PSD). PSD is represented by the plot of differential pore volume
distribution (in cm3/g) with respect to pore radius (in nm). Activated carbon
exhibits a broad pore size distribution. Although two activated carbons may be
activated in the same way (i.e. steam-activated), they may exhibit quite different
pore size distributions because of the differences in the original material (22).
Except for the adsorption of very large molecules, macropores are usually of
little value since their surface area is too small. The importance of mesopores may
vary depending on the surface area they provide. However, for the adsorption of
most adsorbates, macropores and mesopores function as conduits in the transfer of
an adsorbate to the micropore surface area where most of the adsorption occurs.
Macro- and mesopores also play a role in desorption.
The pore structure distribution in an activated carbon is crucial for the
adsorption of organic molecules with different sizes. The relative proportions of
micropores, mesopores, and macropores in an activated carbon vary considerably
according to the raw material (16). For example, micropores dominate in a coconut
shell based carbon and constitute 95 % of the available internal surface area.
Therefore, such a structure allows adsorption of small molecular weight compounds. In contrast to that, meso/macropore structures dominate in wood and
peat based carbons; therefore these carbons are ideal for the adsorption of large
molecules. In accordance with this, they are often used in decolorization processes
where the removal of large molecules is of interest. The pore structures of coal
based carbons are somewhere between coconut shell and wood (16).
Small organic molecules such as phenol can access micropores. On the other
hand, natural organic matter (NOM) found in water supplies can access only
mesopores. Bacteria have typically a diameter in the range of 2002000 nm; they
can therefore have an access to macropores only (11,12).
The textural properties of an activated carbon need also to be characterized.
The pore size distribution is determined by mercury porosimetry which is effective
from about 3.6 nm up to about a few millimiters (33). Micropores and mesopores
are identified by the analysis of adsorption isotherms which are usually generated
with the use of N2 gas at 77 K. Intrinsic pores can be identified by X-ray diffraction
(XRD). Extrinsic pores on the surface of carbon materials can be directly observed

10

ACTIVATED CARBON

by coupling microscopy with image processing techniques. Among these techniques the most commonly used one is the scanning electron microscopy (SEM)
which shows pore sizes in the range of 10 nm-100 mm (33).
Surface Functional Groups. Besides the physical characteristics like the
particle size, pore structure and surface area, also chemical properties of carbon
surface play an important role in adsorption. The edges, dislocations and discontinuities in the aromatic sheets in an activated carbon, containing unpaired
electrons and residual valencies, are highly reactive places called active sites or
active centers. These sites can interact with different species such as oxygen,
hydrogen, nitrogen and sulfur, giving rise to different types of surface groups (1).
In an activated carbon these sites are responsible for surface reactivity, surface
reactions, and catalytic reactions (1).
Activated carbon surfaces generally contain various oxygen complexes arising from the raw material as well as from chemisorption of oxygen during the
activation process. Although, in general, activated carbons are of hydrophobic
nature, the presence of oxygen-containing groups on the surface increases the
hydrophilicity of activated carbons since water molecules can form hydrogen
bonds with oxygen atoms (3). Thus, the chemical structure of an activated carbon
determines its interaction with polar or nonpolar adsorbates.
Activated carbon possesses three types of oxygen-containing surface groups
such as acidic, neutral and basic (1). Most oxygen complexes exist in the form of
acidic surface oxides that have been postulated as carboxyls, lactones, and
phenols. The presence of acidic surface oxides renders the carbon surface hydrophilic and polar in character which in turn gives rise to adsorption of polar and
ionic species such as heavy metals. The basic surface oxygen groups are much less
characterized. They have been postulated as pyrones and chromenes structures.
The neutral surface oxygen groups are formed by the irreversible chemisorption of
oxygen at the ethylene type unsaturated sites present on the carbon surface (1).
The nature and concentration of surface functional groups may be modified
by thermal treatment or chemical treatment in which agents such as carbon
dioxide, ammonia, ozone, nitric acid or hydrogen peroxide are employed (3,12,34).
Although the surface sites associated with functional groups have a small contribution to total surface area, small variations in surface chemistry may have a
large influence on adsorption capacity (3). In addition to surface groups, the
presence of large quantities of minerals such as calcium, sulfate and phosphate
ions has an influence on the surface properties of activated carbon (35).
Many experimental methods are used to characterize the surface of activated
carbons. Wet techniques include potentiometric titrations and zeta potential or
electrochemical methods whereas dry techniques include temperature-programmed desorption (TPD) and spectroscopic methods such as X-ray photoelectron
spectroscopy (XPS) and diffuse reflectance infrared spectroscopy (DRIFT) (36).
Functionalities of Activated Carbon. Adsorption. Adsorption is
defined as accumulation of a substance at a surface. Adsorption can occur between
two phases, namely liquid-liquid, gas-liquid, gas-solid, or liquid-solid interfaces.
The adsorbing phase is termed the adsorbent whereas the material adsorbed is the
adsorbate.
Adsorption is the most well-known mechanism for the removal of a species in
the presence of activated carbon. Activated carbon can adsorb a large number of

ACTIVATED CARBON

11

organics and some inorganics, both from the liquid and gas phase. Among the
organic classes one can list aromatics, polynuclear aromatics, chlorinated aromatics, phenolics, high molecular weight hydrocarbons, chlorinated aliphatics,
aliphatic and aromatic acids, ketones, esters, ethers and alcohols, surfactants and
soluble organic dyes. Inorganics such as radionuclides and metal ions may also be
adsorbed onto activated carbon. The adsorption of many adsorbates is usually
induced by van der Waals forces. This type of adsorption is generally termed
physical adsorption or physisorption. In some cases, adsorbates may be removed
by chemical adsorption, or chemisorption, where the adsorbate undergoes chemical interaction with activated carbon. The bonds formed between activated carbon
and the adsorbate are much stronger in chemisorption compared to physisorption.
When the adsorbent (activated carbon) and the adsorbate are placed into the
same medium, the adsorbate is transported to carbon surface by the mechanisms
of bulk solution transport (advection), external diffusion and intraparticle (internal) diffusion. After the transport of the adsorbate to an available site, an
adsorption bond is formed. In batch adsorption systems the kinetics of adsorption
indicates the rate of approach to equilibrium. After a sufficiently long contact
time, the rates of adsorption and desorption of an adsorbate equal to each other. In
other words, an equilibrium is established between the adsorbent and the
adsorbate in the bulk phase and the maximum adsorption is reached. If adsorption
capacity onto activated carbon is plotted against the equilibrium concentration
(for liquids) or equilibrium pressure (for gases) of the adsorbate at a constant
temperature, the obtained curve is known as an isotherm. Thus, an isotherm
represents simply the distribution of a material between the solid phase (activated
carbon in this case) and the liquid or gas phases at a given equilibrium condition.
The most well-known mathematical expressions of adsorption equilibrium are the
Freundlich, Langmuir and BET (Brunauer, Emmettt, Teller) isotherms.
Reduction. Another well-known functionality of activated carbon is its
reducing property. In dechlorination of residual chlorine in water, for example,
activated carbon acts as a reducing agent. The principal of this reduction depends
on a chemical reaction involving the transfer of electrons from the surface of
activated carbon to chlorine.
Catalysis. Activated carbon has a large surface area with various functional groups that act as catalytic sites. Due to this surface property and relative
hardness, activated carbon can often serve as a catalyst. The surface chemistry
of activated carbon plays a crucial role in catalysis (36). If the catalytic activity of
the original activated carbon is not sufficient, for some applications in industrial
processes, the surface properties are often modified by impregnation with
metals and their oxides (1,32). Today, a variety of activated carbons are
produced by manufactures who tailor the properties of activated carbon to
very specific needs. Such activated carbons are used as a catalyst in chlorination
(i.e. chlorination of hydrocyanic acid to cyanogen chloride and ultimately
cyanuric chloride), as an oxidation catalyst for glyphosate production, as a
catalyst in zinc-oxygen depolarisation in batteries, as a catalyst for the production of phosgene, and as precious metal catalyst carriers for use in the pharmaceutical and chemicals industry (37).
In advanced oxidation processes applied to water treatment, activated
carbon in the form of GAC was shown to play a catalytic role in the transformation

12

ACTIVATED CARBON

of ozone into highly oxidative speices such as hydroxyl radicals and thus contribute to the reduction of dissolved organic carbon (DOC) and micropollutants (38).
Furthermore, activated carbon can be used as a catalyst support or can act as a
catalyst on its own in Catalytic Wet Air Oxidation (CWAO), which is a process
leading to the total oxidation of pollutants in water and wastewater treatment at
moderate temperatures and pressures using oxygen or air (39,40). Activated
carbon was also used as a support or adsorbent in applications of photocatalytic
decomposition of organic compounds in liquid phase and removal of pollutants
from air (41).
Synergism between Activated Carbon and Biomass. In biological
treatment systems, if biomass and activated carbon are present in the same
reactor, biomass can often be attached onto activated carbon to form a biofilm.
This is often observed in biological activated carbon (BAC) filters (Section 4.2)
used in water/wastewater treatment. Also, activated carbon in the form of PAC
can be added to a suspended-growth biological reactor like activated sludge to
assist biological removal of pollutants.
The main interactions between activated carbon and biomass are as follows:
Slowly biodegradable and nonbiodegradable organics are adsorbed to the surface of
activated carbon to be retained there for a long period of time. This long retention
enables the acclimation of attached and suspended biomass to these organics,
eventually leading to the biodegradation of slowly biodegradable organics. Further,
biomass in the bulk phase is protected from toxic/inhibitory effects if such
organic and inorganic compounds are adsorbed onto activated carbon. Moreover,
due to long retention on carbon surface, microbial processes taking place on the
surface of activated carbon can even convert a specific toxic organic pollutant into an
innocuous one. Another feature of activated carbon is the ability to concentrate
pollutants or substrates (such as oxygen) on surface. Particularly, if the pollutant
has a low concentration in the bulk phase, its concentration can be a factor
enhancing biodegradation. Moreover, activated carbon can retain a number of
volatile organic compounds (VOCs) on the surface and prevent their emissions
into the air. This retention in turn may also increase the probability of VOC
biodegradation. Depending on operation conditions, activated carbon has also
the ability to desorb pollutants. Desorption of adsorbed pollutants often occurs
upon the reversal of concentration gradient between the surface of carbon and the
bulk phase. Following this desorption, pollutants may be removed by surrounding
suspended or attached biomass. This is one of the significant functions of activated
carbon in biological processes and is described as bioregeneration of activated
carbon (11). In contrast to thermal and chemical methods of activated carbon
regeneration (Section 5.2), bioregeneration is an environmentally-friendly and
cheap alternative.

3. Characterization and Testing of Activated Carbons

There are several hundreds of commercial activated carbons available with
different characteristics to be used in specific applications (12). In environmental,
industrial and other applications the use of an activated carbon grade requires a
knowledge of its physicochemical and adsorptive properties.

ACTIVATED CARBON

13

3.1. Physicochemical Parameters used in the Characterization of

Activated Carbon. The density of the skeleton of a carbon granule is known as
the real density which is also known as the absolute or helium density since the
determination bases on the use of helium. On the other hand, for practical
applications manufacturers of activated carbon usually report about the apparent density which is the mass of a unit volume of the carbon particle including its
pore system or the bulk density which is defined as the mass of a unit volume of
the sample, including both the pore system and the voids between the particles
(12).
The particle size is a very important criterion in the choice of activated
carbon since it affects adsorption kinetics, flow characteristics and filterability.
However, in supplied form activated carbon does not have a uniform particle size.
Therefore, in many cases manufacturers also report the particle size distribution (PSD) in an activated carbon. Using the results of standard PSD tests, often
the mean particle diameter (MPD), effective size, and uniformity coefficient are
also calculated (42). Manufacturers of activated carbon usually report the effective size and uniformity coefficient along with particle size.
The hardness/abrasion number is a measure of activated carbons resistance to abrasion or attrition (43). Activated carbon needs a high mechanical
strength and attrition resistance where backwashing forces, pressure drop and
carbon losses may be significant such as in GAC filters operated in water/wastewater treatment (43).
The ash content of activated carbon varies in the range of 112% and is
mainly composed of silica, alumina, iron, alkaline and alkaline earth metals. The
ash content is a factor increasing the hydrophilicity of activated carbon (27).
Lignocellulosic materials such as soft- and hardwoods produce an activated
carbon with a lower ash content than coal-based precursors (12).
Further, there are other physicochemical parameters to be considered such
as moisture content, ignition temperature, self-ignition, pH value, water-soluble
content etc. (12).

3.2. Adsorptive Parameters used in the Characterization of

Activated Carbon. Several tests are used to determine the adsorptive properties of activated carbon. The iodine number is the standard measure for liquidphase applications of unused or reactivated carbons. Higher iodine numbers
indicate higher degree of activation. This number represents the amount of iodine
absorbed (in milligrams) by 1 g of carbon under specified test conditions. It may be
used as an approximation of internal surface area for some activated carbons. For
many carbons, it is reported to be close to the BET area (12,44). Because iodine is a
small molecule, the iodine number test is a measure of the microporosity of
activated carbon. It is thus showing the effectiveness of an activated carbon
when very small molecules are to be adsorbed (45).
Activated carbons with a mesoporous structure are able to adsorb medium
size molecules such as the methylene blue dye. Thus, the methylene blue
adsorption, reported in g/100g, is indicative of adsorption in mesopores.
Carbon Tetrachloride (CCl4) Activity (CTC activity) is defined as the
ratio (in percent) of the weight of CCl4 adsorbed by an activated carbon sample to
the weight of the sample, when the carbon is saturated with this compound. It is
basically a measure of the pore volume of the activated carbon sample and

14

ACTIVATED CARBON

represents the degree of completion of the activation process. It is usually used for
quality control for gas-phase activated carbons.
The molasses decolorizing efficiency or molasses number is a measure
of the ability to decolorize a standard molasses solution and is a more appropriate
parameter in the case of medium and large-sized molecules or the simultaneous
presence of small and larger molecules (46).
The macropores and mesopores in an activated carbon can adsorb tannins
that are a mixture of large and medium size molecules. As such, the tannin value
indicates the ability of activated carbon to adsorb medium and large size molecules. The benzene adsorption test, mainly used for granular activated carbons,
provides very relevant information about the adsorptive capacity of carbons used
in gas phase.
There are also other tests that give information about the adsorptive
behavior of activated carbon, such as the phenol adsorption, butane adsorption,
and phenazene adsorption.
The properties of some selected commercial activated carbons used in
liquid- and gas-phase applications are shown in Table 1 and 2, respectively
(4752).
3.3. Standard Procedures in Testing of Activated Carbon. As
shown in Table 3, there are various standards developed by the American Society
for Testing and Materials (ASTM) for testing and evaluating activated carbon
grades (53). These carbon standards are followed by many manufacturers to
determine the physicochemical properties of activated carbon, its adsorption
properties, reactivation possibilities etc. in both liquid- and gas-phase applications. Moreover, the American Water Works Association (AWWA) has issued a
number of standards related to the use activated carbon. Examples to such
standards are the B604-96 Standard for Granular Activated Carbon (54) covering
the use of granular and extruded activated carbons as a filter medium and
adsorbent in water treatment and the B600-10 Standard for Powdered Activated
Carbon (55) covering PAC for use in adsorption of impurities for water supply
service applications. Also, standards about activated carbon have been issued by
the Deutsches Institut f
ur Normung e.V (DIN) like the DIN EN 15799 standard
addressing the use of PAC for the treatment of swimming pool water.
In testing and evaluation of virgin and spent activated carbons, depending
on the use of activated carbon, manufacturers often follow also other standards
such as the FCC (Food Chemicals Codex) for food grade applications, CEFIC
(Conseil Europ
een des F
ed
erations de lIndustrie Chimique) (22), USP for pharmaceutical grade applications, and NIOSH (National Institute for Occupational
Safety and Health) for respirator applications.

4. Application of Activated Carbon in Various Fields

4.1. Choice of Activated Carbon Type and Technology. Choice of
Activated Carbon Type. A broad range of different activated carbon types are
available in the market to suit different uses. The effectiveness of adsorption onto
activated carbon depends on both the physical and chemical characteristics of
activated carbon (source of raw carbon, method of activation, pore size

15

Wastewater
treatment

Suitability

mean diameter (mm)

uniformity coefficient (max)
moisture by weight, %
abrasion number
ash content, wt %
pH of aqueous extract
BET surface area, m2/g
iodine number, mg/g min
methylene blue adsorption,
g/100 g
carbon tetrachloride
(CTC) activity, %
pore volume, cm3/g
micropore volume, cm3/g

0.34

1.04

65

0.01
6
1070
1000+

6 (max)

882
900

0.47
0.41

Dechlorination
in pharmaceutical,
and food processing
industries

Coal-based
GAC

RES-KARB
JCL-1240 (48)

5 (max)

19.71

0.29-0.39

Wood-based
PAC

Type

apparent density, g/cm3

bulk density, g/cm3
effective size, mm

MD3545WB
powder (47)

Property

8
Alkaline
875
700
11

1.8
2

1.2

0.29

Purification of
potable alcohol
and vodka

Steam
activated
GAC

NORIT
PK1-3 (49)

0.88

8
950
900
20

1.21.7
2

0.41.8

0.5

Wide range of
drinking water
applications

Coal-based
GAC

AQUASORB
1000 (48)

1.0

6
Alkaline
900
1050
21

0.38
0.8 (pellet
diameter)

Purification
of foods and
fine chemicals

Steam activated
peat- based
extruded
carbon

NORIT RO 0.8 (48)

Table 1. Properties of Some Selected Activated Carbons Used in Liquid-Phase Operation

500

4.5

2.1
8
70

0.70.9

1000

1.9 (max)
2 (max)
75 (min)

0.550.75

0.54

Removal of
dissolved
organics
from water,
wastewater,
industrial and
food processing
streams

Removal
of large
and small
molecular
pollutants
from water
and wastewater
0.38

Bituminous
coal-based GAC

Calgon
Filtrasorb
400 (50)

Lignite
coal-based
GAC

NORIT
HYDRODARCO
3000 (48)

16

H2S breakthrough
capacity (g H2S/cc
carbon)

On 4 mesh:8.0 %
(max)
Through 10 mesh:
5.0 % (max)

815 (min)

Removal of
elemental and
organic mercury
from natural gas,
air, and by-product
hydrogen streams
0.58

Suitability

apparent density, g/cm3

bulk density, g/cm3
sulfur content, % wt.
BET surface area, m2/g
particle size, mm
moisture by weight, %
hardness/abrasion number
iodine number, mg/g min
benzene adsorption
from air at 20
C [wt.%]
p/ps:9/10
CCl4 activity (wt.%)
screen size by wt.,
US sieve series

Sulfur-impregnated
GAC

Calgon Carbon
HGR (51)

Property

Name

<100 US mesh:
100 % (min)
<325 US mesh:
95 % (min)

400600

8 (max)

0.50.8

Enhanced mercury
capture in flue-gas
treatment

Calgon Carbon
Fluepack1
LMC (51)
Brominated PAC

0.3

95 (min)

4 (mean)

Odor removal in
sewage treatment
operations (removal
of H2S and VOCs)

Calgon Carbon
MinotourTM
OC (51)
Extruded
carbon pellet

Table 2. Properties of Some Selected Activated Carbons Used in Gas-Phase Operation

382

>60
80

1000
4

0.470.03

Coal-based
cylindrically
shaped carbon
Gas cleaning,
solvent recovery

Donau Carbon
Desorex K3 (52)

482

>99

1250
4

0.420.03

Donau Carbon
Supersorbon
K42 (52)
Coal-based
cylindrically
shaped carbon
Solvent recovery

17

D7385 - 13

D5159 - 04(2009)
D5160 - 95(2008)
D5228 - 92(2010)
D5742 - 95(2010)
D5832 - 98(2008)
D6646 - 03(2008)

D6647 - 01(2011)
D6781 - 02(2007)
D6851 - 02(2011)
Gas-Phase Evaluation Tests
D2854 - 09
D2862 - 10
D2866 - 11
D2867 - 09
D3466 - 06(2011)
D3467 - 04(2009)
D3802 - 10
D3803 - 91(2009)
D4069 - 95(2008)

D6385 - 99(2011)
D6586 - 03(2008)

D5919 - 96(2011)

D4607 - 94(2011)
D5029 - 98(2009)
D5158 - 98(2005)

Liquid-Phase Evaluation Tests

D3838 - 05(2011)
D3860 - 98(2008)

Method number
Title
Standard Test Method for pH of Activated Carbon
Standard Practice for Determination of Adsorptive Capacity of Activated Carbon by Aqueous
Phase Isotherm Technique
Standard Test Method for Determination of Iodine Number of Activated Carbon
Standard Test Method for Water Solubles in Activated Carbon
Standard Test Method for Determination of Particle Size of Powdered Activated Carbon
by Air Jet Sieving
Standard Practice for Determination of Adsorptive Capacity of Activated Carbon by a Micro-Isotherm
Technique for Adsorbates at ppb Concentrations
Standard Test Method for Determining Acid Extractable Content in Activated Carbon by Ashing
Standard Practice for the Prediction of Contaminant Adsorption On GAC In Aqueous Systems Using
Rapid Small-Scale Column Tests
Standard Test Method for Determination of Acid Soluble Iron Via Atomic Absorption
Standard Guide for Carbon Reactivation
Standard Test Method for Determination of Contact pH with Activated Carbon
Title
Standard Test Method for Apparent Density of Activated Carbon
Standard Test Method for Particle Size Distribution of Granular Activated Carbon
Standard Test Method for Total Ash Content of Activated Carbon
Standard Test Methods for Moisture in Activated Carbon
Standard Test Method for Ignition Temperature of Granular Activated Carbon
Standard Test Method for Carbon Tetrachloride Activity of Activated Carbon
Standard Test Method for Ball-Pan Hardness of Activated Carbon
Standard Test Method for Nuclear-Grade Activated Carbon
Standard Specification for Impregnated Activated Carbon Used to Remove Gaseous Radio-Iodines
from Gas Streams
Standard Guide for Dusting Attrition of Granular Activated Carbon
Standard Guide for Gas-Phase Adsorption Testing of Activated Carbon
Standard Test Method for Determination of Butane Working Capacity of Activated Carbon
Standard Test Method for Determination of Butane Activity of Activated Carbon
Standard Test Method for Volatile Matter Content of Activated Carbon Samples
Standard Test Method for Determination of the Accelerated Hydrogen Sulfide Breakthrough Capacity
of Granular and Pelletized Activated Carbon
Standard Guide for Estimating Carbon Saturation by Temperature Rise upon Immersion

Table 3. Standard Tests for the Evaluation of Activated Carbon (53)

18

ACTIVATED CARBON

distribution, surface area, hydrogen and oxygen content etc.) and the characteristics of the species to be removed by adsorption or other mechanisms.
The affinity of a species for activated carbon depends on a number of factors
such as its solubility, polarity, molecular weight, structure, dissociation and
concentration. Physical and chemical characteristics of activated carbon can
give only some insight into its potential to adsorb a specific species. In reality, in
each case experimentation is almost always needed for the selection of the best
activated carbon in both liquid- and gas-phase operations. The adsorptive
capacity of an activated carbon grade for the particular species has to be
determined by a) adsorption isotherms (batch equilibrium capacity tests) and
b) PAC jar tests or bench- and pilot-scale GAC column tests. Experimental
determination is particularly needed if the liquid or gas to be treated contains
more than a single species.
The choice of activated carbon grade and the technology are closely related to
each other. In that regard, the first issue to consider is the characteristics of the
species. Water or wastewater samples usually consist of a mixture of compounds
with different physicochemical and adsorptive properties. For example, if a water
or wastewater contains predominantly large molecules such as proteins, a carbon
grade with a large pore structure is recommended. Similarly, activated carbon
grades to be used in liquid- and gas-phase applications differ from each other
significantly. Pollutants found in gas phase usually consist of small-sized molecules, whereas those in liquid phase are relatively larger molecules. In accordance
with this, in gas-phase operations activated carbon types with microporous
structure are preferred. In contrast, in liquid-phase applications, such as those
in decolorization of solutions consisting of large molecules, activated carbons with
a high macropore volume are preferred which permit molecules to diffuse more
rapidly into the meso- and micropores. In each case, besides the pore structure
many factors play a role such as the shape and surface chemistry of an activated
carbon (12).
Apart from the selection of activated carbon grade that best adsorbs the
species to be removed, a key issue to address is the type of technology. Depending
on the need, PAC or GAC operation and batch- or continuous-flow operation may
be chosen. Criteria such as operational flexibility, process reliability, economics,
and investment costs also determine which type of technology is to be selected.
Selection of PAC or GAC Systems. The main difference between PAC
and GAC is the particle size. The small particle size in PAC allows a more rapid
diffusion and affects the kinetics of adsorption of a species. In accordance with
this, operations with smaller particle sizes require a lower contact time. However,
due to its small particle size, PAC is not preferred in filtration systems such as
those in water or wastewater treatment since small particle sizes often lead to
clogging and a high pressure drop (43,56).
The application of PAC involves the dosing into a process stream (gas or
liquid). After the contact of PAC and the adsorbent for a prescribed contact time, a
proper separation (filtration or settling) is needed to obtain a treated effluent.
Some of the key criteria to be considered in PAC systems are the contact time,
single- or multistage operation, separation of carbon, and safety measures. PAC
systems can be operated in both batch- and continuous-flow mode. The batch
method can be for example used for decolorization of sugar solutions or

ACTIVATED CARBON

19

decolorization and clarification of organic compounds in the pharmaceutical and

chemical industries (1).
The use of PAC allows a great flexibility in operation since it can be dosed
temporarily when needed and the dose can be adjusted to actual needs. Moreover,
PAC investment costs such as storage and dosing equipment are lower than in the
case of GAC (57). However, regeneration of PAC is rather difficult, because fine
PAC particles have to be separated first from the treated stream. Therefore, in
conventional operations spent PACs are either disposed of in landfills or sent to
incineration units (19).
GAC is usually applied when there is a continuous need for activated carbon
treatment. For this purpose, most often GAC systems are used which are composed of continuous-flow carbon adsorbers, carbon storage units, carbon transport, and carbon regeneration systems. The carbon adsorber consists of a tank in
which the carbon is placed to form a filter bed. GAC is mostly used in fixed(packed) filter beds, or alternatively in expanded- and fluidized beds. GAC
adsorbers may be designed to operate in downflow or upflow mode. In GAC
adsorbers, very low residual concentrations of target species can be achieved
since GAC beds can be fully saturated. Thus, GAC adsorbers allow a more
complete use of the adsorption capacity of the carbon, thus reducing make-up
costs. GAC particles are hard and abrasion resistant which makes them suitable
for long-term vigorous applications.
Some of the key criteria to be considered in the design and operation of GAC
adsorbers are empty bed contact time (EBCT), hydraulic loading rate, bed depth,
the number of adsorbers, and filling and emptying facilities. Further, a crucial
point to consider is the possibility of in situ or off site regeneration of spent GAC.
Although GAC is more expensive compared to PAC, it can be usually regenerated.
Nowadays, many activated carbon manufacturers accept spent GACs from municipal and industrial sites and regenerate them in their own facilities.
Nowadays, activated carbons are also produced in some special forms to meet
specific needs. For example, pelletized or extruded activated carbons are cylindrical pellets with diameters ranging from 1 to 9 mm. Their big size and relative
hardness allows them to be used in heavy-duty applications. The extruded pellet
form leads to a low pressure drop and such carbons are therefore suitable for gasphase uses. Main applications are in solvent recovery, gas purification, gold
recovery and automotive emissions control (19,58).
4.2. Liquid-Phase Applications of Activated Carbon. A large fraction of activated carbon products is used in liquid-phase applications. These
applications consist primarily of environmental activities (treatment of drinking
water, municipal wastewater, industrial wastewater and groundwater, remediation of contaminated groundwater and soil). But, activated carbon is also applied
in industrial production processes, and in the preparation of water for industrial
and domestic uses.
Use of Activated Carbon in the Environmental Field. Many organic
compounds are encountered nowadays in industrial and municipal wastewaters,
and to some extent also in drinking water supplies. Compounds falling into
organic groups such as pesticides, aromatic solvents, polynuclear aromatics,
chlorinated aromatics, phenolics, chlorinated solvents, high molecular weight
(HMW) aliphatic and aromatic acids, HMW aliphatic amines and aromatic

20

ACTIVATED CARBON

amines, fuels, esters, ethers, alcohols, surfactants, and soluble organic dyes can
generally be removed by adsorption onto activated carbon. On the other hand,
activated carbon has usually a low affinity for compounds with low molecular
weight (LMW) and a high polarity, such as LMW amines, nitrosamines, glycols,
and certain ethers (59).
Drinking Water Treatment. Today, the biggest market for activated
carbon is in the purification of municipal water supplies (60). Initially, activated
carbon was first used in the form of GAC for dechlorination of chlorinated drinking
water (61). However, in dechlorination activated carbon does not function as an
adsorbent. The use of activated carbon as an adsorptive material in water
treatment began in the late 1920s (59). Then, in the early 1960s activated carbon
gained much importance as an adsorbent. At that time PAC and GAC were mainly
introduced in water treatment for the removal of taste, odor and color from
drinking water. Then, beginning from the 1970s great attention was paid to
the removal of Natural Organic Matter (NOM) which acts as a precursor in the
formation of Disinfection By-Products (DBPs). Adsorption onto activated carbon
appears still to be a very reliable method for the removal of NOM and DBPs while
this type of treatment is usually conducted in GAC filters.
Nowadays, for improving the quality of drinking water, a large number of
toxic, endocrine-disrupting, mutagenic or carcinogenic pollutants need to be
removed during drinking water treatment. Most of those compounds are often
present as micropollutants and amenable to adsorption onto PAC and GAC. The
microporous nature of activated carbon allows the adsorption of a group of
compounds from water called Synthetic Organic Compounds (SOCs) (62). However, dissolved organic matter (DOM) concentrations in natural matters are much
higher than those of SOCs and taste and odor compounds. This factor leads to a
great competition between these groups for adsorption onto activated carbon.
Besides organic pollutants, activated carbon treatment may lead to an
effective reduction in the concentration of some inorganic pollutants encountered
in drinking water. For example, the degradation of specific inorganic pollutants
such as bromate, forming as a result of ozonation of bromide-containing waters,
can be catalyzed in GAC filtration. Further, in GAC filtration the synergism
created between GAC and the surrounding biofilm can be helpful in enhancing
ammonia and nitrate removal, by nitrification and denitrification, respectively.
The presence of GAC has also a positive effect on the microbial degradation of
perchlorate (11). Moreover, PAC is often used as an assisting material in membrane filtration of drinking water where the advantages of adsorption and
membrane filtration are combined in the same unit.
PAC is often used in drinking water treatment for removal of color, taste and
odor compounds (geosmin, MIB, etc.), organic pollutants and micropollutants
(such as endocrine disruptors). Similarly, in drinking water treatment GAC
filtration is often used for removal of taste and odor, organic pollutants and
micropollutants, biodegradable organic carbon (BDOC) and assimilable organic
carbon (AOC) whereby GAC filtration is often preceded by preozonation (63). The
use of PAC and GAC in drinking water treatment is illustrated in a simplified way
in Figures 5 and 6, respectively.
Care is advised in the selection of carbon grades to be used in drinking water
treatment. Depending on the type of raw material, activated carbon may contain

ACTIVATED CARBON
PAC

Water

PAC (optional)

Coagulation

21

PAC (optional)

Flocculation
Sedimentation

Filtration

Fig. 5. Addition of PAC in drinking water treatment.

Optional:
Preozonation

Coagulation

Flocculation

Sedimentation

Filtration

Optional:
Postozonation

GAC
filtration,
eventual
conversion
into
BAC
filtration

Disinfection

Fig. 6. Positioning of GAC filtration in drinking water treatment.

impurities such as metals which may leach into finished water. Furthermore,
the impurities in an activated carbon may adversely affect its catalytic activity.
Those impurities can also exert toxic effects on biological treatment if biological
removal and adsorption are combined in the same unit (17).
Besides the treatment of surface waters, activated carbon is employed in
remediation of polluted groundwaters. Pollutants can be either directly adsorbed
onto activated carbon or transferred into the gas phase to be then adsorbed by
activated carbon.

Wastewater Treatment.
Municipal Wastewater Treatment: The use of activated carbon in the form of
GAC adsorbers began in the 1960s as a tertiary (advanced) treatment step
where the aim was to reuse the effluent of municipal wastewater treatment
plants to be used as industrial cooling water or for irrigation of parks etc.
(59). The usual placement of GAC filtration in wastewater treatment is
shown in Figure 7. Today GAC filtration or PAC-assisted membrane operation find wide use in tertiary treatment for the removal of dissolved and
refractory organic matter from secondary effluents. However, now the scope
of application has been extended from the reuse of treated wastewater to the
removal of numerous micropollutants that are increasingly detected in
municipal wastewater and thus enter receiving waters.
Industrial wastewater treatment: In industrial wastewater treatment activated
carbon adsorption, usually in the form of GAC filtration, is often applied as a
stand-alone unit process after physicochemical treatment steps such as
coagulation/clarification, filtration, and dissolved air flotation. However,
activated carbon adsorption can also be introduced prior to biological treatment to remove toxic compounds which possibly would have adverse effects

22

ACTIVATED CARBON

Municipal
wastewater

Primary
Treatment

Industrial
Wastewaters
or
landfill
leachates

Biological
(Secondary)
Treatment

Optional ozonation/
Advanced oxidation

Physicochemical
treatment

Biological
(Secondary)
Treatment

Tertiary Treatment
by
Granular Activated Carbon
(GAC) filtration:

Discharge
or reuse

Eventual conversion into

Biological Activated Carbon (BAC)

Fig. 7. Positioning of GAC filtration in wastewater treatment.

on biomass. As shown in Figure 7, activated carbon adsorption is more

frequently placed in tertiary treatment of industrial wastewaters for the
removal of residual refractory organics and for reuse purposes. To some
extent also inorganics can be effectively eliminated by this type of treatment.
Nowadays, activated carbon finds wide application in the treatment of
wastewaters emerging from industries such as food, textile, chemical, pharmaceutical, pesticides production, coke plant, munitions factories, petroleum
refineries and storage installations, organic pigments and dyes, mineral processing plants, resins, detergent, explosives, dyestuffs. It is also employed in the
treatment of sanitary and hazardous landfill leachates.

Combination of Activated Carbon with Biological Processes in Wastewater and Water Treatment. Since the 1970s activated carbon has been
integrated into biological processes for a more effective removal of pollutants
from both water and wastewater. In that respect, in wastewater treatment a
major process is the Powdered Activated Carbon Treatment (PACT) developed by
DuPont which relies on a modification of the activated sludge process by the
addition of PAC. Zimpro Environmental purchased the patent rights to the
PACT1 process from DuPont and extended the technology. The application of
concurrent adsorption and biodegradation in the same suspended-growth reactor
is an effective alternative for the removal of biodegradable and nonbiodegradable
species. Although the initial PACT process was developed for the aerobic removal
of pollutants, it has been also adopted to anaerobic treatment. The reader may
consult other sources for more information on mechanisms and technologies (11).
The typical placement of the PACT process in the treatment scheme is shown
in Figure 8. In recent years PAC has also been integrated into Membrane
Bioreactors (MBR) to bring about a positive effect on micropollutant removal
in municipal wastewater treatment and to prevent membrane biofouling (11).
Besides the elimination of pollutants from the liquid phase, addition of PAC brings
about positive effects in sludge settling and dewaterability.
Another integrated process is the Biological Activated Carbon (BAC) which
essentially bases on the establishment of biological activity in a GAC adsorber. As
shown in Figure 7, in the long term a GAC adsorber may eventually be converted
into a BAC filter by the gradual formation of a biofilm around activated carbon. In
such a system, at the beginning of operation, the filter acts solely as an adsorber.

ACTIVATED CARBON
Industrial
Wastewaters or
landfill
leachates

23

Physicochemical
treatment

Addition
of
PAC

Pretreatment
Discharge to POTW

Municipal wastewater

Primary
treatment

Powdered Activated
Carbon Treatment
(PACT)

Further
treatment or
discharge

Fig. 8. Positioning of Powdered Activated Carbon Treatment (PACT) in wastewater

treatment.

As time passes, biofilm formation takes place and the filter is active both as an
adsorber and a biological reactor. Bacteria can only colonize the outer surface of
activated carbon since they cannot penetrate into pores. In the very late stages of
operation, the adsorptive capacity of the filter is exhausted and it acts as a biofilm
reactor only (11).
In full-scale, PACT and BAC processes are primarily applied to industrial
effluents such as organics chemical production, synthetics production, refinery
and petrochemical wastewaters, pharmaceutical wastewaters, textile/dye wastewaters, landfill leachates, and in the co-treatment of municipal and industrial
wastewaters (11). They are also applied in the treatment of leachates emerging
from sanitary and hazardous landfills. Detailed discussion of such applications is
presented in literature (11).
Activated carbon can also be integrated into drinking water treatment. In
that regard, Biological Activated Carbon (BAC) filtration is a well-known process
that unifies the advantages of GAC filtration and biological activity in the same
reactor (Figure 6). In fact, in drinking water treatment the BAC process was
initially developed as the result of efforts to extend the life time of GAC adsorbers
by pretreatment of water with ozone in M
ulheim/Germany; it was therefore
named as the M
ulheim process. Besides removing NOM and organic micropollutants from drinking water supplies, it is known nowadays that BAC filtration can
help elimination of inorganics such as ammonia, perchlorate and bromate. The
characteristics of these processes are extensively discussed in literature (11).
Use of Activated Carbon in Industrial Production Processes. Nowadays,
activated carbon finds large application in the production scheme of many smalland large-scale industries. A large user of activated carbon is the pharmaceutical
industry. In fact, activated carbon was initially used in the purification of the
antibiotic penicilline. However, this procedure is rarely applied today (1). Nowadays, activated carbon is used for decolorization in production of vitamins, antibodies, dextrose, gelatin enzymes, for parenterals and for blood fractionation (64).
Activated carbon is also used as an Active Pharmaceutical Ingredient (API) for
pharmaceutical products, for example for the treatment of diarrhea and poisoning
(6). Since manufacturers of activated carbon have the ability to control the

24

ACTIVATED CARBON

activation process and the purity of activated carbon, for the pharmaceutical
industry and the like, they can supply tailor-made activated carbon grades
targeting the relevant problem (6).
In the chemicals industry activated carbon is used for bulk pharmaceutical
actives and intermediates, decolorization of solvents, decolorization of fine chemicals, removal of organic contaminants. In the cosmetics sector it finds use in
alcohol deodorization and decolorization of perfumes (64).
As mentioned in the introduction, at the very beginning of adsorption
applications, activated carbon was introduced in decolorization of sugar syrups.
Also today activated carbon finds large use in the food and beverage industry to
remove undesirable odors, colors, and to improve the quality of the food material
(1). In that respect, activated carbon is applied for removal of trace organic
contaminants from gelatin, pectin, juices, for decolorization of oils and fats, for
decolorization of wine and cider, decolorization of sugar, spirit purification, fatty
haze removal (64).

4.3. Gas-Phase Applications of Activated Carbon in Environmental

and Other Systems. Gas-phase applications of activated carbon constitute a
smaller part of the total use than liquid-phase applications. Approximately only
20 % of the total activated carbon production is directed to gas-phase applications
(1). In those applications, typically activated carbon in the form of GAC is
employed to serve various purposes such as protection, removal, separation,
recovery, and gas storage.
GAC is usually used for personal protection purposes in gas masks to remove
gases from breathing air, for protection against warfare gases, in respirators when
working in hostile environment, and in industrial processes (1).
In air and gas cleaning, the substances to be removed are frequently present
at very low concentrations and recovery is usually not the choice. Fine-pore
activated carbons with a high adsorptive capacity are used for removal and are
discharged once they are exhausted (65).
Industrial production facilities, automobiles and other activities generate
pollutants such as VOCs, oxides of sulfur and nitrogen (the most important being
SO2 and NO), hydrogen sulphide, organosulfur compounds, mercury vapor etc.
that can be effectively removed from flue gases by the adsorptive or catalytic
function of activated carbon. Activated carbon adsorption finds also application in
the removal of indoor air pollutants such as radon, formaldehyde and other
aldehydes (1).
In some industries such as printing, dry cleaning, and the manufacture of
paints, polymers, adhesives, celluloid, rubber (e.g., rubber-coated fabrics), rayon,
and gunpowder, and extraction processes, solvent-containing air streams are
produced that contain different types of solvents such as benzenes, alcohols,
and aliphatic hydrocarbons. Activated carbon may recover many of those solvents
by adsorption. The principle of solvent recovery here bases on the adsorption of the
solvent followed by desorption. The desorption from activated carbon is carried out
by means of superheated steam or hot inert gas (58). While micropores are very
crucial for the adsorption of solvents, meso- and macropores are also essential
since they facilitate desorption of adsorbed pollutants (58). The recovery of organic
solvents helps the recovery of valuable materials.

ACTIVATED CARBON

25

VOCs emitted from combustion sources such as internal combustion engines

and power plants can be held by adsorption onto activated carbon (1). The removal
of some VOCs from gaseous streams contributes to the protection of the environment (1). Manufacturers often offer different grades of activated carbon for each
specific application.
PAC is effectively applied in the adsorption of dioxins/furanes and the heavy
metals, in particular mercury, from flue gases that are generated in waste
incineration facilities (65). Coal fired power plants, cement kiln, industrial boilers,
municipal waste combustors, hazardous waste combustors and hospital waste
incinerators generate mercury and dioxins which are effectively removed by PAC
addition. For mercury removal from flue gases, PAC injection is considered to be
the Best Available Control Technology (BACT) by EPA (51).
The impurity H2S present in several types of gases like ethylene, natural gas,
biogas and landfill gas can be removed using activated carbon (65,66). Further,
other impurities such as siloxanes and mercaptane can be eliminated, usually by
the use of impregnated activated carbons (65).
Activated carbon can be used also in the cleaning of polluted soil. By
suctioning off ground air, solvents in the soil are removed to be then adsorbed
onto activated carbon (58,65). Nowadays, for the purpose of soil clean-up, manufacturers often offer mobile adsorption units (58).
Odor-imparting species such as VOCs, hydrogen sulphide, mercaptanes and
ammonia can also be removed effectively from gas using nonimpregnated or
impregnated activated carbons (65). For the control of odors like H2S in municipal
wastewater treatment plants catalytic or impregnated activated carbons are
recommended (67). Specific activated carbon media have been developed by the
industry that allow the removal of odorous compounds at a capacity up to 10 times
the capacity of conventional activated carbon (68). There are also on-site GAC
biofiltration examples to remove gaseous pollutants like odorous sulfur and
nitrogen compounds and chlorinated and nonchlorinated VOCs in municipal
wastewater treatment plants or other facilities (69).
Activated carbon can also be employed in natural gas storage and delivery. A
favored storage method for natural gas consisting mainly of methane is storage by
adsorption onto activated carbon, a process designated as adsorbed natural gas
(ANG). Today, ultra-high surface area carbon materials are applied in natural gas
storage systems (70). Also, activated carbons have been specifically designed for
gas storage and delivery purposes for applications in non VOC/HFC aerosols,
drinks carbonation and delivery, mobile air conditioning. In such systems under
pressurised conditions the extensively developed carbon porosity provides for
greatly enhanced volume storage of either a pure gas, such as carbon dioxide or
nitrogen, or a gas mixture such as air (66). Activated carbons have also been
successfully used in both refrigeration and heat pumping cycles (66).
Activated carbon is also an effective adsorbent for the removal of radionuclides from gas phase. Since many decades GAC filters have played a role in the
removal of radioactive isotopes like iodine, krypton and xenon from the gaseous
effluents of nuclear power plants (71). For this purpose nuclear-grade activated
carbons are available whose performances can be estimated by standardized
procedures.

26

ACTIVATED CARBON

The growing concern about global warming has led to a search for the
capture or separation of CO2 from industrial streams or others such as natural
gas, refinery gas or combustion processes. In that regard, adsorption onto activated carbon is one of the alternatives. The most widely used adsorption process is
the pressure swing adsorption (PSA) in which selective adsorption of a gas from a
mixture is enhanced by operation at high pressure while desorption is achieved
upon depressurization. Many patents are available on the removal of CO2 by this
type of adsorption separation (72). In the PSA process, special types of activated
carbons called molecular sieve carbons (MSC or CMS) are used that have supermicro pores smaller than 10 Angstrom in pore diameter (73). These carbons can be
considered as a form of activated carbon, different from conventional activated
carbons (1). Due to their molecular sieve characteristics these carbons exclude
some gas molecules from their structure and restrict the adsorption of larger
molecules (20). Compared to PSA, less attention has been paid to the desorption of
CO2 by temperature swing adsorption (TSA) (74).
4.4. Miscellaneous Uses of Activated Carbon. Activated carbon is
used in mining, for example for the recovery of precious metals such as gold (1).
For such applications, manufacturers design specific activated carbon grades that
maximize gold loading and enable rapid adsorption (75).
Silver Impregnated Activated Carbons (SIAC) are used in the catalytic
detoxification of cyanide solutions (76). A specific use of activated carbon is
also seen in the medicine to combat bacterial ailments, for adsorption of toxins,
and purification of blood. Activated carbon also finds use in veterinary applications (1). Activated carbon is also employed in soil amendment, pesticide removal,
in nuclear and vacuum generation technologies (1).
Another application of activated carbon is in the preparation of water for
industrial and domestic purposes. Industrial facilities often utilize activated
carbon for the production of ultrapure water, and for the production of water
for steam generators, heat exchangers, and cooling towers. In households small
GAC adsorbers are often used to improve the quality of tap water by removing
trace organic compounds. Today, also specific activated carbons made from coal
and coconut are in use that have been impregnated with silver for the control and
prevention of bacterial growth (77).
Activated carbon can effectively remove radionuclides from contaminated
water and gas streams. In small water supplies appropriate removal of radon can
be achieved by adsorption onto activated carbon. The radioactive radon gas is first
adsorbed on the filter and then starts to decay in the carbon. However, as
recommended by the EPA in the Consumers Guide to Radon Reduction this
procedure should be used if the radon concentration in the water is below
5000 pCi/L because of the concern over the accumulation of radioactivity in the
carbon. In the case of high radon levels, GAC filters may cause a handling hazard
and require special disposal methods (78,79).
Today, also attempts are made to produce new materials by nanoarchitecturing carbon nanospheres onto the surface of activated carbon in order to
increase the activity of surface functional groups (80).
Many different carbon forms can be used as active materials in electrochemical double layer capacitor (EDLC) applications. EDLCs are energy-storage
systems using porous carbon electrodes, also called as supercapacitors or

ACTIVATED CARBON

27

ultracapacitors (81). The commercial forms today consist largely of high-surface

area activated carbon electrodes. Activated carbons in powdered form are also the
most widely used active materials for EDCLs, because of their high surface area,
relatively low cost and availability and variability of precursor material (82,83).
Activated carbon fabrics have also high specific surface areas. However, their high
price limits their use to speciality applications (84).
There are also studies about the use of Carbon Nanotubes (CNTs) as EDLCs.
Some studies have shown that the energy density of CNT-based EDLCs is
potentially up to seven times that of commercial activated carbon-based EDLCs
(85). While activated carbons have a very high surface area, CNTs have a
moderate surface area but higher electrical conductivity, higher charge transport
capability, higher mesoporosity, and higher electrolyte accessibility (86). Therefore, CNT/activated carbon composites are manufactured that combine the features of both materials.

5. Handling of Activated Carbon

5.1. Safety of Activated Carbon. For each activated carbon grade
manufacturers provide material safety and technical data sheets. Material safety
data sheets usually contain information about emergency overview, potential
health effects, first aid measures, fire fighting measures, accidental release
measures, handling and storage, exposure controls and personal protection,
physicochemical properties, stability and reactivity, toxicological and ecological
information. No serious human health effects such as carcinogenicity or toxicity
arise upon the exposure of a person to activated carbon. In most material safety
data sheets the information is provided that only slight irritations may occur upon
the contact of the skin, eyes and the respiratory system with the dust of activated
carbon.
It is advised to dispose virgin (unused) carbon in the case of waste or spillage
in a facility permitted for non-hazardous wastes. Unused activated carbons are
nontoxic. On the other hand, spent (used) activated carbon may exhibit characteristics of the adsorbed material and should be disposed of in accordance with
applicable laws (87).
5.2. Regeneration, Reactivation and Disposal of Spent Activated
Carbon. The regeneration of spent activated carbon is difficult and costly.
Although regeneration and reactivation terms are often used interchangeably,
they indicate two different concepts. Regeneration involves the removal of contaminants from activated carbon surface by steam or hot gas without leading to
the destruction of adsorbed contaminants (88). Regeneration is usually ineffective
in restoring the capacity of GAC since most of the adsorbed material cannot be
displaced (88). On the other hand, reactivation is a more vigorous procedure. It is
conducted in the same manner as in activated carbon manufacturing in multiple
hearth furnaces or rotary kilns at very high temperatures utilizing steam as a
selective oxidant. In this procedure, adsorbed organics are either volatilized or
pyrolysed to a carbon char (89). Thus, this procedure leads to destruction of
contaminants, as well as to reactivation of activated carbon by the redevelopment
of pore structure.

28

ACTIVATED CARBON

Care is advised in reactivation of some spent carbons. An activated carbon

which is reactivated for use in drinking water treatment must adhere to the
requirements of the AWWA standard B605 (90,91). Manufacturers of activated
carbon offering reactivation services report that spent carbons from drinking
water treatment are not co-mixed with industrial carbons, but are reactivated in a
separate furnace. Similarly, spent carbons from food applications are reactivated
separately and are not mixed with industrial carbons (92).
Manufacturers report that spent carbon is returned to a 9597% or greater
adsorption capacity upon reactivation (93,94). Reactivation can be accomplished
thermally or using chemicals, solvents, hot gas, or biological methods (88).
Reactivation and reuse of activated carbon is advantageous because it eliminates
the disposal of activated carbon as a waste into a landfill (94). However, if
regeneration of a spent carbon is not feasible or possible, it is either disposed
of in landfills or used as a primary fuel in the production of materials such as
calcium carbide (95).
In activated carbon regeneration primarily thermal volatilization, pressure
swing adsorption and thermal swing regeneration processes are applied. In
thermal destruction/scrubbing systems organic contaminants are destroyed during the regeneration process at a high temperature (typically in excess of 800
C).
During reactivation the loss of carbon can be held at 315% (5).
Regeneration by wet air oxidation (WAO) is a liquid-phase oxidation
reaction using dissolved oxygen to oxidize sorbed contaminants in a spent
carbon slurry. WAO is commonly used in the industry for the treatment of
spent caustic wastewater streams generated by ethylene plants and refineries
and oxidation of reduced sulfur species and complex organic contaminants such
as phenols (96). The process converts organic contaminants to CO2, water, and
short chain organic acids. Sorbed inorganic constituents such as heavy metals
are converted to stable, nonleaching forms that can be separated from the
regenerated carbon.
Wet Air Regeneration (WAR), a form of WAO, can be used to regenerate
activated carbon in the sludges emerging from combined adsorption and
biological treatment systems, namely PACT and BAC operations described in
Section 4.2. WAR is more frequently used for PACT systems at large-scale
plants. The patented Zimpro1 WAR technology regenerates PAC in slurry form
without applying dewatering steps; it therefore overcomes the difficulty of PAC
separation which is the main burden limiting the regeneration of PAC in
conventional approach. In this technology, biological sludge and adsorbed
organics are destroyed simultaneously. Nowadays, the Zimpro1 WAR operates
at moderate temperatures so that the spent carbon is regenerated without
damaging the surface (97).
Chemical regeneration involves the treatment of activated carbon with
chemicals such as sodium hydroxide, potassium hydroxide and hydrochloric
acid. This regeneration option is most effective when activated carbons have
been loaded with a single adsorbate only (19). Patented chemical regeneration
processes are reported for the regeneration of GAC in a simple and economic way
using a combination of alcohol, alkali, and oxidant, preferably ethanol, sodium
hydroxide, and hydrogen peroxide (98). There are also methods for electrochemical regeneration of activated carbon.

ACTIVATED CARBON

29

GAC regeneration has several advantages including reduced solid waste

handling problems due to spent carbon and reduced carbon cost. However, GAC
regeneration has also some disadvantages in terms of air pollution. Air emissions
from the furnace of a thermal regeneration unit may contain particulate matter
and volatile organics. In addition, carbon monoxide may be formed as a result of
incomplete combustion. Therefore, afterburners and scrubbers are usually needed
to treat exhaust gases (99). Moreover, thermal regeneration is energy intensive
and requires large amounts of energy.
A specific type of activated carbon regeneration is bioregeneration which is
the regeneration of activated carbon by the action of microorganisms. In that
respect, the type of activated carbon used is very decisive since it affects adsorption reversibility and bioregeneration (100,101). The conditions leading to bioregeneration are extensively discussed in literature (11).

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LIST OF FURTHER READING

1. F.S. Baker, C. E. Miller, A. J. Repik, E. D. Tolles, Carbon, Activated in Kirk-Othmer
Encyclopedia of Chemical Technology, 2003, pp. 741761.

34

ACTIVATED CARBON

2. E. Worch, Adsorption Technology in Water Treatment: Fundamentals, Processes, and

Modeling, Walter de Gruyter GmbH & Co., KG, Berlin/Boston, 2012.
3. H. Sontheimer, B.R. Frick, J. Fettig, G. Horner, C. Hubele, C. and G. Zimmer,
Adsorptionsverhalten zur Abwasserreinigung, DVGW-Forschungsstelle am EnglerBunte Institut der Universit
at Karlsruhe (TH), G. Braun GmbH, Karlsruhe,
Germany, 1985.

FERHAN C
S ECEN
BogaziSc i University, Institute of Environmental Sciences
34342 Bebek, Istanbul, TURKEY