CHAPTER ONE

1.0 INTRODUCTION

In recent years, increasing awareness of water pollution and its harmful effects has incited diverse
efforts towards pollution abatement. The rate at which effluents are discharged into the
environment and water bodies, have been on the increase due to rapid growth of cities in the world.
Generally, water bodies are major sites of heavy metal deposits due to the fact that streams and
rivers flow through agricultural areas where pesticides and fungicides may have been used,
through industrial districts where there may have been many metals wastes deposits or direct
discharge of effluents into these water bodies. The primary sources of heavy metals pollution in
coastal lagoons are input from rivers, sediments and atmosphere, which can affect aquaculture
profitability in certain areas [1]. The anthropogenic sources of heavy metals include wastes from
the electroplating and metal finishing industries, metallurgical industries, tannery operations,
chemical manufacturing, mine drainage, battery manufacturing, leather and tanning industries,
fertilizer industries, pigment manufacturing industries, leachates from landfills and contaminated
ground water from hazardous waste sites [2]. Heavy metals are also emitted from resource
recovery plants in relatively high levels on fly ash particles [3]. Metal ions in water can also occur
naturally from leaching of ore deposits. The presence of heavy metal contaminants in the treated
or untreated waste water from the industries either producing or using these metal bearing products
introduces these metals into water bodies [4].

These metal pollutants are conservative contaminants that are not easily degradable chemically or
biologically. They are therefore permanent chemical overload in the environment [5]. When these
metals are present in significant quantities in the environment they constitute source of pollution
and pollutants and pose threat to the environment, human, animal and aquatic lives, even though
in small quantities they can be beneficial in the sustenance of life. The toxicity of metal ions is
owing to their ability to bind with protein molecules and prevent replication of DNA and thus
subsequent cell division [6].

Lead is one of these heavy metals with high toxicity when in excess. In children, lead causes a
decrease in intelligent quotient (IQ) score, retardation of physical growth, hearing impairment,
impaired learning as well as decreased attention and classroom performance.

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In individuals of all ages, lead can cause anemia, kidney malfunction, brain diseases and impaired
function of peripheral nervous system, high blood pressure, reproduction abnormality,
developmental defects, abnormal vitamin D metabolism, colic-like abnormal pains, dementia,
madness and, in some situations, death [7]. Lead as Pb2+ ion has a large affinity for the thio (-SH)
and phosphate ion (PO4) containing enzymes, ligands and bio molecules, thereby, inhibiting the
biosynthesis of haeme units, affecting membrane permeability of kidney, liver, and brain cells.
These result in either reduced functions or complete breakdown of these organs [8]. Lead forms
complexes with oxo-groups in enzymes to affect virtually all steps in the process of hemoglobin
synthesis and porphyrin metabolism [9]. Copper is another heavy metal with high toxicity when
in excess. It has been reported as one of the most widely used heavy metal and is mainly employed
in electrical and electroplating industries [10]. It is, also, an essential trace element for human
beings. However, it can cause harmful and acute effects. The major effects of excessive large doses
of copper in the human body include high blood pressure, severe mucosal irritation, widespread
capillary damage, anemia, hepatic damage and necrotic changes in the liver and kidney [11].

The bioaccumulation of these metal pollutants has increased the interest of researchers in
developing suitable remediation strategies [12]. Presently, the majority of heavy metals in
wastewater are removed by means of precipitation by adding calcium hydroxide, in which large
amounts of nontoxic metal compounds such as calcium sulfate are also precipitated together with
heavy metals as a precipitated sludge, which are dumped in the landfill sites. It is not only difficult
to meet stringent environmental regulation by means of precipitation technique, but also
unavailability of landfill sites due to the occupation by large amounts of polluted sludge.
Adsorptive recovery and removal using ion exchange chelating resin are also used. However, this
approach is expensive taking account of the post-treatment of spent resin, and, in addition, it also
poses other environmental problems if such synthetic plastic materials are incinerated [13].
Oxidation, reduction, sedimentation, lime softening, sorptive floatation, reverse osmosis, electro
dialysis, ultrafiltration, phytoremediation, etc. have also been employed. These methods also have
disadvantages like high cost, not being readily available, introducing novel chemicals into the
environment and not being environmentally friendly [14].

The need to develop an alternative, more environmentally friendly and cost effective method
therefore, became imperative. Adsorption is one of the easiest, safest and most cost-effective

2
methods for the removal of these metals [15]. The major advantage of an adsorption system for
water pollution control are less investment in terms of both initial cost and land, simple design and
easy operation and no effect of toxic substances compared to conventional biological treatment
processes [16]. Activated carbon can be used to remove heavy metal pollutants from wastewater
due to its good adsorption properties [17].

1.1 AIMS AND OBJECTIVES

To determine the optimum production conditions of low cost activated carbon from fluted pumpkin
and star apple seed shells.

To characterize the activated carbons produced.

To determine their potentials for the removal of Pb2+ and Cu2+ from simulated waste water.

To test the data obtained from the work on various kinetic models and also,

To also determine the isotherm behavior of the adsorption processes.

1.2 SCOPE OF STUDY

The focus of the present study is to compare the adsorptive capability of fluted pumpkin and star
apple seed shell activated carbon for treatment of waste water and stimulated waste water to assess
the potentiality of fluted pumpkin and star apple seed shell activated carbon by varying adsorbent
dosage, pH, initial concentration, temperature, and contact time to test the adsorption capability
using Freundlich, and Langmuir isotherm model and also to determine the kinetics model.

1.3 LIMITATION OF STUDY

The major limitation of this experiment was the regeneration of the adsorbent and due to precision
of equipment, various influencing factors was limited to parameters such as adsorbent dosage, pH,
initial concentration, contact time and temperature.

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 CHAPTER TWO

2.0 Historical Background of Activated Carbon

The use of activated carbon in the form of carbonized wood began many centuries ago. During the
1500s BC, it was used by the Egyptians as a purifying agent and also as an adsorbent for medicinal
purposes in which it was used to adsorb odor from rotten wounds [18].

In 1773, Scheele recognized the specific adsorptive powers charcoal had with various gases [19].

In 1777, Fontanna disclosed an experiment in which glowing charcoal was plunged under mercury
and allowed to rise into an inverted tube containing a gas, whereupon much of the gas disappeared
[20]. In 1785, Lowitz [21] observed the ability of charcoal to decolorize many liquids. In 1794,
natural forms of activated carbon, such as charred animal bones (called bone black), were used for
the refinement of sugar [22].

Since the 1800’s, production of activated carbon moved from woody precursors and bones to
various other precursors in search of more effective adsorbents. In 1822, Bussy applied heat to a
mixture of potash and blood which resulted in carbon with much more decolorizing effect than
bone char and was called blood char [23]. In 1856, Stenhouse, prepared a decolorizing char by
heating a mixture of flour, tar, and magnesium carbonate and in 1863, Lee prepared a deodorizing
carbon by the action of superheated steam and air on peat [20].

Commercial production of activated carbon started first in Europe in 1909 with the production of
a powdered carbon called Eponite [24]. The manufacture of higher quality gas adsorbent carbons
was given new encouragement in the period of World War I, during which they were used in gas
masks for protection against poisonous gases [25]. In 1929, Spadling [26] demonstrated that
activated carbon could correct taste conditions in municipal waste supplies at a very moderate cost.

In 1963, activated charcoal became more widely accepted in the management of ingested toxins
[27]. In 1970, Smisek Cerny [28] discussed the general principles of production of low cost
chemically activated carbon from several materials such as sawdust, rice husk, etc. using activating
agents like ZnCl2, potassium sulphide, H2SO4 and phosphoric acid. Ozer et al [29] in 1996 prepared
activated carbon by carbonizing sugar beet pulp in a constant flow rate of carbon dioxide at
different temperatures and for different lengths of time. They found that percentage yield of

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activated carbon decreased while percentage ash content and pH increased with increase in
carbonization temperature from 350oC to 750oC and with increase in carbonization time from 15
to 120minutes. The produced carbons were tested for adsorption of Cd2+ and the most effective
activated carbon for the adsorption process was the one produced by carbonization at 700oC for
120minutes. They also found the optimum pH for the adsorption process to be 7 and adsorption
equilibrium was attained after a contact time of 120minutes. They carried out isotherm studies of
the adsorption process and found that the adsorption of Cd2+ was better described by Langmuir
isotherm than Freundlich isotherm. Arivoli and Thenkuzhali [30], in 2008, prepared activated
carbon from phoenix sylvestric leaves by chemical activation using concentrated sulphuric acid as
activating agent and carbonizing in a furnace at 800oC for twelve hours. They studied the effects
of agitation time, initial dye concentration, carbon dose, pH and temperature on the adsorption of
Rhodamine B on the produced carbon.

They found that percent adsorption decreased while the actual amount of chromium ion adsorbed
per unit mass of carbon increased with increase in initial chromium ion concentration from 10 to
60mg/L. The percent adsorption also decreased with increase in pH up to pH value of 8, beyond
which the percent adsorption increased with further increase in pH. Both percent adsorption and
actual amount of chromium ion adsorbed per unit mass of carbon increased with increase in
temperature from 30 to 60oC. The percent adsorption also increased with increase in carbon dosage
from 0.5 to 5mg/l. The adsorption followed first order kinetic model and the rate was mainly
controlled by intra-particle diffusion.

The adsorption capacity obtained from the Langmuir isotherm plots at initial pH of 7.0 were
51.546, 47.236, 44.072 and 41.841 mg/g at 30, 40, 50 and 60oC, respectively.

2.1 Methods of Production of Activated Carbon

Activated carbon can be produced from most carbon containing materials. Various natural and
synthetic materials have been used as raw materials for the manufacture of activated carbons.
Young fossil materials such as wood, peat and wastes of vegetable origin, which include sawdust,
nutshells and fruit stones were preferred in early production procedures since the chars from them
can be easily activated yielding reasonably high quality activated carbon. However, presently,
there is an increasing use of various kinds of natural coal which are readily available and relatively
cheap, though this still ranks second to the use of wood and other plant materials [31]. Various

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wastes, such as sulphite liquors, waste lignin and wastes from processing of petroleum and
lubricating oil industries have also been used as raw materials for the production of activated
carbon. Commercially, the most frequently used raw materials are peat, coal, lignite, wood and
coconut shells.

In general, the raw materials to make activated carbon must accomplish a sort of requirements like
high carbon content, low mineral content, easily activation, low degradation during storage, and,
of course, low cost [32]. The phase of application of an activated carbon also determines the type
of raw material to be employed in the production of the carbon.

For vapor phase applications, carbon from lignin and wood, which are low density materials and
have high volatile content are not very suitable because they have large pore volume but low
density.

However, the quality of the carbon can be improved by densification, reconstitution or

compression during carbonization. Carbons from fruit pits, semi-hard coals, coconut shells and
other nut shells, which have higher density than wood and possess high volatile contents, are hard
and granular with large micropore volumes and are therefore quite suitable for solution as well as
vapor phase application [33].

The processing technique to be used for the production of activated carbon depends on the nature
and type of raw material available as well as the desired physical form of the activated carbon. The
production of activated carbon involves two major steps; carbonization and activation. These
processes are carried out after the raw material has been prepared and put in a form that will be
easy to handle.

Preparation of Raw Materials

The following processes are carried out on the raw material to put it in a form suitable for
carbonization.

(i) Sizing – This involves breaking down of the raw material into lumps or granules of appropriate
sizes, which can be handled effectively in subsequent operations.

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(ii) Sieving – This is done using wire gauze in the case of materials with fibre or fluffy particles
in order to remove these particles and leave the desired material for carbonization. Winnowing
could also be carried out alongside the sieving.

(iii) Reconstitution – This involves pulverization of the raw material followed by agglomeration
by extrusion or briquetting. It is usually done on low-density materials in order to improve their
quality.

2.1.1 Carbonization

Carbonization is the thermal separation of carbonaceous materials, elimination of organic

materials and production of porous fixed carbon [34]. This process is usually carried out in a muffle
furnace or in rotary kilns at elevated temperatures. It involves thermal decomposition of the raw
material as it is heated under a time schedule to remove the volatile or non-carbon entities leaving
basically carbon possessing a partially developed or rudimentary pore structure. Usually, basic
microstructure of carbon is formed at 500℃, although there may be blockages of the micropores
by pyrolytic products, which can only volatilize at higher temperatures.

According to Hassler [35], temperatures below 600℃ are suitable for the production of chars that
are to be activated with steam but this is not an invariable rule.

Carbonization product is non-active material as a result of its small surface area [36].

2.1.2 Activation

This is the process of transforming inert carbon into highly adsorbent material by conferring on it
a porous material structure and large specific surface area [37]. The objective is to enhance the
volume and enlarge the pores which were created during the carbonization process, and also to
create new pores. Activation is of two main types, namely physical and chemical activation.

 Physical Activation

Physical activation involves the treatment of carbonized materials with oxidizing gases at elevated
temperatures between 700 -1000oC. Common gases used include CO2, steam, and O2. The reaction
between steam and charcoal takes place at all the internal surfaces of the carbon structure,
removing carbon from the pore wall and thereby enlarging them [38].

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This creates more sites for adsorption with the liberation of gases such as H2, CO2 and CO. The
active oxygen in the activating agent basically burns away the more reactive portions of the carbon
skeleton as CO and CO2. The extent of this depends on the nature of the gas employed and the
temperature of activation. The endothermic gasification reactions of carbon with steam and
CO2with their respective heats of reaction (ΔHr) are shown in equations (2.1) and (2.2).

C(s)+ H2O(g) →CO(g)+ H2(g) + 117 kJ/(g.mol) (2.1)

C(s)+ CO2(g) →2CO(g) + 159 kJ/(g.mol) (2.2)

The reaction of steam with carbon also produces a side reaction whereby the carbon surface
catalyzes an exothermic reaction of CO and steam to yield CO2 and H2 as shown in equation (2.3)

. CO(s)+ H2O(g) →CO2(g)+ H2(g)+ 42 kJ/(g.mol) (2.3)

This reaction retards activation, since the H2(g) becomes strongly adsorbed at active sites on the
carbon surface. In general, steam is preferred to CO2 as an activation gas because the water
molecule has a smaller van der Waals’ radius than CO2 (~3.8Å vs. ~4.8Å) [39]. This leads to a
faster diffusion of steam in the porous matrix of the carbon and a subsequent faster reaction rate.

The reaction of solid carbon and CO2 (equation 2.2) can be retarded by the addition of CO(g) to
drive the thermodynamic equilibrium to the left, which may improve microporous structure
through a decreased gasification rate.

The process of steam activation produces a carbonaceous substance with many small pores and
thus a very large internal surface area. This carbon is then crushed, if desired, to yield a pulverized
product.

 Chemical Activation

Chemical activation is typically employed when wood products are used as raw material and it
involves impregnation of the feedstock with chemicals either before or after pyrolysis
(carbonization). Typical chemicals used as activating agents in chemical activation include
phosphoric acid (H3PO4), ammonium chloride (NH4Cl), sulfuric acid (H2SO4), potassium sulfide
(K2S), carbonates of alkali metals, and metal chlorides. The common property of chemical
activation compounds is to dehydrate the carbonaceous material which usually enhances pyrolytic
decomposition and inhibits formation of tar. This process has an advantage over physical

8
activation processes since it normally occurs at temperatures lower than those used in the latter
[40].

This may also benefit the development of a microporous structure. The mechanism of chemical
activation is not fully understood. According to Byrne and Marsh [41], during chemical activation,
the chemistry of pyrolysis is changed and a different, macromolecular network is established with
enhanced porosity.

However, the chemical detail of this remains unexplored. Distribution of pore sizes in the product
depends on the degree of impregnation. Therefore, it is of productive and economic interest to use
the ratio of activating agent to raw material that gives the best results.

The obtained carbon is then washed to neutral pH and then dried and preserved.

2.2 Characteristics of Activated Carbon

Activated carbon represents substances with high carbon content which have undergone the
process of activation. It also refers to carbons in which the adsorptive powers have been supposedly
increased by man-made operations. According to Soleimani and Kaghazchi [42] activated carbon
is the trade name for a carbonaceous adsorbent that has high porous structure and a large surface
area. A generalized definition is that activated carbons are nonhazardous, processed, carbonaceous
products having a high degree of porosity and an extended inter-particulate surface area [43].
Hence, they are able to adsorb a wide variety of substances and are good adsorbents.

Structurally, activated carbon is an amorphous form of carbon. This implies that it has no regular
atomic structure unlike the other allotropes (forms) of elemental carbon (diamond, fullerenes or
nanotubes). Activated carbon is hydrophobic and non-polar.

2.2.1 Classifications of Activated Carbon

Activated carbons are complex products which are difficult to classify on the basis of their
behavior, surface characteristics and preparation methods. However, some broad classification is
made for general purpose based on their physical characteristics.

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  Powdered activated carbon (PAC)

PAC material is defined as fine activated carbon material. PAC is made up of crushed or ground
carbon particles. They are so finely powdered that most of them can easily pass through a
designated mesh size. Due to their small size they form large internal surface having small
diffusion distance (barrier to adsorption) and large pore diameters. Hence, their rate of adsorption
is high and mass transfer problems are very low. PAC is not commonly used in a dedicated vessel,
owing to the high head loss that would occur. PAC is generally added directly to other process
units, such as raw water intakes, rapid mix basins, clarifiers, and gravity filters. In general, PAC
is used to adsorb materials from liquids.

 Granulated activated carbon (GAC)

GAC is usually prepared from coal, petroleum, heavy oils, rubber, and the pyrolysis of waste
rubber tyres. They come in both granular and extruded form. Granulated activated carbon forms
are of larger particle size than the powdered activated carbon forms. Granulated carbons are mainly
used for treating water.

Their main function includes deodorization and separation of components of flow system. They
are generally used for the removal of hazardous and/or pollutant chemicals from wastewater and
for purification of water, air and other materials. Hard granules and relatively dust free pellets are
usually used for adsorbing gaseous materials in packed beds.

 Pelleted activated carbon

They are granulated in smaller size and come in extruded and cylindrical shape with diameters
from 0.8 to 5 mm. These are mainly used for gas phase applications because of their low pressure
drop, high mechanical strength and low dust content.

 Impregnated carbon

These are porous carbons which have been impregnated with other substances. They are usually
prepared for specific applications in air pollution control especially in museums and galleries.
Silver loaded activated carbon is used as an adsorbent for purification of domestic water. Drinking
water can be obtained from natural water by treating the natural water with a mixture of activated

10
carbon and flocculating agent [Al(OH)3]. Impregnated carbons are also used for the adsorption of
H2S and mercaptans.

2.2.2 Properties of Activated Carbon

An activated carbon particle can be depicted as in Figure 2.1.

Figure 2.1: Activated carbon particle.

Activated carbon is not a pure carbon. It contains other elements in various proportions depending
on the source material and on the mechanism of its production. Such other elements, which are
chemically combined with the carbon atoms, include hydrogen, oxygen, nitrogen, sulphur, etc.
The adsorptive and catalytic powers of the activated carbons are traced to the presence of these
elements in the carbon. The morphology of an activated carbon as observed by an electron
microscopy is greatly determined by the raw material that was used for its production. This is as a
result of the fact that the nature of the starting material is directly reflected in the final product.
The properties of commercially available activated carbons are responsible for their use as either
gas-phase or liquid-phase adsorbents. These properties are grouped into two broad classes;
physical and chemical properties.

2.2.2.1 Physical properties

 Forms

Activated carbons are available in different forms such as symmetrical pellets, irregularly shaped
granules, powder and specialties like pre-formed shapes, example, wool and slurry for coating

11
supports. The major forms of activated carbon are the powdered form, the granular form and the
pellets.

 Particle size

This property is important due to the fact that adsorption rate varies inversely with particle size.
Mathematically,

r α (1/s) (2.4)

where r is the rate of adsorption and s is the particle size. This means that, an increase in particle
size will lead to a decrease in adsorption rate while a decrease in particle size will favour high
adsorption rate. The finer the particles size of an activated carbon, the better the access to the
surface area and the faster the rate of adsorption kinetics. In vapor phase systems, this needs to be
considered against pressure drop which will affect energy cost. Careful consideration of particle
size distribution can provide significant operating benefits.

 Bulk density

Apparent or bulk density is a measure of the weight of material that can be contained in a given
volume under specified conditions. It is determined by measuring the volume of a weighed sample
of activated carbon after tapping till no further reduction in volume occurs. The volume used in
this determination includes, in addition to the volume of the skeletal solid, the volume of the voids
among the particles and the volume of the pores within the particles. Bulk density of carbon
determines how much of it can be contained in a given container. Bulk density is affected by the
raw material used and the degree of activation.

The density does not affect the effectiveness of the activated carbon measured in adsorption per
unit weight, but will have an effect on adsorption per unit volume. Higher density provides greater
volume activity.

 Surface area

Activated carbons have very large surface area, typically ranging from 500 – 1400m2g-1. This is
an important property of activated carbon as it greatly affects the adsorptive properties of the
carbon. Increase in surface area enhances the adsorptive capabilities of activated carbon by
exposing a wide surface for physical as well as chemical adsorptions.

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2.2.2.2 Chemical properties

 pH

The pH of an activated carbon is a measure of the surface acidity/basicity of the carbon. The
numerical values of the pH are affected by the experimental conditions when carrying out the
experiment. A carbon pH of 6-8 is acceptable for most application such as sugar decolorization,
water treatment, etc. The pH of many of the commercial carbons is due to inorganic components
originating from the raw material used or added during the manufacturing process. After activation
(with acid) and carbonization, activated carbons are usually washed to bring them to neutral pH.

 Moisture content

This is determined by drying an isolated portion of an activated carbon in an oven at 105 – 110oC
until constant weight is attained. This property is important in adsorptive capacity test.

 Inorganic constituents

Activated carbons contain different inorganic substances, which originate from the raw materials
used and also from the ingredients added during the processing of the carbon. However, the total
amount of these inorganic constituents varies from one grade of activated carbon to another. The
inorganic constituents include:

(1) Ash

This is the form in which the inorganic constituents of carbon exist after the carbon has undergone
complete combustion at controlled temperature. Ash in an activated carbon is an impurity and is
not desired. It reduces the overall activity of the activated carbon and reduces the efficiency of re-
activation. The metals (Fe2O3) can leach out of activated carbon resulting in discoloration.
Acid/water soluble ash content is more significant than total ash content. In some carbons, not all
inorganic constituents remain as ash after combustion of the carbons.

Therefore, in such carbons, the amount of inorganic substances that can be eluted from them is
less than the water soluble inorganic substances found in their ash.

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(2) Inorganic constituents as ion exchangers

Some types of activated carbon usually contain a normally soluble inorganic compound bonded to
the carbon in the form of an ion exchanger, usually an anion exchanger. These ions exchangers
attract free ions in solution or suspension. The capability of an activated carbon to exchange a
particular type of ion often depends on the way the carbon is treated.

2.3 Adsorption Phenomena

Adsorption is the occupation of the surface and pores (if any) of a substance (solid, liquid or gas)
by molecules of another substance as a result of some attractive forces between the adsorbing
surface and the substance adsorbed. This becomes feasible only when the substance to be adsorbed
is in contact with the adsorbing surface. The adsorbing surface is called the adsorbent while the
adsorbed substance is called the adsorbate. The chemical equilibrium which represents the
adsorption of molecules on a surface is as follows:

A + B ⇄AB (2.5)

where, A is the adsorbate, B is the adsorbent and AB is the product of the adsorption process. For
adsorption of compounds on activated carbon, which is a reversible reaction, molecules continue
to accumulate on the surface of the carbon until the rate of the forward reaction (adsorption
process) is equal to the rate of the backward reaction (desorption process). At this point,
equilibrium state is attained and no further accumulation of the adsorbate on the adsorbent surface
occurs. Hence, adsorption stops. This equilibrium state enables relationship known as adsorption
isotherm. Based on the energy associated with adsorption and the type of bond responsible for the
adherence of the adsorbate on the adsorbent, adsorption process can be classified into physical and
chemical adsorption.

 Physical Adsorption (Physisorption)

Generally, the process of physical adsorption begins as an adsorbate molecule which is transported
from the bulk adsorbate phase to the surface of the adsorbent. Next, the molecule then diffuses
into the pore and then physically bonds with the surface.

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Heat is usually evolved, making adsorption an exothermic process. In the first step, the bulk
adsorbate stream must be intimately mixed with the adsorbent to promote good contact between
the two components. In the second and third stages, the concentration gradient between the amount
of adsorbate present in the bulk adsorbate stream and that within the micropore provides the
driving force for adsorption.

 Chemical Adsorption (Chemisorption)

This type of adsorption is one in which chemical bond is formed between the adsorbate and the
adsorbent. The chemical bond involved is usually covalent bond and the adsorbent tends to find
sites that will maximize its co-ordination number with the substrate. Chemisorption is specific and
involves forces which are stronger than those associated with physisorption.

Hence, the heat of adsorption in this case is high and is of the same order as heat of reaction.

This process requires generally high temperature and is often irreversible. Unlike physisorption,
in which multilayer coverage is possible, chemisorption does not exceed monolayer coverage. This
is because the valence force holding the molecules on the adsorbent surface diminishes rapidly
with distance. Generally, chemical adsorption is linked to the porosity and surface chemistry of
the carbon, since chemisorption is associated with the number of active sites and carbon surface.

2.3.1 Adsorption Isotherm

Adsorption isotherm is a set of data which represents constant temperature measurements of the
quantities adsorbed by a unit weight of adsorbent in equilibrium with each of a number of different
activities (concentration for liquids and partial pressure for gases) of the mobile phase or an
analytical expression representing such data. In a closed system, the adsorption of an adsorbate
onto a solid can be measured by monitoring the decrease in adsorbate activity within a known
volume or by measuring the mass gain of the adsorbent due to the adsorbing molecules. The
amount of an adsorbate adsorbed in moles per gram solid is a function of the activity of the
adsorbate, the temperature of the system, the pH of the solution, the amount of contact between
the adsorbate and the adsorbent, dose rate of the adsorbent, particle size of the adsorbent and the
presence of other substances that could be adsorbed. The models used to describe the isotherm
function of adsorption include the Langmuir isotherm, Freundlich isotherm, and Temkin isotherm.

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2.3.1.1 Langmuir Isotherm

Based on Langmuir adsorption theory, molecules are adsorbed at a fixed number of well-defined
active sites which are homogenously distributed over the surface of the adsorbent. These active
sites have the same affinity for adsorption of a mono molecules layer and affinity for adsorption
of a mono molecules layer and there is no interaction between the adsorbed molecules.

For Langmuir equation, it is written as:

qe = (Co – Ct) V (2.6)

Where qe is the metal adsorption capacity of adsorbent and intensively depends on the physical
and chemical properties of adsorbate and adsorbent, Co and Ct are the liquid phase concentration
at initial concentration, V is the volume of solution, W is the mass of dry adsorbent used. Langmuir
isotherm can be explained based on the assumption; the adsorption process is only limited to mono-
layer adsorption and reversible process when no interaction occurs between the molecules
adsorbed on the active site and the neighboring sites.

2.3.1.2 Freundlich Isotherm

Freundlich isotherm model interprets the adsorption on heterogeneous surfaces with interaction
occurring between the adsorbed molecules and is not restricted to the formation of a monolayer.
This isotherm is commonly used to described the adsorption of organic and inorganic compounds
on a wide variety of adsorbents.

For Freundlich equation, it is written as:

qe = Kf I (2.6)
n
Where Kf is the adsorption equilibrium constant while I/n is the heterogeneity factor which is
related to the capacity and intensity of the adsorption and C is the equilibrium
concentration(mg/L). This model assumes that when the adsorbate concentration increases, the
concentration of adsorbate on the adsorbent surface also increases and, correspondingly, the
sorption energy exponentially decreases over the completion of the sorption centre of the
adsorbent.

16
 CHAPTER THREE

3.0 Chemicals and Instrumentation

The chemicals used will be of analytical grade. Stock solutions (1000mg/L) will be prepared from
CuSO4.5H2O for copper and from Pb(NO3)2 for lead using de-ionized water. All working solutions
will be prepared by proper dilution of the stock solution with de-ionized water. 0.1M NaOH and
0.1M HCl stock solutions will be used to adjust the solution pH.

The concentration of the solution before and after sorption will be measured using atomic
absorption spectrometer. Muffle furnace will be used for carbonization of samples.

Air drying oven will be used for drying of samples. Weighing balance will be used for weighing
of samples.

3.1 Production of Activated Carbon

The raw materials, fluted pumpkin seed shell and star apple seed shell, will be obtained from Ngor-
Okpala, Imo state.

They will be thoroughly cleaned to remove extraneous materials, dried and ground to smaller
particle sizes. They will be sieved using conventional sieves to get the desired particle sizes. The
portions taken wil be those that passed through 1.75mm and retained in 1mm sieve mesh size and
those that passed through 1mm and retained in 0.5mm sieve mesh size.

3.1.1 Effect of Activating Conditions

To determine the effect of activating conditions on the resulting carbon, the sieved material with
size 0.5mm - 1mm will be used. 60% by weight H3PO4 and 60% by weight NH4Cl solutions will
be used as the activating agents. The raw materials will be impregnated with the activating agents
in 1:1 wt. ratio for 24 hours, after which they will be drained and dried in an oven at 80°C. They
will be then put in crucibles and placed in a muffle furnace set at 300°C for carbonization. FPSS
will be left for 60 minutes while SASS will be left for 90 minutes since it is harder. The resulting
carbons will be washed with distilled water until the pH of the leachate was up to 6. They will then
be dried in an oven at 105°C for 4 hours. For SASS, the raw SASS will be used as the blank while
for FPSS, a third sample will be carbonized without prior activation and will be used as the blank.

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3.1.2 Effect of Carbonization Temperature

To determine the effect of carbonization temperature on resulting carbons, the portion of the
samples with particle size of 0.5mm - 1mm will be activated with phosphoric acid and then divided
into four portions. These portions will be carbonized (for 60minutes for FPSS and 90minutes for
SASS) at 300°C, 400°C, 500°C and 600°C.

3.1.3 Effect of Carbonization Time

To determine the effect of carbonization time on the resulting carbons, the portion of the samples
with particle size of 1mm – 1.75mm will be used. The samples will be activated with phosphoric
acid and then divided into five different portions, each. The portions will be carbonized (at 500°C
for FPSS and 600°C for SASS) for 60, 90, 120, 150 and 180 minutes.

3.2 Characterization of Adsorbents

3.2.1 Determination of %Yield and %Weight Loss

The yield of activated carbon is defined as the ratio of the weight of the activated carbon product
to that of the original raw material (both weights were on a dry basis).

That is;

%Yield = (W1 ∕ W0) x 100 (2.7)

where W0(g) is the original weight of the precursor on a dry basis and W1(g) is the weight of

the carbon after carbonization, washing, and drying.

The weight loss will be calculated according to equation (2.8).

%Weight loss = [(W0– W1) ∕ W0] x 100 (2.8)

3.2.2 Surface Area Measurement

In the process, 1.5g of activated carbon will be agitated in 100ml of HCl that had been diluted to
pH of 3. Then 30g of NaCl will be added while stirring the suspension. The volume will be then
being made up to 150ml with de-ionized water resulting in the change of the pH to 4.0. 0.10M
NaOH will be used to raise the pH from 4 to 9 and the volume (V) of NaOH used, will be recorded.
The surface area will be calculated using the following equation:

18
 S = 32V – 25 (2.9)

where, S is the surface area (m2/g).

3.2.3 Determination of % Ash Content

In the process, a weighed sample of each adsorbent will be pre-dried at 150°C, and then burnt in a
muffle furnace at 650°C for 4 hours in the presence of air. The % ash content will be calculated
from the combustion residue as follows.

% Ash content = Wash / Wads x 100 (3.0)

where, Wash is the weight of dry ash (g) and Wads is the weight of dry adsorbent (g).

3.2.4 Determination of Bulk Density

A known weight of each sample, after being dried at 105°C, will be parked into a 10ml capacity

graduated cylinder. The bottom of the cylinder will be tapped gently on the laboratory bench top

several times until there will be no further diminution of the sample level. The bulk density will
be calculated using the following equation.

Bulk density (g/ml) = Wmat / Vmat (3.1)

where, Wmat is the weight of dry material (g) and Vmat is the volume of dry material (ml).

3.3 Adsorption Tests

3.3.1 Effect of Particle Size

To determine the effect of particle size, the adsorption tests will be carried out using the

following particle sizes of the adsorbents:

1– 1.75mm, 0.5 – 1mm, 0.25 – 0.5mm, and 0.125 – 0.25mm.

3.3.2 Effect of pH

To determine the effect of pH, the adsorption tests will be carried out using metal solutions
adjusted to pH values of 2,3,4,5 and 6 using 0.1M NaOH and 0.1M HCl stock solutions.

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3.3.3 Effect of Adsorbent Weight

In order to determine the effect of adsorbent weight, the adsorption tests will be carried out using
the following weights of the adsorbent:

0.063g, 0.125g, 0.25g, 0.5g, and 1g.

3.3.4 Effect of Adsorption Temperature

In order to determine the effect of adsorption temperature on the adsorption processes, the
adsorption experiments will be carried out at the following temperatures:

20oC, 30oC, 40oC and 50oC.

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 CHAPTER FOUR

4.0 CONCLUSION

The production of activated carbon will be prepared from fluted pumpkin seed shell and star apple
seed shell. The techniques used in the production of activated carbon is the carbonization and
activation techniques. Activated carbon are classified based on their physical characteristics;
powdered activated carbon, granulated activated carbon, pelleted activated carbon etc.

Different model will be used to described the isotherm function of adsorption which include the
Langmuir, freundlich, temkin isotherm.

21
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