6

CHAPTER 2

LITERATURE REVIEW

This chapter deals with the importance of water and various water
treatment techniques such as physical, chemical and biological water
treatment methods and also discussed about the different types of adsorbent
used for water treatment

2.1 IMPORTANCE OF WATER

Water resource is one of the essential and fundamental needs to

sustain all forms of life in the emerging world. Water on the earth is a readily
available source in the form of rivers, lakes and streams. The surface water
comes from rivers, streams, ponds, lakes and reservoirs, while ground water
comes from wells, mines and springs. Water is essential for survival of human
beings and animals in the world. Besides other needs, the demand for water
has increased tremendously in agricultural, industrial and domestic sectors,
which consume 70, 22 and 8% respectively from available fresh water and
this leads to generate the large amounts of waste water (School energy and
environment 2011). The global water consumption has doubled for every
fifteen years and this may be due to various factors like modern civilization,
industrialization and urbanization. This emphasizes the close relationship
between water usage and the above mentioned aspects (Babu 2014)

The recent developments in both industrial and domestic activities

have generated a large amount of waste water, consequently leading to
 7

environmental disorder and a large pollution problem. The indiscriminate

discharging of untreated waste water from various industries into the
environment, which causes a severe impact to human health directly or
indirectly and it’s also pollutes the air, water and soil. The industrial waste
water has undesirable color, odor, taste and many numbers of toxic pollutants
such as soluble organics, inorganic matter, suspended solids, heavy metals,
volatile materials, nitrogen, phosphorous and phenolic compounds.

The textile industry waste water contains non- biodegradable

synthetic organic dyes, metals, phosphates and aerosols. Most of the textile
industries do not have any effluent treatment plants to process and discharge
the waste water in a proper manner; as a result they directly discharge the
untreated, coloured and toxic effluents into nearby canals, rivers, lakes, and
streams. The dyes and chemicals in the untreated waste water have changed
the properties of natural water bodies, which cause serious environmental
problems. Water quality has become a major global concern because of
increasing human developmental activities, depletion of natural resources and
pollution of surface and groundwater. The drastic environmental changes and
rapid industrialization have lead to change the water quality. Hence, the needs
to tackle the water pollution problem and necessity to provide a safe source of
water have increased dramatically in recent years.

2.2 TEXTILE DYES IN WATER

The discovery of synthetic dyes overwhelmed the role of natural

dyes in the society due to its low production cost, bright colours, better
resistance towards environmental factors and easy-to-apply factor. This has
led to a higher consumption of synthetic dyes over natural dyes for most of
the industrial applications. However synthetic dyes are often highly toxic and
carcinogenic in nature.
 8

Dyes are important pollutants, which are generally present in the

waste water of textile, plastics, leather, food processing, dyeing, cosmetics,
paper and paint manufacturing industries. Dyes are synthetic aromatic organic
compounds, which are embodied with various functional groups.

The extensive usage of dyes in various industries and discharged

coloured waste water lead to polute the environment. The textile industries are
generating a large amount of waste water containing number of pollutants
(Hao et al. 2000). One of the important pollutants of the textile waste water
is synthetic organic dyes and once it enters into water, which is no longer in
dye form and it is also difficult to treat because dyes are in a complex
molecular structure, which makes them more stable and difficult to
biodegrade (Odjegba et al. 2012). Dye molecules are comprised of two key
components such as chromophores, and auxochromes, where chromopores
(containing OH, NH2, NHR, NR2, Cl and COOH) are responsible for the
production of colours and auxochromes (containing NO2, NO, N=N) enhance
the affinity of the dye towards the fibres (Rocha Gomes 2001). Worldwide
approximately 7  105 to 1  106 tons of dyes are produced per year.
However, it is reported that only 10-15% of the used dyes are transferred into
the environment through waste water (Garg et al. 2003). The largest amount
of dyes are used in textile, paper and pulp, tannery and paint industries.
Hence, the waste water discharged from these industries containing
objectionable dye pollutants are more toxic in nature. The release of the
colorant effluent into water resources has triggered a major concern on the
human health as well as marine life. Generally, the oral ingestion of coloured
water causes skin, eye irritation, and skin sensitization due to the presence of
carcinogenicity. The colored water not only affects human beings but also
interferes with the transmission of light and troubles the biological
metabolism processes thereby damaging the aquatic beings present in
ecosystem. Further, the dyes may cause micro toxicity to fish and other
 9

organisms (Nigam et al. 2000). Thus, the removal of dyes from the waste
water is very essential, before it enters into remaining unpolluted natural
water bodies.

2.3 TEXTILE DYES

Dyes are classified on the basis of their solubility; soluble dyes

include acid mordant metal complex, direct, basic and reactive dyes; while
insoluble dyes include azoic, sulfur vat and disperse dyes.

2.3.1 Direct Dyes

Direct dyes are water-soluble anionic dyes and have been used for
dyeing of cotton, rayon, paper, leather and cellulosic fibres. Direct dyes are
highly affinity with cellulose fibers through dipole interaction, van der Waals
forces and hydrogen bonding. The sulphonic acid groups in direct dyes are
responsible for water solubility. Mostly the direct dyes structures are Polyazo
compounds along with some stilbenes, phthalocyanines and oxazines groups.
(Wood, 1980)

Figure 2.1 Chemical structure of direct dye (cango red)

 10

2.3.2 Reactive Dyes

Reactive dyes have highly coloured organic compounds, which are

being commonly used for dyeing of cotton, other cellulosic, wool and nylon.
The reactive groups of the reactive dyes are forms covalent bonds with OH-,
NH-, or SH- groups in the cotton, wool, silk and nylon fibres (Panswad and
Luangdilok, 2000). In reactive dyeing process, the hydrolysis of reactive
functional groups occurs in the dye bath, which leads to lower dye fixation
efficiency. As a result, large quantity of reactive dyes was discharged into
water stream. The most common structures of reactive dyes are azo, metal
complex azo, anthraquinone and phthalocyanine (An, et al., 2004)

Figure 2.2 Chemical structure of reactive dye (reactive red 194)

2.3.3 Vat Dyes

Vat dyes quinonic dyes, which mainly contains anthra quinones and
indigoids. These dyes are included natural dye stuff like indigo. The artificial
dyes are called as indanthrene and flavanthrene. Vat dyes are insoluble in
water and cannot be applied directly on the fibre. Therefore the vat dyes are
converted into soluble leuco dye form under alkali condition and commonly
applied for dyeing of cotton, other cellulosic fibres and wool. After the alkali
reduction, the vat dyes are more affinity toward textile fibres, subsequently
oxidized to water insoluble dye. The vat dyeing process required more
 11

amount of reducing agent, which also lead to create the water pollution
(Msmelcerovic et al. 2010).

Figure 2.3 Chemical structure of VAT dye (Anthroquinone VAT Dye)

2.3.4 Disperse Dyes

Disperse dyes are being widely used in various industries such as

textiles, paper, and leather. The disperse dyes non-ionic aromatic substances.
These dyes are water insoluble but soluble in organic solvent. The common
structure of disperse dyes are azo, azo-metal complex, anthraquinone, and
phthalocyanine. These dyes can be used for the dyeing of polyester, nylon,
cellulose acetate and Polyacrylonitrile. The textile industry waste water
contains carcinogen and mutagen chemicals such as Benzedrine, metals that
lead to create serious environmental problem (Bajpai, 2018)

Figure 2.4 Chemical structure of disperse dye (disperse red 19)

 12

2.3.5 Acid Dyes

Acid dyes are anionic azo compounds contains sulphonic groups

that lead to soluble in water. Acid dyes are mainly applied for dyeing of
polyamide and wool. They are also used for nitrogen-containing fibres like
silk and modified acryl (Bajpai 2018). Anionic mono azo dyes and their metal
salts are widely used for dyeing of papers and leathers. Acid dyes are highly
disposed into waste water and are lead to environmental problem. The most
common structures of acid dyes are azo, anthraquinone and triarylmethane
(Hunger 2003).

Figure 2.5 Chemical structure of acid dye (Acid red 138) (Monoazo dye)

2.3.6 Basic Dyes

Basic dyes are called as powerful cationic coloring agents because

of the presence of chromopores in the basic dye molecules which contains
positive charge. Basic dyes are usually soluble salts having chlorides, which
creates a positive charged radical on the dyestuff in basic medium. The basic
dyes produce bright shades with high tinctorial values on textile fibres. Basic
dyes are applied to anionic substrates like wool, silk cotton and acrylic fibres
where the electrostatic attraction is formed by dye molecules and fibres. The
anionic property of acrylic fibres makes to suitable for dyeing with cationic
dyes (Bajpai 2018). The most common structures of basic dyes are azo,
 13

diarylmethane, triarylmethane, and anthraquinone. eg., methylene blue,

crystal violet, aniline yellow etc.

2.3.7 Methylene Blue Dye

Methylene Blue dye is prepared by oxidizing a mixture of dimethyl

aniline and p-amino-dimethyl aniline (equimolar quantities) and sodium
thiosulphate with sodium dichromate and hydrochloric acid in the presence of
zinc chloride (to get the final dye as zinc chloride double salt). Methylene
Blue (or MB) is a basic aniline dye with the molecular formula of
C16H18N3SCl and molecular weight of 373.9 g mol-1. Methylene blue dye
appears as a solid, odorless, dark blue powder that yields a blue solution when
it is dissolved in water.

Figure 2.6 Structural formula of methylene blue

Methylene blue (MB) is a cationic basic thiazine dye extensively

used for dyeing acrylic, silk and wool fibres, because, it is inexpensive and
also easily available. The release of methylene blue dye into water causes
some harmful effects to human beings, which include shortness of breath,
burning sensation, increased heart rate, vomiting, headache, cyanosis,
jaundice, quadriplegia, tissue necrosis, urinary infection and
methemoglobinemia (Vadivelan et al. 2005). Therefore, the removal of MB
dye from the waste water is very essential to protect the environment.
 14

2.4 TREATMENT METHODS

Many treatment methods have been developed to remove the dyes

from the waste water, which can be generally classified into three types such
as physical, chemical and biological methods.

2.4.1 Physical Methods

2.4.1.1 Filtration technology

Filtration is a new membrane technique for decontaminating the

drinking water and waste water, which includes nanofiltration, ultrafiltration,
and microfiltration and reverses osmosis. These techniques have been used as
porous membrane to remove the colour from the waste water. Among these
techniques, microfiltration is not much used for waste water treatment,
because its large molecules frequently block the membrane pores, thus it
decreases the filtration efficiency (Marcucci et al. 2001). The membrane is
comparatively better for filtration of the larger molecules like salts; however
it is not suitable for smaller organic molecules, which have molecular weight
below 200mg. Reverse osmosis is a valuable technique for removal of colour
and chemical auxiliaries from the dye waste water (Vandevivere et al. 1998).
Reverse osmosis requires external pressure to force the water through
membrane pores, because of impermeable contaminant molecules
(Ramesh Babu et al. 2007). Generally, the major drawbacks associated with
the filtration method are high working pressure, energy consumption, high
cost of membrane and short life time of membrane, thus it is limitedly used
for the treatment of dye waste water (Ranganathan et al. 2007; Cooper 1993).

2.4.1.2 Adsorption process

Adsorption is the most established effective equilibrium processes

for the removal of dissolved coloured components from the waste water
 15

(Dabrowski 2001; Ahmad et al. 2009; Rafatullah et al. 2009). Adsorption

method has been found to be most easy and economically feasible for the
removal of dyes from the textile waste water (Tehrani-Bagha et al. 2011).
Adsorption method is superior than other methods in terms of flexibility and
simple design, initial cost, insensitivity to toxic pollutants and easy operation.
Adsorption is the procedure of choice and gives the best results as it can be
used to remove different types of colouring materials. Adsorption method is
an efficient, simple technique, sludge free process, easy to recover and recycle
the adsorbents (Kapdan & Kargi 2002). The term adsorption refers to a
process in which an adsorbate is accumulated on a solid surface from its
liquid surroundings. Adsorption may be classified as physical adsorption and
chemisorptions. The attraction which occurs between the solid surface and the
adsorbate molecules is called as physical adsorption (Young & Crowell
1962). Generally, in physical adsorption, the attractive forces between the
adsorbed molecules and the solid surface lead to creation of Vander Waals
forces and as they are weak in nature as a result in reversible reaction. On the
other hand, the attractive force occurring between the adsorbate and adsorbent
due to chemical bonding is called as chemisorptions (Dawood et al. 2014).
Due to the higher strength of the bonding in chemisorption, it is difficult to
remove the chemisorbed species from the solid surface. Adsorption is a
unique process for the removal of both organic and inorganic contaminants
from the drinking and waste water (Kant 2012).

2.4.2 Chemical Methods

2.4.2.1 Coagulation process

This method involves the addition of coagulation agent into the dye
containing waste water then this coagulant destabilizes the dye existing in the
waste water (Aguilar et al. 2002). Common coagulation agents such as
ferrous sulphate Fe(SO4) and ferric chloride FeCl3 are used to induce the
 16

coagulation (Semerjian & Ayoub 2003). Generally the coagulation process is

economically viable for satisfactory removal of disperse, sulfur, and vat dyes.
However, the major drawback of this method is the large quantity of
concentrated sludge produced which is responsible for secondary pollution
(Papic et al. 2004). This process is not suitable for highly water soluble dyes
such as direct, reactive, acid and basic dyes and also not convenient for
removal of azoic dyes (Aguilar et al. 2002).

2.4.2.2 Oxidation process

In oxidation method, waste water is treated with oxidizing agents

such as chloride, hydrogen peroxide, fenton’s reagent, ozone or potassium
permanganate. Generally two types of oxidations are used for waste water
treatment namely chemical oxidation and UV assisted oxidation. Oxidation
process is one of the most suitable methods for decolourisation of dye waste
water with little quantity of catalyst and very short reaction time. Oxidation
methods also can be used for partial or complete degradation of compounds
with lower molecular weight such as aldehydes, carboxylates and sulfates.
However, a complete oxidation takes place by production of hydroxyl radicals
which degrades the dye molecules into carbon-dioxide (CO2) and water
(H2O). It is observed that the pH and catalyst play an important role in the
oxidation process. This method is widely used as disinfectant for water
treatment and also extensively used for the reduction of dye colour in waste
water like reactive, acid, direct and metal complex dyes. However, the
oxidation method is not suitable for water insoluble dyes like disperse and vat
dyes, which is challenging to decolourisation of reactive dyes generally
requires long contact times, whereas metal complex dyes solution remains
partially colored even after the treatment.
 17

2.4.2.3 Photochemical process

In advanced oxidation process more than one oxidation system is

used, because sometimes single oxidation process is not sufficient for the
degradation of dyes. Advanced oxidation processes are alternative treatment
methods (O3, O3/H2O2, O3/UV, H2O2/UV, O3/H2O2/UV, Fe2+/ H2O2) for the
degradation of organic synthetic dyes in the textile waste water
(Antoniadis et al. 2010). Advanced oxidation processes form unstable
hydroxyl free radicals as reactive intermediate and these free radicals are used
as a strong oxidizing agent with high reaction rates, oxidation potential, low
selectivity for the degradation of organic compounds (Gogate et al. 2004).
The main drawback of this process is the broken dye molecules
present in treated water henceforth causing for secondary pollution
(Neyens et al. 2003).

2.4.2.4 Photo catalytic process

Photo catalytic degradation is one of the most attracted methods for

removal of toxic organic pollutants in waste water. In photo catalysis, light
energy from a light source excites an electron from the Valence Band (VB) of
the catalyst to the Conduction Band (CB) which leaves the positive holes in
valence band. These electrons in CB and positive holes in VB are the charge
carriers responsible to drive oxidation and reduction respectively, which
produce the active hydroxyl radicals (Marin et al. 2012). The hydroxyl
radicals have high oxidizing potential and therefore it can attack the structure
of the targeted organic molecules. Most widely known photocatalysts such as
TiO2, ZnO, ZrO2, CeO2 etc have been used for catalytic oxidation process.
This technique has also been used for photo-mineralization of wide number of
dyes such as methylene blue, direct, acid dyes, azo dyes, reactive black, vat
dyes and disperse dyes (Upadhyay et al. 2014).The photocatalytic mechanism
is shown as.
 18

TiO2 + hυ h+ (VB) + e-(CB)

e- (CB) + O2 ˙O2 (reduction)

h+(VB) + H2O ̇ OH + H+ (oxidation)

Although the advanced oxidation process has proved as a potential and

technically effective method for color removal, however the major drawback
of photocatalytic process is the production of some undesirable by-products
and it is also quite expensive especially for small-scale sector.

2.4.2.5 Ozonisation process

Ozone is a very good powerful oxidizing agent due its higher

reduction potential. Hence it has been utilized for the degradation of various
organic pollutants from the drinking and polluted water
(Pera-Titus et al. 2004; Ozbelge et al. 2002). Ozone is found to be relatively
compatible for oxidizing chlorinated hydrocarbons, phenols, pesticides and
aromatic hydrocarbons (Robinson et al. 2001). The ozonisation reaction
mechanism involves two stages. In first Stage, the reaction occurs at
pH 5 - 6, where the ozone O3 selectively attacks the double bond of dye
molecules. In Stage 2, the reaction taking place at above pH 8, here the ozone
readily decomposes and generates hydroxyl radicals that react non-selectively
with organic compounds (Joshi et al. 2004). Degradation of reactive dyes
with O3 shows good result whereas moderate for basic dyes and poor results
for disperse dyes (Southern 1995). The major advantage of this method is the
O3 used in the form of gaseous state and no sludge generation, which makes it
effective for decolourization of dyes. However its high cost and half-life time
are major problems associated with ozonization process (Slokar et al. 1998).
 19

2.4.2.6 Electrochemical process

In this method the current supply is applied through iron electrode

into dye waste water to produce ferrous hydroxide coagulant in waste water.
The iron electrode generating ferrous and hydroxyl ions then followed by the
formation of hydroxyl ions that leads to neutralized electrostatic charge of
solids and enhanced rate of agglomeration (Vandevivere et al. 1998). The
process is found to be quite effective for the removal of contaminants,
colloidal particles, metal ions and dyes. Mechanism involving aluminum
electrode- upon oxidation Al tends to produce aluminum hydroxide ions
which further polymerizes to form Al (OH) 3n species.

Step 1 Al(s) → Al3+ (aq).

Step 2 Al3++ 3H2O → Al (OH) 3 +3H+

Step 3 nAl (OH) 3 → Al (OH) 3n

Mechanism involving iron electrode

The dissolution of iron electrode undergoes to produce ferrous-

hydroxide ions Fe(OH)2 in an electrolyte solution.

Fe → Fe2+(aq) + 2e-

Anodic reaction

Fe2+(aq)+2OH-(aq) → Fe (OH) 2 (S)

Cathodic reaction

2H2O (l) + 2e- → H2 (g) + 2OH-(aq)

 20

Overall reaction

Fe (s) + 2H2O (l) → Fe (OH) 2 (s) + H2 (aq)

The ferrous hydroxide formed acts as a coagulant that binds the organic
pollutants by electrostatic attractions and removes them through coagulation
phenomena (Ceron-Rivera et al. 2004). However the main drawback of this
process is high cost, required high electrical energy, and the electrodes with
limited life time (Kobya et al. 2003)

2.4.2.7 Ion exchange process

In this method, waste water is passed over the ion exchange resin
until the available exchange sites are saturated. Both cationic and anionic dyes
can be removed in this ion exchange method. The advantage of ion exchange
method is that there is no loss of adsorbent on regeneration. Water soluble
dyes are also possible to remove in ion exchange process
(Robinson et al. 2002). A major disadvantage of the ion exchange method is
high cost of solvents to regenerate the ion-exchanger and also the ion
exchangers cannot accommodate a wide range of dyes (Slokar et al. 1998).

2.4.2.8 Drawbacks of chemical methods

The chemical treatment techniques are helpful in the removal of

dyes from the waste water, however they are not much used because of high
cost, high electrical energy demand, large consumption of chemical agents
and sludge disposable problem.

2.4.3 Biological Treatment Methods

Biological treatment is an economical alternative method, when

compared with other physical and chemical techniques in waste water
 21

treatment (Barragan et al. 2007). A large number of fungal strain species

have been used for dye degradation (Vasdev et al. 1995). The biological
treatment has significant advantages like relatively less expensive, low
process costs and non-toxicity. Biodegradation methods such as fungal
decolorization, microbial degradation, and adsorption have been used for
decolouration of dyes using biomass. The Biodegradation processes are
commonly applied to the treatment of industrial effluents, because many
microorganisms such as bacteria, yeasts algea and fungi are having a tendency
to degrade different pollutants (McMullan et al. 2001; Fu & Viraraghavan
2001; Banat et al. 1996). The biological process can take place in both
conditions such as aerobic (in the presence of oxygen), anaerobic (without
oxygen) or combined aerobic - anaerobic.

2.4.3.1 Aerobic treatment

In aerobic method, Bacteria and fungi are the most microorganisms

that have been widely studied for their ability to treat the dye waste water.
Enzymes are secreted by the microorganisms, which lead to break the organic
dye molecules in the waste water. However, aerobic method is an inefficient
system for the treatment of azo dye waste water, because aerobic bacteria can
not reduce the azo linkages and also ability to degrade the dye chromogens is
lesser as compared with anaerobic bacterium. The degradation of various dyes
using isolate aerobic bacteria has been going on since more than two decades
(Rai et al. 2005). However, the synthetic dyes are not uniformly susceptible
to decomposition by activated sludge in a conventional aerobic process
(Husain 2006). Developed aerobic bacterial strains for dye decolourization
often resulted in a specific strain, which showed a strict ability on a specific
dye structure (Kulla 1981). Although the aerobic treatments are suitable for
some dyes, most of them are recalcitrant to biological breakdown or
 22

nontransferable under aerobic conditions (Pagga & Brown 1986;

Rai et al. 2005).

2.4.3.2 Anaerobic treatment

The degradation of synthetic dyes has been carried out in anaerobic

treatment (Forgacs et al. 2004). Many researchers have found that aerobic
method is not convenient for decolouration of azoic dyes. The anaerobic
treatment has several advantages over the aerobic treatment like less
expensive, simple and inexpensive reactors. Rai et al. 2005 reported that the
anaerobic method is a successful process for decolorization of azoic dyes and
anaerobic process can also be applied to the treatment of more complex
industrial effluent containing compounds with multiple chloro, nitro, and azo
groups that are resistant to aerobic biodegradation. The major drawback of the
anaerobic system is unsuccessful method for decolouration of dispersed dye
and anthroquinone based dye even at low concentration (Delee et al. 1998).

2.4.3.3 Drawbacks of biological methods

Generally, the main drawbacks of the biological treatment are low

biodegradability of the dyes, less flexibility in design and operation, large
land area requirement and longer time for decolouration-fermentation
processes (Bhattacharyya & Sarmas 2003). Biological treatment has been
observed that it is not satisfactory with current conventional biodegradation
process (Robinson et al. 2001) and also many organic molecules are not
degraded. Particularly azo dyes are not totally degraded in biological process
(Ravi Kumar et al. 1998).
 23

2.5 TYPES OF ADSORBENTS

2.5.1 Low Cost Adsorbents

Materials which are locally and abundantly available such as

agricultural wastes and industrial by-products can be utilized as low cost
adsorbents. Conversion of these materials can be used as adsorbents for waste
water treatment and it would help to reduce the cost of waste disposal and
provide an alternative to commercial activated carbon.

2.5.1.1 Industrial waste

The waste materials generated in various industries are dumped as

unwanted materials in remote areas. These waste materials are used as an
adsorbent for protecting the environment from pollution. Metal hydroxide
sludge is one of the industrial waste materials contains insoluble metal
hydroxide and salts, which have been used as adsorbent for the removal of
methylene blue dye from textile waste water (Otero et al. 2003). Metal
hydroxide sludge waste produced from industries was found to be 4.2%
adsorption capacity of rhodamine B dye (Santos et al. 2008). Red mud solid
waste from aluminium industries discharged as bauxite processing residue,
which has been used as an adsorbent for removal of malachite Green dye
from aqueous solution. The Red mud has also been studied for the removal of
Safranin-O dye from aqueous solution (Namasivayam, et al. 1997). It has
also been studied for the adsorption of methylene blue by Wang et al. (2005).

Fly ash is one of the solid by-products of coal burning industries

that can be mainly used for the construction of roads, bricks and cement
production. The fly ash can also be used for the removal of dyes
(Viraraghavan & Ramakrishna 1999). Bagasse fly ash is the by- product of
sugar industry, which has been used as adsorbent, because it is cheap and
widely available (Kumar & Sivanesan 2006). Acid and Base hydrolyzed fly
 24

ash has also been studied for the removal of methylene blue and crystal violet
dye respectively (Nang et al. 2005; Harja et al. 2016).

2.5.1.2 Naturally occurring adsorbents

The clays are hydrous alumino silicates broadly defined as those

minerals that are made-up through colloid fraction of soils, sediments and
rocks and may be composed of mixtures of fine grained clay minerals and
clay-sized crystal of other minerals such as quartz, carbonate and metal oxides
(Pinnavaia 1983). The clays naturally contain exchangeable ions on their
surface and play a vital role in the environment by acting as a natural
scavenger of pollutants. In recent years, many researchers have been showing
their interest on clay minerals such as bentonite, kaolinite and diatomite due
to their affinity towards both inorganic and organic molecules. The
exchangeable ions in clay minerals make it a very good adsorbent for the
removal of various cationic and anionic dyes from textile waste water
(Babel & Kurniawan 2003).

2.5.1.3 Agricultural waste

Agricultural waste materials are cheap and easily available

adsorbents for the removal of textile dyes. The agricultural waste by-product
is an economic and environment friendly, which is most widely used for
decolourization. Agricultural by-products from industries such as bark,
sawdust and agricultural solid waste have been applied as adsorbents for dye
removal. In recent years many researchers have used various agricultural solid
wastes to investigate the removal of inorganic/organic pollutants including
dyes from waste water (Salleh et al. 2011).

Sawdust is easily available abundant by-product of wood industry;

it contains various organic compounds like cellulose, hemicellulose and lignin
 25

with polyphenolic groups, which show good adsorption efficiency for the
removal of MB from aqueous solution (Garg et al. 2004). Bark is an another
waste by-product of timber industry, it contains rich polyphenol groups and
high tannin content, which makes it an effective candidate for the removal of
Methylene blue from aqueous solutions (Mckay et al. 1999).

Rice husk is an agricultural waste of rice milling industry and major

chemical constituents present in the rice husk are carbon and silica (SiO2) in
hydrated amorphous form like silica gel. It has been used as an adsorbent for
the removal of Methylene Blue (MB) from aqueous solutions and the
monolayer surface adsorption capacity of rice husks for MB adsorption has
also been studied (Vadivelan & Kumar 2005).

2.5.1.4 Activated carbon

Activated carbon is a highly porous material employed as solid

adsorbents and widely used in the removal of certain organic and inorganic
pollutants from waste water (Ramakrishna & Viraraghavan 1997). However,
amongst all the sorbent materials proposed, the activated carbon is one of the
commonly adopted absorbent materials for the removal of organic pollutants
from textile waste water. The higher absorption capacity of activated carbon
is mainly due to their structural characteristics like porous, surface area and
chemical nature, which can be easily modified by chemical treatment in order
to increase their dye adsorption properties. The activated carbon has been
found to be quite effective absorbent for removal of dyes, however high cost
and loss of adsorbent during the deactivation occurs. Therefore the
researchers are finding alternate low cost adsorbent to activated carbon (Babel
& Kurniawan 2003). Hence, there is a need for the development of low cost
and easily available materials for adsorbents, which can be used more
economically on large scale.
 26

2.5.2 Bio Adsorbents

The dyes from aqueous solutions are removed by the use of

biological materials as bio adsorbent. Bio-decolourization process is carried
out with variety of micro-organisms such as algae, fungi and bacteria. These
bio-sorbents are of low cost, available as dead or living micro-organism, from
the breeding of mushrooms. It has been found that the usage of bio adsorbents
derived from algae biomass is increasing for waste water treatment, because
of its availability in large quantities at low cost and environment friendly
nature (Deng et al. 2008). Bio-adsorbent is a novel approach, often much
more selective, cost effective than traditional ion-exchange resins and
commercially available activated carbons. Wide variety of micro organisms
such as algae, yeasts, bacteria and fungi have been investigated for
decolourizing of dyes of wide varieties (Fulekar et al. 2013).

Different kinds of bacterial specious such as Pseudomonas putida,

pseudomonas aeruginosa, Aeromonas hydrophila, Pseudomonas
plecoglossicida Sp, lysinibacillus fusiformis, Pseudomonas monteilii and
Corynebacterium glutamicum have been used for removal of Methylene blue
dye (Eslami et al. 2017; Vijayaraghavan et al. 2008). The removal of
Malachite green dye from waste water has been studied for various bacterial
specious such as kurthia, pseudomonas putida, Aeromonas hydrophila,
Pseudomonas plecoglossicida, Lysinibacillus fusiformis and Pseudomonas
monteilii (Sani & Banerjee 1999). For the degradation of Rhodamine-B dye,
bacteria like pseudomonas putida, Aeromonas hydrophila, Pseudomonas
plecoglossicida, Lysinibacillus fusiformis and Pseudomonas monteilii have
been used (Fulekar et al. 2013). Researchers have also investigated the
removal of crystal violet dye with the use of Pseudomonas putida, Aeromonas
hydrophila, Micrococcus lylae, Bacillus pumilus, Pseudomonas aerugiosa and
Proteus vulgaris (Ali & Akhtar 2014; Ogugbue et al. 2012). Aspergillus
 27

fumigates, has also been studied for the removal of methylene blue
(Selim et al. 2015). Other fungal Sp. such as Ischnoder maresiosum, Fusarium
solani, Aspergillus flavus and Alternaria solani have been investigated for
removal of malachite green dye. Marine derived Pencillium janthinellum Pl
fungi sp. has been studied broadly for the bio-adsorption of crystal violet dye.
The fungi Fusarium solani and Ischnoderna resinosum have also been tested
as biosorbent for the removal of crystal violet (Eichlerova et al. 2006; Abedin
2008; Ali et al. 2009; Wang et al. 2015). Algae are one of the microorganisms
used as bio-adsorbent for the decolourisation of dyes. Some of the algae such
as Chlorella, Cosmorium and Euglena have been used as bio-adsorbents for
the removal of various dyes (Khataee et al. 2009).

2.5.3 Nanomaterials as Adsorbent

Nanotechnology is a developing science and technology, which can

be implemented in many fields. It includes materials with smaller size than
100 nm in at least one dimension (Rickerby et al. 2007). Generally
nanomaterials have been used for multi utilization such as food industry,
optoelectronics, medicine, drug carriers, agriculture and biosensors
(Gopikrishnan et al. 2010). Moreover, nanosized metal oxides possess high
surface area and specific affinity, which has been extensively used for
decontamination of water. The nanoparticles are more attractive and efficient
adsorbents for waste water treatment, because they have higher surface areas
than bulk particles and they can be modified with various chemical groups to
increase their chemical affinity towards target compounds (Feng et al. 2010).

Nanomaterials used for adsorption can be classified into different

categories such as: (a) nanoparticles (metallic, metal oxide, nanostructured
mixed oxides, magnetic), (b) carbonaceous nanomaterials (carbon nanotubes,
carbon nanoparticles and carbon nanosheets), (c) silicon nanomaterials
(silicon, nanotubes, silicon nanoparticles, and silicon nanosheets), (d)
 28

nanoclays, (e) nanofibers, (f) polymer-based nanomaterial and (g) xerogels

and aerogels. lt has been demonstrated that the nanomaterials such as carbon
nanotubes (CNTs), graphene, ferric oxide (Fe3O4), manganese oxide (MnO2),
titanium oxide (TiO2), magnesium oxide (MgO) and zinc oxide (ZnO), play
an important role in the waste water treatment processes (Wang et al. 2013);
Singh et al. 2011; Feng et al. 2010; Tuzen et al. 2007). Metal oxides possess
minimal environmental impact, low solubility, and are not formed in
secondary pollution formation; they have also been used as adsorbents for
removal of heavy metals and dyes.

2.5.3.1 Zinc oxide nanoparticles

Nano-sized ZnO has been applied in the field of optoelectronics,

sensors, transducers, cosmetics, medicine, drug carries, and bio sensors. ZnO
has been extensively investigated for removal of dyes from waste water.
Nano-sized ZnO has attracted candidates in the field of bio-logical and
environmental applications, because of its bio-compatibility and bio safety
(Gopikrishnan et al. 2010).

In addition, compared to traditional adsorbents, such as activated

carbon, ZnO nano-particle (ZnO NPs) shows a short diffusion route, a higher
adsorption capacity and rapid adsorption kinetics. Moreover it has a series of
advantages like easy preparation, low cost of operation, non-toxicity, and
unique properties; it can be also be used as an effective adsorbents for
environmental pollutants, especially for bulky adsorbates such as organic dyes
(Li et al. 2008). ZnO nanoparticles have been used as adsorbents for the
removal of acid black (AB210) and reactive blue (RB19) from aqueous
solutions. Zinc oxide nano particles (ZnO NPs) have been prepared by the
precipitations method and employed as a potential adsorbent for the removal
of AB210 and RB19 dyes from aqueous solutions. The maximum of
adsorption capacities for AB210 and RB19 have been found as 34.13 and
 29

38.02 mg / g, respectively (Khoshhesab et al. 2018). ZnO nanoparticles (ZnO

NPs) have been prepared through facile precipitation method and used as
adsorbents for the removal of reactive black 8 (RB8) from aqueous solutions
with the maximum adsorption capacity found as 27.6 mg g-1
(Khoshhesab et al. 2015). Zinc oxide (ZnO) nanoparticles have been used as
low cost, efficient adsorbent for the removal of methylene blue dye from
waste water under batch process and also showed the good removal efficiency
(Kulkarni et al. 2016).

2.5.3.2 Titanium dioxide (TiO2) nanoparticles

TiO2 nanoparticles are well known candidate for the photocatalytic

degradation of dyes present in the industrial effluent. Nanoparticles of
titanium dioxide were taken to decompose organic dyes in the contaminated
water. Titanium dioxide has been widely used as a photocatalyst for dye
degradation due to its physical and chemical stability, non-toxicity, low cost,
and insolubility under various conditions (Saleh & Gupta 2012). TiO2 is a
good semiconductor oxide with high band gap energy of 3.2 eV to enhance
pollutant degradation, when exposed to high energy light (Dai et al. 2014).
Abou-Gamra et al. 2015 reported that the TiO2 nanospheres are an excellent
adsorbent for removal of malachite green dye and suggested that the spherical
TiO2 nano particle can be considered as a good candidate for adsorption and
removal of various organic dyes. Nyangiwe et al. 2018 have investigated that
nano-TiO2 particles are more efficient absorbents for removal of the methyl
orange dye.

Faisal (2017) has observed that when treated with TiO2 three
different dyes (methyl orange, methylene blue, and eriochrome black) the
maximum degradation percentage was obtained under pH 7. However,
particulate adsorbents might re-pollute treated water because of the
tremendous difficulties in recovery of adsorbent and also require tiresome
filtration steps along with sample loss and generation of secondary pollution
(Xiao et al. 2010; Qureshi et al. 2017).
 30

2.5.3.3 Iron oxide (Fe2O3) nanoparticles

The iron oxide (-Fe2O3) nanoparticles are highly potential

candidate for environmental applications, because of their unique properties,
such as higher surface area per unit mass with tunable specific functinality
(Nassar et al. 2014).The hydroxyl group at the surface of the iron oxide
makes bonds with the adsorbate molecules during the chemisorptions.
Moreover, the magnetic properties of iron oxide nanoparticles can be easily
separated from waste water after the adsorption process (Subha et al. 2018).
Therefore, the magnetic nano particles may be a very good potential matter
for adsorption of different dyes. The -Fe2O3 nanoparticles have been
employed successfully for removal of dye from textile waste water.

Tavallali (2014) has reported that the separation and determination

of Brilliant Green dye (BG) using Sodium Dodecyl Sulfate (SDS)
modified iron oxide nanoparticles.The SDS modified iron oxide nanoparticles
have shown better dye adsorption for BG. Ujillo Hernandez et al. 2015 used
Fe2O3 nanoparticle for adsorption of methylene blue dye. The methylene blue
dye could be removed from aqueous solution using iron oxide nanospheres by
both adsorption and ultrasonic degradation methods. The rate of methylene
blue dye removal by ultrasonic radiation has been found to be slightly higher
than adsorption. Iron oxide nanospheres have some advantages such as, ease
of operation of iron oxide nanospheres and lower energy consumption
(Mahmoudi et al. 2014).

2.5.3.4 Manganese dioxide

Nano structured manganese dioxide (MnO2 NPs) can be used as

advanced materials in batteries, as well as other applications, such as water
treatment and imaging contrast agents (Chen & He 2008). MnO2 nano
particles have been found to be a good adsorbent to remove azo and reactive
 31

dyes from waste water. Nano scale MnO is very promising nanomaterials
have been used as adsorbents due to their destructive sorbent properties,
(Mishakov et al. 2002) its higher surface reactivity and adsorption capacity
as compared with commercial adsorbents (Richards et al. 2001) and the
simplicity of their production from abundant natural minerals. Furthermore,
the pH of the zero point of charge (pHzpc) of MnO is 12.4 (Crittenden et al.
2005) and MnO is favorable towards electrostatic attraction, it is suitable for
adsorption of anions. Numerous studies have reported the removal of dye by
various Mn (III/IV) oxides through catalytic degradation and adsorption.
Manganese oxides with different crystal structures have been prepared and
used to decolorize the rhodamine B (RhB) (Cui et al. 2015).

Ramprasath et al. (2016) have studied the adsorption of Brilliant

Green (BG) and rhodamine B (RhB) by MnO2 nanoparticle and adsorption
behavior of MnO2 nanoparticle has been compared with ordinary MnO2. The
percentage removal of MnO2 nano particle for Brilliant Green (BG) and
rhodamine B (RB) has been found to be higher as compared with the
ordinary MnO2. Methylene blue degradation performance has been
observed using layered manganese oxide by Becerra et al. (2018),
Pradeep Kumar et al. (2006). The MnO2 nanoparticles have been successfully
prepared by the simple solution combustion synthesis method and studied its
adsorption capacity for removal of malachite green dye.

The ability of the freshly prepared MnO2 for MB removal in single

batch system from aqueous solution under various environmental conditions
has been investigated by Qin et al. (2017) and they have reported that freshly
prepared MnO2 has small particle size (20-100nm), relatively high surface
area and exhibited good adsorption efficiency in methylene blue.
Hu et al. (2010) have investigated the removal of Congo red and reactive
 32

brilliant red X-3B from nanoplates of MgO possessing the polar (111) face as
the primary surface has been studied as adsorbents for dye pollutants removal
from waste water.

2.5.3.5 Graphene oxide

Graphene is also one of the families of carbon nanomaterials; it

seems to be the most potential candidate due to its excellent physical,
chemical and electronic properties. Graphene is a two dimensional material
having single layer of sp2 network of carbon atoms and also the thinnest and
hardest material. Novoselow et al. (2004) have first reported the synthesis of
“miracle material” the graphene, which has good unique properties like large
surface area (2630 m2/g), optical transparency, high charge carrier mobility of
100,000 cm2/Vs) at room temperature, excellent mechanical strength
(2.4± 0.4 TPa), high thermal conductivity (2000 to 5000 Wm/K) and capacity
of sustaining large electrical current density (108Acm2). These unique
properties of graphene make it an attractive material for wide applications
such as liquid crystal devices, solar cells, batteries, capacitors, sensors and
waste water treatment (Upadhyay et al. 2014)

Graphene Oxide (GO) is highly oxidized and chemically modified

graphene material, which contains various functional groups, such as
hydroxyls, epoxides and carboxyls in plane edge. The carboxylate group at
edge of the graphene oxide can be improved by the colloidal stability and
negative interfacial charge distribution (Park et al. 2009; Kim et al. 2010).
This unique functional property of GO makes it a very good adsorbent
material. Therefore, the GO based adsorbent materials have been established
for the separation of dye from aqueous solution (Geng et al. 2012;
Ming Yan et al. 2014, Liu et al. 2012). Graphene has been used in various
forms like GO, chemically-functionalized graphene, reduced Graphene Oxide
(rGO), Exfoliated Graphene Oxide (EGO) and graphene nano composites for
 33

removal of organic pollutants and dyes from industrial effluents (Chowdhury

et al. 2014; Ramesha et al. 2011).

Many researchers have reported that the graphene and graphene

oxide were used as potential adsorbents to remove the methyl orange
(Zheng et al. 2011; Li et al. 2011), naphthalene and 1-naphthol
(Zhao et al. 2011), arsenic (Chandra et al. 2010), and heavy metals from
aqueous solution. It showed better adsorption and fast adsorption rates
(Deng et al. 2010, Zheng et al. 2011; Yang et al. 2010).
Ramesha et al. (2011) have studied the adsorbtion of anionic and cationic
dyes using Exfoliated Graphene Oxide (EGO) and reduced Graphene Oxide
(rGO) and they observed that EGO shows higher dye removal efficiency for
cationic dyes than anionic dyes. This may be in parallel with the charge based
interactions between EGO and the adsorbate. Many researchers have reported
that rGO is the most suitable material for removal of anionic dyes and
cationic dyes, Konicki et al. 2017 have attempted to investigate the adsorption
of anionic azo-dyes with graphene oxide.

2.5.3.6 Carbon nanotube

The carbon nanotubes (CNTs) discovered in Iijima (2011) has

attracted materials in scientific research because of their unique properties
such as extraordinary electrical, optical, mechanical and chemical properties.
Currently CNTs have been used as an adsorbent for removal of
environmental pollutants due to their high porosity, large surface area
(Sankararamakrishnan et al. 2014). Carbon nanotubes are basically rolled up
graphene sheets (hexagonal structures) into cylindrical form and capped with
half shape of fullerene structure (Stafiej & Pyrzynska 2007). There are two
forms (a) Single-Walled Carbon Nanotubes (SWCNTs), that can be
considered as a single graphene sheet rolled into (a) cylinder and
(b) Multi-Walled Carbon Nanotubes (MWCNTs), which can be considered as
 34

stacking of concentric layers of several graphene sheets in the form of

cylinders with an interspacing of 0.34 nm. The CNT adsorbents have
extremely high specific surface area, sorption sites; short inter-particle
diffusion distance, tunable pore size as well as hollow and layered structures
(Derakhshan & Moradi 2013). Carbon nanotubes have been extensively
investigated as potential material to use in various applications in last decade.
The CNTs have also been investigated for the removal of organic and
inorganic pollutants. CNTs could be considered as one of the most promising
adsorbents for dye removal because of their large adsorption capacity
(Gupta & Kumar 2013). Compared with other adsorbents such as clay and
activated carbon, CNTs are more attractive material for removal of textile
dye, because of their high selectivity, structural diversity and favorable
physico – chemical stability. However, only a few studies on the application
of CNTs for dye removal from aqueous solution have been
reported (Bajgat et al. 2013; Ghaedi et al. 2011; Gupta et al. 2014;
Ghaedi et al. 2011). Functionalization of CNTs has been taken with
introduction of various functional groups; it can be increased by the
adsorption sites on adsorbent for removal of synthetic dyes.
Oxidized MWCNTs have been investigated for its good adsorbent property
for the removal of synthetic basic dyes (Ghaedi & Kokhdan, 2007;
Gupta et al. 2013).

Multi-walled and single-walled carbon nanotubes have been used

as adsorbents for the removal of reactive blue 4 dyes from aqueous solution
(Machado et al. 2014). Kumar et al. (2014) have synthesized with MWCNTs
using Chemical Vapor Deposition (CVD) and studied the rhodamine B dye
remoal efficiency. Mohammed et al. (2014) have synthesized and
functionalized MWCNTs by CVD technique and it has been found to be an
efficient adsorbent for the adsorption of basic orange and methyl violet dyes
and commercial MWCNTs has been used for the removal of bismarck
 35

brown R from aqueous solution (Kamil et al. 2014). Adsorption of reactive

blue dyes has been studied using MWCNTs and MWCNT-COOH
(Dehghani et al. 2013). They observed that the adsorption capacity of pristine
MWCNTs was higher than oxidized MWCNTs due to the negative charge
created on the surface of MWCNT-COOH at lower pH.

Adsorption efficiency of Congo red on to MWCNTs from aqueous

solution has been investigated by Kamil et al. (2016). The Multi Wall Carbon
Nanotubes have been used to investigate the adsorption of Reactive Blue 4
(RB4) and Acid Red 183 (AR183) from single and binary dye systems. The
MWCNTs showed higher efficiency for RB4 than AR 183 in single and
binary dye systems, due to stronger electrostatic interactions (Wang et al.
2012).

2.5.4 Nanofibrous Composite Adsorbents

The powdered and particle adsorbents might be re-polluted in

treated water due to the difficulties in separation of adsorbent from the treated
water (Qureshi et al. 2017). Hence many researchers have made an attempt to
overcome the above problems by polymer based composites. Porous
nanofibrous composites can be fixed and reclaimed and have exhibited great
advantages over conventional media in environmental applications such as air
and water filtration. Polymeric adsorbents have been widely used to remove
and recover organic pollutants from waste water, due to their high adsorption
capacity (MohyEldina et al. 2012). Polymeric adsorbents have been
extensively applied in both scientific and industrial fields because
of their simplicity of operation and reusability (Chowdhury et al. 2004;
Rezvani et al. 2014; Bhaumik et al. 2016). Electrospun nanofibrous
membrane is the best option for environmental applications due to their
remarkable characteristics such as high porosity; large surface area per unit
mass, high gas permeability, and smaler in fibrous pores. Polymer based
 36

nanofibrous material with porous structure and high surface area to volume
ratio, has been be considered as promising candidates for excellent sorption
capacity (Bhaumik et al. 2014; Janaki et al. 2012b). Moreover, electrospun
nanofibrous composites have more advantages as compared with traditional
adsorption membranes, because it can be easily tailored to obtain specific
functional surface adsorption sites and structure (Huang et al. 2014).

In the adsorption process, functional groups present in the

adsorbent surface are one of the main factors influencing the dye adsorption
efficiency. The various researchers have been made great efforts to fabricate
the electrospun nanofibrous based adsorbent for waste water treatment.
Uyar et al. (2009) have produced and used beta- cyclodextrin functionalized
electrospun polystyrene fibres as a molecular filter. A modified
polyethylenimine (m-PEI) and Polyvinylidene Fluoride (PVDF) blended
nanofibrous mat has been produced by Ma et al. (2016) and used for the
removal of methyl orange dye (MO) from aqueous solution. The researchers
proved that the nanofibrous adsorbent has attained maximum adsorption
capacity.

Electrospinning nanofibres have been produced from Chitosan (CS)

blended with poly (vinyl alcohol) (PVA) by Norouzi et al. (2018) and used
for separation process. Qureshi et al. (2017) have investigated the nylon 6
nanofibrous mat, which showed higher adsorption rate for the Acid Blue
(AB 17) as compared to its pellet form. Poly (Ether Sulfones)/Poly
(Ethyleneimine) (PES/PEI) nanofibrous membrane have been fabricated by
Min et al. (2012) and utilized as an adsorbent for the adsorption of anionic
dyes and heavy metal ions from aqueous solutions.

Polyacrylonitrile (PAN) / Polyamidoamine (PAMAM) composite

nanofiberous mat have been produced using electrospinning technique and the
maximum dye removal ability has been investigated with Direct Red (DR80)
 37

and direct red 23 (Almasian et al. 2015). Zarrini et al. (2017) have produced
and used polyaniline coated nylon – 6 nanofibrous mat as adsorbent for
removal of methyl orange as an anionic dye. Yana et al. (2015) have
developed a novel adsorbent of poly (vinyl alcohol) / poly (acrylic acid)
membranes with poly dopamine coating on electrospun PVA / PAA fibers
through a simple biologically inspired immersion process. The prepared
membranes have been used as an adsorbent for methyl blue adsorption and
also found that the nanofibrous absorbent showed higher adsorption capacity
as compared with nanoparticle adsorbents.

The combination of organic and inorganic components can be

increased by the number of surface functional groups and consequently
enhance the dye adsorption property (Kango et al. 2013). The introduction of
specific functional groups in to the electrospun nanofibres or addition of
inorganic nanoparticle into polymer matrix was used for the removal of dyes
from aqueous solution (Ma et al. 2006; Lin et al. 2009). The combinations of
linear polymers blended with different nanomaterials (containing functional
groups of carboxyl, amine, and hydroxyl) have been established as adsorbents
for the removal of dyes from waste water (Saeed et al. 2008).
Teng et al. (2011) have synthesized PVA/SiO2 nanofiberous composite
functionalized with cyclodextrin groups for the adsorption of indigo carmine
dye.

Polyacrylonitrile (PAN) / Organic Modified Montmorillonite

(O-MMT) nano fibrous composite mats have been produced and coated with
Titanium di Oxide (TiO2). The adsorption and photo degradation capability of
the TiO2- coated PAN / OMMT composite nanofibrous mats have been
investigated with MB (Wang et al. 2012). Vinyl-modified mesoporous
poly(acrylic acid) / SiO2(PAA / SiO2) composite nanofibre membranes have
been produced through a sol-gel electrospinning process by Xu et al. (2012)
 38

and the adsorption behavior of the nanofibrous mat has been studied with
Malachite green. The adsorption of indigo carmine and acid red dyes has been
investigated with thiol-functionalized polyvinyl alcohol (PVA / SiO2 nano
fibrous composite mats (Li et al. 2012).

2.5.5 Electrospinning

The electrospinning technique is a versatile technique to produce

nanofibres from polymer solution for various applications, including
filtration, desalination, and waste water treatment (Burger et al. 2006). The
most commonly used techniques for preparation of polymeric porous fibrous
material include phase inversion, interfacial polymerization, stretching, track-
etching and electrospinning. However, the electrospinning technique has a
better advantage like viability and reliability, as compared to other techniques
(Princea et al. 2012).

Electrospinning is a unique technique to produce polymeric fibres

in the diameter range of 100 nm –10 μm. Fibres are produced by
electrospinning approach at least one or two times of smaller size in
diameter, than those produced by other conventional technique like melt or
solution spinning (Srinivasan & Reneker 1995, Subbiah et al. 2005). Based
on the previous literature report, it is evident that the average diameter of the
electrospun fibres ranges from 100 nm – 500 nm, which is generally referred
as nanofibres. Electrospun fibres have specific properties such as small pore
size, high surface area to volume ratio and layered structure. There is also
evidence for considerable inflexible charges in electrospun materials that
could be effectively tailored to produce three dimensional structures.

The electrospinning setup generally consists of four major parts

such as high-voltage power supply, syringe pump, spinneret, and collector.
High electric potential is applied while a viscoelastic polymer fluid is pumped
 39

out through the spinneret (Yarin et al. 2001). The polymer solution ejected as
a droplet from spinner jet is covered with the same charge of applied high
electric potential. The repulsion of the same charges will counteract the
surface tension of the droplet and destabilize the spherical shape. The strong
applied electric field overcomes the surface tension and the droplet will be
distorted into a conical shape. As a result of the combined effect of the
electric field and the repulsion among surface charges, the jet continues to
decrease in diameter until it starts to bend. The ejected jet under the influence
of applied electrical field, travels rapidly to the collector and collects in the
form of a non-woven web as the jet dries (Reneker et al. 2008). Before
reaching the collector, the jet undergoes a series of electrically driven bending
instabilities in the base region and emerges from the needle to form a cone
known as the Taylor cone (Hsu & Shivkumar 2004).

Figure 2.7 Electrospinning setup

The shape of the base depends upon the surface tension of the liquid and the
force of the electric field; jets can be ejected from surfaces that are essentially
flat if the electric field is strong enough. The charging of the jet occurs at the
base with solutions of higher conductivity being more conducive to jet
formation
 40

(Pham et al. 2006). The diameter of the electrically charged jet decreases
under electro-hydrodynamic forces, and under certain operating conditions
this jet undergoes a series of electrically induced bending instabilities during
passage to the collection plate, which results in extensive stretching. The
stretching process results in the diameter of jet which drastically decreases by
evaporation of the solvent and leads to solidification of the jet and production
of ultrafine fibres (Kowalewski et al. 2005).

The polymer based nanofibrous composites overcomes the

problems associated with the powdered and particulate adsorbents while
going for remval of dyes from aqeous solutions. Therefore an attempt has
been made for preparation of appropriate adsorbent for dye removal
applications.

In the present study, the Polyacrylonitrile yarn based nanofibrous

composites were prepared with four types of nano fillers like grapheme oxide,
multiwall carbon nanotubes, carboxylic group functionalized multiwall
carbon nanotubes and hydroxylic group functionalized multiwall carbon
nanotubes using electrospinning technique. The adsorption rate, adsorption
capacity and dye removal efficiency of nanofibrous composites were
investigated with methylene blue.