31

CHAPTER 2

LITREATURE REVIEW

2.1 INTRODUCTION

The main sources of heavy metal contamination include mining

wastes, landfill leaches, municipal wastewater, urban runoff and industrial
wastewaters, particularly from the electroplating, electronic and metal
finishing industries. With increasing usage of metals by technological
activities, the problem of waste disposal has become one of dominant risk
nowadays. Many aquatic environments facing a metal concentration that
exceeds water quality criteria designed to protect the environment. Problems
are exacerbated, because metals have the tendency to bioaccumulate in the
food chain.

Increasing problem of heavy metal contamination of soil, water and

other environment has stimulated a search for new mechanisms to remove
these pollutants. Recent research in the area of heavy metal removal from
wastewater and sludges has focused on the development of materials with
increased affinity, capacity, and selectivity for target metal (Pazirandeh et al
1998).

In the past fifteen years importance was given to adsorption for the
removal of heavy metals, as it played an essential role in many industrial
separation and purification applications. As early as in the 18th century,
adsorption was effectively used in the removal of toxic gases and
 32

decolouration of dye solutions. Adsorption has been commonly used in the

water and wastewater treatment processes to remove trace amounts of heavy
metals and organic compounds that cause odour and taste. It has been
demonstrated that adsorption is economically favourable to remove
chemically stable compounds.

Adsorbents are very essential material in adsorption process and

play an important role. Many of the adsorption behaviours are directly related
to the physical or chemical properties of the adsorbents, like morphology,
surface area and surface functional groups. Therefore, it is essential that
adsorbents with desired properties be developed for the various industrial
separation and purification applications. To be eligible as a “good” adsorbent,
the adsorbent material should have good mechanical properties and be
resistant to acidic or basic environment. In addition, the adsorbents should
possess high surface area to weight ratio in order to achieve a high adsorption
capacity. Furthermore, the adsorbents are also expected to have rapid
adsorption kinetics, so that the adsorption process can be greatly shortened.
Other factors to be considered include the ease of regeneration for reuse,
installation and maintenance cost.

2.2 ADSORPTION MECHANISM

Adsorption is the adhesion of atoms, ions, biomolecules or

molecules of gas, liquid, or dissolved solids to a surface. This process creates
a film of the adsorbate on the surface of the adsorbent. Similar to surface
tension, adsorption is a consequence of surface energy. In a bulk material, all
the bonding requirements the constituent atoms of the material are filled by
other atoms in the material. However, atoms on the surface of the adsorbent
are not wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates. The exact nature of the bonding depends on the details of the
 33

species involved, but the adsorption process is generally classified as physical

adsorption or chemisorption (Alley 2000).

2.3 ION EXCHANGE ADSORPTION MECHANISM

Whenever a permanently adsorbed ion present on the ion exchange

medium is removed out and is replaced by another ionic species from aqueous
solution is generally refer to as “ion exchange” process. There are synthetic
materials available that have been specially designed to enable ion exchange
operations at high performance levels. Among many other applications, ion
exchangers can be used in processes of environmental protection such as
purification, decontamination, recycling or even for the design of new
environment-friendly production processes. Synthetic and industrially
produced ion exchange resins consist of small, porous beads that are insoluble
in water and organic solvents. The most widely used base-materials are
polystyrene and polyacrylate. The diameter of the beads is normally in the
range of 0.3 to 1.3 mm. The beads contain around 50% of water, which is
dispersed in the gel-structured compartments of the material.

Since water is dispersed homogenously through the bead, water

soluble materials can move freely, in and out. To each of the monomer units
of the polymer, so called “functional groups” are attached. These functional
groups can interact with water soluble species, especially with ions. Ions are
either positively (cations) or negatively (anions) charged. Since the functional
groups are also charged, the interaction between ions and functional groups is
exhibited via electrostatic forces. Positively charged functional groups
interact with anions and negatively charged functional group (a sulfonic,
phosphonic or carboxylic acid group) will interact with cations. The binding
force between the functional group and the attached ion is relatively loose.
 34

The exchange can be reversed by another ion passing across the functional
group.

2.3.1 Adsorption/Ion Exchange in Wastewater Treatment

Adsorption phenomena are operative in most natural physical,

biological, and chemical systems, and adsorption operations employing solids
such as activated carbon and synthetic resins are used widely in industrial
applications and for purification of waters and wastewaters (Benefield 1982).
It is widely used in industrial applications such as activated charcoal,
capturing and using waste heat to provide cold water for air conditioning and
other process requirements (adsorption chillers), synthetic resins, increase
storage capacity of carbide-derived carbons for tuneable nanoporous carbon,
and water purification. Adsorption, ion exchange, and chromatography are
sorption processes in which certain adsorbates are selectively transferred from
the fluid phase to the surface of insoluble, rigid particles suspended in a vessel
or packed in a column.

2.4 FACTORS INFLUENCING ION EXCHANGE ADSORPTION

Molecules of solute are removed from solution and taken up by the

adsorbent during the process of adsorption. The majority of molecules are
adsorbed onto the large surface area within the pores of adsorbent particles
and relatively few are adsorbed on the outside surface. These transfer process
continue until equilibrium is achieved (Benefield et al 1982). The factors
which influence the ion exchange adsorption process are contact time, initial
concentration, adsorbent, characteristics, size of adsorbate molecules,
solubility of the adsorbate, pH and temperature (Foul 2007).
 35

2.4.1 Batch Studies

2.4.1.1 Effect of pH

The pH at which adsorption is carried out has been shown to have a

strong influence on the extent of adsorption. This is partly due to the fact that
hydrogen ions themselves are strongly adsorbed and partly that pH influences
the ionization, of many compounds. Organic acids are more adsorbed at low
pH, whereas the adsorption of organic bases is favoured by high pH.

Various studies reported in the literature indicated that the optimum

pH offers maximum metal ion removal. In general, metal adsorption increases
as pH increases (Seco et al 1999; Evans et al 2002). Isa et al 2006 suggested
that the optimum pH value for the adsorption of colour occurred at acidic
conditions. This is due to the positive charge dominating the surface of the
adsorbent which slightly increase the electrostatic attraction between the
negatively charged species and the positively charged surface of the adsorbent
(Namasivayam and Kavitha, 2002). In removal of COD, lower pH values
give greater removal. At lower value of pH, the precipitation of solids will
increase which improves the removal efficiency of COD. Removal of iron at
acidic condition is better than at alkaline conditions. Higher removal of iron
efficiency at pH over 10 may be contributed by the effect of adsorption and
precipitation (Isa et al 2004).

Panda et al (2008) studied the effect of pH on the biosorption of

cadmium and Ni(II) by functionalized husk of Lathyrus sativus. They
reported that the adsorption process optimum at pH of 5.0–6.0.

Kizilkaya et al (2010) reported the effect of pH on the removal of

Cu(II) ions from aqueous solution using pretreated fish bones. The highest
adsorption capacity was found to be 102.9 mg g 1 at pH 5.0. The effect of pH
 36

plays an important role on the phosphate and hydroxyl groups of HAP during
the cation-exchange reaction on the bone surface.

2.4.1.2 Effect of contact time

In general, adsorption increases with the increase in contact time

until equilibrium is reached (Sag and Aktay 2002). Contact time in the
adsorption system affects the rate adsorption, which is controlled by either,
film diffusion or pore diffusion. If the contact time is relatively small, the
surface film of liquid around the particle will be thick and film diffusion will
likely be the rate-limiting step. If adequate contact time is provided, film
diffusion rate will increase to the point that pore diffusion becomes the rate-
limiting step (Benefield et al 1982).

Krowiak et al (2011) reported the biosorption of Cu(II) and Cr(III)

ions from aqueous solutions by peanut shell biomass as a function of initial
pH, initial biomass concentration and temperature. Typical biosorption
kinetics exhibits a rapid initial uptake, followed by a slower process. It has
been observed that maximum removal took place within the first 20 min.
After this period, the amount of bound metal ions did not change during the
course of the process.

Ozturk et al (2004) investigated the effect of contact time on the

biosorption of Ni(II) and Cu(II) from aqueous solution by Streptomyces
coelicolor A3(2). Maximum removal of Ni(II) and Cu(II) ion was observed
within 5min.

2.4.1.3 Effect of dosage

The amount of sorbent available for adsorption usually influences

the metal removal percentage. High sorbent dosage enhances the sorption due
 37

to the greater availability of the exchangeable sites or surface area. High

sorbent dosage results in lower metal uptake because the available metal ions
are insufficient to cover all the exchangeable sites on the sorbent.

Wasewar (2010) reported the effect of various tea factory waste

dosages on the removal of the total amount of metal ions removed. They
found that the % removal of metal ion increased with the amount of
adsorbent. As the adsorbent concentration increases, the number of adsorbent
particles surrounding the metal ions or ratio of adsorbent particles to metal
ions increased, therefore, these particles attach more ions to their surfaces.
Increase in adsorption with adsorbent dose can be attributed to increased
adsorbent surface area and availability of more adsorption sites.

Kannan and Veemaraj (2009) studied the effect of dose of Bamboo

dust carbon (BDC) and Commercial activated carbon (CAC) on the
percentage removal of Pb(II). The percentage removal increased with increase
in dose of adsorbent. This may be due to the rapid increase in surface area and
number of available active sites for the adsorption of Pb(II) ions, or due to
conglomeration of carbons at higher dosages. The relative increase in the
percentage removal of Pb(II) ions is found to be insignificant after a dose of
20 g L 1 of BDC and 10 g L 1 of CAC, which is fixed as the optimum dose.

2.4.1.4 Effect of EDTA

In addition to metal ions industrial effluents also contains certain

concentrations of strong chelating agents like ethylene diamine tetra acetic
acid (EDTA) (Al-Subu et al 2001). This chelating agent forms a stable
complex with the metal ion of interest in treatment processes causing the
treatment process difficult.
 38

Kaewsarn et al (2004) studied the effect of anionic ligands EDTA

on the removal of Cu(II) ions by marine algae durvillaea potatorum. They
observed that Cu(II) uptake was significantly affected by other heavy metals
and EDTA in solution (1.5-100% suppression) but not significantly affected
by light metal ions and other anionic ligands studied.

Escudero et al (2008) studied the effect of EDTA on the removal of

divalent metal ions Cu(II) and Ni(II) ions onto grape stalk and exhausted
coffee wastes. Effects of pH and metal–EDTA molar ratio, kinetics as a
function of sorbent concentration, and sorption equilibrium for both metals
onto both sorbents were evaluated in batch experiments. Metal uptake was
dependent of pH, reaching a maximum from pH around 5.5. EDTA was found
to dramatically reduce metal adsorption, reaching total uptake inhibition for
both metals onto both sorbents at equimolar metal: ligand concentrations.

2.4.1.5 Effect of co-ions

Other sorbable ions in the solution may compete with the metal ion
of interest for adsorption sites. The binding of the interested metal ion then
decreases. The amount of inhibition depends on the binding strength of the
respective ions to the ion exchange resins.

Kaewsarn et al (2004) studied the effect of various co existing light

metal ions on the removal of Cu(II) ions by marine algae durvillaea
potatorum. The adsorption capacity of biosorbent for Cu(II) from aqueous
solutions containing co-ions of light metal ions (K+, Na+, Ca2+, and Mg2+),
other heavy metal ions (Ag+, Mn2+, Co2+, Ni2+, Zn2+, Fe3+, Cd2+, and Pb2+),
and anionic ligands (EDTA, CO32-, SO42 , and PO43-) were obtained. The
results showed that Cu(II) uptake was significantly affected by other heavy
metals and but not significantly affected by light metal ions and other anionic
ligands studied.
 39

2.5 BATCH REMOVAL OF HEAVY METAL IONS

In most batch shaking adsorption processes, the investigators

mainly focussed on the effect of pH, contact time, dosage, temperature,
sorbent size and co-ions. Most of the investigators also concentrated on the
regeneration of the adsorbent. Various isotherm models have been used to
describe the sorption equilibrium data. The varieties of adsorbents were used
for the removal of heavy metals.

The important adsorbents are as follows

(i) Activated carbon

(ii) Clay
(iii) Industrial wastes and sludges
(iv) Flyash
(v) Agricultural wastes
(vi) Ion exchange resin

2.5.1 Heavy Metal Removal by Activated Carbon

Activated carbon has undoubtedly been the most popular and

widely used adsorbent in wastewater treatment throughout the world. In the
treatment of wastewater, it is used for purification, decolourization, and the
removal of toxic organics and heavy metal ions (Kim et al 2001). Commercial
activated carbons are prepared from a variety of carbonaceous raw materials.
The qualities and characteristics of activated carbons depend on the physical
and chemical properties of the starting materials and the activation methods
used. Presently, lignite, peat, wood and coconut shell are the main common
precursors for commercial activated carbons (Yang and Lua 2006).
 40

In recent years, researches are focused on the production of

activated carbon from cheap material such as agricultural waste. Activated
carbon production from agricultural waste has two advantages. First, waste
material is converted to useful, value added adsorbents. Second, produced
activated carbons are used for removing organic chemicals and metals from
wastewater (Johns et al 1998). Rice hulls (Teker et al 1999; Pendyal et al
1999), rice straw (Oh and Park 2002; Ahmedna et al 2000), hazelnut shells
(Demirbas 2003), coir pith (Santhy and Selvapathy 2006) and cotton seed
shell (Kim et al 2003) were used for activated carbon production.

Kalavathy and Miranda (2010) studied the applicability of Moringa

oleifera (MO) wood, a solid waste for the preparation of activated carbon
(ACMO) and tried for the removal of Cu(II), Ni(II) and Zn(II) from synthetic
wastewater. The optimum pH for the adsorption for all the above mentioned
metals was found to be 6. The adsorption process was found to be
endothermic for Cu(II) ion and exothermic for Ni(II) and Zn(II) ions. Kinetic
studies showed that the adsorption followed a pseudo-second-order model.
The ACMO was regenerated using 0.1M H2SO4, with up to 98% recovery for
all the three metals.

Mustafa and Tekir (2008) investigated the removal of Cu(II) and Pb

(II) ions from aqueous solutions by adsorption on activated carbon from a
new precursor hazelnut husks. Activated carbon was prepared from hazelnut
husks with Zn(II) chloride activation at 973 K in nitrogen atmosphere. BET
surface area of the activated carbon was found 1092 m2g 1. The effects of
initial pH, contact time, activated carbon dosage and initial metal
concentrations were investigated. The activated carbon exhibited good
adsorption potential for Cu(II) and lead ions. The maximum adsorption
capacity of the adsorbent for Cu(II) and Pb (II) ions was calculated from the
Langmuir isotherm and was found to be 6.645 and 13.05 mg g 1, respectively.
 41

Issabayeva et al (2010) reported the removal of Cu(II) using palm

shell activated carbon (PSAC) from aqueous solutions. The results of batch
and continuous adsorption experiments showed high adsorption capacity of
the untreated PSAC to adsorb Cu(II) at pH 3.0 and 5.0. Presence of
complexing agents, boric and malonic acids, did not improve Cu(II) uptake.
In addition, removal of Cu(II) from the solutions containing Pb(II) showed
that adsorption capacity of Cu(II) was not significantly different compared to
the single Cu(II) system. Whereas, the uptake of Pb (II) onto activated carbon
was substantially reduced in the presence of Cu(II), especially at pH of 5.0.

Liu and Zhang (2011) checked the feasibility of hydrothermal char

(HTC), a by-product from biomass hydrothermal liquefaction for bio-oil
production, as raw material for preparation of porous carbons. The Cu(II)
adsorption onto HTC-derived carbons was strongly affected by the pH value
of the solution in comparison with phenol adsorption. The carbons derived
from pinewood and rice husk HTC exhibited high adsorption capacity of
1 1
83.88 and 39.30 mg g for phenol and 25.18 and 22.62 mg g for Cu(II),
respectively. The adsorption data for Cu(II) and phenol onto the carbon
adsorbents could be well described by Langmuir and Freundlich models. In
comparison with pinewood sawdust HTC-derived carbon, the adsorption onto
rice husk HTC-derived carbon preferentially followed Freundlich model due
to the presence of silica on the surface.

Kannan and Veemaraj (2009) conducted a study on the removal of

lead (II) ions by adsorption onto indigenously prepared bamboo dust carbon
(BDC) and commercial activated carbon (CAC). Effect of various process
parameters has been investigated by following the batch adsorption technique
at 30±1°C. Percentage removal of Pb(II) was found to increase with the
decrease in initial concentration and increased with increase in contact time
and dose of adsorbent. Amount of Pb(II) ions adsorbed increases with the
 42

decrease in particle size of the adsorbent. The first order kinetic equations
proposed by Natarajan–Khalaf, Lagergren and Bhattacharya and Venkobachar
and intra-particle diffusion model were found to be applicable. Removal of
Pb(II) ions by bamboo dust carbon (BDC) found to be favourable and
hence BDC could be employed as an alternative adsorbent to commercial
activated carbon (CAC) for effluent treatment, especially for the removal of
Pb(II) ions.

In spite of its prolific use, activated carbon remains an expensive

material since higher the quality of activated carbon, the greater its cost.
Activated carbon also requires complexing agents to improve its removal
performance for inorganic matters. Therefore, this situation makes it no
longer attractive to be widely used in small scale industries because of cost
inefficiency.

The maximum adsorption capacity and some operational

parameters of activated carbon used for the removal of heavy metals available
in litreature are summarized in Table 2.1.

2.5.2 Heavy Metal Removal by Clay

There are three basic species of clay in nature: Smectites (such as

Montmorillonite), Kaolinite, and Micas; out of which Montmorillonite has the
highest cation exchange capacity and its current market price is 20 times
cheaper than that of activated carbon (Ken Salazar and McNutt 2010).
Numerous studies have been reported using Montmorillonite to determine
their effectiveness in removal of metal ions such as Zn(II), Pb(II), and Al(III)
ions from aqueous solutions.
 Table 2.1 Removal of heavy metals using activated carbon and their optimal operational conditions

Contact Initial Maximum

Metal ions Optimum time Dosage concentration adsorption
Adsorbent References
removed pH required (g L 1) studied capacity (Qmax)
(min) (mg L 1) (mg g 1)
Silk Cotton Hull Pb(II) 5.0 – 10.0 90 2.4 20 NA Shanmugavalli et al
Carbon 2.8 30 (2006)
3.0 40
Carbon prepared Fe(III) 3.0 20 250 20 1.569 Karthikeyan and Siva
from Recinius Cu(II) 1.194 Ilango (2008)
Communis Linn Co(II) 1.762
Hazelnut shell Ni(II) 7.0 180 NA NA 5.77 Demirbas et al (2002)
activated carbon
Kadirvelu et al (2001)
Coir pith carbon Ni(II) 5.0 40 1.2 NA 62.5

Palm shell Cu(II) 5.0 75 1.0 Mixed metals of 1.581 Onundi et al (2010)
activated carbon Ni(II) 5.0 75 1.0 2.0 Cu, 1.5 Pb 0.130
Pb(II) 5.0 30 1.0 and 0.8 Ni 1.337
Granular activated Ni(II) 4.0 -10.0 300 1.2 20 1.49 Periasamy and
carbon Namasivayam (1995)
Peanut hull carbon Ni(II) 4 .0 – 10.0 90 0.09 20 53.65
5
Rice hull activated Cu(II) 6.9 80 40 15 5.10×10 Teker and Imamoglu
6
carbon Cd(II) 15 6.76×10 (1999)

43
 44

Srivastava et al (1989) studied the removal performance of

Montmorillonite and Kaolinite for lead and cadmium. They found that the
adsorption capacity of Pb(II) and Cd(II) is greater on montmorillonite (Pb:
0.68, Cd: 0.72 mg g 1) than on kaolinite (Pb: 0.12, Cd: 0.32 mg g 1). It was
also observed that the presence of cationic surfactant reduced the uptake of
both ions, while the anionic surfactants enhanced their removal.

Whereas, when clay minerals are used for industrial application, the
swelling factor should be taken into account since it may cause remarkable
pressure drop due to their different structural characteristics and ion exchange
mechanism. This is different from zeolites, which do not show any swelling
when embedded in liquid medium. Although the removal efficiency of clays
for heavy metals may not be as good as that of zeolites, their easy availability
and low cost may compensate for the associated drawbacks.

Potgieter et al (2006) studied the possibility of palygorskite clay,

mined in the Dwaalboom area of the Northern Province of South Africa, as an
adsorbent for the removal of metal ions such as Pb(II), Ni(II), Cr(VI) and
Cu(II) from aqueous solution. The Langmuir model represented the sorption
process better than the Freundlich one, with correlation coefficient (R2) values
ranging from 0.953 to 0.994. The adsorption capacity (Q 0) calculated from the
Langmuir isotherm for Pb(II), Ni(II), Cr(VI) and Cu(II) at a pH of 7.0 were
found to be 62.1, 33.4, 58.5 and 30.7 mg g 1 at 25±1°C for a clay particle size
of 125 m.

Shama and Gad (2010) investigated the use of Hebba clay for the
removal of Fe(III), Cu(II), Zn(II), Pb(II), Cr(III), and Cd(II). The effect of
weight of Hebba was studied and the results showed that the removal
percentage increased as the weight of sorbent increased. The effect of contact
time was also studied and the results showed that the removal percentages
increased as the contact time increased. The removal percentage for (Cu(II),
Zn(II) and Cd(II)) were slightly affected by change in pH value whereas the
 45

effect was significant for Fe(III), Pb(II) and Cr(III).The order of increasing
removal percentage of metal ions at pH 4.8, concentration of metal ion
30 mgL 1, and four hours contact time was Pb(II) < Cu(II) < Cd(II) < Cr(III)
< Zn(II) < Fe(III).

Kamel et al (2004) studied the adsorption of Pb (II), Cu(II),

Fe(III), Mn(II) and Zn(II) by sorption on Kaolinite. The effects of
contact time, pH, volume of an aqueous to mass of kaolinite clay and
concentration of metal ions were studied. The adsorption capacity towards
Fe(III), Pb(II), Mn(II), Zn(II) and Cu(II) was found to be 4.68, 2.89, 5.78,
1.482 and 3.648 mg g 1.

Stathi et al (2010) prepared Montmorillonite clay and tried as

adsorbent for the removal of Pb(II), Cu(II), and Cd(II) and Zn(II). Effect of
pH study revealed that maximum removal of metal ions obtained at the pH
value of 4.05, 2.88, 3.48 and 2.55 mg g 1 for Pb(II), Cd(II), Cu(II) and Zn(II).
The maximum adsorption capacity and operational parameters of clay for
the removal of heavy metals reported in the litreature are summarized in
Table 2.2.

2.5.3 Heavy Metal Removal by Fly Ash

Fly ash is a coal combustion residue and has a great potential in

environmental applications and an interesting alternative to replace activated
carbon for the treatment of wastewaters. Adsorption capacity of fly ash highly
depends on their origin and pre treatment techniques followed. The alkaline
nature of fly ash minimizes the need of pH adjustment (Ahmaruzzaman
2010). Fly ash has been widely used as a low cost adsorbent for the removal
of heavy metals. Table 2.3 summarizes the results of the important metals
investigated by various researchers using fly ash as adsorbent.
 Table 2.2 Removal of heavy metals using clay material as adsorbent

Metal ions Maximum adsorption

Adsorbent References
removed capacity (Qmax) (mg g 1)
Clay – Kaolinite Zn(II) 27.78 Amer et al (2010)
Pb(II) 40.00
Cd(II) 13.21
Clay – Kaolinite Cu(II) 10.478 Yavuz et al (2003)
Ni(II) 1.669
Co(II) 0.919
Mn(II) 0.446
Clay – Calcium Bentonite Cr(III) 44.4 Ayuso and Sanchez (2003)
Ni(II) 6.32
Zn(II) 5.75
Cu(II) 7.72
Cd(II) 7.28
Clay – Sodium Bentonite Cr(III) 49.8 Ayuso and Sanchez (2003)
Ni(II) 24.2
Zn(II) 23.1
Cu(II) 30.0
Cd(II) 26.2
Kaolinite, Ni(II) 10.4
Acid activated Kaolinite Ni(II) 11.9 Bhattacharyya and Gupta (2008)
Montmorillonite Ni(II) 28.4
Acid-activated Montmorillonite Ni(II) 29.5

46
 Table 2.3 Removal of heavy metals using fly ash and their optimal operational conditions

Maximum adsorption capacity

Type of Fly ash Metal ions removed References
(Qmax) (mg g 1)
Fly ash Zn(II) 6.5–13.3 Banerjee et al (2003)
Ni(II) 9.0–14.0
Cr(VI) 1.379 Banerjee et al (2004)
Hg(II) 11.00
Fe impregnated fly Zn(II) 7.5–15.5 Banerjee et al (2003)
Ash Ni(II) 9.8–14.93
Cr(VI) 1.667 Banerjee et al (2004)
Hg(II) 13.40
Al impregnated fly Zn(II) 7.0–15.4 Banerjee et al (2003)
Ash Ni(II) 10–15.75
Cr(VI) 1.820 Banerjee et al (2004)
Hg(II) 12.50
Bagasse fly ash Zn(II) 13.21 Gupta et al (2003)
Cu(II) 2.26–2.36
Ni(II) 1.12–1.70

47
 48

Among these metals, Ni(II), Cr(VI), Pb(II), As(III), Cu(II), Cd(II)

and Hg(II) are the most investigated. Fly ashes with different quantities of
carbon and minerals were also used for the removal of Cu(II) from aqueous
solution and the carbon fraction in fly ash was important in the removal
of Cu(II). The specific adsorption capacities of carbon ranged from 2.2 to
2.8 mg g 1, while those for mineral were only about 0.63-0.81 mg g 1.

Papandreou et al (2007) used fly ash can in pellets shape for the
removal of Cu(II) and Cd(II) from aqueous solutions. In this work, fly ash
was shaped into pellets that have diameter in-between 3-8 mm, high relative
porosity and very good mechanical strength. The effect of agitation rate,
equilibration time, pH of solution and initial metal concentration were
studied. The adsorption of both cations followed pseudo-second order kinetics
reaching equilibrium after an equilibration time of 72h. The calculated
adsorption capacities of pellets for Cu(II) and cadmium were found to be
20.92 and 18.98 mg g 1, respectively.

Banerjee et al (2004) studied the adsorption ability of fly ash and

Al; Fe impregnated fly ash on Ni(II) and Zn(II), Cr(III) and Hg(II) ions. The
impregnated fly ash showed much higher adsorption capacity for all the ions
as compared to that of untreated fly ash. The adsorption was found to be
exothermic for Ni(II) and endothermic in case of Zn(II). The adsorption
capacity of FA, Al-FA, and Fe-FA for Cr (VI) was found to be 1.379, 1.820,
and 1.667 mg g 1 and that of Hg(II) was 11.00, 12.50, and 13.40 mg g 1.

Luo et al (2011) studied the removal of Cu(II) ions from aqueous

solutions using fly ash adsorbent. Fly ash dosage as well as initial Cu(II) ion
concentration, temperature and pH value was varied to find the optimum
conditions for Cu(II) adsorption. The results from sorption process showed
 49

1
that the maximum adsorption rate was obtained at 50 mgL when different
dosage of fly ash was added into the solution. When pH was 6, the removal
rate reached the maximum of 99.60%. When initial Cu(II) content was
50 mg L 1, pH value was 6 the adsorption capacity of fly ash sample reached
0.98 mg mg 1. The main removal mechanisms were assumed to be the
adsorption at the surface of the fly ash together with the precipitation from the
solution.

Cho et al (2005) studied the removal of Zn(II), Pb(II), Cd(II) and

Cu(II) from aqueous solution using fly ash at various pH values (3–10) at
25 C and metal concentrations of 10-400 mg L 1 using fly ash dosages of 10,
20 and 40 g L 1. The test results using real wastewater indicated that fly ash
could be used as a cheap adsorbent for the removal of heavy metals in
aqueous solutions if not strongly acidic. Between pH 5 and 8, where the
influence of precipitation is negligible, the removal for Zn(II) was 86-98%,
96-99% for Pb(II), 51-95% for Cd(II) and 60-99% for Cu(II) when
concentrations were below 100 mg L 1. The maximum adsorption capacity
and operational parameters of flyash for the removal of heavy metals reported
in litreature are summarized in Table 2.3.

2.5.4 Heavy Metal Removal by Ion Exchange Resin Adsorption

Ion exchange adsorption experiments are often carried out in batch

and column mode. Even though, batch operations are often not used in
industries for metal ion removal, they are useful in evaluation the
performance of adsorbent and the factors affecting it. Therefore, preliminary
batch experiments are of great importance as they provide fundamental
information regarding the adsorption process.
 50

Ion exchange adsorption is a process in which cationic or anionic

heavy metal ions in a liquid phase are exchanged by adsorbed cations or
anions of a polymeric resin. The process is reversible (regeneration), which
allows extend use of the sorbent. The stability of the polymeric resin in wide
range of pH, high treatment capacity, high removal efficiency and fast
kinetics makes this process quite attractive. Natural and synthetic resins have
been used by many researchers; among this synthetic resins are commonly
preferred as they are effective for nearly complete removal of the heavy
metals from the aqueous solution (Alyuz and Veli 2009).

The most common cation exchangers are strongly acidic resins with
sulfonic acid groups ( SO3H) and weakly acid resins with carboxylic acid
groups ( COOH). Hydrogen ions in the sulfonic group or carboxylic group of
the resin can serve as exchangeable ions with metal cations. As the solution
containing heavy metal passes through the cations column, metal ions are
exchanged for the hydrogen ions on the resin with the following ion-exchange
process:

2Resin – SO3 H+ + Cu2+ (Resin – SO3 )2 Cu2+ + 2H+ (1.1)

2Resin COO H+ + Cu2+ (Resin COO )2Cu2+ + 2H+ (1.2)

Alyuz and Veli (2009) experimented and reported the kinetics and
equilibrium data of removal of Ni(II) and Zn(II) from aqueous solutions by
ion exchange resin Dowex HCR S/S. The effects of pH, dosage of resin and
contact time on removal process were studied by batch shaking experiments.
It was observed that more than 98% removal efficiency was achieved under
optimal conditions for Ni(II) and Zn(II). The equilibrium data were tested for
the Langmuir, Freundlich and Temkin isotherms and the correlation
 51

coefficients indicated the following order of fit: Langmuir > Freundlich >
Temkin for both Ni(II) and Zn(II). It was found that removal of Ni(II) and
Zn(II) was well fitted by second-order reaction kinetics.

Lee et al (2007) reported the equilibrium and kinetics of Cu(II),

Zn(II) and Cd (II) removal by ion exchange resin Amberlite IR 120. The
equilibrium data were analyzed by the Langmuir isotherm, Freundlich
isotherm, and selectivity coefficient approaches. The thermodynamic
parameters such as Gibbs free energy change, enthalpy change, and entropy
change were calculated. By comparison of the selectivity coefficients, the
affinity sequence to IR-120 is Cu(II)> Zn(II)> Cd(II). The activation energies
calculated from the rate coefficients at different temperatures were found to
be 15.41, 7.04 and 17.01 kJ mol 1 for Cu(II), Zn(II) and Cd(II) respectively.

Vinodh et al (2011) investigated on the separation of heavy metals

from water samples using anion exchange polymers by adsorption process.
Solutions with different concentrations of the heavy metals were prepared and
the efficiency of the ionomer in separation of the metals was evaluated by
adsorption technique. Quaternized poly styrene ethylene butylene poly
styrene (QAPSEBS) was used as the ionomer and it was prepared by two step
method, viz. chloro methylation and amination. The membrane was prepared
by solution casting method using an appropriate solvent. There are various
factors affecting the metal ion adsorption on the polymer membrane such as
metal ion concentration, pH, treatment time and temperature were studied.
From the results obtained, they reported that the percentage adsorption
increased with (a) increase in the metal ion concentration, (b) increase in the
treatment time up to 2h after which it levels off, (c) decrease in temperature
from 75- 35 °C.
 52

Rengaraj et al (2004) investigated the removal of Cu(II) from

aqueous solutions by using ion exchange resins 1200H and IRN97H at
different initial metal ion concentrations, contact time and pH in a batch
mode. The adsorption process, which is pH dependent, showed maximum
removal of Cu(II) in the pH range 2.0-7.0 for an initial Cu(II) concentration of
10 mg L 1. The experimental data have been analysed by using the
Freundlich, Langmuir, Redlich-Peterson, Temkin and Dubinin-Radushkevich
isotherm models. The batch sorption kinetics have been tested for a first-
order, pseudo-first order and pseudo-second order kinetic reaction models.
Results showed that the intra particle diffusion and initial sorption into resins
of Cu(II) in the ion exchange resins was the main rate limiting step.

Rengaraj et al (2007) investigated the adsorption characteristics of

Cu(II) onto ion exchange resins AMBERJET 1500H and AMBERSEP 252H
from waste waters. All the studies were conducted by a batch method to
determine equilibrium and kinetic studies at the solution pH of 5.8 in the
concentration ranges from 10 to 20 mg L 1. The experimental isotherm data
were analysed using the Freundlich, Langmuir, Redlich Perterson, Temkin,
Dubinin-Radushkevich equations. Based on the adsorption isotherm studies
the uptake capacity of Cu(II) on 1500H was found to be larger than that of
252H due to the intrinsic ion exchange capacity, while the adsorbate/
adsorbate interaction of 1500H was smaller than that of 252H. Kinetic studies
showed that the adsorption followed a pseudo-second-order reaction.

Priya et al (2009) reported the recovery and reuse of Ni(II) from

rinse water of electroplating industries using Amberlite IR 120 cation
exchange resin. The applicability of both the isotherm models to the Ni(II)-
cation-exchange resin system implied that both monolayer sorption and
heterogeneous surface conditions exit under the experimental conditions used.
 53

The sorption of Ni(II) ions on the resin is thus complex, involving more than
one mechanism. The maximum adsorption capacity, Q 0 (mg g 1), was found
to be 49.75.

Valverde et al (2001) studied the ion exchange equilibria of Cu(II),

Cd(II), Zn(II), and Na(I) on the cationic exchanger Amberlite IR-120. The
experimental equilibrium data have been satisfactorily correlated using the
homogeneous mass action law model (LAM). This model assumes non ideal
behaviour for both the solution and the solid phase. Wilson and Pitzer
equations have been used to calculate activity coefficients in the solid and
liquid phases, respectively.

Kim et al (2002) reported the simultaneous removal of heavy

metal-cyanide complexes by Ion Exchange Dowex1X8-50. Strong base anion
exchange resin beads were contacted with water containing heavy metal
(Cu(II), Cd(II), and Zn(II)) and cyanide ions in semi-fluidized and fluidized
beds. Compositions of the heavy metal-cyanide complexes formed for
different heavy metal and cyanide concentrations are used to explain the ion
exchange behaviour. Ion exchange equilibrium data of this study were fitted
well with the Langmuir isotherm. The ion exchange capacity of CN as metal
complexes increased to about three times that of free cyanide due to higher
selectivity of metal complexes on the anion exchange resin. The ion exchange
efficiency of the three heavy metal cyanide systems decreased as the
concentration ratio of cyanide and heavy metal increased. The regeneration
rates of the regenerants used was in the order of NaSCN>NaCN>NaOH, and
the regeneration rate of NaOH was substantially lower than other two.

Senthil kumar et al (2010) reported removal of Ni(II) from aqueous

solutions by Ceralite IR120 cationic exchange resins. Batch studies indicated
 54

that the percent adsorption decreased with increasing initial concentration of

Ni(II) and maximum removal was observed near a pH of 5.0. The monolayer
adsorption capacity was found to be 28.57 mg g 1. The sorption of Ni(II) on
the resin was rapid during the first 25 min. and the equilibrium was found to
be attained within 35 min. The maximum removal of Ni(II) was obtained in
the adsorbent dose of 20 g L 1.

Dave et al (2011) studied the removal of Ni(II) from electroplating

wastewater by weak basic chelating anion exchange resins: Dowex 50x4,
Dowex 50x2 and Dowex M-4195. Effect of initial metal ion concentration,
resin dose and pH on exchange capacities of ion exchange resins was studied
in a batch mode. The adsorption process, which is pH dependent, shows
maximum removal of Ni(II) in the pH range 4-6 for an initial Ni(II)
concentration of 05-30 mg L 1 and with resin dose 25-700 mg L 1. The uptake
capacity of Dowex 50x4 was found to be more than that of Dowex M-4195
due to the intrinsic exchange capacity.

The maximum adsorption capacity and some operational

parameters of ion exchange resin for the removal of heavy metals reported in
litreatures are summarized in Table 2.4. The removal of heavy metals using
different microbial species, agricultural wastes and other adsorbents reported
in the litreature are presented in Tables 2.5, 2.6 and 2.7 respectively.
 Table 2.4 Removal of heavy metals using Ion exchangers and their optimal operational conditions

Maximum Contact Initial

Metal ion adsorbent Optimum time Dosage concentration
S.No Adsorbent Reference
studied capacity, Qmax pH required (g/L) studied
(mg g 1) (min) (mg L 1)
1. Zeolite stuff Pb(II) 25.233 4.0–4.5 NA NA NA Ali and
Ni(II) 0.460 Bishtawi (1997)
2. Natural zeolites Cu(II) 141.12 6.0–7.0 330 10 100 - 400 Erdem et al
Co(II) 244.13 (2004)
Zn(II) 133.85
Mn(II) 76.78
3. Amberjet 1200H Cr(VI) 84.04 2.0-6.0 1440 NA 10 Rengaraj et al
Amberjet 1500H 188.67 2.0-6.0 (2003)
Amberlite IRN97H 58.17 2.0-6.0
4. Amberjet 1200 H Cu(II) 26.73 5.8 360 1 10 Rengaraj et al
Amberlite IRN97H 43.29 5.8 360 1 10 (2004)
5 Duolite GT-73 Cu(II) 122.25 4.8 90 2 NA Zacaria et al
Zn(II) 61.60 (2002)
Ni(II) 55.59
6 Amberlite IRC-718 Cu(II) 290.08 4.8 90 2 NA Zacaria et al
Zn(II) 127.00 (2002)
Ni(II) 156.96

55
 Table 2.4 (Continued)

Maximum Contact Initial

Metal ion adsorbent Optimum time Dosage concentration
S.No Adsorbent Reference
studied capacity, Qmax pH required (g/L) studied
(mg g 1) (min) (mg L 1)
7 Lewatit TP 207 Cu(II) 198.9 4.8 90 2 NA Zacaria et al
Zn(II) 85.09 (2002)
Ni(II) 89.60
8 Amberlite 200 Cu(II) 352.24 4.8 90 2 NA Zacaria et al
Zn(II) 88.90 (2002)
Ni(II) 85.60
9 Purolite C100 - MB Cu(II) 121.50 2.0-7.0 300 0.5 - 3.0 200 Hamdaoui
(2009)
10 Amberlite IR120 Ni(II) 46.75 5.8 NA NA NA Gomathi priya
et al (2009)
11 Aminophosphonate
resin Cu(II) 56.24 3.0 - 3.1 NA NA NA Kiefer et al
Purolite S 940 Ni(II) 53.41 4.0 - 4.2 (2001)
Zn(II) 53.62 3.2 -3.3
Cu(II) 75.31 2.8 - 2.9
Purolite S 950 Ni(II) 65.73 3.9 - 4.0
Zn(II) 66.37 3.0

56
 Table 2.5 Removal of heavy metals using microbial biomass and their optimal operational parameters

Metal ions Optimum Maximum adsorption

S.No Microorganism used References
removed pH capacity (Qmax) (mg g 1)
1 Aspergillus niger Cu(II) 4.0 – 5.0 28.7 Dursun (2006)
Pb(II) 32.6
2 Sargassum muticum Cd(II) 4.5 65.0 Lodeiro et al (2004)
3 Ulva reticulate Cu(II) 5.5 74.63 Vijayaraghavan et al (2004)
4 Chlorella vulgaris Ni(II) 4.5 63.25 Aksu (2002)
5 brown sea weeds Cu(II) 4.0 – 5.0 94 Yeoung - Sang et al (2001)
6 Ecklonia species Cu(II) 5.0 Not used Park et al ( 2005)
7 Aspergillus niger Cd(II) 5.0 26.72 Barros et al (2003)
8 Saccharomycescerevisiae , Cd(II) 5.0 35 Bashar et al (2003)
Kluyveromyces fragilis 40
9 Magnetically modified yeast cells Hg(II) 5.0 133.3 Handan Yavuz et al 2006
10 Sargassum wightii Ni(II) 81.2 Vijayaraghavan et al 2006
11 Baker’s yeast Zn(II) 7.0 3.39 Green-Ruiz (2008)
12 Baker’s yeast Ni(II) 6.75 3.73 Padmavathy (2008)
13 Cedar sawdust Cu(II) 5.0-6.0 0.59 Djeribi and Hamdaoui (2008)
14 Sargassum wightii Ni(II) 3.0 2.85 Vijayaraghavan et al (2006)
16 Bacillus –bacterial biomass Zn(II) 4.0 - 4.5 0.5 Ahluwalia and Goyal (2006)
Cu(II) 1.64
Ni(II) 0.4
17 Aspergillus species Ni(II) 7.0 Not used Congeevaram et al 2007
Cr(VI)

57
 Table 2.6 Removal of heavy metals using agricultural waste as adsorbent

Agricultural waste Metal ion Results Reference

Oriza sativa husk Pb(II) 98% Zulkali et al (2006)
Agricultural by product Humulus Pb(II) 75% Gardea-Torresdey et al (2002)
lupulus
Agro waste of black gram husk Pb(II) Upto93% Saeed et al (2005)
Rose biomass pretreated with Pb, Zn(II) 75% Nasir et al (2007)
NaOH
Rice bran Pb(II), Cd(II), Cu(II), Zn(II) >80.0% Montanher et al (2005)
Saw dust of Pinus sylvestris Pb(II), Cd(II) 96%, 98% Taty-Costodes et al (2003)
Maple saw dust Pb(II), Cu(II) 80–90% Yu et al (2001)
Waste tea leaves Pb(II), Fe(II), Zn(II), Ni(II) 92%, 84%, 73% Ahluwalia and Goyal (2005)
Activated carbon from coir pith Pb(II), Hg(II), Cd(II), Ni(II), Hg-100% Pb-100%,Cu- Kadirvelu et al (2001)
Cu(II) 73%, Ni-92%, Cd- !00%
PFP (petiolar felt sheath palm)- Pb(II), Cd(II), Cu(II), Zn(II), >70% Iqbal et al (2002)
peelings from trunk of palm tree Ni(II), Cr(VI) Pb > Cd > Cu > Zn > Ni
> Cr
Activated carbon of peanut shells Pb(II), Cd(II), Cu(II), Ni(II), Up to 75% Wilson et al (2006)
Zn(II)

58
 Table 2.7 Removal of heavy metals using various biosorbents

Absorption
S.No Biosorbent Metal ion Optimum pH References
capacity (mg/g)
1 Sour orange residue Cu(II) 9.52 4.5 Khoramaei et al (2007)
2 Sour orange residue (NaOH) Cu(II) 5.52 4.5
3 Living ureolytic mixed culture Ni(II) 1.55 6.0 Isik (2008)
4 Litter of poplar forest Cu(II) 6.14 4.5 Dundar et al (2008)
5 Pretreated aspergillus niger Cu(II) 5.35 5.5±0.5 Mukhopadhyay et al (2007)
6 Lentil shell Cu(II) 0.65 6.0 Aydin et al (2008)
7 Wheat shell Cu(II) 0.019 NA Aydin et al (2008)
8 Rice shell Cu(II) 0.108 NA Aydin et al (2008)
9 Protonated rice bran(using Ni(II) 2.64 6.0
Zafar et al (2007)
H3PO4)
10 Pretreated arca shell biomass Cu(II) 3.98 NA
Dahiya et al (2008)
11 Pretreated arca shell biomass Ni(II) 3.54 NA
12 Maizze husk(unmodified) Zn(II) 0.49 7.5 Igwe (2007)

59
 60

2.5.5 Nano Particles Impregnated Ion Exchange Resin (Hybrid

Technology)

Recently, some researchers reported that the surface of ion

exchange resin loaded with amorphous Fe-oxide nano particles and some
nano catalysts significantly improved the exchange capacity of parent resin.
The introduction of nano clusters, nano particle into the resin matrix for the
improved removal of heavy metals becomes more interesting topic nowadays.
The porous resin impregnated with nano particles offered many advantages
over the other sorbents, due to characteristics of the solid phase. These
advantages include, selectivity, mechanical stability, size controllable nano
particles, easy regeneration for multiple sorption-desorption cycles and good
reproducibility of the sorption characteristics (Uzun et al 2001). The sorption
of precious metals on a macro porous resin impregnated with magnetite nano
particles (Rabelo et al 2001), Amberlite XAD-4 modified with non ionic
surfactant– trioctylamine (TOA) (Saitoh et al 2007), D001 impregnated with
PEI (Chen et al 2010), Amberlite-200 composite with PEI, TBAI, TMAH
solutions (Amara et al 2003) has been reported.

Among these Polyethyleneimine (PEI) is a polymeric nano cluster

used for a wide variety of applications. These include electrochemical
biosensors, cell flocculating agents, permeabilization of bacterial cell walls,
retention of nicotinamide adenine dinucleotide (NADH) in membrane
reactors, adsorption of biomass, and microencapsulation of silicone oils. The
immobilization of PEI in a suitable matrix can provide an attractive
alternative to membrane processes. Chanda and Rempel (1997) applied PEI-
containing granular sorbents for the selective removal of Cr(III) in a mixture
of Cr(III), Cu(II), Ni(II), and Fe(III). This sorbent was found to be superior to
the commercial resin Chelex-100.
 61

Sheha and El-Zahhar (2008) synthesized some ferromagnetic

composite resins (R1 and R2) and studied removal of Cr(VI) at different pH,
equilibrium time, initial concentrations and temperature. They observed the
sorption process was very fast at the initial stage and maximum sorption was
achieved within 3h and pH of 5.1. The kinetic of the system has been
evaluated with pseudo first order model, second order model, Elovich model,
intra-particle diffusion model and liquid film diffusion model. Chromium
interaction with composite particles followed second-order kinetics with a
correlation coefficient extremely high and closer to unity and rate constant
4 4
(ks) values 1.68×10 and 1.9×10 g (mg 1min 1) for R1 and R2, respectively.
The value of equilibrium sorption capacity (qe) was consistent with the
modelled data and in the range 893–951 mg g 1. The sorption data gave good
fits with Temkin and Flory–Huggins isotherm models. The isotherm
1
parameters related to the heat of sorption was in the range 8-16 kJ mol
which was the range of bonding energy for ion exchange interactions and
suggest an ion exchange mechanism for removal of Cr(VI) by the composite
sorbents.

Saitoh et al (2007) prepared trioctylamine impregnated polystyrene

divinyl benzene for the removal of heavy metal cations Au(III), Pt(II), and
Pd(II) from water. A water-insoluble extracting solvent, trioctylamine (TOA)
was solubilized in the aqueous micellar solution of a polyoxyethylene-type
non-ionic surfactant, polyethylene glycol (10)-mono-4-nonylphenyl ether
(PONPE-10). By mixing the solution and a polystyrene–divinylbenzene
porous resin (Amberlite XAD-4), TOA was successfully impregnated into the
resin. Au (III), Pt (II), and Pd (II) were well extracted from hydrochloric acid
to the TOA-impregnated resins. The extents of the extraction of Pt(II) and
Pd(II) increased with increasing the amount of TOA impregnated.

Dev et al (1999) studied the Sorption behaviour of lanthanum (III),

neodymium(III), terbium(III), thorium(IV) and uranium(VI) on Amberlite
 62

XAD-4 resin functionalized with bicine ligands. The complexing properties of

a chelating resin, containing bicine ligands, were investigated for La(III),
Nd(III), Tb(III), Th(IV) and U(VI). Trace amounts of these metal ions were
quantitatively retained on the resin and recovered by eluting with 1M HCl.
The capacity of the resin for La(III), Nd(III), Tb(III), Th(IV) and U(VI) was
found to be 0.35, 0.40, 0.42, 0.25 and 0.38 mmol g 1, respectively. Separation
of U(VI) and Th(IV) from Ni(II), Zn(II), Co(II) and Cu(II) in a synthetic
solution was carried out. The resin can be applied over a wide pH range
(4.5–9.0) for collection of trace metals. The resin shows selectivity for these
metal ions over some transition metal ions and permits their separation from
the latter. The capacity of the resin is sufficiently high to pre concentrate more
than one metal ion simultaneously.

Tokalioglu et al (2006) studied the preconcentration of trace

elements by using 1-(2-pyridylazo)-2-naphthol functionalized Amberlite
XAD-1180 Resin. The proposed preconcentration method consists of a simple
and low cost procedure which permits the quantitative recovery of the
elements Mn(II), Fe(III), Ni(II), Cu(II), Cd(II), and Pb(II) from waters, except
for Cr(III) and the certified reference sediment sample (except for Cr(III) and
Mn(II)). Owing to the synthesized chelating resin having high affinity for the
metal ions, the selective determination of the metal ions is possible. The
recovery values for all the elements except for Cr(III) were found to be 92%
and the relative standard deviation was 8.5%. The LODs for Cr(III), Mn(II),
Fe(III), Ni(II), Cu(II), Cd(II) and Pb(II) were found to be 4.1, 0.13, 2.7, 1.2,
0.19, 0.06, and 0.13 g L 1, respectively. The method has an enrichment
factor of 100 for Cu(II), Ni(II), Fe(III) and Pb(II), 80 for Cr(III), 150 for
Cd(II) and Mn(II).

Mourad and Hacene (2003) modified the cation exchange resin

Amberlite 200 properties by impregnating Polyethyleneimine solution. The
 63

modified resin was applied for the removal of Cu(II), Li(I), K(I), Cd(II),
Ag(II) and Fe(III) ions from waste waters. The modification of the surface of
the resin deals with a change in the order of the affinities of the resins towards
cations. The conditions of modification (pH, PEI concentration and time of
immersion) have been examined and the modification was confirmed by the
determination of the exchange capacities, the distribution coefficient (P) and
the selectivity factors (S). The obtained results revealed the effect of PEI on
the exchange properties of the resin. The pH range selected (6.0-8.0)
permitted a good adherence of PEI onto the resin surface. The quantity of the
adsorbed PEI was increased by raising the initial concentration and the
immersion period. The exchange capacity for Cu(II) passed from 2.6 mmol g
1
, in the case of unmodified resin, to 3.9 mmol g 1 for the modified one.

Amara and Kerdjoudj (2004) studied the separation and recovery of

heavy metals using a cation-exchange resin in the presence of organic macro-
cations. Commercial polymer cation-exchange resins investigated for the
separation and recovery of Cu(II) and Ag(I) from synthetic solutions. They
contain various ionic species after modification of the cation-exchange resin
properties by fixation of organic macro-cations under different experimental
conditions. The modification was carried out by impregnation of the resin
under different conditions (time of immersion, concentration, pH) into
solutions containing tetramethylammonium, tetrabutylammonium and
polyethyleneimine. The selectivity coefficient and the capacity of the resin for
the ions Li(I), K(I), Fe(III), Cu(II), Ag(I) and Cd(II) in batch operations were
determined and the kinetics of metal adsorption by both the modified and the
unmodified resin was also studied. After the adsorption of the organic macro-
cation, ion-exchange capacity was varied and the rate of the ion-exchange
reaction of monovalent ions became slow, though exchange capacity for
Cu(II) ions increased when the cation-exchange resin was modified in
polyethyleneimine solution.
 64

Khan et al (2009) Amberlite IR-400 was chemically modified using

Titan Yellow as a chelating agent. Adsorption studies such as effect of
concentration, pH, time and temperature on the resin studied and distribution
coefficient of metal ions in varied solvent systems was explored. On the basis
of Kd values, important binary as well as ternary separations viz. Mn2+-Hg2+,
Zn2+-Hg2+, Mg2+-Bi3+, Cu2+-Hg2+, Pb2+-Sn4+, Pb2+-Bi3+&Cd2+-Hg2+, Ca2+-
Hg2+-Zr4+, Cd2+-Hg2+-Co2+,Ni2+- Hg2+-Co2+,Pb2+-Hg2+-Co2+ and Ce3+-Hg2+-
Co2+ was achieved on columns of Titan Yellow modified Amberlite IR-400
resin. In order to check the selectivity and reproducibility of the method,
different amounts of Hg2+ was loaded in synthetic mixtures containing
(Mg2+=2.43mg), (Ca2+=4.01mg), (Ba2+=13.74 mg), (Sr2+ =8.76 mg), (Pb2+=
20.72 mg), (Zn2+= 16.54 mg), (Cd2+=11.24 mg). This material can be utilized
for the removal and isolation of Hg2+ from waste water produced from
industrial units.

Chanda and Rempel (2001) prepared a new method of gel-coating

Polyethyleneimine (PEI) on organic resin beads and studied its applicability
of Uranium ion removal.

2.6 PACKED BED COLUMN ADSORPTION

The batch experiments are useful in understanding fundamental

information regarding the application of sorbent and the factors influencing
the process. However, they do not give accurate scale-up data for industrial
treatment systems where a continuous flow system is normally employed
(Wong et al 2003). In process applications, a packed bed column is an
effective for cyclic adsorption/desorption, as it makes the best use of the
concentration difference driving force for heavy metal adsorption (Kratochvil
et al 1997) and allows more efficient utilization of the sorbent capacity and
result in a better quality of the effluent (Volskey and Prasetyo 1994).
 65

Hamdaoui (2009) studied the dynamic removal of Cu(II) from

aqueous phase using Purolite C100-MB cation exchange resin in a packed
column at different flow rate and bed height. To predict the breakthrough
curves and to determine the characteristic parameters of the column useful for
process design Bohart–Adams, Bed Depth Service Time (BDST), Clark and
Wolborska models are applied to experimental data. All models are found
suitable for describing the whole or a definite part of the dynamic behaviour
of the column with respect to flow rate and bed height. The simulation of the
whole breakthrough curve is effective with the Bohart–Adams and the Clark
models, but the Bohart–Adams model is better. The breakthrough is best
predicted by the Wolborska model.

Wojtowicz and Stoklosa (2002) studied the removal of heavy

metals by Smectite Ion-Exchange column for the removal of Zn(II), Cd(II),
Pb(II) ions from waste waters. The effect of ion exchange Zn(II), Cd(II),
Pb(II) from model solutions prepared out of nitrate salts of these metals was
examined under dynamic conditions. The efficiency of ion-exchange column
with Smectite bed was determined by measuring in the column efflux till the
moment when the concentration of metals in efflux is equal to concentration
in influx. The ion-exchanging column was determined by stating the
following parameters: sorption capacity of exchanger, volume of solution till
the moment of column breakthrough (Vmax) and column dynamics, which
means the relative concentration of metal ions C/C0 in the efflux as a function
of efflux volume. Out of the model waste water containing three heavy
metals, the best eliminated is Pb(II) and subsequently Zn(II).

Bai and Bartkiewicz (2009) studied the removal of Cd(II) from

wastewater using ion exchange resin Amberjet 1200H in a packed column.
Ion exchange resin 1200H has been identified as a potentially efficient
material for use in the treatment of water contaminated with select heavy
 66

metals. Heavy metals removal by ion exchange worked effectively in a pH

range of 4.0-7.0.

Juang et al (2003) reported the removal of equimolar metal ions

(Co(II), Ni(II), Mn(II), Sr(II)) from aqueous solutions using a strong-acid
resin in a fixed bed column. The solution contained water-soluble complexing
agents including ethylene diamine tetra acetic acid, nitrilo triacetic acid, and
citric acid. Experiments were performed under different solution pH and
molar concentration ratios of complexing agent to the total metals. It was
found from batch studies that the equilibrium exchange of metals and the
resin mainly depended on solution pH, and partly on the type of complexing
agent used. A mass transfer model was proposed to describe the breakthrough
curves of the resin bed and the calculated breakthrough curves agreed well
with the measured ones with a standard deviation <6%. In fixed bed tests at
pH 2, the type of complexing agent had little effect on the breakthrough data.
For a given complexing agent, the metal with a larger overall formation
constant (kf) showed a smaller exchange capacity.

Popuri et al (2009) studied the adsorptive removal of Cu(II) and

Ni(II) from water using chitosan coated PVC beads in column contactors. For
this a new biosorbent was developed by coating chitosan, a naturally and
abundantly available biopolymer, on to polyvinyl chloride (PVC) beads and
packed in a column of desired dimension. The breakthrough curves were
obtained from column flow experiments. The experimental results
demonstrated that chitosan coated PVC beads could be used for the removal
of Cu(II) and Ni(II) ions from aqueous medium through adsorption.

Sousa et al (2010) used green coconut shells as adsorbent for

removal of toxic metal ions in a fixed-bed column. The results show that a
1
flow rate of 2 mL min and a based height of 10cm are most efficient. The
 67

breakthrough curves for multiple elements gave the order of adsorption

capacity: Cu(II)> Pb (II)> Cd (II)> Zn(II)> Ni(II). Real samples arising from
the electroplating industry was efficiently handled.

The experimental operating parameters which influence the mass

transfer process in the packed bed column study are flow rate, bed height and
initial concentration of metal ions etc. has been studied by various authors.

Yahaya et al (2011) studied the adsorption potential of rice husk

based Activated carbon (RHAC) to remove Cu(II) from aqueous solution in
a fixed-bed adsorption column. The effects of inlet Cu(II) concentration
(5-15 mg L 1), feed flow rate (10-30 mL min 1) and RHAC bed height
(30-80 mm) on the breakthrough characteristics of the adsorption system were
1
determined. The highest bed capacity of 34.56 mg g was obtained using
10 mg L 1 inlet Cu(II) concentration, 80 mm bed height and 10 mL min 1 flow
rate. The adsorption data were fitted to three well-established fixed-bed
adsorption models namely, Adam- Bohart, Thomas and Yoon-Nelson models.
The results fitted well to the Thomas and Yoon-Nelson models with
correlation coefficient of R2 0.96.

Vijayaraghavan et al (2005a) studied the biosorption of Co(II) and

Ni(II) by Sargassum wightii seaweeds: batch and column studies. Six species
of green, brown and red seaweed were compared for their biosorption abilities
in the uptake of Co(II) and Ni(II) from aqueous solutions containing
1
100 mg L initial metal concentrations. Batch experiments showed that the
pH influenced the metal uptake of all seaweeds examined. In general, brown
seaweeds were performed well with Sargassum wightii outperformed all
seaweeds with an uptake of 20.63 mg Co(II)/g at pH 4.5 and 18.58 mg
Ni(II)/g at pH 4.0. Batch desorption and regeneration experiment revealed
that 0.1M CaCl2 (in HCl) performed well in eluting Co(II) and Ni(II) and
 68

caused least damage to S. wightii biomass. The ability of S. wightii to biosorb

Co(II) and Ni(II) in a packed column was investigated as well. The design
parameters such as bed height and flow rate affected the biosorption
characteristics of the biomass.

Lodeiro et al (2006) studied the protonated Sargassum muticum

seaweed as a possible biosorbent for Cd (II) removal in a fixed-bed column.
The experiments were conducted in order to determine the effect of flow rate
(0.42, 5, 10 and 20 mL min 1) and bed height (0.6 and 15.3 cm for the lowest
flow rate or 7.4, 13.0 and 16.6 cm for the others) on breakthrough curves
behaviour. The determined breakthrough and exhaustion times increased with
the diminution in flow rate and with the increase in bed height. The bed depth
service time (BDST) model was applied to analyse experimental data,
determining the characteristic process parameters. The optimal lowest sorbent
usage rate was evaluated at 2 min contact time and the minimum bed height
values necessary to prevent the effluent solution concentration from
exceeding 0.02 mg L 1 at zero time were 5.3, 6.9 and 7.5 cm for flow rates of
5, 10 and 20 mL min 1, respectively. Several empirical models proposed in
the litreature (Bohart–Adams, Yan, Belter and Chu models) were investigated
in order to obtain the best fit of column data, describing in a simple manner
the breakthrough curves.

Vijayaraghavan et al (2005b) investigated the biosorption of Cu(II),

Co (II) and Ni(II) by marine green alga Ulva reticulata in a packed bed up-
flow column. Experiments were conducted to study the effect of important
design parameters such as bed height and flow rate. At a bed height of 25 cm,
the metal-uptake capacity of U. reticulata for Cu(II), Co (II) and Ni(II) was
found to be 56.3 ± 0.24, 46.1 ± 0.07 and 46.5 ± 0.08 mg g 1, respectively. The
column regeneration studies were carried out for three sorption–desorption
cycles. The elutant used for the regeneration of the biosorbent was 0.1 M
 69

CaCl2 at pH 3 adjusted using HCl. For all the metal ions, a decreased
breakthrough time and an increased exhaustion time were observed as the
regeneration cycles progressed, which also resulted in a broadened mass
transfer zone. The pH variations during both sorption and desorption process
have been reported.

2.7 ELECTROCHEMICAL METHODS

Electrochemical technology contributes in many ways to a cleaner

environment and covers a very broad range of technology. During the last two
decades, a special research field, viz. environmental electrochemistry has
been developed. Environmental electrochemistry (Rajeshwar and Ibanez
1997; Genders 1992; Pletcher and Walsh 1993) involves electrochemical
techniques or methods to remove impurities from gases, liquids and soil to
prevent or minimise environmental pollution. The best way to attack the
problems is at their source, viz. mainly processes in the chemical and related
industries. Environmental electrochemistry can give a great deal in reaching
this goal. Especially, the purification of dilute heavy metal process
liquids/recovery of the metal ions has been investigated. Moreover, the
simultaneous removal of COD in short period can be achieved only by means
of the electrochemical techniques. Removal/recovery and destruction of
pollutant species can be carried out directly or indirectly by electrochemical
oxidation: reduction processes in an electrochemical cell without continuous
feed of redox chemicals. In addition, the high selectivity of many
electrochemical processes helps to prevent the production of unwanted by-
products, which in many cases have to be treated as waste.

Recently the three electrochemical technologies namely

Electrooxidation (EO), Electrocoagulation (EC) and Electrodialysis (ED) are
widely used for the PCBs degradation, in situ chlorine production, ozone
 70

generation, destruction of cyanides and nitrites, purification of waste water

were possible by combination of electrochemcical methods.

Dermentzis et al (2010) studied the removal of Ni(II), Cu(II), Zn(II)

and Cr(VI) from synthetic and industrial wastewater by electrocoagulation.
Parameters affecting the electrocoagulation process, such as initial pH,
current density, initial metal ion concentration, COD and contact time were
investigated. Best removal capacity for all studied metals was achieved in the
pH range 4.0-8.0. Mixed solutions containing the same concentrations of all
1
metals i.e. 75, 150 and 300 mg L were tested. Ni(II), Cu(II) and Zn(II)
showed similar removal rates. They were completely removed in 20, 40 and
50 minutes respectively, while for the corresponding complete removal of
Cr(VI) 40, 60 and 80 minutes were needed. Increased current density
accelerated the electrocoagulation process, however, on cost of higher energy
consumption. Results revealed that best removal was achieved at a current
density of 40 mA cm 2. The electrocoagulation process was successfully
applied to the treatment of an electroplating wastewater sample, where the
concentrations of Ni(II), Cu(II), Zn(II), Cr(VI) and COD were effectively
reduced under the admissible limits in 60 min. Consequently, the
electrocoagulation process is a reliable, safe and cost effective method for
removing heavy metals and COD from water and wastewater.

Vasudevan et al (2010) studied the electrochemical coagulation for

Cr(VI) removal process optimization and predicted the kinetics, isotherms and
sludge characterization. The effects of pH, current density, concentration,
temperature, adsorption kinetics and adsorption isotherms on chromium
removal were investigated. The results showed that an optimum removal
efficiency of 98.6% was achieved at a current density of 0.2 A dm 2 and a pH
of 7.0. The adsorption kinetics showed that the first order rate expression
fitted the adsorption kinetics. The equilibrium isotherm was measured
 71

experimentally. Results were analysed by Langmuir, Freundlich, Dubinin-

Redushkevich and Frumkin isotherms using linearized correlation
coefficients.

Szpyrkowicz et al (2000) tried the Cu(II) Electrodeposition and

oxidation of complex cyanide from wastewater in an electrochemical reactor
with a Ti/Pt Anode. Both a direct Electrooxidation process and an indirect
electrooxidation in a chloride-rich medium proved feasible, with direct
electrooxidation being preferable because of the lower energy consumption.
The results showed that the process of the direct electrooxidation under
alkaline conditions lead to the formation of an electro catalytic film on the
anode. Simultaneous Cu(II) Electrodeposition on the cathode was feasible and
economically convenient, particularly if conducted at pH 13 or higher. The
process can be described by the pseudo-first-order kinetics, with the rate
constant for Cu(II) removal equal to 0.013 h-1 for very alkaline conditions.
Energy consumed for Cu(II) Electrodeposition proved to be inversely
proportional to the initial Cu(II) concentration. For wastewater bearing 1100
mg dm-3 Cu(II), 5.46 kWh is needed to eliminate 1 kg of metal. The current
efficiency for chemical oxygen demand removal reaching 100% or higher was
obtained, indicating reactions other than electrooxidation occurring
simultaneously. Under the best conditions, the total cyanide concentration
was lowered from 250 to 7.9 mg dm-3.

Bonev and Nenov (2006) reported the recovery of Cu(II) from acid
mine waste water. Two membranes, the ED membranes -40 (anion
exchange membrane) and -40 (cation exchange membrane) were utilized.
The results obtained show that a partial separation of Sulphuric acid is
achievable at low time of recirculation. At time of recirculation 4hr the Cu(II)
concentration in concentration compartment is around 25 mg L 1, while the
Sulphuric acid concentration is 15 g L 1. At higher extent of Sulphuric acid
 72

transfer into the concentration compartment, the selectivity of membranes

towards heavy metals is not satisfactory;

Hunsom et al (2005) carried out the electrochemical treatment of

heavy metals (Cu(II), Cr(VI), Ni(II)) from industrial effluent and modelling of
Cu(II) reduction. The experiments were performed in a membrane reactor
having a capacity of 1L. Stainless steel sheets with surface area of 0.011m2
and titanium coated with ruthenium oxide were used as cathode and anode,
respectively. The electrolyte was circulated at a constant flow rate (0.42 L
min 1) and the pH was kept constant at 1.0. Applied current densities were 10
and 90 Am 2. According to the experiment, it was found that a membrane
reactor with plane electrode was capable for treating plating wastewater with
low energy consumption (42.30 kWh kg 1 metal) and low operating cost (5.43
US$/m3). More than 99% of metal reduction was achieved and the final
concentrations of Cu(II), Cr(VI) and Ni(II) in treated water were 0.10-0.13,
0.19-0.20 and 0.05-0.13 mg L 1, respectively. The brightener had no effect on
Cu(II) reduction whereas Cr(VI) had strong effect. The kinetic of Cu(II)
reduction in the presence of Cr(VI) was modelled as a two-step process with
respect to Cu(II) concentration.

Ahmed Basha et al (2011) studied the removal of heavy metals

from Cu(II) smelting effluent using electrochemical filter press cells. The
performance of electrochemical filter-press cells, operated in a batch
recirculation mode, for the removal of heavy metals from Cu(II) smelting
effluent was investigated. The effect of flow rates (26, 35, 46, 53 and 61 mL
min 1) and current density (1, 2 and 3 A dm 2) on percentage removal of
heavy metals and energy consumptions were studied. Significant removal of
heavy metals (more than 99%) and the specific energy consumption of 15.24
kWh kg 1 have been achieved for the current density of 2 A dm 2 and the flow
rate of 61 mL min 1. In the present work, the removal of arsenic by
 73

electrochemical ion exchange technique was also studied. The operating

parameters of 12.5 V and a circulation rate of 10.7 mL min 1, has been
observed better results in the removal of arsenate/arsenite ions from
the effluent (more than 99%) with a specific energy consumption of
152.22 kWh kg 1.

There are several operating parameters which effects the removal

efficiency of electrochemical processes thus includes, influence of applied
current density, flow rate, initial metal ion concentration and pH.

Prabhakaran et al (2009a) studied Mediated electrochemical

oxidation process for destruction of TOC in a batch recirculation reactor.
Influence of anode material, influence of flow rate and influence of current
densities on the removal efficiency of TOC by the electrooxidation process
was studied by the author and reported. Investigation was carried out using
the traditional noble metal oxide coated anode, RuO2/Ti and the mediator
used for the experiment was FeSO4, with NaCl as supporting electrolyte. The
concentration of NaCl was maintained at 5, 8, 12 g L 1. The experiment was
carried out in batch recirculation reactor with current densities 1.25, 2.50,
2
3.75, 5.00, 6.25, 7.50, 8.75, 10.00 A dm for various flow rates 20, 40, 60,
80, 100 L h 1. The study highlighted that in batch reactor set up the best effect
2
of TOC reduction was found to occur at 3.75 A dm with flow rate of 20 L
h 1. The simulated studies were carried out for different volumes of effluent
and current densities.

Prabhakaran et al (2009b) reported the treatability of resin effluents

by electrochemical oxidation using batch recirculation reactor. Influence of
anode material, influence of flow rate and influence of current densities on the
removal efficiency of organic wastes by the Electrooxidation process was
studied by the author and reported. Investigation was carried out using the
 74

traditional noble metal oxide coated anode, ruthenium oxide-titanium and the
mediator used for the experiment was ferrous sulphate, with sodium chloride
as supporting electrolyte. The concentration of sodium chloride was
maintained at 5, 8, 12 g L 1. The experiment was carried out in batch
recirculation reactor with varied current densities for various flow rates.
The study highlighted that in batch reactor set up the best effect of total
organic content reduction was found to occur at 3.75 A dm 2 with flow rate of
20 L h 1. The simulated studies were carried out for different volumes of
effluent and current densities.

Adhoum et al (2004) studied the treatment of electroplating

wastewater containing Cu(II), Zn(II) and Cr(VI) by electrocoagulation. The
performance of electrocoagulation, with aluminium sacrificial anode, in the
treatment of metal ions (Cu(II), Zn(II) and Cr(VI)) containing wastewater, has
been investigated. Several parameters, such as pH, current density and metal
ion concentrations were studied in an attempt to achieve a higher removal
capacity. Results obtained with synthetic wastewater revealed that the most
effective removal capacities of studied metals could be achieved when the pH
was kept between 4 and 8. In addition, the increase of current density, in the
range 0.8-4.8 A dm 2, enhanced the treatment rate without affecting the
charge loading, required to reduce metal ion concentrations under the
admissible legal levels. The removal rates of Cu(II) and Zn(II) were found to
be five times quicker than Cr(VI) because of a difference in the removal
mechanisms. The process was successfully applied to the treatment of an
electroplating wastewater where an effective reduction of (Cu(II), Zn(II) and
Cr(VI)) concentrations under legal limits was obtained, just after 20 min.
1
The electrode and electricity consumptions were found to be 1 g L and
32 A h L 1, respectively. The method was found to be highly efficient and
relatively fast compared to conventional existing techniques.
 75

Kusakabe et al (1986) investigated the simultaneous removal of

Cu(II) ions and COD causing chelating agents from the wastewater by packed
bed electrode cell. The cathode packing was either graphite particles or
graphite felt; the anode packing was either platinum-plated titanium pellets/ß-
PbO2 particles or oxidized lead spheres used. Electro winning of Cu(II) and
the removal of COD were simultaneously achieved in the cathodic and anodic
chamber, respectively. As cathode packing, the graphite felt was superior to
the pulverized graphite particles because of the large surface area of the felt.
The Pt-Ti pellets and the -PbO2 particles were comparable as anodic packing
in their suitability for COD removal.

2.8 COMBINATION OF METHODS (HYBRID TECHNOLOGY)

In recent years combination of two or more treatment techniques

shows better performance than the individual. Hence, the number of
researchers focussed on the hybrid technology. In hybrid technology the
necessary solution for problems in lab scale and industrial scale could be
achieved.

Papadopoulos et al 2004 studied the possibility of ion exchange

process individually as well as in combination with the precipitation process
for the removal of Ni(II) in a wastewater stream originating from a rinse bath
of aluminium parts after sealing in the anodizing process of a metal surface
treatment industry. They reported that the individual application of the ion
exchange led to removal of Ni(II) up to 74.8% as well as the metal uptake
rates were higher in the first stage of the process. They happened to found that
higher removal of Ni(II) concentrations by using the combination of ion
exchange and precipitation processes (from 94.2 to 98.3%).

Combination of electro dialysis and ion exchange for removal of

metal ions from solution has received great attention. This method was first
 76

presented at the Achema Fair in Frankfurt, Germany, in 1994 and has been
developed at the research centre Julich for the prediction of ion exchange and
electrochemical regeneration of ion exchangers in ultra pure water production.
The combined technique was investigated for the case of Ni(II) and the
migration rate of ions in the resin bed was shown to depend strongly on the
resin flexibility and on the intensity of the electrical field, as expected.

Doan and Saidi (2008) reported the simultaneous removal of metal

ions and linear alkyl benzene sulfonate by combined electrochemical and
Photocatalytic process. Combined electrochemical removal of Zn(II) and
Ni(II) and photo-oxidation of linear alkyl benzene sulfonate (LAS) by
suspended TiO2 particles was investigated. The effect of different process
variables such as current density, pH and liquid flow rate on the sole
electrochemical reduction of metal ions was also evaluated. At pH of 5.0, the
removal of Zn(II) increased by 28% with increases in the liquid flux from
0.0021 to 0.0172m3 m 2
s 1
while the removal of Ni(II) was only enhanced
marginally. Under optimum operating conditions used in the present study
(liquid flux = 0.0172m3 m 2 s 1, current density = 0.166mAcm 2, pH 5.0 and
in the presence of LAS), Zn(II) and Ni(II) were reduced by 86 and 56%,
respectively, over 7h of the sole electrochemical treatment. For the sole
Photocatalytic treatment of LAS at pH of 5.0, a 60% LAS degradation was
obtained. However, the liquid flow rate did not have any considerable effect
on the LAS oxidation. Finally, they achieved in the combined Photocatalytic–
electrolytic process, the LAS degradation increased to 76%. Nonetheless, in
the combined system the Zn(II) and Ni(II) removal remained at comparable
levels to those obtained in the sole electrochemical system.

Feng et al (2007) studied the removal of metal ions from

electroplating effluent by EDI process and recycle of purified water. The
operational parameters that influenced the electro-regeneration of cation
exchange resins loaded with Ni(II) were optimized, and the result showed that
 77

addition of a small amount of Na2SO4 into the electrode solution, moderate

increase of applied voltage and initial metal ion concentration could get better
regeneration effect. A steady and continuous process of electroplating
wastewater treatment could be achieved with current efficiency of 33-38%,
removal efficiency of at least 99.8% and enrichment factor of 22-36.
Concentration of metal ions in purified water was 0.03-0.09 mgL 1 for Ni(II),
1 1 1
0.07-0.10 mgL for Cu(II), 0.06-0.1 mgL for Zn(II), 0.07-0.10 mgL for
1
Cd(II) and 0.08-0.17 mgL for Cr(VI), respectively. This demonstrated the
applicability of recovering heavy metals and purified water from
electroplating effluent for industrial reuse.

Cabuk et al (2006) investigated the biosorption characteristics of

Bacillus sp. ATS-2 immobilized in silica gel for removal of Pb(II) in column
mode of operation. The column performance of immobilized biosorbent was
investigated with the various bed lengths at a constant flow rate (180 mL h 1)
and 100 mg L 1of inlet Pb(II) ion concentration. Maximum value of column
capacity (Ci, ) of silica gel-immobilized Bacillus sp. ATS-2 for Pb(II)
max

sorption was obtained at a bed length of 10 cm. The biosorption yields of

Pb(II) ions decreased with a decrease in the bed length from 10 to 3 cm.

They also reported the effect of inlet Pb(II) ion concentration for
the concentration range of 25-300 mg L 1. The Pb(II) biosorption capacity
and Ci, max of the immobilized biomass first increased with increasing of
the initial concentration of Pb (II) and then reached a saturation value at
1
200 mg L of Pb(II) concentration. The maximum biosorption yields for
1
silica gel immobilized Bacillus sp. ATS-2 at 25 and 50 mg L of initial Pb
(II) concentration were determined as 91.72 and 91.73%, respectively.

Cabuk et al (2006) also reported the effect of flow rate on the

1
removal of Pb(II) ions for the concentration of Pb(II) ion (100 mg L at
 78

initial pH 4.0) and bed length (10 cm) were kept constant, flow rates were
changed from 60 to 300 mL h 1. The decrease in the flow rate of the column
resulted in an increase in the biosorption yield. The higher yield values were
obtained at flow rates of 60 and 180 mL h 1. C i,max values were increased with
1 1
flow rates up to 300 mL h but decreased at 300 mL h of flow rate. This
could be attributed to metal solution leaved the column before the biosorption
equilibrium attained when the flow rate increased.

Smara et al (2005) studied the electroextraction of heavy metals

(Pb(II), Cu(II), Zn(II) and Cd(II)) from diluted solutions was achieved by
continuous electro permutation combining ion-exchange resins and
membranes. Experimental parameters such as current density, flow rate,
initial concentration of metal ions, receiver compartment solution type and
influence of regenerating acid in the catholyte have been studied and reported
by the author. The operations were performed under various experimental
conditions of current density (2.0-7.0 Am 2), flow rate (0.09-0.9 dm3 h 1),
cation concentration (40-400 mg dm 3) and nature of regenerating acid
solutions (HNO3, HCl, H2SO4). Despite the resins were loaded with the
metallic cations before introducing in the feed compartment of the cell, high
levels of removal (up to 99%) were achieved. High mass transfer was
obtained leading to a concentration factor of about five in the receiver.

2.9 CONVENTIONAL METHODS AVAILABLE FOR HEAVY

METAL REMOVAL

Researchers have developed numerous methods for the removal of

heavy metals from wastewaters including precipitation, adsorption, ion
exchange, membrane processes, electrochemical techniques and filtration
techniques.
 79

2.9.1 Precipitation

Chemical precipitation is the most widely used for heavy metal

removal from inorganic effluent. It depends on the solubility product Ksp of
the metal involved, pH of the wastewater and concentration of metal ions and
relevant anions. Adjustment of pH to the basic conditions (pH 9-11) is the
major parameter that significantly improves heavy metal removal by chemical
precipitation. Lime and limestone are the most commonly employed
precipitant agents due to their availability and low cost in most countries
(Mirbagherp and Hosseini 2004; Aziz et al 2008). Lime precipitation can be
employed to effectively treat inorganic effluent with a metal concentration of
higher than 1000 mg L 1. Other advantages of using lime precipitation include
the simplicity of the process, inexpensive equipment requirement, and
convenient and safe operations.

However, chemical precipitation requires a large amount of

chemicals to reduce metals to an acceptable level for discharge. Other
drawbacks are its excessive sludge production that requires further treatment,
slow metal precipitation, poor settling, the aggregation of metal precipitates,
and the long term environmental impacts of sludge disposal (Aziz et al 2008;
Fabiani 1997).

2.9.2 Coagulation–Flocculation

Heavy metals present the wastewater can by removed by

coagulation - flocculation techniques. The principle behind the coagulation
process is complexing of heavy metals by adding suitable coagulants
(Shammas et al 2004). To increase the particle size of the coagulated heavy
metals flocculation of the unstable particles into bulky floccules has been
carried out followed by coagulation (Semerjian and Ayoub 2003). The
 80

general approach for this technique includes pH adjustment, addition of

ferric/alum salts as the coagulant (Licsko et al 1997) and flocculation.

In spite of its advantages, coagulation-flocculation has limitations

such as high operational cost due to chemical consumption. The increased
volume of sludge generated from coagulation - flocculation may hinder its
adoption as a global strategy for wastewater treatment. This can be attributed
to the fact that the toxic sludge must be converted into a stabilized product to
prevent heavy metals from leaking into the environment (Ayoub et al 2001).

Li et al (2003) removed the Cu(II) ions from wastewater using

Poly-ferric sulphate and Poly-acryl amide as coagulants for a dosage of
5g L 1.

2.9.3 Biological Methods

The search for new technologies for the removal of toxic heavy
metal ions from wastewaters has directed attention to biosorption, based on
metal binding capacities of various biological materials. Biosorption can be
defined as the ability of biological materials to accumulate heavy metals from
wastewater through metabolically mediated or physico - chemical pathways
of uptake. Recently microbial systems like fungus, bacteria and algae have
been successfully used as adsorbing agents for removal of heavy metals
(Munoz et al 2006; Munoz and Guieysse 2006). Microbial populations in
metal polluted environments adapt to toxic concentrations of heavy metals
and become metal resistant (Prasenjit and Sumathi 2005). Different species of
Aspergillus, Pseudomonas, Sporophyticus, Bacillus, Phanerochaete, etc.,
have been reported as efficient chromium and Ni(II) reducers (Yan and
Viraraghavan 2003; Gopalan and Veeramani 1994). The response of
microorganisms towards toxic heavy metals is of importance in view of
 81

Algae, bacteria and fungi and yeasts have proved to be potential metal
biosorbents.

The major advantages of biosorption over conventional treatment

methods includes low cost, high efficiency, minimisation of sludge formation,
no additional nutrient requirement, possibility of regeneration of biosorbent
and possibility of metal recovery.

The biosorption process involves a solid phase (sorbent or

biosorbent; biological material) and a liquid phase (solvent, normally water)
containing a dissolved species to be sorbed (sorbate, metal ions). Due to
higher affinity of the sorbent for the sorbate species, the latter is attracted and
bound there by different mechanisms. The process continues till equilibrium
is established between the amount of solid bound sorbate species and its
portion remaining in the solution. The degree of sorbent affinity for the
sorbate determines its distribution between the solid and liquid phases.

In recent years, a great deal of interest in the research for the

removal of heavy metals from industrial effluent has been focused on the use
of agricultural by- products and biological wastes as adsorbents. The use of
agricultural by-products in bioremediation of heavy metal ions is known as
bio sorption. This utilizes inactive (non - living) microbial biomass to bind
and concentrate heavy metals from waste streams by purely physico -
chemical pathways (mainly chelation and adsorption) of uptake (Igwe et al
2005). New resources such as hazelnut shell, rice husk, pecan shells, jackfruit,
maize cob or husk can be used as an adsorbent for heavy metal uptake after
chemical modification or conversion by heating into activated carbon. Ajmal
et al (2000) employed orange peel for Ni(II) removal from simulated
wastewater. They found that the maximum metal removal occurred at pH 6.0.
The applicability of coconut shell charcoal (CSC) modified with oxidizing
 82

agents and/or chitosan for Cr(VI) removal was investigated by Babel and
Kurniawan (2004). Cu(II) and Zn(II) removal from real wastewater were
studied using pecan shells- activated carbon (Bansode et al 2003) and potato
peels charcoal (Amana et al 2008). Bishnoi et al (2003) conducted a study on
Cr(VI) removal by rice husk-activated carbon from an aqueous solution. They
found that the maximum metal removal by rice husk took place at pH 2.0.
Rice hull, containing cellulose, lignin, carbohydrate and silica, was
investigated for Cr(VI) removal from simulated solution (Tang et al 2003).

2.9.4 Photocatalytic Removal

Advanced oxidation processes (AOP’s), uniting together ozone and

high output ultraviolet technologies, in conjunction with hydrogen peroxide
and catalyst are successfully used to decompose many toxic and bio resistant
organic pollutants in aqueous solution to acceptable levels, without producing
additional hazardous by products or sludge which require further handling.
Advanced oxidation processes involve the generation of hydroxyl (•OH)
radicals which oxidize the pollutants. Fluorine is a well known strong oxidant
in our chemistry, after that the hydroxyl radical is the second most strong
oxidant having an oxidation potential of 2.8 eV. It is able to oxidize and
mineralize almost every organic molecule, yielding CO2 and inorganic ions as
shown in Equation (2.1) and (2.2).

•
OH + RH R•+ H2 O (2.1)

R• + O2 ROO• Products and CO2 (2.2)

Different combinations of homogenous and heterogeneous methods

which involve the generation of free radicals are, (i) photochemical irradiation
with ultraviolet light (ii) Fenton and Photo Fenton catalytic processes
(iii) Electron Beam Irradiation technique and (iv) sonolysis.
 83

Barakat et al (2004) studied the Photocatalytic degradation using

UV- irradiated TiO2 suspension for destroying complex cyanide with a
concurrent removal of Cu(II). Results revealed that free Cu(II) was
completely removed in 3 h. The co - existence of Cu(II) and CN enhanced the
removal efficiency of both CN and Cu(II); the removal (%) increased with
increase of Cu: CN molar ratio reaching a complete removal for both Cu(II)
and cyanide at a ratio of 10:1. Various unmodified and modified
semiconductors were synthesized and characterized as photo catalysts. TiO2
thin films immobilized on glass plates and prepared by so -gel technique
(Kajitvichyanukula et al 2005). Photocatalytic reduction of Cr(VI) over TiO2
catalysts was investigated in both absence and presence of organic
compounds (Papadam et al 2007; Wang et al 2008).

Though the Photocatalytic process is efficient and attractive in the

removal of heavy metals, the process is failed to be installed in large scale.
The high cost of the UV lamp and their low life showed their uselessness in
industrial application.

2.9.5 Membrane Filtration

Membrane filtration has received considerable attention for the

treatment of heavy metal contaminated wastewaters, since it has the capability
to remove not only suspended solid and organic compounds, but also
inorganic contaminants. Depending on the size of the particle that can be
stopped, various types of membrane filtration such as ultra filtration (UF),
nanofiltration (NF) and reverse osmosis (RO) can be used for heavy metal
removal from wastewater.

2.9.5.1 Ultrafiltration (UF)

Ultra filtration UF utilizes permeable membrane to separate heavy

metals, macromolecules and suspended solids from inorganic solution on the
 84

basis of the pore size (5-20 nm) and molecular weight of the separating
compounds (1000-100,000 Da). These unique specialties enable UF to allow
the passage of water and low molecular weight solutes, while retaining the
macromolecules, which have a size larger than the pore size of the membrane
(Vigneswaran et al 2004).

Juang and Shiau (2000) reported the removal of Cu(II) and Zn(II)
ions from synthetic wastewater using chitosan-enhanced membrane filtration.
The amicon- generated cellulose YM10 was used as the ultrafilter. About
100% and 95% rejection were achieved at pH ranging from 8.5 to 9.5 for
Cu(II) and Zn(II) ions, respectively. The results indicated that chitosan
significantly enhanced metals removal by 6-10 times compared to using
membrane alone. This could be attributed to the major role of the amino
groups of chitosan chain, which served as coordination site for metal binding.

UF presents some advantages such as lower driving force and a

smaller space requirement due to its high packing density. However, the
decrease in UF performance due to membrane fouling has hindered it from a
wider application in wastewater treatment (Kurniawan et al 2006).

2.9.5.2 Reverse Osmosis and Nanofiltration (NF)

The nanofiltration NF technique is primarily used for the removal

of bivalent and monovalent ions such as heavy metals. NF essentially uses a
coarse form of a RO membrane. NF has a lower fouling rate than RO. NF is a
special process selected when RO and UF are not the ideal choice for
separation. NF can perform separation applications that are not otherwise
economically feasible, such as demineralization, colour removal, and
desalination. This method not only removes organic substances, but also
inorganic content from wastewater. Based on the disposal of heavily loaded
industrial wastewater, recovery of substances from wastewater, reduction in
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the load on treatment plants and the wastewater quantity produced, RO is a

very economical and safe process that has already been shown to be
successful for practical use (Heitmann 1990).

Membranes employed in RO are usually made of cellulose acetate,

aromatic polyamide, polyimide, polysulfones, or thin film composites.
Membranes can be designed to remove specific inorganic and organic
contaminants, such as trihalomethanes. Commercial RO membranes including
cellulose acetate and polyamide membranes are suitable for water treatment
on a technical scale. These membranes have salt rejection rates of cellulose
acetate and polyamide of 94 - 97% and 94%, respectively (Heitmann 1990).
Pre treatment processes are essential to all systems to ensure a long service
life of membranes and trouble-free operation. Karelin et al (1996)
investigated the capacities of NF and RO high pressure membrane systems to
separate a high concentration solution. Membrane separation techniques have
also been applied for the reuse of salts and water from dyeing effluent (Xu,
Spencer 1997; Allegre et al 2004), water recovery from brackish water
(Almulla et al 2002; Lee et al 2004), separation of salt from wastewater
produced by chemical industries (Freger et al 2000; Castelblanque and
Salimbeni 2004). Membrane technology was also used to recover sodium
chloride from waste brine at a sugar decolourization plant RO coupled with
NF was found to be more economical than a multiple effect evaporator for
salt recovery from textile effluents (Vishnu et 2008). Economically, RO is
relatively inexpensive to install, operate, and maintain, and it consumes less
energy than other desalination methods. However, membrane separation
always produces a relatively large volume of concentrate that must be
disposed off or receive further processing.
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2.10 MATHEMATICAL MODELLING OF EXPERIMENTAL

DATA

2.10.1 Batch Data Modeling

The adsorption isotherm is fundamental in understanding the

mechanism of adsorption. Important information regarding how the adsorbate
molecules distribute between the liquid phase and the solid phase once the
equilibrium state is reached can be interpreted based on the adsorption
isotherm.

Langmuir isotherm assumes that the adsorption occurs at specific

homogeneous adsorption sites within the adsorbent. Furthermore, it assumes
monolayer adsorption and maximum adsorption occurs when adsorbed
molecules on the surface of the adsorbent form a saturated layer. All
adsorption sites involved are energetically identical and the intermolecular
force decreases as the distance from the adsorption surface increases (Unlu
and Ersoz, 2006; Uysal and Ar, 2007). The Freundlich isotherm expresses
adsorption at multilayer and on energetically heterogeneous surface (Hasan
et al 2008; Unlu and Ersoz, 2006).

Gandhi et al (2011) the sorption behaviour of Cu(II) on chemically

modified chitosan beads from aqueous solution. They modelled their batch
data with standard isotherms Langmuir and Freundlich models to predict the
type of adsorption as well as to determine the maximum adsorption capacity
of the sorbent used.

Ngah and Fatinathan (2010) studied the adsorption of Pb (II) and

Cu(II) ions onto chitosan-tripolyphosphate beads and fitted the batch data
with Langmuir and Freundlich isotherm models and calculated their
constants.
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Onundi et al (2011) studied the Heavy metals removal from

synthetic wastewater by a novel nano-size composite adsorbent. They fitted
their batch data with the standard isotherm models namely Langmuir and
Freundlich isotherms. They reported that the Langmuir’s adsorption isotherm
model gave a higher R2 value of 0.93, 0.89 and 0.986 for Cu(II), Ni(II) and
Pb(II) respectively over that of Freundlich model during the adsorption
process of the three metals in matrix solution.

2.10.2 Column Data Modeling

Column adsorption is an important step in industrial downstream

processing. It is required to stop the adsorption stage before the saturation of
the adsorbent is completed, for which a thorough understanding of adsorption
characteristics is essential (Bautista et al 2003). At industrial scale, the time of
stopping the operation must be determined after an economic and, eventually,
environmental evaluation of the process. Because not only the amount of
solute adsorbed but the operating time has an important impact on the
effective use of the column and on the final throughput of the process, too.
The optimization of this and other operating conditions can be accomplished
with the help of reliable mathematical models.

Several types of models are used for modelling column data and
among them the important models are Thomas, Adam – Bohart, Yoon– Elson
and BDST models. According the Chu et al (2010), when the sorption process
is highly favourable with rectangular isotherm (bC C >>1 in Langmuir
isotherm model), then the Thomas column model reduces to Adam-Bohart
model. Hence, the remaining three models are widely used.

Vijayaraghavan et al (2005b) investigated the biosorption of Cu(II),

Co and Ni(II) by marine green alga Ulva reticulata in a packed bed up-flow
column. The Bed Depth Service Time (BDST) model was used to analyze the
experimental data. The computed sorption capacity per unit bed volume (N0)
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was 2580, 2245 and 1911 mg L 1 for Cu(II), Co and Ni(II), respectively. The
1 1
rate constant (Ka ) was recorded as 0.063, 0.081 and 0.275 L mg h for
Cu(II), Co(II) and Ni(II), respectively. In flow rate experiments, the results
confirmed that the metal uptake capacity and the metal removal efficiency of
U. reticulata decreased with increasing flow rate. The Thomas model was
used to fit the column biosorption data at different flow rates and model
constants were evaluated.

Kose and Ozturk (2008) studied the removal of Boron from

aqueous solutions by ion-exchange resin column. The breakthrough curve was
obtained as a function of feed flow rate and the total and breakthrough
capacity values of the resin were calculated. The Thomas and the Yoon–
Nelson models were applied to experimental data to predict the breakthrough
curves and to determine the characteristic column parameters required for
process design. The results proved that the models would describe the
breakthrough curves well.

Quintelas et al (2007) studied the Biosorption of Cr(VI) by a

Bacillus coagulans biofilm supported on granular activated carbon (GAC)
and modelled their column data with Adams–Bohart and the Wolborska
models. Those models were found suitable for describing the dynamic
behaviour of the columns with respect to the inlet chromium concentration.

2.10.3 Electrochemical Ion Exchange Modeling

One possible mode of operation of EIX (Electrochemical ion

exchange) reactor is that which involves the continuous recirculation of the
effluent. Due to this, there is a gradual depletion of the concentration of metal
ions will occur in the process stream. In order to design the plant for EIX
processes, development of the models is essential which explains the variation
of the concentration of metal ions with time in the reservoirs. Therefore, the
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modeling of the batch recirculation EIX reactor data is essential for the
designing of the rector in large scale applications.

Ahmed Basha et al (2008b,c) studied the removal/recovery of

Cr(VI) ions by EIX from rinse waters and predicted a model for EIX reactor
batch recirculation process. Ahmed Basha et al (2011) studied and predicated
a model for Heavy metals removal from Cu(II) smelting effluent using
electrochemical filter press cells. Table 2.8 show the overall advantages and
disadvantages of various methods available in litreature.

Table 2.8 Advantages and disadvantages of physical and chemical

methods of heavy metal ions from waste water

Physical and/or
Advantages Disadvantages
chemical methods
Oxidation Rapid process for toxic High energy costs and formation
pollutants removal of
By products
Adsorption flexibility and Adsorbents requires regeneration
simplicity of design,
ease of operation and
insensitivity to toxic
pollutants
Coagulation/flocculation Economically feasible production and formation of
High sludge large
particles
Membrane filtration Good removal of heavy Concentrated sludge production,
Technologies metals expensive

Ion exchange Good removal of a Absorbent requires regeneration

wide range of heavy or
metals Disposal
Biological treatment Feasible in removing Technology yet to be established
some and
Metals. Commercialized.
Photochemical No sludge production Formation of by products
Electrochemical Rapid and effective Slightly high costs
Treatment process