CH 2: Literature Review

Fresh water resources such as lakes and rivers are called surface water and the great
contribution (0.6% of the world’s total water supply) to the fresh water is groundwater
(Baird, 1999). Ordinarily, surface water is easily polluted however, groundwater resources
also can be affected by pollution for instance, when pesticides in particular weed killers are
applied in the garden and drain into the ground. Well sampling data collected in 2010 found
that more than 21 pesticides and their degradates were detected in 286 wells located in 18
counties out of 51 counties sampled in Sacramento, California (Cal/EPA, 2012). Samples
from several creeks in urban areas which are located in the residential neighbourhoods,
commercial industries and construction areas also detected pesticides such as malathion,
diazinon, carbaryl, simazine and diuron (Cal/EPA, 2013).

Production

Product
Wastewater

Agriculture Residential Public Health

Fig. 01. Source of pollutions

Wastewater Treatment Process

Generally, wastewater effluent streams originating from various sources are treated using
different methods in order to produce suitable and safe treated effluent streams which can be
discharged into the environment. Conventional wastewater treatment is a combination of
physical and biological processes to remove organic matters. Separation processes can be
based on fluid mechanics (sedimentation, centrifugation, filtration and flotation) or on
synthetic membrane separation techniques (filtration, reverse osmosis). Additionally,
physico-chemical processes (i.e., adsorption, chemical precipitation, coagulation,
flocculation, and ionic exchange processes) can be used to separate dissolved, emulsified and
solid components from the water environment.

Adsorption represents a fundamental process in both industrial wastewater treatment and

water purification. It has so far proven to be a very effective and economical method for
removing organic contaminants even at low concentrations. A wide range of adsorbent such
as activated carbon, zeolites and silica are utilized for the removal of organics, inorganics
and heavy metal contaminants in varying composition. This results in the reduction of COD,
BOD, odour and colour from wastewater which otherwise is fairly resistance to biological
degradation and are not effectively removed by other physio-chemical treatment method,
such as filtration, coagulation and sedimentation.

Of all the adsorbents used in industrial wastewater treatment and in the majority of research
work, activated carbon is employed extensively due to its high affinity to organic compounds
even at low concentrations. Activated carbon is often used either in its granular or powdered
form. For an adsorption process using granular carbon, the water to be treated is either fed
from the top of the packed bed and flows downwards (down-flow mode) or is fed under
pressure at the bottom of the cell and flows upwards (up-flow mode). Suspended solids
present in the wastewater get trapped between the packed bed and are removed by
backwashing the bed in order to reduce flow restriction. Alternatively, the bed can be
partially fluidized by increasing the up-flow pressure so as to prevent or minimize blockage.
If the powdered form or activated carbon is utilized, the activated carbon is added to the
wastewater and the slurry is often mixed to encourage mass transfer.

Although fairly limited there have been a number of studies undertaken to investigate
adsorption of organic contaminants onto Nyex™, and results have shown significant and
rapid uptake of organics though with low adsorption capacity due to the low surface area of
the adsorbent as a result of its non-porous characteristics. Research on the adsorption of
inorganic contaminants onto Nyex™ is currently limited, recent studies of the adsorption of
ammonia onto Nyex™ showed that Nyex™ was able to adsorb ammonia. The solution used
in this study contained only ammonium chloride which makes it difficult to compare with
adsorption in grey water solution, where ammonia is present with other compounds. There
are several reports on the adsorption of inorganics onto other adsorbents such as zeolites,
activated carbon and silicate from single component solutions. Unfortunately, reports on the
adsorption of organic and inorganic contaminants from multicomponent solutions such as
grey water are limited. The work in this thesis would for the first time investigate the
adsorption of organic and inorganic contaminant from a multicomponent solution onto
Nyex™ adsorbent.

2.1. Physical Treatment Methods for removal of pesticide pollutants Wastewater

2.1.1 Adsorption
The tendency of a contaminant to be adsorbed by an adsorbent depends on the
hydrophobicity/solubility of the contaminant, or the affinity of the contaminant to the
adsorbent. This is because the less soluble a contaminant is in water, the easier it will be to
remove from water compared to contaminant which is completely soluble in water.
Similarly, non-polar contaminants will be more easily removed compared to polar
contaminant as polar substances have a greater affinity to water.

Adsorption techniques have gained favor recently due to their efficiency in the removal of
pollutants. Thus, adsorption techniques have been found to be among the most effective and
proven treatments of pesticides wastewater. It is a rapid process of separation of the
adsorbate from the aqueous phase of the waste water, producing a high-quality water. It is a
process, which is economically feasible. This process consists in the transfer of soluble
pollutants from wastewater to the surface of a solid, highly porous material (the adsorbent).
Adsorbents can be of organic or inorganic nature. Inorganic adsorbents are china clay,
bentonite clays, silica gel, metal oxides, zeolites and fly ash. Typical natural organic
adsorbents that have been used are peat and woodchips. One of the most used adsorbents is
activated carbon. Thus, using activated carbon remains the most commonly used method of
pollutants removal by adsorption.

Since adsorption is a surface process, the surface area of the adsorbent is also important. The
surface area available for adsorption increases with decrease in the size of the adsorbent
particles. Other factors which affect adsorption are electrostatic effects, concentration
gradient, molecular size of adsorbate, surface chemistry, pH and steric effects.
Adsorption can occur at various locations on the adsorbent such as the outer surface or
within the pores of the adsorbent. The adsorption process takes place in four major steps as
follows:

 Bulk solution transport – the movement of contaminants (adsorbate) from the bulk
liquid phase to the surface of the adsorbent. This phase is usually fast and depends on
agitation of the solution
 Film diffusion transport – transport of the contaminant through the fixed liquid film
surrounding the adsorbent to the surface of the adsorbent, by diffusion
 Pore transport (intra-particle diffusion) – transport of the contaminant through the
adsorbent pores, typically by molecular diffusion.
 Adsorption – attachment of contaminant on an available adsorption site.

If physical adsorption is the principal adsorption method, the rate limiting step (the slowest
step) is usually step 2 or 3. For non-porous adsorbent, intra-particle diffusion (step 3) is
eliminated in the adsorption process which often results in increased adsorption rate and
eases recovery of the adsorbent at the expense of reduced adsorption capacity. In contrast,
the rate limiting step for chemical reaction is the step 4 due to bond formation between
contaminants and adsorbent

Adsorption types
Adsorption can be classified as either physical adsorption (physisorption) or chemical
adsorption (chemisorption). Physical adsorption is due to Van der Waal’s attraction forces
and can under the correct conditions be easily reversed. Under certain conditions,
physisorption can result in multilayer adsorption where molecules already adsorbed in the
adsorbed phase attract molecules from the liquid phase. Chemical adsorption relies on a
chemical reaction resulting in the formation of chemical bond, unlike physisorption,
chemisorption is more difficult to reverse and does not form multilayers. Depending on the
adsorbate and the surface of the adsorbent, adsorption can also result in electrostatic
interaction due to charged adsorbate forming ionic bond with charges on the surface of
adsorbent.

Adsorption is the phenomenon of accumulation of a large number of molecular species at the

surface of solid or liquid phase in comparison to the bulk. These phenomena can be classified
into two types depending on the nature of the bonding between the molecules of the
adsorbate and the surface of adsorbent, namely chemisorption and physisorption. Both types
take place when the molecules in the liquid phase (sorbate) become attached to the surface of
the solid phase (adsorbent) as a result of the attractive forces at the adsorbent surface
overcoming the kinetic energy of the adsorbate molecules.

 Physisorption
Physisorption or physical adsorption occurs when, as a result of energy difference and / or
electrical attractive forces (weak Van der Waals forces), adsorbate molecules become
physically fastened to the adsorbent surface. Physisorption takes place with the formation of
single or multiple layers of adsorbate on the adsorbent surface and is characterized by a low
activation energy (enthalpy) of adsorption (20−40 KJ mol−1).

 Chemisorption
Chemisorption or chemical adsorption occurs when a chemical reaction occurs between the
adsorbed molecules and the adsorbent. Chemisorption takes place with the formation of a
single layer of adsorbate attached to the adsorbent surface by chemical bonds. This type of
interaction is strong with a covalent bond between adsorbate and the surface of the adsorbent
is characterized by a high enthalpy of adsorption (200−400 KJ mol−1).
GIC (graphite Intercalated compounds) as Sorption Material in Adsorption Processes

Graphite is a crystalline allotropic form of carbon with moderate electrical conductivity. The
graphite structure is made up of succession of graphene layers parallel to the basal plane of
hexagonal lattice of carbon atoms. The distance between the carbons (C-C) in the hexagonal
lattice is 1.42 Å, compared to a distance of 3.35 Å between the graphene layers. The
graphene layers are held in place by Van der Waal’s force which is significantly weaker than
the carbon-carbon bonds within the hexagonally linked layers held together by strong
covalent bonds.

Graphite can react with a range of intercalant to form graphite intercalated compound with
different properties and several have already been manufactured. Two forms of GIC, namely
acceptor and donor type GIC, can be generated depending on the method of electron transfer
between the intercalant and the host graphite. An acceptor type GIC is manufactured by
oxidization of the graphite to accept anionic intercalates and requires a strong oxidant. Whilst
for donor type GIC, graphite is reduced to accept cationic intercalates using strong reducing
agent. The distinct property of graphite compared to other anisotropic type system which can
also react with intercalants is that GIC has a constant layer of graphene layer between two
monolayers of intercalant. This regular ordering of graphene and intercalants is called
staging. Stage 1 indicates that a monolayer of intercalant is present between each graphene
sheets whilst a stage 2 indicates the presence of intercalants monolayer between two
graphene layers. Control of the condition of the intercalation reaction can control the stage
number of the GIC.

Application of GICs

Due to their high electrical conductivity, electrochemical activity and thermal insulation,
GIC has received vast interest for various uses. The insulating properties of GICs have led to
their use as thermoelectric materials for thermal energy storage and in power sources such as
electrodes and batteries. For instance, potassium and lithium intercalated graphite
compounds are superconducting GIC which have been used in batteries. Nickel and
potassium intercalated graphite have also proved effective for use as catalysts, the high
electrical and low thermal conductivity properties of GICs has been very well exploited for
industrial use.

The majority of literature available on the use of GIC as an adsorbent material is limited. The
literature that has so far been published was as a result of work done using Nyex™
adsorbent. There has however been some information on the use of graphite oxide as an
adsorbent.

Graphite oxide is a similar compound to GIC but is more highly oxidized and rich in
functional groups containing oxygen. Graphite oxide was successfully used to adsorb humic
acid from an aqueous solution.it was reported an adsorption capacity of 190 mg/g which is
much higher than that of activated carbon. The high adsorption capacity of graphite oxide is
brought about as a result of the oxygen functional group present in the graphene structure.
However, in synthesis of graphite oxide, the graphene layers of the host graphite lose
planarity which results in a decrease in the electrical conductivity of the resulting graphite
oxide also reported successful adsorption of lead from wastewater onto graphite oxide.
Graphite oxide intercalated with n-hexa-decyl-amine was used to adsorb pyrene from a
water-ethanol solution. An adsorption capacity of 28.5 mg/g was reported with pyrene
adsorbed both on the external graphite surface and between graphene layers.

Exfoliation of GIC produces a light weight material with a large surface area. The use of
exfoliated GIC has been investigated for the adsorption and recovery of heavy oils and for
the adsorption of organic pollutants from wastewater.

GIC are the most versatile and frequently used adsorbents, and GIC are widely used for
purifying contaminated water. Their large internal surface area and pore volume, their ability
to adsorb most dye pollutants and the low cost associated with them make activated carbons
one of the most practical adsorbents Although carbon materials, especially carbon
nanomaterials, can be synthesized by decomposition of alkanes and cycloalkanes or by using
acetylene as the carbon source. The usual source of activated carbon are lignocellulose
containing organisms. Activated carbons derived from different plant sources have been used
for the removal of dyes from wastewater. Some of these sources are agricultural wastes. A
typical such source is bagasse, which is an agricultural/industrial by-product produced in
large amounts by sugarcane mills. Bagasse is a cost-effective material and it has an inherent
ability to adsorb waste chemicals such as dyes from aqueous systems. Removal of pollutants
from aqueous solutions using bagasse was studied extensively. Bagasse fly ash has also been
used for the removal of colorants and dissolved organics from sugar mill effluent. Applied
bagasse as an adsorbent for the removal of malachite green from aqueous solutions.
Monolayer adsorption of malachite green at alkaline pH was observed as bagasse contains
various oxides and hydroxylated species on the surface. All these studies prove the utilization
of a waste to treat another waste. Other agricultural waste substrates for activated carbon that
have been used are neem leaf powder, wheat straw, corn-cob, tree bark, rice husk, coconut
shell powder, and ground sunflower seed shells. The activated carbons derived from the
above have been used for the removal of pollutant and organic colored matter from effluents.

Characteristics of Nyex™ Adsorbent

Nyex™ adsorbent is a novel, non-porous and highly-conducting graphite-based material.

Mercury porosimetry showed there were no internal pores in the adsorbent material, thus
proving the non-porous structure of the Nyex™ adsorbent. The non-porous nature of the
Nyex™ results in lower adsorption capacity of 2 mg g-1 (5 mg l-1 of crystal violet dye)
compared to its carbon-based alternatives such as activated carbon, which has an adsorption
capacity of 40.6 mg g-1 (1.9 mg l-1 of crystal violet dye) (Brown et al. 2004b). Nyex™ was
selected because it has no internal surface area, this characteristic was thought likely to result
in quick adsorption and electrochemical regeneration as intra-particular diffusion is
eliminated. The higher electrochemical conductivity of Nyex™ also enables simple and
quick electrochemical regeneration which is an extremely important part of the Arvia™
process.

Table. 02. Characteristics of different adsorbent

Adsorbent Characteristics Uses Disadvantage Typical Surface
Type Area
GIC Hydrophobic Removal of Small surface
(nyex 1000) favours organic area
organics over compound
water
Activated Hydrophobic Removal of Difficult to 600-2000
Carbon favours organic regenerate
organics over compound
water
Silica Gel Hydrophilic, Drying gas Trace removal 500-750
high capacity stream not effective
Zeolite Hydrophilic, Air separation Low total 400-500
polar, regular dehydration capacity
channels
Activated Hydrophilic Drying gas Trace removal 50-300
high capacity stream not effective

The main purpose of searching new adsorbent is to replace activated charcoal and ion
exchange resins, which are very expensive to use on larger scale but more efficient. The
researchers are trying to find an alternative adsorbent of electrochemical regeneration and
cheap nature with great adsorbent efficiencies, Characteristics of importance in choosing
adsorbent types for adsorption include pore structure, particle size, total surface area, and
void space between particles. The comparison between a typical activated carbon and
Nyex®1000 which has been tested in this work as an adsorbent for adsorption and
electrochemical regeneration of organic materials from aqueous solution are shown in Table
02. Nyex®1000 was selected as an adsorbent for the following reasons:

 The high density of Nyex® allows rapid settlement

 A tenfold increase in electrical conductivity of Nyex® aids electrochemical
regeneration
 Lack of Nyex® pores facilities more complete and rapid regeneration
  Lower surface area of Nyex® is compensated by continuous recycling and
regeneration.
However, it should be noted that the low surface area of the Nyex®1000 means that it is a
low capacity adsorbent material.

Table. 03. Physical and electrochemical properties of adsorbent

Charateristic Nyex 1000 Total Activated Carbon
Bulk density (g cm-3) 0.4-0.5 0.5-0.6 (coal- based carbon)
0.24-0.3(wood- based carbon)
Particle density (g cm-3) 0.74-0.8
Real density (g cm-3) 2.1-2.2
Pore volume (cm3 g-1) 0 0.8- 1.2 (coal based carbon)
2.2-2.5 (wood based carbon)
Surface area m2 g-1 1 600-800
Bed Electrical conductivity 0.8 0.025
Resistivity Ώm 1.25 39.45 (GAC)
85.11 (GAC)

2.1.2. Ionic Exchange

Ion-exchange process is extremely useful to remove different dense metals from wastewater.
Ion-exchange resins are simply recovered and re-used as re-generation operations proceses.
Ions present in solution are shifted to a solid matrix in process, which can discharge diverse
types of, but correspondingly charged ions. It is physical split-up process, where the ions
exchanged are not chemically changed. The key benefits of ion exchange are retrieval of
metal value, a lesser amount of sludge volume formed, selectivity, and the meeting of strict
discharge conditions. Moreover, the ion exchange resin is considered based on functional
groups for example an-ion exchange resins, cat-ionic exchange resins and chelating exchange
resin.

2.1.3 Membrane Processes

Membrane filtration can work in mix with-other waste treatments actions. This strategy isn't
just limited to natural microorganisms and contaminants existent in wastewater yet to salts
filtration has been utilized for color evacuation, BOD decrease, salt decrease, polyvinyl acetic
acetate retrieval (PVA) recuperation or latex recuperation amongst others. The strategy is
impervious to temperature. The layer filtration can be adversely affected by organisms. The
staying, concentrated buildup after detachment can present expulsion issues. The procedure
experiences high capital expense and has a danger of stopping up. Visit film substitution is one
more detriment of this procedure. This strategy is reasonable, if the effluent contains a low
convergence of colors. The normal film filtration types are Ultra-Filtration (UF), Micro-Filtration
(MF), Reverse Osmosis (RO) and Nano-Filtration (NF). The decision of the membrane procedure
is affected by the required nature of the last effluent.

2.1.4. Filtration

This process is fit for rinsing baths and baths, which hold waste water pollutants.
Microfiltration is used as pretreatment for reverse osmosis or Nano-filtration. It can isolate
postponed solids and colloids, via macro-molecules with pores of 0.1-1 micron. Micro
filtration (MF) show leads classically to >90% decline for turbidity. Typically, micro-
filtration membranes are prepared from particular polymers for example poly (vinylidiene-
fluoride), poly (ether sulfone), poly (sulfone), poly-propylene, poly-carbonate, polytetra-
fluoroethylene (PTFE), amongst others. Ceramic, glass, alumina carbon, sintered metal
membranes and zirconia coated carbon are utilized where unfamiliar chemical resistance or
high temperature act is necessary.

2.1.5. Reverse Osmosis

Reverse osmosis is utilized in retrieval of municipal waste-water in treatment plants and is

utilized to eliminate maximum of ionic compounds, mineral salts, chemical auxiliaries and
hydrolyzed reactive dyes. Similarly RO,NF is precise complex to fouling and influent stream
must be wisely pre-treated. The lesser the pore size of the RO, the advanced the operating
pressure, the primary stock and the operating costs.
2.1.6. Coagulation-Flocculation and Precipitation

Coagulation is one and only of the foremost technologies utilized in wastewater treatment. It
is a difficult phenomenon which contains a number of inter-related parameters. As a result, it
is very important to state how thriving a coagulant will role. Principally, in this method
minor particles are transformed into bigger aggregates (flocs) and until that time solidified
organic matter adsorb on-to the particulate aggregates. From now, these impurities can be
detached in subsequent flotation/sedimentation and filtration phases. The coagulation process
comprises three following steps: coagulant formation, particle/colloid de-stabilization and
particle aggregation. Subsequently addition treatment chemicals, the coagulant formation and
particle/colloid destabilization can be supported in a fast-mixing step. Subsequently, particle
aggregation (floc development) is stimulated in a flocculation step, where inter-particle
collisions generate bulky floc particles cooperative to departure from the treated water. In
water and wastewater treatment practice, the terms ‘Coagulation’ is utilized to pronounce the
preliminary process whereby the unusual colloid dispersion is destabilized frequently by
charge neutralization and the term ‘Flocculation’ state to the consequent process whereby the
damaged colloids in the micron and sub-micron size range go through aggregation and
particle evolution into millimeter-sized flocs. Then the coagulation step, and the early phase
of the flocculation, take place very quickly, their difference in a practical treatment
intelligence has very minor meaning.

2.1.6. Electrocoagulation

Electro-coagulation is electro-chemical procedure associated to chemical coagulation. It

consist of the quantity of coagulant ions (Al3+, Fe3+). Coagulant ions are formed by an
electric current to a sacrificial anode which is located into a system tank. The types of the
particle aggregates (flocs) created through the electrocoagulation method change intensely
from those produced by chemical coagulation. As a result, flocs produced in an
electrocoagulation method have fewer bound water and additional shear resistance and are
more freely filterable. Further benefits of electro-coagulation above chemical coagulation
are: the quantity of chemicals required is minor, the salinity of the wastewater does not rise
and the monetary cost for the treatment is also minor. Moreover, the gas bubbles created at
the cathode can pay to the flotation of the flocs, which can be simply well again. In
conclusion, at the end of the method the produced sludge is divided by filtration.

2.2. Chemical Treatment Process

2.2.1. Irradiation
The irradiation treatment is a promising technology to eliminate organic contaminants, and
disinfect harmful microorganism using gamma rays or electron beams and electron beam
accelerators are more suitable for versatility and lower costs. A high quantity of dissolved
oxygen is required for an organic dye to be effectively broken down by irradiation. The
dissolved oxygen is consumed very rapidly and so a constant and adequate supply is
required. Dissolved oxygen is required to break down the effluents by irradiation . So, a
regular and sufficient supply of oxygen is necessary. This process is very important for
sanitary engineering.

2.2.2. Oxidative processes

Chemical oxidation represents the transformation of pollutants by chemical oxidation agents.

The modern textile dyes are resistant to mild oxidation conditions such as those existing in
biological treatment systems. Therefore, efficient dye and colour removal must be
accomplished by more powerful oxidizing agents such as chlorines, ozone, Fenton reagents,
UV/peroxide, UV/ozone, or other oxidizing procedures o combinations.

2.2.3. Ozonation Process

Ozonation can cause significant resolubilization of precipitated dyes. Complete removal of

waste water pollutants precipitate should be accomplished prior to treatment of wastewater
via ozonation. Higher gas-phase ozone concentrations lead to higher decolorization rates due
to more rapid ozone transfer. In general, a greater ozone utilization efficiency was achieved
at lower pH levels. Where direct ozone reactions predominate. The main advantage of using
ozone in water treatment is that ozone can be applied in its gaseous state and therefore does
not increase the volume of the wastewater and sludge. A disadvantage of ozonation is its
short half-life, typically being 20 min, the destabilization by the presence of salts, pH, and
temperature, and the additional costs for the installation of ozonation plant.

Electrochemical Regeneration Process

Introduction to electrochemical reaction
An electrochemical reaction is a chemical reaction brought about as a result of the transfer of
electrons between electrodes and species in solution. Initially, unpaired electrons attach to
molecules in the substrate to form reactive intermediates, these reactive intermediates are
then transformed into electrically charged ions. The transformation of reactive intermediates
involves a sequence of bond forming and bond cleaving reactions, and the process by which
chemical species are transformed to electrically charged ions is termed electrolytic
dissociation. The reaction which occurs during the electrolytic dissociation process is called
an electrochemical reaction.
An electrochemical reaction system requires both a cathode and an anode electrode. The ions
formed in the process move in an electric field as a result of their charge. The type of
electrochemical cell used for the electrolytic dissociation process is known as an electrolytic
cell, which means electrochemical reaction only occurs when energy is applied. Once energy
is applied across the cell, electrons enter the electrochemical system via the negatively
charged cathode and leaves through the anode.
In addition to the electrodes, the system also requires an electrolyte to conduct electricity by
providing ions that flows to and from the electrode when energy is applied. During
electrochemical reaction, species at the anode undergo oxidation reaction and those at the
cathode reduction reaction. The application of various electrochemical techniques in water
and wastewater treatment are reviewed in the following section as well as the mechanism of
electrochemical reaction focusing particularly on electrochemical oxidation reaction, which
is used in the Arvia™ process.

Electrochemical technologies in water and wastewater treatment

Industries are facing increasing pressure to meet more stringent effluent legislations, this has
resulted in elevated demands for economical and environmentally friendly treatment
processes. Electrochemistry offers a promising alternative for wastewater treatment and is
finding increasing use in treatment purposes such as metal ion removal and recovery, as well
as removing organic contaminants from industrial wastewaters. Electrochemical treatment
processes can be cost effective, energy efficient and is environmentally friendly as it
produces no waste and does not require use of harmful chemicals. Another advantage of the
electrochemical process is that controlling the applied voltage enables selective treatment in
which a specific pollutant is targeted, thus the production of byproducts from
electrochemically active species can be avoided. However, there are some disadvantages of
electrochemical process where in some cases a high operating voltage is required which
result in high operating cost, there is also the potential for the formation of toxic products
and risk of electrode corrosion resulting in operational issues and potential contamination.
Various electrochemical techniques have so far been applied for removal of various
contaminants from water and wastewater, this includes

Electrodialysis
Electrodialysis is a versatile process used for removing ions and ionizable species from
aqueous solution and is often applied to deionization/desalinization of aqueous solution as an
alternative to reverse osmosis. It is an electro-membrane process which uses ion permeable
anion membrane and cation membranes, which under the influence of an electric field has
the ability to selectively transport negative (anion) and positive (cation) charged ions
respectively in order to achieve separation of electrolytes. Two types of chambers are
created, the concentrate chamber which holds high ionic concentration and the dilute
chamber holding the low ionic concentration solution. The main application of
electrodialysis is in the production of potable water from brackish water or seawater. Other
applications include the regeneration of ion exchange resin and treatment of radioactive
wastewater in nuclear plants. Although electrodialysis is effective at removing low molecular
weight ionic components, non-charged higher molecular weight compounds will not be
significantly removed. The process also becomes less economical when the influent/feed
solution has low conductivity as there are fewer ions available in solution to carry current
which means ion transport and energy efficiency decreases.
Electrodeionisation
Electrodeionisation process eliminates the disadvantages of the electrodialysis process by
using ion exchange resins to concentrate the ions as well as to act as an ion bridge thus
increasing the overall conductivity of the system. The treatment process of
electrodeionisation consist of two steps. In the first step of the process, ions are bound by the
ion exchange resin and in the second step, ions bound to the ion exchange resin are
transported through the ion exchange membrane into the concentrate chamber. As a result of
the increased conducting nature of the electrodeionisation process, it can be used in the
production of ultra-pure water used in food or pharmaceutical processing.

Electrocoagulation
Electrocoagulation is an electrolytic process used for treating organic and inorganic
wastewater with the tendency to coagulate. It has been applied in removing contaminants that
are difficult to remove by filtration and chemical treatment systems such as wastewater
containing oil and grease, dyes, suspended solids and heavy metals. Electrochemical
coagulation offers an alternative to coagulation process in that it does not require chemical
coagulation agent as this is generated in situ by electrolytic oxidation of the appropriate
species. The process utilizes sacrificial metal electrodes such as iron and aluminum to
produce metal ions which then diffuse into the bulk solution to be treated. These metal ions
are further hydrolyze to form coagulants which interact with charged ionic contaminants in
the bulk solution to facilitate coagulation and resulting in precipitation of contaminants from
the aqueous phase.

Electrofloatation
Electrofloatation is the process of removing pollutants from water through the electrolytic
formation of fine bubbles which collects contaminants from the bulk solution and carry them
to the surface of the solution where they are removed by skimming. Electrofloatation is often
combined with electrocoagulation technique, where coagulated species are brought to surface
using electrofloatation technique. The process has been applied for the removal of oils and
other low density emulsions and suspended solids from wastewater.

Electrolytic wet air oxidation

Wet oxidation is the oxidation of dissolved or suspended contaminants in aqueous solution
using oxygen as the oxidizer. Electrolytic wet oxidation is a novel process which integrates
wet oxidation and electrolytic reaction. The oxidation reaction is often catalysed using very
high temperature and pressure which means high operating cost.

Electrochemical oxidation
Electrochemical oxidation is a widely studied technique used in the removal of organic
contaminants in wastewater. It involves the oxidation of organic contaminants in the anode
of an electrolytic cell by the action of in-situ electrochemically generated oxidants.
Extensive investigation of this technology started around the late 1970s and interest have
since continued to grow especially for wastewater possessing high electric conductivity,
whilst addition of electrolyte is required for the treatment of low conducting wastewater.
Over the last two decades, research work has been focused on the efficiency of oxidizing
different organic pollutants on different electrodes. Some of the more recent research report
findings on the electrochemical oxidation of phenol, polyvinyl alcohol, naphthalene
sulphonates, oxalic acid, benzoic acid, acid orange 7 and salicylic acid.

Study on electrochemical reaction process has highlighted a number of disadvantages in its

application:

 Difficulty in treating wastewater with very low organic concentration

 Treatment of wastewater with high organic concentration can be energy intensive
 Low electric conductivity of wastewater solution result in high operating voltage

When the organic concentration of the wastewater is very low, mass transfer of reactant to
the surface of the electrode is limited thus making it difficult to treat electrochemically. As
mentioned earlier, the conductivity of the wastewater can be increased by adding an
electrolyte such as NaCl. However, NaCl cannot be removed by the electrochemical reaction
process thus increasing the dissolved solid content of the treated wastewater which limits its
reuse. The use of adsorption technique to concentrate the contaminants in wastewater using a
highly conducting adsorbent material, known as Nyex™, has been proposed by Brown
(2005). The Nyex™ adsorbent eliminated the disadvantages mention earlier by acting as
both a conducting bridge to reduce or eliminate the need for NaCl in low conduction
wastewater solution and a concentrating medium to increase the contaminant concentration
in solution. This therefore results in a reduction in the cell potential, and thus operating cost.

Electrochemical regeneration of GICs

Published literature on the electrochemical regeneration of GICs are limited to those
undertaken for Nyex™ adsorbent, no other form of GICs have to date been investigated. A
comprehensive study conducted by Brown et al. (2004a) on the electrochemical regeneration
of a GIC adsorbent demonstrated the following:
 Increasing the thickness of the adsorbent bed resulted in high cell potential
requirement due to increased ohmic drop across the bed. Although the inter electrode
distance from which high regeneration efficiencies can be achieved is greater than
normal due to the electrical conductivity of the Nyex™.
 Regeneration efficiency increase with current density but a reduction in regeneration
efficiency was observed as the current density is increased over 20 mA/cm2. This
reduction in regeneration efficiency was likely due to an increase in side reactions
that occur at higher voltages.
 Regeneration efficiency increased with charge passed, however no further increase
was noted above a charge of 25 C/g.
 Increasing the electrolyte concentration leads to increased regeneration efficiency up
until around 3% sodium chloride concentration, after which no additional benefit was
observed.
In general, the optimum operating parameters proposed are current density of 20 mA/cm2,
charge of 25 C/g, and a 3% sodium chloride concentration. A key finding in this research is
that that a 100% regeneration of the adsorbent capacity was achieved within a very short
time of around 10 minutes.
Since the GICs act as an anode in the electrochemical cell, it is highly likely that
electrochemically formed oxidizing agents such as chlorine and hypochlorite are attached to
the surface.

Study showed that rinsing the GIC adsorbent to remove adsorbed oxidising species before
readsorption increased the adsorption capacity (Brown et al. 2004a). SEM photographs of
the GIC surface after regeneration showed that there is no formation of internal pores and the
rough surface observed after regeneration provide evidence of shearing of some graphene
layers thus resulting in the reduction of particle size distribution (Brown et al. 2004a).

2.2.4. Electrochemical Oxidation Process

The electrochemical treatment of dye-containing effluents is a promising technique. This

technique offers an alternative solution to many environmental problems in the process
industry, because electrons provide a versatile, efficient, cost-effective, easily automatable,
safe and clean reagent.

2.3. Biological Treatments

There are different biological treatments, performed under aerobic or anaerobic or combined
anaerobic/aerobic conditions. The processing, quality, adaptability of microorganisms, and
the reactor type are key parameters for removal efficiency. Biological treatment systems can
be used in combination with chemical processes.

Table 4. The summery of the waste water treatment

Treatment Sort Advantage Disadvantage
Adsorption on AC Good removal Blocking filter
High operating cost to regenerate
Ozonation No sludge production High operating and, capital cost
 No alteration of V Short half life
Goog declourization No reduction of COD
Chemical Effective for all -dye-s High ooperating cost
precipitation Elimination of -dye-s High sludge production
Low cost
Filtration Low P (10-100 psi) Insufficiency quality of treated
wasteH2O
High capital cost
Electrochemical No sludge production No effective for all the -dye-s
oxidation Breaking down compound are High capital cost
non -hazardous
Biological processes Environmentally friendly Slow process
Economical attractive Need adequate nutrients
Low cost Narrow operating T range