Alexandria university

Faculty of engineering
Chemical engineering department

Removal of methylene blue

dye from wastewater by
electrocoagulation

Presented by:
Mohammed Hesham bd Elmoneam

Presented to:
prof.Dr. Yehia Eltaweel
Table of contents

1. Introduction .............................................................................................................................1
2. Theoretical background ...........................................................................................................3
2.1 Wastewater overview .........................................................................................................3
2.2 Wastewater characteristics .................................................................................................4
2.2.1 Physical characteristics ............................................................................................5
2.2.2 Chemical characteristics ..........................................................................................6
2.2.3 Biological characteristics ........................................................................................10
2.3 Wastewater treatment ........................................................................................................11

2.3.1 Preliminary treatment .............................................................................................12

2.3.2 Primary treatment ...................................................................................................13

2.3.3 Secondary treatment ...............................................................................................14

2.3.4 Tertiary and/or advanced treatment ........................................................................16

2.3.5 Disinfection ............................................................................................................16

3. Electrocoagulation ..................................................................................................................18
3.1 Overview of Electrocoagulation........................................................................................18
3.2 Zeta potential.....................................................................................................................19
3.3 Mechanism of electrocoagulation......................................................................................20
3.4 Kinetics of Electrocoagulation process..............................................................................22
3.5 Cell design of Electrocoagulation .....................................................................................23
3.5.1 Physical design issues .............................................................................................23
3.5.1.1 Geometry ...................................................................................................23
3.5.1.2 Current density ..........................................................................................23
3.5.1.3 type of operation .......................................................................................24
3.5.1.4 Reactor scale up ........................................................................................25
3.5.2 Chemical design issues ...........................................................................................25
3.5.2.1 Electrode material .....................................................................................25
3.5.2.2 Passivation ................................................................................................26
3.5.2.3 pH of the solution .....................................................................................26
 3.6 Electro flotation.................................................................................................................26
3.7 Parameters affecting on electrocoagulation process ........................................................27
3.7.1 Initial pH.................................................................................................................27
3.7.2 Current density........................................................................................................28
3.7.3 Conductivity (concentration of NaCl) ...................................................................28
3.7.4 Time of electrocoagulation ....................................................................................28
3.7.5 Initial dye concentration ........................................................................................29
3.7.6 Addition of surfactants ...........................................................................................29
3.8 Advantages of electrocoagulation ....................................................................................29
3.9 Disadvantages of electrocoagulation ...............................................................................30
4. Experimental part ..................................................................................................................31
4.1 Apparatus .........................................................................................................................31
4.2 Dimensions of the cell .....................................................................................................32
4.3 Method and procedure .....................................................................................................32
5. Results and discussion ...........................................................................................................33
5.1 Effect of different parameters on electrocoagulation process ..........................................33
5.2 Methylene blue dye ..........................................................................................................33
5.2.1 effect of time of electrocoagulation ........................................................................33
5.2.2 Effect of initial dye concentration ..........................................................................34
5.2.3 Effect of of current density .....................................................................................35
5.2.4 Effect of NaCl concentration ..................................................................................36
5.2.5 Effect of initial pH of solution of dye .....................................................................36
6. Conclusion and Recommendation ..........................................................................................38
6.1 Conclusion ........................................................................................................................38
6.2 Recommendation ..............................................................................................................38
References ......................................................................................................................................38
Table of figures

Figure 1 .........................................................................................................................................3
Figure 2 ........................................................................................................................................12
Figure 3 ........................................................................................................................................12
Figure 4 ........................................................................................................................................13
Figure 5 ........................................................................................................................................19
Figure 6 ........................................................................................................................................24
Figure 7 ........................................................................................................................................31
Figure 8 ........................................................................................................................................34
Figure 9 ........................................................................................................................................35
Figure 10 ......................................................................................................................................35
Figure 11.......................................................................................................................................36
Figure 12 ......................................................................................................................................39
Table of tables
table (1) ..........................................................................................................................................10
Summary

The aim of this presented work is to solve the problem of presence of dyes in wastewater from
textile factories, and other industries, that problem is solved with a lot of treatments methods, but
in modern age, it is more efficient to use electrical methods (e.g. Electrocoagulation), in which
( in this presented projected), simple reactor cell is used with new design of high surface area
anode to study Electrocoagulation efficiently and some parameters affect on this method to reach
best case and best color removal of the dye from aqueous solutions of dyes, it is done by locating
cathode and anode made from iron in aqueous solutions, in which each solution has different
properties and under different conditions, to know best conditions for electrocoagulation.
Chapter (1): Introduction
Because of the hazards associated with the large amounts of textile wastewater, several studies
were conducted worldwide resulting in a number of treatment techniques for this water. The
complexity of these techniques depends on the intended fate of the treated water and the
environmental laws of the country on which it exists. In recent years, there has been increasing
interest in the use of electrochemical techniques such as electrocoagulation, electro-flotation,
electro-decantation, catalytic wet air oxidation etc for the treatment of dye house effluent. Among
these techniques electrocoagulation emerges as one of the promising techniques for the treatment
of organic effluent, it is not a new technique because Electrocoagulation with aluminum and iron
electrodes was patented in the United States in 1909 and this technique is used too in England in
the early 20th century. Although later processes of electrocoagulation proved that they need high
operational cost but, successful treatment of various industrial effluents has been reported by
several researchers last decade as it is considered to be potentially an effective tool for treatment
of wastewaters with high removal efficiency.
The principle of electrocoagulation is the same that the principle of chemical coagulation, the
difference between two methods is the way to add coagulants, in chemical coagulation, it is done
by adding chemical dose (coagulant) to the wastewater as chemical substance such as Alum
[Al2(SO4).18H2O] which has been widely used for ages for water treatment, but in case of
electrocoagulation, it depends on responses of water contaminants to strong electric fields and
electrically induced oxidation and reduction reactions and direct current causes sacrificial
electrode (iron or aluminum) ions to remove undesirable contaminants (corrosion of sacrificial
anode) so, anodes can release the coagulants if an applied potential difference occurs between the
electrodes, there are electrolytic gases are released from the electrochemical cell such as
Hydrogen which is produced at the cathode when water is decomposed, this reaction produces
OH- ions which can react with metal ions and form hydroxides, these hydroxides of metal (Fe)
can contribute in the precipitation of other metallic ions and salts.
The target of this project is to study the different parameters with different values such as: applied
current, initial dye concentration, electrolyte concentration, initial pH of the aqueous solution and
time of electrocoagulation to remove contaminants of methylene blue dye from aqueous solutions
of methylene blue by using a fixed bed electrochemical batch circular reactor with horizontal iron
electrodes the cathode is made of a horizontal iron plate rested on the cell bottom, and the anode

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consists of number of very low height cylinders drilled in the centers (rings), this cylinders are
connected by thin rod of iron located above the iron cylindrical plate, as there is perforated plastic
sheet is located between them to prevent short circuit.

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Chapter (2): Theoretical background

2.1 Wastewater overview:

Every community produces both liquid and solid wastes and air emissions. The liquid
waste (wastewater) is essentially the water supply of the community after it has been used in a
variety of applications (see Fig.1). From the standpoint of sources of generation, wastewater may
be defined as a combination of the liquid or water-carried wastes removed from residences,
institutions, and commercial and industrial establishments,together with such groundwater,
surface water, and storm water as may be present.

Fig.1

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When untreated wastewater accumulates and is allowed to go septic, the decomposition of the
organic matter it contains will lead to nuisance conditions including the production of
malodorous gases. In addition, untreated wastewater contains numerous pathogenic
microorganisms that dwell in the human intestinal tract. Wastewater also contains nutrients,
which can stimulate the growth of aquatic plants, and may contain toxic compounds or
compounds that potentially may be mutagenic or carcinogenic. For these reasons, the immediate
and nuisance-free removal of wastewater from its sources of generation, followed by treatment,
reuse, or dispersal into the environment is necessary to protect public health and the environment.
Wastewater engineering is that branch of environmental engineering in which the basic principles
of science and engineering are applied to solving the issues associated with the treatment and
reuse of wastewater. The ultimate goal of wastewater engineering is the protection of public
health in a manner commensurate with environmental, economic, social, and political concerns.
To protect public health and the environment, it is necessary to have knowledge of:
(1) constituents of concern in wastewater.
(2) impacts of these constituents when wastewater is dispersed into the environment.
(3) the transformation and long-term fate of these constituents in treatment processes.
(4) treatment methods that can be used to remove or modify the constituents found in wastewater.
(5) methods for beneficial use or disposal of solids generated by the treatment systems.
To provide an initial perspective on the field of wastewater engineering, common terminology
is first defined followed by:
(1) a discussion of the issues that need to be addressed in the planning and design of wastewater
management systems.
(2) the current status and new directions in wastewater engineering.

2.2 Wastewater characteristics

The selection and design of treatment facilities is based on a study of:
(1) the physical, chemical and biological characteristics of the wastewater.
(2) the quality that must be maintained in the environment to which the wastewater is to be
discharged or for the reuse of the wastewater.
(3) the applicable environmental standards or discharge requirements that must be met.

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The main chemical characteristics of wastewater are divided into two classes, inorganic and
organic. Because of their special importance, priority pollutants and volatile organic compounds
(VOCs) are usually considered separately.

2.2.1 Physical characteristics

The principal physical characteristics of waste-water are its solids content, color, odor and
Temperature.
The total solids in a wastewater consist of the insoluble or suspended solids and the soluble
compounds dissolved in water. The suspended solids content is found by drying and weighing the
residue removed by the filtering of the sample. When this residue is ignited the volatile solids are
burned off. Volatile solids are presumed to be organic matter, although some organic matter will
not burn and some inorganic salts break down at high temperatures. The organic matter consists
mainly of proteins, carbohydrates and fats.Between 40 and 65 % of the solids in an average
wastewater are suspended. Settleable solids, ex-pressed as milliliters per liter, are those that can
be removed by sedimentation. Usually about 60 % of the suspended solids in a municipal
wastewater are settleable. Solids may be classified in another ways well: those that are volatilized
at a high temperature (600 ºC) and those that are not. The former are known as volatile solids, the
latter as fixed solids.Usually, volatile solids are organic.

Color is a qualitative characteristic that can be used to assess the general condition of wastewater.
Wastewater that is light brown in color is less than 6 hrs old, while a light to medium gray color is
characteristic of wastewaters that have undergone some degree of decomposition or that have
been in the collection system for some time. Lastly, if the color is dark gray or black, the
wastewater is typically septic, having undergone extensive bacterial decomposition under
anaerobic conditions. The blackening of wastewater is often due to the formation of various
sulfides, particularly, ferrous sulfide. This results when hydrogen sulfide produced under
anaerobic conditions combines with divalent metal, such as iron, which may be present.Color is
measured by comparison with standards.

Odor, the determination of odor has become increasingly important, as the general public has
become more concerned with the proper operation of wastewater treatment facilities. The odor of

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fresh wastewater is usually not offensive, but a variety of odorous compounds are released when
wastewater is decomposed biologically under anaerobic conditions. The principal pound is
hydrogen sulfide (the smell of rotten odorous com-eggs). Other compounds, such as indol, skatol,
cadaverine and mercaptan, formed under anaerobic conditions or present in the effluents of pulp
and paper mills (hydrogen sulfide, mercaptan,di methyl sulfide etc.), may also cause a rather
offensive odor. Odor is measured by successive dilutions of the sample with odor free water until
the odor is no longer detectable.

Temperature of wastewater is commonly higher than that of the water supply because warm
municipal water has been added. The measurement of temperature is important because most
wastewater treatment schemes include biological processes that are temperature dependent. The
temperature of wastewater will vary from season to season and also with geographic location. In
cold regions the temperature will vary from about 7 to 18 ºC, while in warmer regions the
temperatures vary from 13 to 24 ºC.

Turbidity, one of the first things we notice about water is its clarity.The clarity of water is usually
measured by its turbidity.Turbidity is a measure of the extent to which light is either absorbed or
scattered by suspended material in water. Both the size and surface characteristics of the
suspended mate-rial influence absorption and scattering. Although algal blooms can make waters
turbid, in surface water most turbidity is related to the smaller inorganic components of the
suspended solids burden, primarily the clay particles. Microorganisms and vegetable material
may also contribute to turbidity. Wastewaters from industry and households usually contain a
wide variety of turbidity producing materials. Detergents, soaps, and various emulsifying agents
contribute to turbidity.

2.2.2 Chemical characteristics

Alkalinity, which is a measure of the ability of water to neutralize acid, or an expression of its
buffering capacity. The major chemical constituents of alkalinity in natural water sup- plies are
the bicarbonate, carbonate, and hydroxyl ions. These compounds are primarily the carbonates and
bicarbonates of sodium, potassium, magnesium, and calcium. These constituents originate from
carbon dioxide (from the atmosphere and as a byproduct of microbial decomposition of organic

6
material) and minerals (primarily from chemical compounds dissolved from rocks and soil).
Highly alkaline waters are unpalatable; however, this condition has little known significance for
human health. The principal problem with alkaline water is the reactions that occur between
alkalinity and certain substances in the water. Alkalinity is important for fish and aquatic life
because it protects or buffers against rapid pH changes.Moreover, the resultant precipitate can
foul water system appurtenances. In addition, alkalinity levels affect the efficiency of certain
water treatment processes, especially the coagulation process.

Hardness is due to the presence of multivalent metal ions,which come from minerals dissolved in
water. Hardness is based on the ability of these ions to react with soap to form a precipitate or
soap scum. In freshwater, the primary ions are calcium and magnesium; however, iron and
manganese may also contribute. Hardness is classified as carbonate hardness or non carbonate
hardness. Carbonate hardness is equal to alkalinity but a non carbonate fraction may include
nitrates and chlorides. Hardness is either temporary or permanent. Carbonate hardness (temporary
hardness) can be removed by boiling. Non carbonate hardness cannot be removed by boiling and
is classified as permanent.Water with a hardness of less than50 ppm is soft. Above 200 ppm,
domestic supplies are usually blended to reduce the hardness value. Scaling occurs when
carbonate hard water is heated and calcium carbonate and magnesium hydroxide are precipitated
out of solution, forming a rock-hard scale that clogs hot water pipes and reduces the efficiency of
boilers, water heaters, and heat exchangers.

pH refers to the hydrogen ion concentration. Acidity, the concentration of hydrogen ions, drives
many chemical reactions in living organisms. A pH value of (7 ) represents a neutral condition. A
low pH value (less than5) indicates acidic conditions; a high pH (greater than 9) indicates
alkaline conditions. Many biological processes,such as reproduction, cannot function in acidic or
alkaline waters. Acidic conditions also aggravate toxic contamination problems because
sediments release toxicants in acidic waters, wastewater normally is in the range of 6.5 to 9.0 .

Organics are organic chemicals in water primarily emanate from synthetic compounds that
contain carbon, such as Poly Chlorinated Biphenyls (PCBs), dioxin, and Dichloro Diphenyl
Trichloroethane (DDT), all of which are toxic organic chemicals. These synthesized compounds

7
often persist and accumulate in the environment because they do not readily breakdown in natural
ecosystems. Many of these compounds can cause cancer in people and birth defects in other
predators near the top of the food chain, such as birds and fish. The presence of organic matter in
water is troublesome for the following reasons:
(1) color formation.
(2) taste and odor problems.
(3) oxygen depletion in streams.
(4) interference with water treatment processes.
(5) the formation of halogenated compounds when chlorine is added to disinfect water.

Sulfur compounds, sulfur (S) is required for the synthesis of proteins and is released in their
degradation. The sulfate ion occurs naturally in most water supplies and is present in waste water
as well. Sulfate is reduced biologically to sulfide,which in turn can combine with hydrogen to
form hydrogen sulfide (H2S). H2S is toxic to animals and plants. H2S in interceptor systems can
cause severe corrosion to pipes and appurtenances. Moreover, in certain concentrations,H2S is a
deadly toxin.

Phosphorous compounds, Phosphorus (P) is a macronutrient that is necessary to all living cells
and is a ubiquitous constituent of waste water. It is primarily present in the form of phosphates,
the salts of phosphoric acid. Municipal wastewaters may contain 10 to 20 mg/L phosphorus as P,
much of which comes from phosphate builders in detergents. Noxious algal blooms that occur in
surface waters have generated much interest in controlling the amount of phosphorus compounds
that enter surface waters in domestic and industrial waste discharges and natural runoff.

Nitrogen compounds result from the biological decomposition of proteins and from urea
discharged in body waste. In wastewater treatment, biological treatment cannot proceed unless
nitrogen, in some form, is present. Nitrogen must be present in the form of organic nitrogen (N),
ammonia (NH3), nitrite (NO2), or nitrate (NO3). Organic nitrogen includes such natural
constituents as peptides, proteins, urea, nucleic acids, and numerous synthetic organic materials.
Ammonia is present naturally in waste waters. It is produced primarily by deaeration of organic
nitrogen containing compounds and by hydrolysis of urea. Nitrite, an intermediate oxidation state

8
of nitrogen, can enter a water system through use as a corrosion inhibitor in industrial
applications. Nitrate is derived from the oxidation of ammonia.

Dissolved gases are gases that are dissolved in wastewater. The specific gases and normal
concentrations are based on the composition of the wastewater. Typical domestic wastewater
con-tains oxygen in relatively low concentrations,carbon dioxide, and hydrogen sulfide (if septic
conditions exist).

Chemical oxygen demand is a measure of the amount of oxidizable matter present in the sample.
The COD is normally in the range of 200 to 500 mg/L. The presence of industrial wastes can
increase this significantly.

Biological oxygen demand is a measure of the amount of biodegradable matter in the wastewater.
It is normally measured by a (5) day test conducted at 20 ºC. The BOD5 for domestic waste is
normally in the range of 100 to 300 mg/L.

Solids, Most pollutants found in wastewater can be classified as solids. Wastewater treatment is
generally designed to remove solids or to con-vert solids to a form that is more stable or can be
removed. Solids can be classified by their chemical composition (organic or inorganic) orby their
physical characteristics (settleable,floatable, and colloidal). Concentrations of total solids in
wastewater are normally in the range of 350 to 1200 mg/L.

(1) Organic solids consist of carbon, hydrogen,oxygen, and nitrogen and can be converted to
carbon dioxide and water by ignition at550°C; also known as fixed solids or loss on ignition.

(2) Inorganic solids are mineral solids that are unaffected by ignition; also known as fixed solids
or ash.
(3) Suspended solids will not pass through a glass fiber filter pad; they can be further classified as
total suspended solids (TSS), vola-tile suspended solids, and fixed suspended solids. They can
also be separated into three components based on settling characteristics:settleable solids,
floatable solids, and colloidal solids. Total suspended solids in waste-water are normally in
the range of 100 to 350mg/L.

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(4) Dissolved solids will pass through a glass fiber filter pad. They can also be classified as total
dissolved solids (TDS), volatile dissolved solids, and fixed dissolved solids.Total dissolved
solids are normally in the range of 250 to 850 mg/L. Water is always the major constituent of
waste water. In most cases, water makes up 99.5 to 99.9% of the wastewater. Even in the
strongest wastewater, the total amount of contamination present is less than 0.5% of the total,
and in average strength wastes it is usually less than 0.1%.

2.2.3 Biological characteristics

In a natural stream, such substances are a source of food for protozoa,fungi, algae, and several
varieties of bacteria. In secondary wastewater treatment, these same microscopic organisms
(which are one of the main reasons for treating wastewater) are allowed to work as fast as they
can to biologically convert the dissolved solids to suspended solids that will physically settle out
at the end of secondary treatment. Raw wastewater influent typically contains millions of
organisms. The majority of these organisms are not pathogenic; however, several pathogenic
organisms may also be present (these may include the organisms responsible for diseases such as
typhoid, tetanus, hepatitis, dysentery, gastroenteritis, and others). Many of the organisms found in
wastewater are microscopic (microorganisms), they include algae, bacteria, protozoa (such as
amoebae, flagellates, free swimming ciliates, and stalked ciliates), rotifers, and viruses.

Table (1) provides a summary of typical domestic wastewater characteristics.

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2.3 Wastewater treatment

The principal objective of wastewater treatment is generally to allow human and industrial
effluents to be disposed of without danger to human health or unacceptable damage to the natural
environment. Irrigation with wastewater is both disposal and utilization and indeed is an effective
form of wastewater disposal (as in slow-rate land treatment). However, some degree of treatment
must normally be provided to raw municipal wastewater before it can be used for agricultural or
landscape irrigation or for aquaculture. The quality of treated effluent used in agriculture has a
great influence on the operation and performance of the wastewater-soil-plant or aquaculture
system. In the case of irrigation, the required quality of effluent will depend on the crop or crops
to be irrigated, the soil conditions and the system of effluent distribution adopted. Through crop
restriction and selection of irrigation systems which minimize health risk, the degree of
pre-application wastewater treatment can be reduced. A similar approach is not feasible in
aquaculture systems and more reliance will have to be placed on control through wastewater
treatment.

The most appropriate wastewater treatment to be applied before effluent use in agriculture is that
which will produce an effluent meeting the recommended microbiological and chemical quality
guidelines both at low cost and with minimal operational and maintenance requirements.
Adopting as low a level of treatment as possible is especially desirable in developing countries,
not only from the point of view of cost but also in acknowledgement of the difficulty of operating
complex systems reliably. In many locations it will be better to design the reuse system to accept
a low-grade of effluent rather than to rely on advanced treatment processes producing a reclaimed
effluent which continuously meets a stringent quality standard.Nevertheless, there are locations
where a higher-grade effluent will be necessary and it is essential that information on the
performance of a wide range of wastewater treatment technology should be available. The design
of wastewater treatment plants is usually based on the need to reduce organic and suspended
solids loads to limit pollution of the environment. Pathogen removal has very rarely been
considered an objective but, for reuse of effluents in agriculture, this must now be of primary
concern and processes should be selected and designed accordingly. Treatment to remove
wastewater constituents that may be toxic or harmful to crops, aquatic plants (macrophytes) and
fish is technically possible but is not normally economically feasible. Unfortunately, few

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performance data on wastewater treatment plants in developing countries are available and even
then they do not normally include effluent quality parameters of importance in agricultural use.

2.3.1 Preliminary treatment

The objective of preliminary treatment is the removal of coarse solids and other large materials
often found in raw wastewater. Removal of these materials is necessary to enhance the operation
and maintenance of subsequent treatment units. Preliminary treatment operations typically
include coarse screening, grit removal and, in some cases, comminution of large objects. In grit
chambers (see fig.2), the velocity of the water through the chamber is maintained sufficiently
high, or air is used, so as to prevent the settling of most organic solids. Grit removal is not
included as a preliminary treatment step in most small wastewater treatment plants. Comminutors
(see Fig.3) are sometimes adopted to supplement coarse screening and serve to reduce the size of
large particles so that they will be removed in the form of a sludge in subsequent treatment
processes. Flow measurement devices, often standing wave flumes (see Fig.4), are always
included at the preliminary treatment stage.

Fig.2 Fig.3

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 Fig.4

2.3.2 Primary treatment

The objective of primary treatment is the removal of settleable organic and inorganic solids by
sedimentation, and the removal of materials that will float (scum) by skimming. Approximately
25 to 50% of the incoming biochemical oxygen demand (BOD5), 50 to 70% of the total
suspended solids (SS), and 65% of the oil and grease are removed during primary treatment.
Some organic nitrogen, organic phosphorus, and heavy metals associated with solids are also
removed during primary sedimentation but colloidal and dissolved constituents are not affected.
The effluent from primary sedimentation units is referred to as primary effluent.
In many industrialized countries, primary treatment is the minimum level of preapplication
treatment required for wastewater irrigation. It may be considered sufficient treatment if the
wastewater is used to irrigate crops that are not consumed by humans or to irrigate orchards,
vineyards, and some processed food crops. However, to prevent potential nuisance conditions in
storage or flow equalizing reservoirs, some form of secondary treatment is normally required,
even in the case of non-food crop irrigation. It may be possible to use at least a portion of primary
effluent for irrigation if off line storage is provided.
Primary sedimentation tanks or clarifiers may be round or rectangular basins, Settled solids
(primary sludge) are normally removed from the bottom of tanks by sludge rakes that scrape the
sludge to a central well from which it is pumped to sludge processing units. Scum is swept across
the tank surface by water jets or mechanical means from which it is also pumped to sludge
processing units.

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In large sewage treatment plants, primary sludge is most commonly processed biologically by
anaerobic digestion. In the digestion process, anaerobic and facultative bacteria metabolize the
organic material in sludge, thereby reducing the volume requiring ultimate disposal, making the
sludge stable (non putrescible) and improving its dewatering characteristics. Digestion is carried
out in covered tanks (anaerobic digesters), The residence time in a digester may vary from a
minimum of about 10 days for high-rate digesters (well-mixed and heated) to 60 days or more in
standard-rate digesters. Gas containing about 60 to 65% methane is produced during digestion
and can be recovered as an energy source. In small sewage treatment plants, sludge is processed
in a variety of ways including: aerobic digestion, storage in sludge lagoons, direct application to
sludge drying beds, in process storage (as in stabilization ponds), and land application.

2.3.3 Secondary treatment

The objective of secondary treatment is the further treatment of the effluent from primary
treatment to remove the residual organics and suspended solids. In most cases, secondary
treatment follows primary treatment and involves the removal of biodegradable dissolved and
colloidal organic matter using aerobic biological treatment processes. Aerobic biological
treatment is performed in the presence of oxygen by aerobic microorganisms (principally bacteria)
that metabolize the organic matter in the wastewater, thereby producing more microorganisms
and inorganic end products (principally CO2, NH3, and H2O). Several aerobic biological
processes are used for secondary treatment differing primarily in the manner in which oxygen is
supplied to the microorganisms and in the rate at which organisms metabolize the organic matter.
High rate biological processes are characterized by relatively small reactor volumes and high
concentrations of microorganisms compared with low rate processes. Consequently, the growth
rate of new organisms is much greater in high rate systems because of the well controlled
environment. The microorganisms must be separated from the treated wastewater by
sedimentation to produce clarified secondary effluent. The sedimentation tanks used in secondary
treatment, often referred to as secondary clarifiers, operate in the same basic manner as the
primary clarifiers described previously. The biological solids removed during secondary
sedimentation, called secondary or biological sludge, are normally combined with primary sludge
for sludge processing.
Common high rate processes include the activated sludge processes, trickling filters or bio filters,
oxidation ditches, and rotating biological contactors (RBC). A combination of two of these

14
processes in series (e.g., bio filter followed by activated sludge) is sometimes used to treat
municipal wastewater containing a high concentration of organic material from industrial sources.

(1) Activated Sludge

In the activated sludge process, the dispersed growth reactor is an aeration tank or basin
containing a suspension of the wastewater and microorganisms, the mixed liquor. The contents of
the aeration tank are mixed vigorously by aeration devices which also supply oxygen to the
biological suspension . Aeration devices commonly used include submerged diffusers that release
compressed air and mechanical surface aerators that introduce air by agitating the liquid surface.
Hydraulic retention time in the aeration tanks usually ranges from 3 to 8 hours but can be higher
with high BOD5 wastewaters. Following the aeration step, the microorganisms are separated from
the liquid by sedimentation and the clarified liquid is secondary effluent. A portion of the
biological sludge is recycled to the aeration basin to maintain a high mixed liquor suspended
solids (MLSS) level. The remainder is removed from the process and sent to sludge processing to
maintain a relatively constant concentration of microorganisms in the system. Several variations
of the basic activated sludge process, such as extended aeration and oxidation ditches, are in
common use, but the principles are similar.

(2) Trickling Filters

A trickling filter or bio filter consists of a basin or tower filled with support media such as stones,
plastic shapes, or wooden slats. Wastewater is applied intermittently, or sometimes continuously,
over the media. Microorganisms become attached to the media and form a biological layer or
fixed film. Organic matter in the wastewater diffuses into the film, where it is metabolized.
Oxygen is normally supplied to the film by the natural flow of air either up or down through the
media, depending on the relative temperatures of the wastewater and ambient air. Forced air can
also be supplied by blowers but this is rarely necessary. The thickness of the bio film increases as
new organisms grow. Periodically, portions of the film slough off the media. The sloughed
material is separated from the liquid in a secondary clarifier and discharged to sludge processing.
Clarified liquid from the secondary clarifier is the secondary effluent and a portion is often
recycled to the bio filter to improve hydraulic distribution of the wastewater over the filter.
(3) Rotating Biological Contactors

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Rotating biological contactors (RBCs) are fixed film reactors similar to bio filters in that
organisms are attached to support media. In the case of the RBC, the support media are slowly
rotating discs that are partially submerged in flowing wastewater in the reactor. Oxygen is
supplied to the attached bio film from the air when the film is out of the water and from the liquid
when submerged, since oxygen is transferred to the wastewater by surface turbulence created by
the discs rotation. Sloughed pieces of bio film are removed in the same manner described for bio
filters.

2.3.4 Tertiary and/or advanced treatment

Tertiary and/or advanced wastewater treatment is employed when specific wastewater

constituents which cannot be removed by secondary treatment must be removed, individual
treatment processes are necessary to remove nitrogen, phosphorus, additional suspended solids,
refractory organics, heavy metals and dissolved solids. Because advanced treatment usually
follows high rate secondary treatment, it is sometimes referred to as tertiary treatment. However,
advanced treatment processes are sometimes combined with primary or secondary treatment (e.g.,
chemical addition to primary clarifiers or aeration basins to remove phosphorus) or used in place
of secondary treatment (e.g., overland flow treatment of primary effluent).
In many situations, where the risk of public exposure to the reclaimed water or residual
constituents is high, the intent of the treatment is to minimize the probability of human exposure
to enteric viruses and other pathogens. Effective disinfection of viruses is believed to be inhibited
by suspended and colloidal solids in the water, therefore these solids must be removed by
advanced treatment before the disinfection step.

2.3.5 Disinfection

Disinfection normally involves the injection of a chlorine solution at the head end of a chlorine
contact basin. The chlorine dosage depends upon the strength of the wastewater and other factors,
but dosages of 5 to 15 mg/l are common. Ozone and ultra violet (UV) irradiation can also be used
for disinfection but these methods of disinfection are not in common use. Chlorine contact basins
are usually rectangular channels, with baffles to prevent short circuiting, designed to provide a
contact time of about 30 minutes. However, to meet advanced wastewater treatment
requirements, a chlorine contact time of as long as 120 minutes is sometimes required for specific
irrigation uses of reclaimed wastewater. The bactericidal effects of chlorine and other

16
disinfectants are dependent upon pH, contact time, organic content, and effluent temperature.

17
Chapter (3): Electrocoagulation

Because of the hazards associated with the large amounts of textile wastewater, several studies
were conducted worldwide resulting in a number of treatment techniques for this water. The
complexity of these techniques depends on the intended fate of the treated water and the
environmental laws of the country on which it exists. In recent years, there has been increasing
interest in the use of electrochemical techniques such as electrocoagulation, electro-flotation,
electro-decantation, catalytic wet air oxidation etc for the treatment of dye house effluent. Among
these techniques electrocoagulation emerges as one of the promising techniques for the treatment
of organic effluent, it is not a new technique because Electrocoagulation with aluminum and iron
electrodes was patented in the United States in 1909 and this technique is used too in England in
the early 20th century. Although later processes of electrocoagulation proved that they need high
operational cost but, successful treatment of various industrial effluents has been reported by
several researchers last decade as it is considered to be potentially an effective tool for treatment
of wastewaters with high removal efficiency.

3.1 Overview of Electrocoagulation

Electrocoagulation is an electrochemical approach, which uses an electrical current to remove
metals from solution. Electrocoagulation system is also effective in removing suspended solids,
dissolved metals, tannins and dyes. The contaminants presents in wastewater are maintained in
solution by electrical charges. When these ions and other charged particles are neutralized with
ions of opposite electrical charges provided by electrocoagulation system, they become
destabilized and precipitate in a stable form, which depends on estabilizing of the colloidal
suspension by reducing any repusion forces, thereby lowering the energy barrier and enbling
particles to aggregate. In electrocoalaton, the poluutant stability is determined by its
physicochemical properties, Ppollutants composed of similarly charged prticles repel each other,
with the repulsive forces creating a stable colloidal system with oppositely charged ions, typically
－
hydroxyl (OH ) or hydrogen ions (H+) being attracted to the charged pollutant particles.

The attraction of counter ions to a charged pollutant forms an electric double layer referred to as
the stern and diffuse layers, electrostatic repulsion between electric double layers drive the

18
particles apart whilst Van Der Waals forces act to bring them together. However, to reach the
stage of separation, a repulsive energy barrier must first be overcome.

3.2 Zeta potential

The zeta potential is used as an experimental measure of effecive charge of the particle as it
moves through solution and that provides direct indicator of solution stability, the liquid layer
surrounding the particle exists as two parts, an inner region (stern layer) where the ions are
strongly bound and an outer (diffuse) region where they are less firmly associated, with in the
diffuse layer there is a notional boundary inside which the ions and particles form a stable entity,
when particles moves (due to gravity), ions within the boundary move it while ions beyond the
boundary stay with the bulk dispersant, te potential at this boundary, surface of hydrodynamic
shear, is the zeta potential, the magnitude of the zeta potential gives an indication of the potential
stability of the colloidal system, if all the particles in suspension have a large negative or positive
zeta potential (see Figure5) they will tend to repel each other and there will be no tendency for
the particles to come together, However, if the particles have low zeta potential values then there
will be no force to prevent the particles from coming together and flocculating.

Fig.5

19
3.3 Mechanism of electrocoagulation
Electrocoagulation is a complex process occurring via series steps. When current is passed
through electro chemical reactor, it must overcome the equilibrium potential difference, anode
over potential, cathode over potential and potential drop of the solution. The anode over potential
includes the activation over potential and concentration potential, as well as the possible passive
over potential resulted from the passive film at the anode surface, while the cathode over
potential is principally composed of the activation over potential and concentration over
potential. Reactions at electrode surfaces, formation of coagulants in aqueous phase, adsorption
of soluble or colloidal pollutants on coagulants shown in fig. (2).Generally, aluminum and iron
are used as an electrode material in the electrocoagulation process.In the iron electrode, two
mechanisms have been proposed .
Mechanism 1
Anode:
－
4Fe(s) → 4Fe+2(aq) + 8e

4Fe+2(aq) + 10H2O(l) + O2 (g) → 4Fe(OH)3 (s) + 8H +(aq)

Cathode:
－
8H+(aq) + 8e → 4H2 (g)

Overall:
4Fe(s) + 10H2O(l) + O2 (g) → 4Fe(OH)3 (s) + 4H2 (g)

Mechanism 2
Anode:
－
Fe(s) → Fe+2(aq) + 2e
－
Fe+2(aq) + 2OH (aq) → Fe(OH)2 (s)

Cathode:
－ －
2H2O(l) + 2e → H2 (g) + 2OH (aq)

Overall:
Fe(s) + 2H2O (l) → Fe(OH)2 (s) + H2 (g)

Due to oxidation in an electrolyte system, iron produces form of monomeric ions, Fe(OH)3 and

20
polymeric hydroxy complex such as:
Fe(H2O)63+, Fe(H2O)52+, Fe(H2O)4(OH)2+, Fe(H2O)8(OH)24+and Fe2(H2O)6(OH)44+ depending
upon the pH of the aqueous medium.
Destabilization mechanism of contaminants, particulate suspension, and emulsion breaking
summarized as follows:
(1) Due to oxidation of the sacrificial anode, generation and interaction of ions are possible.
Compression of the diffuse double layer can be possible around the charged ions.
(2) Electrochemical dissolution of the sacrificial anode produced counter ions. These counter ions
are responsible for presence of charged neutralization of ionic species which present in the
waste water. These counter ions are responsible of the reduction of the electrostatic
interparticle repulsion so that Van Der Walls attraction predominates hence coagulation
occurs which approach to the zero net charge.
(3) Coagulation causes a flock formation and creates a sludge blanket which entraps and bridge
colloidal particles which is present in the still aqueous medium.
(4) The negative surfaces of the solid oxides, hydroxides, and oxy hydroxides are responsible for
adsorption of contaminated contents.
(5) Due to dissolution of (Fe) electrodes from the anode respective metal ions are generated.
These ions are immediately hydrolyzed into polymeric ions or hydroxides of (Fe).

Main function of sacrificial anode is to generating polymeric hydroxides nearby the anode. These
polymeric hydroxides are act as a excellent coagulating agents. Due to electrophoretic action
negative ions which are produce from the cathode moves towards the anode. Due to combination
of the metal cations with these negative particles which turns into the coagulation. Due to
electrolysis is continuously carried out, water is electrolyzed. At anode small bubble of oxygen
and at the cathode small bubbles of hydrogen are generated which are responsible of electrolysis
of water. The flocculated particles attract by these bubbles and these flocculated particles float
due to the natural buoyancy towards the surface Physio chemical reaction also occurs in the
electrocoagulation cell.
(1) At the cathode metal ions reduction take place.
(2) In the waste water impurities are responsible for catholic reduction.
(3) Colloidal particles being generated by electrode erosion.

21
(4) Coagulation and discharge of colloidal particles by electro flotation or sedimentation and
filtration.
(5) Ions migration done due to electrophoretic in the solution.
(6) Oxygen and hydrogen bubbles which are produced at anode and cathode,
(7) Responsible of electro flotation of coagulated particles.
(8) Other chemical and electrochemical process occurs.
(9) Electrocoagulation process carried out by an external power supply.

3.4 Kinetics of Electrocoagulation process

Electrode reactions are heterogeneous and take place at the interfacial region between the
electrode and solution, Both potential and concentration gradients exist between the electrode
surface and the bulk solution. Thus, the chemical species to be reduced or oxidized must diffuse
from the bulk phase to the electrode surface through (mass transfer) process before electron
transfer can occur at the surface.So, from that, electrochemical reactions are either charge transfer
or mass transfer controlled.But, in many practical cases, both charge and mass transfer are
relevant in determining the overall rate of reaction.
For reactors that use both iron cathode and iron anode, there is dissolution in excess 100% where
efficiency calculations were based on anodic dissolution following Faraday’s law, which is used
to relate the current passed through the cell to the mass of electrolytically generated material
within the reactor and in hat case, Faraday’s law determines the theoretical estimate of the
amount of iron going into the solution.
The quantity of electricity passed through is actually responsible for dissolution and deposition of
metal ions at the electrodes. A relationship between current density (A/cm2) and the quantity of
the metals (M) dissolved (g of (M)/cm2) find out by using Faraday’s law:
W = (I × t × M) / ( Z × F )

W = the amount of dissolution of electrode (g of M/cm2 )

I = Current density (A/cm2 )
t = time in second
M = Relative molar mass of the electrode
Z = no. of electrons in oxidation/reduction reaction
F = Faraday’s constant, 96,500 C/mol.

22
3.5 Cell design of Electrocoagulation
The electrocoagulation process has been combined with many units including microfiltration,
sand filtration and electroflotation. Obviously, pre-water treatment and post-water treatment
impacts significantly the performance of the electrocoagulation reactor. The design of the
electrocoagulation process has great influence on its operation and efficiency. Although it is very
difficult to compare different designs of reactors, there are common factors on which the deign
relies on.
There are chemical factors and physical design issues.

3.5.1 Physical design issues

Which includes reactor geometry, current density, type of operation (batch or continuous) and
Reactor scale up.

3.5.1.1 Geometry
Geometry of the reactor affects operational parameters including bubble path, flotation
effectiveness, floc formation, fluid flow regime and mixing, settling characteristics. The most
common approach involves plate electrodes (Al or Fe) and continuous operation, water is dosed
with dissolved metal ions as it passes through the electrocoagulation cell, a downstream unit is
often required to separate pollutants and water. But, in this presented work, there is good design
of the cell in which, fixed bed electrochemical batch circular reactor with horizontal iron
electrodes the cathode is made of a horizontal iron plate rested on the cell bottom, and the anode
consists of number of very low height cylinders drilled in the centers, this cylinders are connected
by thin rod of iron located above the iron cylindrical plate, as there is perforated plastic sheet is
located between them to prevent short circuit. That design insures high surface area and gas
bubbles diffusion, which in turns, favors flotation of flocs.

3.5.1.2 Current density

It is the amount of current delivered to the electrode divided by the active area of the electrode.
By varying the current easily controls this parameter, current density determines both the rate of
electrochemical metal dosing to the water and the electrolytic bubble rate of production. High
current densities are desirable for separation processes involving flotation cells or large settling

23
tanks, while small current densities are appropriate for electrocoagulation systems that are
integrated with conventional sand and coal filters.

3.5.1.3 type of operation

The first major distinction between alternative designs is whether a reactor was configured as a
batch or continuous type, it is clear that the majority of applications fall into latter type, in which
it has a continuous feed of wastewater and operating under steady state conditions. The most
important advantage for such reactor systems is that their coagulant requirements are essentially
fixed in terms of both design and operation conditions. Batch reactor applications on the other
hand typically operate with a fixed wastewater volume per treatment cycle but suffer from the
perceived disadvantage, from a design and operational standpoint, which is the change in
conditions within the reactor with time, (Fig.6) represents the different systems classified
according to the type of operation, the role of the produced gas bubbles and the pollutant removal
techniques.
A continuous system operates under fixed conditions, specifically a fixed pollutant loading and
flow rat. By contrast, the dynamic nature of the batch reactor enables a range of conditions to be
examined during the course of single run. The batch system provides a greater insight to the
operational response range. So, batch reactor design is preferred and chosen for research and
study.

Fig.6

24
3.5.1.4 Reactor scale up
Increasing reactor size or scale up, is typically as result of increasing feed flow rate. In order to
maintain similar performance between different reactor sizes, it is necessary that the main
operational parameters (e.g. Mixing patterns and reaction kinetics) be maintained a comparable
levels In order to achieve similar flow patterns within a reactor system, dynamic, geometric and
kinetic similarity must be maintained, this approach was adopted by scaling an electrocoagulation
flotation system from laboratory to experimental scale, and finally to industrial scale, there are
parameters to be considered in scale up to ensure correct sizing between reactor systems:
- Reynolds number which provides a measure of the fluid flow regime.
-Froude number which provides a measure of the importance of gravitational forces in the
system.
-Weber criteria which provides a measure of the importance of the surface tension related forces
in the system.
-Gas saturation similarity which is related to the volumetric bubble density in the system.
-Geometric similarity.
One basic scale up design parameter is the electrode surface area to reactor volume ratio (SA/V),
which is a measure of the potential for delivering coagulant and bubbles to a system (on
volumetric basis of course). Current density is also an important scale up design parameter. As
(SA/V) ratio increases, the treatment time decreases and consequently the optimal current density
decreases.

3.5.2 Chemical design issues

The chemical interactions affect the performance of the system. That is the chemical interactions
of the pollutants with the electrode material, electrode passivation and solution pH.

3.5.2.1 Electrode material

The electrode material impacts markedly on the performance of the electrocoagulation reactor.
The anode material determines the cation introduced into solution, The most common electrodes
materials were (Al or Fe). The optimal electrocoagulation conditions varied with the choice of
iron or aluminum electrodes, which in turn is determined by initial pollutant concentration, type
and stirring rate.

25
3.5.2.2 Passivation
One of the greatest operational factors in electrocoagulation is electrode passivation. The
passivation of electrodes is a measure of longevity of the process. Passivation of Al electrodes has
been widely observed in previous studies and it was observed that during electrocoagulation with
iron electrodes, deposits of calcium carbonate and magnesium hydroxide were formed at the
cathode and an oxide layer was formed at the anode. Various methods were investigated for
preventing and controlling electrode passivation including:
- Changing polarity of the electrode.
- Hydromechanical cleaning.
- Introducing inhibiting agents.
- Mechanical cleaning of the electrodes.

3.5.2.3 pH of the solution

It determines the type of metal ions formed in solution. The pH influences the state of other
species in solution and the solubility of products formed. So, pH of the solution influences the
overall efficiency and effectiveness of the electrocoagulation.

3.6 Electro flotation

The final step of electrocoagulation is pollutant removal. So, electro flotation
provides an alternative technique for the removal of pollutants from wastewater, the process
involves the application of an electric current to electrically soluble electrodes, usually iron,
inside a processing reactor, the reactions at the anode and cathode respectively are typically iron
ions as coagulating agent as well as gas bubbles by reactions:
－
Fe(s) → Fe+2(aq) + 2e
－ －
2H2O(l) + 2e → H2 (g) + 2OH (aq)

The well known properties of iron ions as a coagulating agent cause them to combine with the
pollutants, the gas bubbles generated can capture the coagulated agglomerates, similar to the
application in a dissolved air flotation (DAF) unit which results in most of the pollutant being
floated to the surface.
Electrolytic hydrogen bubble production has two main influences in the batch electrocoagulation
reactor, mixing and pollutant removed by flotation, te bubbles create an upward momentum flux,

26
so if sufficient bubbles were present to create a large enough upward momentum, the aggregated
pollutant particles float to the surface. So, the pollutant removal by flotation is the function of the
bubbles formed and their interaction with the aggregate. Operation at low current density suited
settling with the slow release of coagulant at constant conditions. As, the bubbles concentration
increases with current density, the probability of interception between aggregates and bubbles
also increases. This interception results in pollutant removal by flotation to the surface.
From the preceding, it is clear that the operating current and removal time were again identified
as the main parameters, determining both the coagulant and electrolytic gas production rates. This
in turn determined the availability of coagulant to the pollutant and the bubble volume
concentration in the reactor. Current and time thus interlink the removal paths and mechanisms
creating an inherently interconnected system.

3.7 Parameters affecting on electrocoagulation process

3.7.1 Initial pH
The effect of pH of water or wastewater on electrocoagulation are reflected by the current
efficiency as well as the solubility of metal hydroxides, when there are chloride ions present, the
release of chlorine also would be affected. It is generally found that the iron current efficiencies
are higher at either acidic or alkaline condition than at neutral, the treatment performance
depends on the nature of pollutants, the power consumption is higher at neutral pH due to the
variation of conductivity, when conductivity is high, pH effect is not significant, the effluent pH
after electrocoagulation treatment would increase for acidic influent but decrease for alkaline
influent, this is one of advantages of this process, the increase of pH at acidic conditions was
－
attributed to hydrogen evolution at cathodes and accumulation of OH at the cathode. In fact,

besides hydrogen evolution, the formation of hydroxides of iron near the anode would release H+
leading to decrease of pH, in addition, there is also oxygen evolution reaction leading to pH
decrease. When there are chlorine ions, there are following chemical reactions take place:
－ －
2Cl + 2e Cl2
－
Cl2 + H2O HOCl + Cl + H+
－
HOCl OCl + H+

The increase of pH due to hydrogen evolution is more or less compensated by the H+ release, the

27
decrease at alkaline conditions can be the result of formation of hydroxide precipitates and
－
formation of Fe(OH)3 .
－ －
Fe(OH)2 + OH Fe(OH)3

3.7.2 Current density

it determines the coagulant dosage rate and gas bubble production rate, as well as influencing the
fluid regime (mixing) within a reactor. As noted a low current produces a low bubble density,
leading to a low upward momentum flux and thus low mixing within the reactor conditions that
encourage sedimentation over flotation. As the current is increased, the bubble density and the
amount of mixing increase favoring flotation over sedimentation. So, current density is not only
an important operational parameter, but also an important factor in determining the removal path
of the pollutant.

3.7.3 Conductivity (concentration of NaCl)

Salt is usually employed to increase the conductivity of the water or wastewater to be treated,
solution conductivity affects the current efficiency, cell voltage and electrical energy consumption
in electrolytic cell. In addition, increasing solution conductivity using NaCl has other advantages
－
like, chloride ions could significantly reduce the averse effects of other anions, such as HCO3
－2
SO4 . The existence of the carbonate ion would lead to the precipitation of Ca+2 ions that forms

an insulating layer on the surface of cathode. These ions will increase the overall resistance of the
electrochemical cell. Reactions as follows:
－ － －2
HCO3 + OH CO3 + H2O
－2
Ca+2 + CO3 CaCO3

3.7.4 Time of electrocoagulation

During electrolysis the positive electrode (anode) undergoes anodic reactions while cathodic
reactions occur on the negative electrode (cathode). The released ions neutralize the particle
charges and thereby initiate coagulation. The color removal efficiency depends directly on the
concentration of the ions produced by the electrodes, when electrolysis period increases, an
increase occurs in the concentration of ions and their hydroxide flocs.

28
3.7.5 Initial dye concentration
The decolorization efficiency for (Fe) is lower as concentration of dye is higher, because of
formation of insufficient number of iron hydroxides complexes produced by the electrode to
coagulate the greater number of dye molecules at higher concentrations.

3.7.6 Addition of surfactants

Surfactants are kind of molecules with a polar head on one side and a long hydrophobic tail on
the other, molecule of the surfactant binds with the active group charge of the dye causing the
neutralization of the dye and then promotes precipitation. Dye surfactant complexes are water
insoluble but are solubilized in excess of surfactant, surfactants (e.g. CTMAB (cetyl trimethyl
ammonium bromide) and SDS (sodium dodecyl benzene sulphonate)) are examined by
researchers for the removal of dyes from wastewater. The results showed 100% purification.

3.8 Advantages of electrocoagulation

(1) EC requires simple equipment and is easy to operate.
(2) EC requires low initial investment with low operating cost.
(3) The electrolytic processes in the EC cell are controlled electrically and with no moving thus
requiring less maintenance.
(4) EC does not require any chemicals. So there is no problem of neutralizing excess chemicals
and no possibility of secondary pollution caused by chemical substances..
(5) EC composed of mainly metallic oxides/hydroxides. Sludge formed by EC tends to be readily
settable and easy to dewater, so low sludge generation can be done.
(6) EC flock tends to be much larger, contains less bound water, is acid-resistant and more stable,
and therefore, can be separated faster by filtration.
(7) EC produces effluent with less total dissolved solids (TDS) content as compared with
chemical treatments. If this water is reused, the low TDS level contributes to a lower water
recovery cost.
(8) The EC process has the advantage of removing the smallest colloidal particles, because the
applied electric field sets them in faster motion, thereby facilitating the coagulation.
(9) The gas bubbles produced during electrolysis can carry the pollutant to the top of the solution

29
 where it can be more easily concentrated, collected and removed.
(10) After treatment EC gives palatable, clear, colorless odorless water with zero discharge.
(11) EC handles large variation in the waste streams with multiple contaminants.
(12) The EC technique can be easily used in rural areas where electricity is not available, since a
solar panel attached which may be sufficient top carry out the process.

3.9 Disadvantages of electrocoagulation

(1) In some EC systems, an impermeable formation of oxides film form on the cathode, so
efficiency of electrocoagulation cell.
(2) High conductivity of the waste water suspension is required.
(3) Gelatinous hydroxide may tend to solubilized in some cases.
(4) Due to oxidation, sacrificial anode dissolved in the waste water, so need to be regularly
replaced.
(5) The use of electricity may be expensive in some cases.

30
Chapter (4): Experimental part
4.1 Apparatus

Fig.7
(1) 20V, 5 A digital DC power supply, (2) 2000 ml glass beaker, (3) solution level, (4) anode
electrode, (5) perforated plastic sheet, (6) cathode electrode, (7) cathode holder, (8) anode holder

31
4.2 Dimensions of the cell
- the batch cylindrical glass container (beaker) is of 12 cm diameter and 24 cm height.
- the cathode is a circular iron sheet with 11 cm diameter connected with vertical rod, the back of
circular sheet is insulated with epoxy resin.
- the anode is made of 4 array of separated horizontal rods, each rod has a length of 15 cm and
0.3 cm diameter and the rods in the array were separated by a distance of 3 cm, the horizontal
rods were fixed at their ends to two Fe rods, there are 29 rings in horizontal rods with outer
diameter of 22 mm, inner diameter of 7 mm and thickness of 2mm.
- the cathode and anode were held in position by a welded and insulated vertical Fe strip to act as
a current feeder.

4.3 Method and procedure

Freshly prepared solutions were used throughout all experiments, A stock of 1000 ppm of the dye
solution was prepared using distilled water. The batch experiments were carried out by placing 2
liters of freshly prepared dye solution of known initial concentration in the container. Then,
electrodes are cleaned by putting them in diluted H2SO4 solution for some minutes to remove
oxidized layers and then electrodes are washed by distilled water.
Electrocoagulation progress was followed by withdrawing a sample by 10 ml pipette from the
cell every 5 minutes from the same location in the cell.
The samples were analyzed using a spectrophotometer to determine the dye concentration.
The effect of pH was carried out by adjusting its value using caustic soda (NaOH) or sulfuric acid
(H2SO4) before each batch.

32
Chapter (5): Results and discussion
5.1 Effect of different parameters on electrocoagulation process
The effectiveness of the cell was measured by measuring the percentage of color removal using
this following equation:

%C.R=[(C0-Ct)/C0]x100
Where C0 is the initial concentration of the dye and Ct is the concentration of the at any time. Ct
is obtained from the relationship between concentration and absorbance explained by
Beer-Lambert law, which relates the amount of light absorbed to the concentration of the sample
and path length (520 nm) a constant temperature. The curve is plotted by preparing samples of
dye solution at different known concentrations and measuring their corresponding absorbance
using a spectrophotometer. The relation can then be expressed by the following equation:
A= a x b x c
Where:
A= absorbance.
a= absorbance coefficient or extinction coefficient.
b= sample path length (1 cm).
c= concentration of sample component.
The effect of current will be expressed in terms of current density which can be calculated using
the following equation:
C.D= current strength/anode area
Where Anode area = number of rings x area of one ring
anode total area = 29 x 8.655 = 250.9975 cm2 ≈ 251 cm2

Active surface area of the one ring = [(π/4) x (D12－D22) x 2] + [π x (D1 + D2) x L]

Where: D1 = 22 mm
D2 = 7 mm
L = 2mm

5.2 Methylene blue dye

5.2.1 effect of time of electrocoagulation
Figure (8) shows that the color removal increases with increasing time, the color removal

33
efficiency depends directly on the concentration of ions produced by the electrodes. When the
electrolysis period increases, an increase in concentration of ions and their hydroxide flocs, this
experiment is done at C.D= 2 A/m2, C0= 100 ppm.

Fig.8

5.2.2 Effect of initial dye concentration

Figure (9) shows the variation of rate of color removal for five initial dye concentrations. It can
be seen that the rate of color removal decreases considerably when the initial dye concentration is
after 100 ppm. One of the most important pathways of color removal by electrocoagulation
process is adsorption on metallic hydroxides flocs, because after 100 ppm, the adsorption
capacity of flocs in not exhausted and the final color efficiency is relatively constant. However,
beyond this initial concentration, the adsorption capacity of flocs becomes exhausted. In other
words, with an increase in the initial dye concentration, the rate of color removal decreases
considerably. This experiment is done at C.D= 2 A/m2

34
 Fig.9

5.2.3 Effect of of current density

Figure (10) shows that as current density increases, Efficiency of color removal increases,
because when the current density increases, the efficiency of ion production on the anode and
cathode increases. So, there is an increase in floc production in the solution and hence an
improvement in the efficiency of color removal takes

Fig.10

35
5.2.4 Effect of NaCl concentration
NaCl is added as electrolyte and the effects of electrolyte concentration on dye removal
efficiency. Figure (11) shows that as NaCl concentration increases, dye removal increases. This
was due to the increase of electrolyte concentration, which increases the conductivity of the
solution and benefited the current flow during electrocoagulation and that results in that the
efficiency of dye removal enhances. The conductivity of the solution strongly depends on the
type and the concentration of the electrolyte solution. Because of the relatively high conductivity,
high solubility, low cost of chloride and strongly oxidizing properties, NaCl is generally added as
a supporting electrolyte and a source of chloride reactant for electrochemical processes.

Fig.11

5.2.5 Effect of initial pH of solution of dye

The main mechanism of coagulation is double layer compression at low values of pH. But at high
values of pH, coagulation is carried out by adsorption, charge neutralization. So, the dominant
chemical species are also different according to the initial pH, at low pH iron ions and cations
iron hydroxides are formed but at high pH, polymeric species are formed and precipitated as iron
hydroxides, at very high value of pH monomeric anions of iron hydroxides are formed and

36
hydroxides of iron will be decreased so best case is at pH=5.2 in figure (12).

Fig.12

37
Chapter (6): Conclusion and Recommendation
6.1 Conclusion
There are parameters are studied at this presented work to study their effects on efficiency of
electrocoagulation process to solution of methylene blue dye by using fixed bed electrochemical
batch reactor. The design of the reactor cell provides surface area of (251 cm2) so, there is low
current and low internal resistance drop so concentration of the methylene blue dye decreases at
short electrocoagulation time. After studying the five parameters of initial dye concentration,
applied current, NaCl electrolyte concentration, pH of the solution and time of
electrocoagulation, there are some results show that: concentration of the dye increases with
increasing initial dye concentration and concentration is decreased by increasing the applied
current and initial pH of the solution. For NaCl, it is found that the concentration of dye decreases
with increasing NaCl concentration. (Fe) consumption decreases with increasing initial
concentration of dye and it increases by increasing initial pH of the solution and increasing the
current, (Fe) consumption decreases with increasing NaCl concentration.

6.2 Recommendation
(1) There is need to remove the sludge formed on the surface of solution by using skimming
device.
(2) more dyes must be studied to know more about electrocoagulation of dyes.
(3) continuous operation and scale up of the process must be studied for industrial applications.
(4) Studying the performance of different reactor designs on electrocoagulation process and
removal efficiency.

38
References
- Frank R. Spellman. (2009) Handbook of Water and Wastewater Treatment Plant Operations.
United States of America: Taylor & Francis Group.
- http://site.iugaza.edu.ps/halnajar/files/2010/02/unit-1.-Itroduction-to-wastewater-treatment.pdf
- http://en.wikipedia.org/wiki/Industrial_wastewater_treatment
- http://www.fao.org/docrep/t0551e/t0551e05.htm
- http://www.sciencedirect.com/science/article/pii/S1319610314000088
- http://www.ijmer.com/papers/Vol3_Issue1/AP3193100.pdf
- http://www.mhhe.com/engcs/civil/metcalf/information/chapter1.pdf
- https://www.google.com.eg/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&ved=0CBoQFjA
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