Republic of Iraq

Ministry of Higher Education and Scientific Research

University of Baghdad
College of Engineering
Chemical Engineering Department

Wastewater Treatment Using Successive

Electrochemical Approaches

A THESIS
SUBMITTED TO THE COLLEGE OF ENGINEERING
OF THE UNIVERSITY OF BAGHDAD
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
IN CHEMICAL ENGINEERING

BY
Maitham Adham Redah
(B. Sc. 2000 & M. Sc. 2008)
Chemical Engineering
2016
 Abstract
The overall goal of this research was to develop a practical
electrochemical approach of treating a wastewater from fuel treatment washing
unit. In this study, combined electrocoagulation-electrooxidation electrodialysis
treatment was employed for the eliminate of some main contaminants like
chemical oxygen demand (COD), oil content, turbidity, total suspended solids
and total dissolved solids (TDS) from oily wastewater. These hybrid
combination approaches are not studied before. The wastewater used in this
work was taken freshly from south Baghdad gas power station/2.
In the first stage of this work, the performance of the combined
electrocoagulation-electrooxidation EC-EO in situ batch treatment process was
studied using graphite electrodes as monopolar electrodes whereas aluminum
was used as sacrificial bipolar electrodes. Taguchi experimental design
methodology has been applied to determine the optimal experimental conditions
for COD removal as the main response.
The performance was evaluated by measuring the effects of the operating
parameters such as current density, solution pH, treatment time and temperature.
It was found that the best conditions for treatment of FWW are: current density
(14.55 mA/cm2), pH (6), reaction time (80 min) and temperature (40 °C). At
these conditions, approximately 90% of COD removal was achieved.
The analysis of variance ANOVA verified that the current density is the
most influent parameters on the electrochemical removal of COD with about
61% contribution.
The dynamic behavior and reaction kinetics of the electrocoagulation,
electrooxidation, and EC-EO in situ processes were studied. It was noticed that
the decreasing of COD concentration in EO process followed the pseudo-first-
order reaction with the rate constant (0.006 min.-1). Whereas for the EC and the
EC-EO processes the kinetics fits the pseudo-second-order reaction with rate
constants (0.069 L/gm min.) and (0.137 L/gm min.) respectively. The EC-EO
process has a stable pH tendency with time which could be considered as a
remarkable advantage of combined EC and EO together to keep pH solution
controlled during treatment.
The EC process was modeled using adsorption isotherm kinetics. it has
been observed that Freundlich isotherm model fit satisfactorily with the
experimental data.
In the second stage of this work, a batch recirculation electrodialysis (ED)
study using locally designed ED stack was performed to reduce TDS and
solution conductivity from pretreated wastewater by EC-EO process. A five cell
electrodialysis stack, with an active membrane area of 60 cm2 per cell was
employed. The effects of electrical applied potential and flow rate of streams on
the performance of the TDS separation and specific power consumption (SPC)
were observed. The results indicate that the process of ED under potential (15
V) and flow rate (1.4 L/min) are recommended as operating conditions. The
removal of TDS achieved was about 95% throughout (80 min.) time of
electrodialysis. Moreover, SPC increased with an increase in the applied
potential of ED stack, while it was not intensely responsive to the change in
flow rate.
The present work illustrated that the electrochemical combination of
hybrid EC-EO in situ process followed by ED process could effectively treat the
FWW in particular for removing of organic compounds, suspended solids, and
TDS.
 Contents

Subject Page
Acknowledgements I
Abstract II
Contents IV
Nomenclature VIII

Chapter One : Introduction

1.1 Preface 1
1.2 Oily Wastewater 1
1.3 Fuel Requirement for GT Power Station 2
1.4 Fuel Washing 4
1.5 Electrochemical Treatment Scope 6
1.6 Aim of the Work 7

Chapter Two : Literatures Survey

2.1 Treatment of Petroleum and Oily Wastewater 8
2.2 Methods of Oily Wastewater Treatment 9
2.3 Electrochemical Treatment Technology 11
2.4 Electrocoagulation 12
2.4.1 Coagulation and Flocculation 12
2.4.2 Principle of Electrocoagulation 14
2.4.3 Electrocoagulation Mechanism 16
2.4.4 The Electrodes Arrangement 17
2.4.5 Advantages and Disadvantages of EC 18
2.4.5.1 Advantages of EC 18
2.4.5.2 The Disadvantages of EC 19
2.4.6 Comparison between EC and Chemical Coagulation 19
2.4.7 Operational Factors Affecting Electrocoagulation 21
2.4.7.1 Effect of Current Density 21
2.4.7.2 Effect of pH 22
2.4.7.3 Effect of Temperature 24
2.4.7.4 Effect of Reaction Time 25
2.4.7.5 Effect of Conductivity 25
2.4.8 Adsorption Isotherm in EC 25
2.4.8.1 Langmuir Adsorption Isotherm 26
2.4.8.2 Freundlich Adsorption Isotherm 27
2.4.8.3 Temkin Adsorption Isotherm 27
2.5 Electrooxidation 28
2.5.1 Principles of Electrooxidation 28
2.5.2 The Electrode Material 30
2.5.3 Operating Conditions Effects on the EO 32
2.5.4 Advantages and Disadvantages of EO 33
2.6 Electrodialysis (ED) 34
2.6.1 The Principle of Electrodialysis 35
2.6.2 Membrane Stack 36
2.6.3 The Electrode and Electrode Chamber 38
2.6.4 Membranes 38
2.6.5 Operating Regimes of the Electrodialysis 39
2.6.5.1 Potentiostatic vs. Galvanostatic Mode 39
2.6.5.2 Batch vs. Flow-through (continuous) Setup 39
2.7 Previous Work on Combined and Hybrid EC and EO Process
40

Chapter Three : Experimental Work

3.1 Introduction 48
3.2 Materials and Methods 48
3.2.1 Effluents 48
3.2.2 Apparatus 49
3.2.3 Chemicals 50
3.3 The EC-EO Experimental Lab Unit 51
3.4 The EC-EO Experimental Procedure 53
3.5 Taguchi Design of the Experiment 53
3.6 Kinetic Models Experiments 55
3.7 The Electrodialysis Setup 55
3.8 Electrodialysis Cell 57
3.9 The ED Experimental Procedure 60
3.10 Analysis Tests 61
3.10.1 COD Analysis 61
3.10.2 Oil Content Analysis 62
3.10.3 Turbidity 63
3.10.4 Total Suspended Solids
63

Chapter Four : Results and Discussion

4 Introduction 64
4.1 The EC-EO in Situ Experiments 65
4.1.1 Effect of Parameters on COD Removal Efficiency 66
4.1.2 Signal to Noise ratio (S/N) and Optimization of Parameters 69
4.1.3 Regression Equation 71
4.1.4 Oil Removal 73
4.1.5 TDS Removal 74
4.1.6 Current Efficiency and Specific Power Consumption (SPC) 75
4.2 Dynamic Behavior and Kinetics 78
4.2.1 Reaction kinetics 78
4.2.2 Dynamic pH Response 85
4.2.3 Conductivity and Voltage Response 86
4.2.4 Modeling EC through Adsorption Isotherm 88
4.3 Electrodialysis 90
4.3.1 Effect of Applied Voltage 91
4.3.2 Effect of Flow Rate 93
4.3.3 Specific Power Consumption
94

Chapter Five : Conclusions and Recommendations

5.1 Conclusions 98
5.2 Recommendations 100

References 101
Appendices
App. A Electrocoagulation-Electrooxidation Experiments Results A-1
App. B Electrocoagulation and Electrooxidation Kinetic Experiments
B-1
Results
App. C Electrocoagulation Adsorption Calculation Results C-1
App. D Electrodialysis Experiments Results D-1
App. E Minitab (17) Software Graphs E-1

1.1 Preface
 Water is a critical necessity for utilization of humanity. It is crucial for
rural and modern development, and also to support developing populaces that
require a harmless drinking water supply (Sadrzadeh and Mohammadi 2009).
During the late years, scientists and researchers have taken an expanding
apprehension toward environmental danger of industrial activities connected
with hydrocarbons, extraction, transportations, food processing and refining.
These industrial activates have increased the risk of oil contamination to the
earth and in this way attendant released into the natural habitat of creates makes
major environmental issue all through the world (Husain et al. 2011).
The harmful effect on the environment results from discharge a lot oily
wastewater to the rivers, lakes, oceans and other water bodies in addition
leakages into soil. In water, the oil is an observable pollutant affecting aquatic
creatures like water plant and fish by impeding oxygen and sunlight from
crossing the water surface.
Oil compounds can kill Organisms that breathe dissolved oxygen in
water. Also the oily base contaminants can be absorbed by animals and plants,
killing or harming their existence (Bremen 2008). So impact of oily wastewater
pollution not only make dangerous environment to aquatic living species but
also can influence human health (Zaini et al. 2010).

1.2 Oily Wastewater

A standout amongst the most difficult issues today is the separation of oil
from wastewater. A lot of wastewater is generated by modern industries that
produce or deliver oil and other organic materials, both miscible and immiscible
in water (Mohammed et al. 2011).
Oil in water can be present in different form as free or suspended,
dispersed, emulsified and dissolved oil. By using simple physical processes, the
suspended and dispersed oil can be easily removed from wastewater. While
emulsified and dissolved oil are more difficult to separate from wastewater (Li
et al. 2010).
 Petrochemical and petroleum industries are very likely oil sources for
pollution surface water caused by overflow from refineries, oil fields, and fuel
treatment process effluent (Ahmed et al. 2005).
According to the form of oily wastewater, various processes have been
used to remove it. Conventional treatment methods of oily wastewater include
skimming and gravity separation, dissolved air flotation (DAF), coagulation and
flocculation, which have many drawbacks like high operation cost, low
efficiency, recontamination and corrosion problems (Yan et al. 2006). Likewise,
these techniques are not powerful in removing very small oil droplets and
emulsions. These weaknesses have advanced the improvement of new
procedures and techniques for oily wastewater treatment.

1.3 Fuel Requirement for Gas Turbine Power Station

Fuel providing is one of the most vital components controlling the

operation and efficiency of a gas turbine. The burn of fuel that does not full fit
gas turbine combustion requirements can cause serious maintenance and
operation troubles and in worst cases, damage of a gas turbine.
In the case of non-accessibility of natural gas and the high cost of
distillate, the utilization of low grade fuel in heavy duty gas turbines is
economically appealing in many power stations in all of the world, and new
plants using crude oils and residual oils continue to be constructed (Homji et al.
2010).
In some cases, the selection of fuel is really not optional, because power
producers are obliged to use whatever fuel is available. In Iraq several new
power plants have been introduced during the last recent years including heavy
duty gas turbines using either privately produced residual grade oil or crude oil
from adjacent refineries, see Table (1.1).
Table (1.1) List of gas turbine power station in Iraq (Wikipedia 2014)
No. Name Location No. Name Location
(Governorate) (Governorate)
 1 Mulla Abdulla Kirkuk 11 Sadr Baghdad
2 Khor Al Zubayr Basra 12 Taza Kirkuk
3 Al-Mansurya Diyala 13 Al-Najybia Basra
4 Al-Anbar Al-Anbar 14 Sulaymaniyah Sulaymaniyah
5 Shatt Al-Basra Basra 15 Duhok Duhok
6 Erbil Erbil 16 Rumaila Basra
7 South Baghdad 1, 2 Baghdad 17 Al-Quds 1, 2 and 3 Baghdad
8 Daura 1 and 2 Baghdad 18 Hilla Babil
9 Al-Rasheed 1 Baghdad 19 Karbala Karbala
10 Taji 1 and 2 Baghdad 20 Al-Najaf Najaf

In fact, the quality of low grade fuel are not perfect, but allowable
successful operation can get by rather fuel treatment programs at the power
stations. Subsequently, many new fuel treatment projects are currently under
construction.
Normally, the heavier oils, such as residual and crude oils are called "Ash
forming oils" because they naturally hold trace metal contaminants. Fuel
treatment is necessary to modify or prevent the effects of harmful elements and
compounds before combustion in the gas turbine.
Destructive trace metal contaminants are: vanadium, sodium, potassium,
lead, calcium and magnesium. These metals are corrosive to the turbine at high
temperatures, especially when found in quantity above design limits. Also these
materials can create irremovable deposits which are not easy to go away with a
typical turbine wash system. These deposits can cause stopping and diminished
power yield (Kaplan and Majchrzak 1996). Table (1.2) lists the trace metals
effects on the turbine, and the means of fuel treatment to eliminate concentration
with permissible limits .
Table (1.2) List of the trace metals effects. (Kaplan and Majchrzak 1996)
Trace Metal Limits in Effect on Type of Limits in Fuel
Raw Turbine Treatment to Turbine
Fuel (ppm)
(ppm)
Sodium and 150 High temperature Fuel washing 1
Potassium corrosion
Calcium 10 Fouling deposits Fuel washing to 10
a limited extent
 Lead 1 High temperature None 1
corrosion
Vanadium ** High temperature Inhibited by 0.5
corrosion magnesium
Magnesium None Inhibits Used to inhibit None
vanadium/ forms vanadium
deposits
** maximum levels may be dictated by local codes.

1.4 Fuel Washing

Residual fuel oils usually require water washing process to eliminate the
water soluble salts of sodium and potassium, since these kind of fuel generally
contain salts and salted water,
Fuel washing treatment process includes mixing hot fuel with 7 to 10
percent of potable water. In order to help in breaking up strong oil in water
emulsions, demulsifying chemicals are continuously supplied to the fuel
(Bromely 2006).
The water flows in a counter current regime corresponding to the fuel
direction in a one or two stage extraction washing procedure.
Every stage has a mixer to get in touch the fuel with the wash water,
followed by a device to remove the salted water from the extracted fuel.
Usually, robust centrifugal devices are used for this separation process where the
water and oil are separated in two streams. Figure (1.1) shows a typical liquid
fuel washing system.
 Figure (1.1) Heavy fuel oil washing system (Alfa Laval 2016)

In Iraq, many gas power plants are using the similar washing fuel units to
get the required fuel specifications of gas turbine. The effluent wastewater of
this fuel washing process is rich in heavy oil particles and salts. This has an
enormous impact on the country's environment, thus cannot be directly
discharged to the environment.
To full fit the local environment regulations, the effluent water may
require a treatment system to remove entrained oil. For example, a customer
specification of “no visible sheen” is equivalent approximately 15 ppm of free
oil content in the water.
The removal of oily wastewater obtained particularly from the fuel oil
washing unit was previously investigated using both adsorption (Sulaymon and
Kshash 2010) and bioremediation technology (Yasin et al. 2014). In contrast of
adsorption process, the results of oil removal using bioremediation did not
achieve the local environmental limitation of oil content, which emphasis the
existence of bio-refractory compounds in this wastewater.
 1.5 Electrochemical Treatment Scope
Electrochemistry can present great solutions for handling environmental
issues. Electrochemical innovation has been mainly developed during the past
15 years for its alternative use in wastewater treatment. The primary point of
interest of this technology is its environmental compatibility, because it involves
only the electron which is considered a very clean reagent.(Martínez-Huitle
and Andrade 2011)
Recently, many authors demonstrate the applicability of electrochemical
technology as an attractive option for use before the biological process.
Electrochemical treatments, for example, electroflotation, electrocoagulation
(EC) and electrochemical oxidation (EO) have been studied broadly due to their
several advantages compared with a conventional wastewater treatment plant.
Generally, electrochemical treatment plants require less space, produce less
sludge and have lower temperature conditions.(Koppad V. B. 2014)
Electrocoagulation is usually used for treatment of water polluted with
macromolecules, colloids or emulsions, so this process can effectively compete
with the ordinary chemical coagulation one. While electrooxidation, that
represents a standout amongst the most encouraging innovations for the
remediation of wastewaters containing little or medium concentrations (COD
from 1 to 104 ppm) of soluble organic compounds.
Throughout the 20th century, very promising results have been reported by
some works that focused on the study of electrochemical technologies.
However, more researches have to be done in the future to promote these
technologies against the conventional technologies that are in use
today.(Rodrigo et al. 2010)

1.6 Aim of the Work:

The differences in the nature of pollutants impose using several separation
technologies to get environmentally acceptable results from wastewater
remediation plants. It could be interesting to combine various electrochemical
methods to simultaneously remove both soluble and insoluble pollutants such as
colloid particles, Oil droplet, organic compounds and total dissolved solids
(TDS) by an integrated system. The aim of the present work is establishing an
integrated electrochemical approaches to effectively reclamation fuel washing
wastewater. The main objectives of the work are:
 Develop and examine the feasibility of the hybrid simultaneous process
combining the electrocoagulation and electrooxidation batch processes
(named as EC-EO in situ) and to evaluate its performance in treating fuel
washing wastewater which sampled from the South Baghdad Gas Power
Plant.
 Determine the optimal operational conditions to efficiently remove
organic and inorganic pollutants. To do this, Taguchi statistical
methodology is used for analysis of the combination of operational
parameters (current density, initial solution PH, time and temperature), to
achieve effective treatment process to eliminate soluble and insoluble
pollutants and to optimize COD removal by the EC-EO in situ process.
 Design an electrodialysis (ED) cell to remove salinity as TDS from EC-
EO effluent and study the suitable conditions for the treatment at
laboratory scale using batch recirculation ED system. The influence of
both applied voltage and water flow rate are studied to obtain the
performance of salts removal.
 Estimate the necessary specific energy consumption in the
electrochemical approach to effectively remove the pollutants.
2.1 Treatment of Petroleum and Oily Wastewater
A lot of industrial processes generate oily wastewaters, such as
petrochemicals, petroleum refining, leather, food, and metal finishing.
Oils present in these wastewaters have to be separated before the water can be
reused in a recycling process or discharged into the surface waters or drain
system (COCA et al. 2011).
These days, oily wastewater treatment has become a critical problem.
Therefore, further attention has been focused on the dealing techniques of oily
wastewater and it must be explored and solved by all industrial, oilfield and
petroleum companies.
Very wide sources of oily wastewater have been treated, such as the oil in
the oil storage, transportation, refining, oil industry and petrochemical industries
in which the production process generate a lot of oily wastewater (Mahesh et al.
2013, Zhong et al. 2003, Fadali et al. 2016).

Oily wastewater contamination is essentially appeared in the affecting

groundwater resources and drinking water pollution. It is endangering aquatic
resources, crop production and human health, in addition to damaging the
natural land (Bensadok et al. 2008) and (Moussavi et al. 2011).
Many research institutions have comprehensively studied oily wastewater
treatment methods, and the aim is the removal of a large quantity of oil, beside
the removal of dissolved organic material, suspended solids particles, ammonia
and sulfide, etc.( Yu et al. 2013).
From any oil source, treatment of wastewater must be accomplished to
comply with severe environmental regulations that obligate a maximum total oil
concentration from 10 to 15 (ppm) in the discharge waters. Wastewater
generated in oil industries may contain oil concentrations in the range of 100 to
1,000 (ppm) (Coca-Prados et al. 2013)

2.2 Methods of Oily Wastewater Treatment

 Conventional methods for treating oily wastewater depend on the oil
concentration, drop size and physical nature of the oil. The methods for oily
wastewaters treatment can be classified as primary, secondary and tertiary. The
three-step processes of oily wastewater treatment are shown in Figure (2.1).

Primary Secondary Tertiary

Gravity Coagulation and

Evaporation
Separation Flocculation

Centrifugal Activated Carbon

Flotation
Separations Adsorption

Hydrocyclones Filtration Biological Treatment

Membrane
Reverse Osmosis
Treatment

Figure (2.1) Conventional treatment process of oily wastewater.(COCA et al.

2011)
Free oil with drop size larger than 40 µm is removed using the primary
treatment which is based on physical separation like gravity or centrifugal
separation to settle suspended solids and the broken emulsion.
The secondary treatment is used to take out the dispersed oil which has drop
size>20 µm, and it includes either break the oil emulsion by chemicals like in
coagulation and flocculation process or physical separation of the dispersed oil
as membrane filtration, filter coalescence and flotation. The final effluent from
these processes could meet the environmental requirements to allow direct
discharge.
Carbon adsorption, reverse osmosis and thermal processes like
evaporation are the most common methods used as the tertiary treatment to
reduce the concentration of dissolved soluble oil fractions and non-organic salts.
(Coca-Prados et al. 2013)
The petroleum effluent has about thirty of non-biodegradable organics
which are difficult to remove by the conventional treatments, so these methods
cannot effectively eliminate all the pollutants present in wastewater due to their
limitation and their weakness to disturbances. Moreover, a high number of
refractory materials are presented in petroleum effluents waste which makes the
process very slow and difficult. Thus, there is a require for supplementary steps
in petroleum industry wastewater treatment, and research hard works are
intended for solving this problem.(Ibrahim D. S. 2013)
A large number of efforts have been take on to develop a better
wastewater treatment processes and to match the environmental challenges
facing the oil industry. The treatment methods that have been investigated for
wastewater treatment in petroleum refineries include: adsorption (Al-Haddad et
al. 2007; El-Naas et al. 2010a; El-Naas et al. 2010b), coagulation (Demirci et
al. 1998; Bensadok et al. 2008; Alta and Bükgüyüngör 2008), coupling
coagulation–flocculation (Santo et al. 2012), chemical oxidation (Huang and
Shu 1995; Ali et al. 2009) and biological techniques (Jou and Huang 2003;
Kuyukina et al. 2009; Lu et al. 2009; Chan 2011; Wenyu et al. 2011).
New technologies such as membranes (Chang et al. 2001; Zhong et al.
2003; Li et al. 2006; Rahman and Al-Malack 2006; Rahimpour et al. 2011),
photocatalytic (Santos et al. 2006a; Shahrezaei et al. 2012) and
electrochemical technology (Yavuz and Koparal 2006; Mansour and Chalbi
2006; Yang C.L. 2007; Abdelwahab et al. 2009; El-Naas et al. 2009; Yavuz
et al. 2010; Wei et al. 2010; Ramalho et al. 2010; Yan et al. 2011), have also
been reported.
Among mentioned technologies, electrochemical processes can offer
remarkable contributions to protect the environment by production-integrated
processes for the diminishing of pollutants and toxic materials in wastewater
effluent.(Juttner et al. 2000)
2.3 Electrochemical Treatment Technology
In 19th century, electricity was exploited to treat water in the United
Kingdom (Chen G. 2004). Because of the growing environmental policy during
the two past decades, the electrochemical technologies have taken importance in
wastewater treatment (Lin and Peng 1998).
Electrochemical methods have achieved a significant level of efficiency in
latest years, particularly in the case of hybrid systems, in which combined
electrooxidation and electrocoagulation are used only, or in which attached with
other technologies such the use of ozone process
(Hernandez-Ortega et al. 2010).
The development, design and application of electrochemical methods
such as electrodeposition, electroflotation, electrocoagulation and
electrooxidation targeted on both water and wastewater treatment
(Drogui et al. 2007).
The electrochemical technologies are a promising choice for the treatment
of effluents containing organic pollutants. The most important advantages of
these processes include energy efficiency, environmental compatibility, safety,
simple to automation and cost effectiveness. (Almeida et al. 2014)
The electrochemical performance in the mineralization of pollutants is
recognized by the interaction of different parameters that may be optimized to
get an economical and effective process.
The main parameters that determine the performance of the
electrochemical processes are, current density, electrode material, cell design,
and mass transport regime and electrolysis medium properties. (Martínez-Huitle
and Andrade 2011).
Electrochemical technology can be used in wide applications, such as
organic degradation (Shao et al. 2016), metal removal (Nouri et al. 2010),
improving the quality of drinking water and electrochemical disinfection (Kraft
A. 2008).
 A broad study has been carried out by a lot of researchers in treating
diverse wastewaters by using electrochemical technologies.
The technical possibility for the treatment of various industrial effluents has
been studied, such as, tannery wastewater (Vijayalakshmi et al. 2011), metal
cutting wastewaters (Kobya et al. 2011), plating effluent (Praveen et al. 2011),
mechanical polishing wastewater (Drouiche et al. 2008), pulp and paper
effluent (Kalyani et al. 2009), textile wastewater (Mohan et al. 2007), dairy
wastewater (Sengil and Özacar 2006), carwash wastewater (Panizza and
Cerisola 2010), oilfield produced water (Ramalho et al. 2010; You and Wang
2011), petrochemical wastewater (Dimoglo et al. 2004), petroleum refinery
effluents (Santos et al. 2013; El-Ashtoukhy et al. 2013), restaurant wastewater
(Chen et al. 2000), vegetable oil refinery wastewater (Un et al. 2009) and oil
mill wastewater (Phalakornkule et al. 2010).

2.4 Electrocoagulation
2.4.1 Coagulation and Flocculation
Coagulation is a phenomenon in which the charged suspension particles
are neutralized with counter ions by mutual collision and are agglomerated/
flocculated, followed by sedimentation. The coagulant is supplemented in the
form of appropriate chemical substances. Alum (Al2(SO4)3·18H2O) is such a
chemical compound which has been generally used for years in wastewater
treatment. (Mollah et al. 2001)
Coagulation, flocculation and sedimentation are used in combination with
subsequent filtration. These processes are summarized below and illustrated in
figure (2.2):
 Coagulation is a water treatment process in which colloidal particles
(mostly negative charged) are destabilized, and is achieved mainly by
neutralizing their electric charge by adsorption of positively charged
coagulant species. The product used for this neutralization is called a
coagulant.
  Flocculation is process following coagulation, which uses kindly mixing to
carry the suspended particles together in the aqueous solution so they will
form larger and more settleable clumps called floc.
 Sedimentation is a solid-liquid separation process, in which particles settle
under the force of gravity. (Oleiwi , 2014)

Figure (2.2) Coagulation, flocculation, and sedimentation processes (Tutor

Vista 2016).

2.4.2 Principle of Electrocoagulation

Electrocoagulation (EC) is a complicated process counting many physical
and chemical phenomena that use metallic electrodes to supply ions into the
water solution. It has been discovered in the last years of 19th century, since the
first patent back to the year 1887 which described a method of treating sewage
by mixing with an amount of sea water. The electrolytic sludge treatment plants
were operated both in batch and continuous as early as 1911 in different parts of
USA (Vik et al. 1984).
The electrocoagulation process essentially involves the electrical
dissolution of metal cations in situ from the anodic electrode with the
simultaneous formation of hydroxyl ions and hydrogen gas at the cathode
(Kabdasl et al. 2012).
The electrochemical reactions with metal "M" as anode in EC may be
summarized as follows:
At the anode:
𝑀(𝑠) → 𝑀𝑛+ + 𝑛𝑒 − (2.1)
2𝐻2 𝑂(𝑙) → 4𝐻+ + 𝑂2(𝑔) + 4𝑒 − (2.2)

At the cathode:
𝑀𝑛+ + 𝑛𝑒 − → 𝑀(𝑠) (2.3)
2𝐻2𝑂(𝑙) + 2𝑒 − → 2𝑂𝐻− + 𝐻2(𝑔) (2.4)

When a potential is applied from an external power source, a current is

passed through a metal electrode, oxidizing the metal (M) to its cation (Mn+) in
an oxidation reaction, Eq.(2.1). At the same time, water is reduced to hydrogen
gas and the hydroxyl ion (OH−) by reduction reaction, Eq.(2.4).
The generated metal ions (Mn+) from the anodic electrodes hydrolyze to
polymeric metal hydroxide immediately. These polymeric hydroxides are
excellent coagulating agents. Coagulation happens when these metal cations
bond with the negative particles moved in the direction of the anode by
electrophoretic motion. Consumable or sacrificial electrodes are used to
continuously produce polymeric hydroxides in the nearby of the anode.
Simultaneously, H2O is also electrolyzed in two different parallel reactions,
producing small bubbles of hydrogen at the cathode as given by Eq.(2.4), and
oxygen at the anode as in Eq.(2.2). These bubbles cause the emulsified oil
droplets to be freed from water molecules and raise the flocculated contaminants
to the water surface by natural buoyancy. The same mechanism is involved in
case of inks, dyes and other type of emulsions. (Chaturvedi S. I. 2013) (Ali
and Yaakob 2012)
 Contaminants present in the wastewater stream are treated either by
chemical reactions and precipitation or by physical and chemical attachment to
colloidal materials being generated by the electrode. They are then removed by
sedimentation, electroflotation and filtration. The basic process can be
summarized in Figure(2.3).

Figure (2.3) Mechanism of electrocoagulation (Chopra et al. 2011)

2.4.3 Electrocoagulation Mechanism

In the EC process, the destabilization mechanism of the particulate
suspension, contaminants and breaking of emulsions may be summarized as
follows (Liu et al. 2010).
1. Compression of the diffuse double layer around the charged species by
the interactions of cations generated from the anodic electrodes.
2. Neutralization of the charged species present in solution by electro-
generated counter ions to reduce the electrostatic repulsion between
particles until the van der Waals attraction predominates, thus an
equivalent charge results in the process causing coagulation.
 3. As a result of coagulation process, the floc is formed which creates a
sludge blanket that bridges and entraps colloidal particles in the aqueous
solution.
The electrodes are usually made of iron or aluminum because these metals
are available cheap, effective, readily and non-toxic to human health. Thus they
have been selected as the frequent electrode materials used in EC systems (Chen
et al. 2000) and (Kumar et al. 2004) .
If aluminum or iron electrodes are used, the produced Al+3or Fe+3 ions will
directly go through further spontaneous reactions to generate corresponding
hydroxides and/or polyhydroxides. These compounds have powerful attraction
for dispersed particles and counter ions cause coagulation. (Malakootian and
Yousefi 2009)
It is well recognized that in EC process the main reactions occurring for
the aluminum electrode during electrolysis are:
𝐴𝑙 → 𝐴𝑙 3+ + 3𝑒 − (2.5)
𝐴𝑙 3+ + 𝐻2 𝑂 → 𝐴𝑙(𝑂𝐻)2+ + 𝐻 + (2.6)
𝐴𝑙(𝑂𝐻)2+ + 𝐻2 𝑂 → 𝐴𝑙(𝑂𝐻)+
2 + 𝐻
+
(2.7)
𝐴𝑙(𝑂𝐻)+
2 + 𝐻2 𝑂 → 𝐴𝑙(𝑂𝐻)3 + 𝐻
+
(2.8)
Electrolytic dissolution of the Aluminum electrode produces aluminum
ions (Al3+) by Eq. (2.5). These cations immediately suffer hydrolysis reactions
which generate diverse monomeric compounds according to the sequence
reactions as in Eq.(2.6) to (2.8). In fact, others complex reactions take place,
since aluminum hydrolysis products can also form: Al2(OH)2+4, Al3(OH)4+5,
Al6(OH)15+3, Al7(OH)17+4, Al8(OH)20+4, Al13O4(OH)24+7 and Al13(OH)34+5
(Bayramoglu et al. 2004).
Hydroxyl ions (OH−) may react with cationic hydrolysis products of
aluminum to form Al(OH)3(s) in the bulk solution which finally precipitates from
the aqueous medium (Mouedhen et al. 2008).
Because electrochemical reactions occur at the surface of the electrodes,
the concentration of reaction products is highest at the electrode surface and
hydrolysis reactions Eq.(2.6) to (2.8) make the anode surrounding area acidic.
On the other hand, hydrogen evolution at the cathode, Eq.(2.4) makes the
cathode vicinity alkaline (Vepsäläinen et al. 2009).

2.4.4 The Electrodes Arrangement

In the simplest form, the EC system is typically constructed of a pair of
plated electrodes which are placed in a well-defined (shape and size) capacity
container and water can flow between the electrodes in a horizontal or vertical
direction (Sahu et al. 2014).
A simple electrocoagulation reactor is made up of one anode and one
cathode. Generally for wastewater treatment, the EC cell with just two
electrodes is not adequate because of a practical rate of electrode dissolution so
large electrodes surface area is needed. The electrodes can be arranged in the EC
cell with monopolar or bipolar mode.
The schematic diagram of electrodes in both monopolar and bipolar
configuration connections is shown in Figure (2.4). (Golder et al. 2007).

Figure (2.4) Schematic of a monopolar and bipolar electrodes configuration in

the reactor

In the monopolar arrangement all sacrificial electrodes (anodes) are

interconnected to each other. Likewise all cathodic electrodes are also connected
to each other. In the bipolar system the sacrificial electrodes are located between
the two parallel electrodes without any electrical connection and only the outer
most parallel electrodes are joined to the power supply. When the current passes
through the electrodes, it polarizes them thus the surface of the electrode facing
the cathode is positively polarized and vice versa on the other side facing the
anode. The bipolar arrangement provides a simple system which facilitates easy
maintenance.(Liu et al. 2010)

2.4.5 Advantages and Disadvantages of EC

2.4.5.1 Advantages of EC
The advantages of electrocoagulation are summarized as follows: (Holt P.
2002 and AL-Abdalaali 2011).
1. Electrocoagulation technique is a cost effective and easy operation since
simple apparatus are required, and can be designed for any size.
2. Almost no chemical addition is needed.
3. No moving parts and low maintenance cost.
4. It can operate even by a solar panel, since low current is required.
5. Small colloidal particles can be effectively destabilized in EC process.
6. Minimal sludge creation and the sludge tends to be easy settled and
readily removed.
7. Wastewater treated by electrocoagulation gives odorless, colorless and
clear water.
8. Gas bubbles created throughout electrolysis can improve flotation.

2.4.5.2 The Disadvantages of EC

The disadvantages of EC are as follows:
1. The anodic electrodes are dissolved into wastewater as a consequence of
oxidation, and should be consistently supplanted.
2. The passivation of the cathodes during large operation time has restricted its
usage.
3. The utilization of power might be costly in numerous places.
4. High electrical conductivity of the wastewater suspension is necessary
(Yildiz et al. 2007).
2.4.6 Comparison between EC and Chemical Coagulation (CC)
EC process and chemical coagulation (CC) have the similar fact in which
the neutralization and agglomeration of charged particles are taking place in
colloidal suspension followed by sedimentation or flotation. This is resulting
from mutual collision between charged particles and metallic hydroxide ions.
However, the dissimilarity between EC and CC is essentially in the method of
which coagulant ions are delivered (Zhu et al. 2005) and (Avsar et al. 2007).
Due to a permanent current density, EC process introduces the coagulant
in situ as the sacrificial anode dissolves. At the same time, the generation of H2
gas at the cathode lets the pollutant separate by flotation. While in CC,
hydrolyzing of metal salts like [Al2(SO4)3, Fe2(SO4)3, AlCl3 and FeCl3] are very
commonly used as coagulants compounds in water and wastewater treatment
(Yilmaz et al. 2007).
EC and CC have been compared in the treatment of ultrafine quartz
suspensions (Kiliç et al. 2009), the removal of Cr(VI) (Golder et al. 2007),
water pretreatment before microfiltration membranes (Zhu et al. 2005; Bagga
et al. 2008) and oil in water emulsion (Canizares et al. 2008). The differences
between EC and CC are illustrated in Table (2.1)

Table (2.1) Comparison between EC and CC processes.(Liu et al. 2010).

Electrocoagulation, EC
The pH neutralization effect made it
effective in a much wide pH range
(4-9).
Flocs formed by EC are much larger
than flocs formed by CC.
EC process can be followed by
sedimentation or flotation.
The gas bubbles produced during
electrolysis can help to carry the
pollutant to the top of the solution.
Chemical coagulation, CC
Final pH always needs to be modulated
because the hydrolysis of the metal salt
will lead to a pH decrease.
The CC is highly sensitive to pH change
and effective coagulation is achieved at
pH 6-7.
CC flocs are smaller than EC flocs.
CC process is always followed by
sedimentation and filtration.
No bubbles generation.
EC is a low-sludge production
technique.
EC process treats water with low
temperature and low turbidity.
EC requires simple equipment and is
easy to be operated.
High sludge production.
The CC has difficulty in achieving a
satisfying result in case of low
temperature and turbidity.
High operating problems.

2.4.7 Operational Factors Affecting Electrocoagulation

2.4.7.1 Effect of Current Density
Among many design and working factors, current density plays important
role in EC system since it is just the operational parameter that can be controlled
straightly. In EC process, the spaces between electrodes are commonly fixed and
current is provided continuously. Both coagulant amount and bubble evolution
rates are determined directly by current density. The rate of electrochemical
reactions has influence on the solution mixing and mass transfer at the
electrodes.
The amount of coagulant produced is dependent on the amount of
electrical energy that passed through the electrolytic solution. A simple equation
for dosage of electrode metal dissolved can be calculated from Faraday’s law
(Sahu et al. 2014) :
𝐼 𝑡 𝑀𝑤
𝑤= (2.9)
𝑒𝐹

Where: w is the amount of metal dissolved (gm)

I is the current intensity (ampere)
t is the time (in seconds)
e is no. of electrons
F is Faraday’s constant 96,500 C/ mole
Mw is molecular weight of metals. (for aluminum = 26.982 gm/mole)
The current density is an operational parameter affecting the process’s
reaction time and also influencing the main pollutant separation mode. The
amount of anodic dissolution material increases with high current densities and
consequently, the extent of hydroxide and polyhydroxide increases also, which
enhances the elimination of color and chemical oxygen demand (COD).
The maximum acceptable current density may not be the most efficient
approach of operating the EC system. The best current density regularly includes
a selection between operational costs and right use of solution flow rate, pH,
temperature, etc. (Liu et al. 2010).
Based on literature, current density was generally investigated with range
of 10-150 (A/m2). However, in order to operate the EC system for an extended
duration time with no maintenance, the EC current density is recommended in
the range of 20–25 (A/m2) unless of cleaning measures are periodically taken for
the electrodes surface. (Sahu et al. 2014)

2.4.7.2 Effect of pH
The pH of the solution is considered as one key parameter in EC and it
affects significantly the performance of both chemical coagulation and
electrocoagulation processes (Chen et al. 2008).The pH has an effect on the
dissolution of the electrodes and nature of hydroxides.
Since the colloid particles are destabilized by metal cations and
hydroxides, effective coagulant form is structured in three pH regions: acidic,
neutral and slightly alkaline. Other than at highly alkaline pH region Fe(OH)4-
and Al(OH)4- ions are generated which they have weak coagulation performance.
Figure (2.5) is the solubility diagram for aluminum hydroxide species
against solution pH. The solubility border line indicates the thermodynamic
equilibrium that is present between the prevailing aluminum species in solution
at a given pH and solid Al(OH)3. At pH approximately (6.3) the minimum
solubility of aluminum hydroxide occurs and the solubility increases as the
solution becomes either more alkaline or acidic (Holt P. 2002).
In fact, Al(OH)+2, Al(OH)2+, Al(OH)3, Al2(OH)2+4 and Al13(OH)32+7are
formed in the pH range between 4–9. These species has a lot of positive charge
at the surface, which can prompt to adsorption electrochemistry neutralization
reaction. At pH higher than 10, Al(OH)4- is prevailing, and the coagulation
impact quickly diminishes. While Al+3 ions is dominant at low pH, which has no
coagulation impact.(Liu et al. 2010)

Figure (2.5) The solubility diagram for aluminum species against solution pH..

Although aluminum electrolysis under constant specific volumetric

loading charge, it has been reported that the dissolution rate of aluminum at pH>
3 is higher compared with pH lower than 3 (Mouedhen et al. 2008).
As pH increases in vicinity of cathodic electrodes to a level that chemical
dissolution of aluminum electrodes may occur and aluminate anion is almost
formed, Eq. (2.10). In contrast, it may be observed that this reaction is inhibited
in acidic bulk solution because the produced hydroxyl ions are consumed by the
acid in the solution.(Vepsäläinen et al. 2009) and (Bazrafshan et al. 2014)
−
2𝐴𝑙(𝑠) + 6𝐻2 𝑂 + 2𝑂𝐻(𝑎𝑞) → 2𝐴𝑙(𝑂𝐻)−
4 + 3𝐻2(𝑔) (2.10)

In case of either EC or CC is selected for the water treatment, initial pH is

suggested to be a key parameter in the process (Canizares et al. 2009). EC is
more appropriate when higher pH is preferred (low pH solutions), whereas CC
is desired when low pH is important prior to discharge.
On the other hand, initial pH shifts and increases throughout the EC
process, making it a constantly varying parameter, so, mechanistic studies of EC
systems are complex to perform.(Saho et al. 2014)

2.4.7.3 Effect of Temperature

The effect of temperature on the EC process has been investigated by few
researchers (Chen G. 2004). By using EC process, affirmative effect of
temperature on boron elimination has been reported (Yilmaz et al. 2008). The
removal efficiency of boron improved from 84% to 96 % when the solution
temperature increased from 20°C to 60°C.
For phosphate removal from wastewater, similar positive temperature
impact has been reported (Vasudevan et al. 2009). Removal efficiency was
29% lower at 20 °C than at greater temperatures. The researchers concluded that
the dissolution of sacrificial electrode occurs with a higher rate at high
temperature.
On the other hand, negative effect of temperature on the EC process
efficiency has been observed when paper mill wastewater was treated by EC.
Removal of phenol, COD, and color had decreased by 10 to 20 % when the
temperature was raised between 20°C and 60°C (Katal and Pahlavanzadeh
2011).
Batch electrocoagulation experiments were carried out in the treatment of
petroleum refinery wastewater (El-Naas et al. 2009). The effect of temperature
on the removal of sulfate and COD from petroleum wastewater was studied at
25°C and 40 °C. After 45 min of the EC process, it was observed that the sulfate
and COD removal rate at 25°C became slightly higher than that at 40°C. They
explained that the increase in solution temperature leads to higher solubility of
aluminum sulfates. So, the precipitation of the aluminum sulfateis increased at
lower temperatures and better removal can be achieved.

2.4.7.4 Effect of Reaction Time

Generated coagulant concentration in the solution is specifically
corresponding to the electric charge supplied per volume. According to
treatment times and identified current, the amount of metal cations delivered by
electrolysis can be estimated based on Faraday’s law. Moreover, electrolysis
time influences the treatment performance of the EC process as it might improve
or reduce with pH of the solution or current density (Abdel-Gawad et al. 2012).
Since the produced amount of aluminum by chemical reaction on the cathodes
depends more on the process time than the coulombs added per
volume.(Mouedhen et al. 2008).

2.4.7.5 Effect of Conductivity

The higher ionic species existence in the treated solution cell, leads to an
increase in current density at the same voltage, or in other words, the cell
voltage lowers with increasing solution conductivity at constant current density.
The conductivity of the solution depends both on the concentration and kind of
electrolyte. In case of low conductivity of solution, there are many types of
electrolyte available such as NaCl, KCl, BaCl2 and Na2SO4. Generally, sodium
chloride is used in order to increase the electrolytic conductivity. It is
recommended that the electrolyte contains more than 200 (ppm) of chloride ions
to make sure of effective EC treatment (Holt et al. 2005).

2.4.8 Adsorption Isotherm in EC

 Separation by EC is the consequence of adsorption of the contaminant on
the solid created from electrochemical dissolution of the anodes. This separation
process as a very sophisticate phenomenon. However, The removal of pollutant
is the same as conventional adsorption except the method of flocs generation
(Balasubramanian et al. 2009). The amount of generated flocs can be
calculated based on Faraday’s Law. As the quantity of coagulant can be
determined for a given treatment time, thus, the pollutant removal can be
modeled via the adsorption isotherm (Benaissa et al. 2014)
The amount of pollutant adsorbed per unit mass of adsorbent (qt) at time t
was calculated according to the following relation (Chithra and
Balasubramanian 2010 ):
𝑉
𝑞𝑡 = (𝐶𝑂𝐷i − 𝐶𝑂𝐷𝑡 ) (2.11)
𝑚

Where qt in mg/g is the amount of the pollutant adsorbed at any time t,𝑚 is the
weight of electrode dissolved in grams,𝑉 is the volume of the treated solution in
liters, CODi is the initial value of COD in the solution in mg/L, and CODt is the
COD value at time (t) in mg/L.
In literature, different adsorption isotherm models are available (Chithra
and Balasubramanian 2010 and Vasudevan et al. 2012). The easiest and most
commonly used way for determination of the isotherm constants is to linearize
the model relation and then apply linear regression. The most fitted models are
determined frequently by using linear regression and finding the parameters of
the models (Basar C. A. 2006).

2.4.8.1 Langmuir Adsorption Isotherm

The Langmuir isotherm assumes monolayer deposition of
adsorbate on homogenous adsorbent (coagulant) surface. It is well
recognized that the Langmuir equation is proposed for a homogeneous
surface. The mathematical expression of Langmuir isotherm is given as
(Ghanim and Ajjam 2013):
𝑞max𝐾L 𝐶e
𝑞e = (2.12)
1+𝐾L 𝐶e
 Where qe in mg/g refers to the amount of pollutant adsorbed at
equilibrium, qmax is the maximum adsorption capacity, Ce refers to COD
value at equilibrium in mg/l, and KL is the Langmuir constant in L/mg.
Eq.(2.12) can be written in a linear form:
𝐶e 1 𝐶e
= + (2.13)
𝑞e 𝑞max 𝐾L 𝑞max

Accordingly, a plot of Ce/qe vs. Ce produces a straight line with a slope of

1/qmax and intercept of 1/(KLqmax).

2.4.8.2 Freundlich Adsorption Isotherm

The empirical Freundlich model links the adsorption strength of the
sorbent towards adsorbent. The isotherm considers the multilayer
adsorption formation with a heterogeneous distribution of active sites and
it assumes that the stronger binding sites are connected first and that the
adsorption strength lowers with increasing number of site occupation.
(Vasudevan et al 2012)
The mathematical expression of Freundlich isotherm (Ghanim and
Ajjam 2013) is represented by:
1
𝑞e = 𝐾F𝐶e𝑛 (2.14)
Where KF is Freundlich constant that indicates the adsorption capacity of
the adsorbent in (mg/g)(L/mg)1/n and n is an empirical constant related to
the degree of the adsorption driving force. The linear form of Freundlich
isotherm can be given in the following form:
1
𝐿𝑛(𝑞e) = 𝐿𝑛(𝐾F) + 𝑛
𝐿𝑛(𝐶e) (2.15)
Accordingly, a plot of ln(qe) against ln(Ce) produces a straight line with a
slope of 1/n and intercept of ln(KF).

2.4.8.3 Temkin Adsorption Isotherm

The Temkin isotherm describes the behavior of adsorption system
in the heterogeneous surface and assumes some indirect interaction
between adsorbate and adsorbent on adsorption isotherms. The linear form of
the isotherm relation is represented as follows (Ghanim and Ajjam 2013):
𝑞e = 𝑏 𝐿𝑛(𝐾T) + 𝑏 𝐿𝑛(𝐶e) (2.16)
Where b is the Temkin isotherm parameter in mg/g, and KT is the
equilibrium binding Temkin constant in L/mg corresponding to maximum
binding energy. A plot of qe against ln(Ce) enables to specify the
constants b and KT.

2.5 Electrooxidation
2.5.1 Principles of Electrooxidation
In late decades, oxidative electrochemical advances have achieved a
promising step of improvement and can be adequately utilized for the
destruction of toxic or resist biodegradation organics (Panizza M., 2010).
Electrochemical oxidation (EO) is a complex process for remediation
wastewater. Electricity is exploited to produce an oxidant which oxidizes the
organic base contaminant existing in the wastewater. EO of wastewater can
follow two different pathways for oxidizing the pollutants as direct and indirect
oxidation. Direct oxidation or electrolysis takes place when the organic
pollutants directly oxidizes on the anode surface as shown in figure (2.6 a).

Figure (2.6) Schemes of (a) direct oxidation (b) indirect oxidation of pollutants
(anglada et al. 2009)
During direct oxidation, two types of oxidant can be created
electrochemically on oxide anodes (MOx).One is through Eq. (2.17) as the active
oxygen in the oxide lattice (MOx+1) which is called chemisorbed while the other
is by adsorbed hydroxyl radicals (•OH) or physisorbed active oxygen through as
in Eq.(2.18)
𝑅 + 𝑀𝑂𝑥+1 → 𝑅𝑂 + 𝑀𝑂𝑥 (2.17)
𝑅 + 𝑀𝑂𝑥 (∙ 𝑂𝐻)𝑛 → 𝐶𝑂2 + 𝑛𝐻+ + 𝑛𝑒 − + 𝑀𝑂𝑥 (2.18)

Where R refers for organic pollutants and n is number of •OH absorbed on the
electrode.
In most cases, chemisorbed oxidation partially converts the organic
pollutants therefore; biological treatment is necessary to achieve complete
organics degradation. In contrast, physisorbed oxidation yields CO2 and H2O to
complete full purification. In both approaches, the electrode activity and
pollutants diffusion rate play important role in the rate of oxidation. (anglada et
al. 2009 and Fıl et al. 2013).
Indirect oxidation pathway benefits from precarious intermediates which
are electrochemically generated such as chlorine, hypochlorite, ozone and
hydrogen peroxide. These powerful oxidizing agents are responsible for the
destruction of inorganic and organic pollutants. The diffusion rate of the
generating oxidants, pH and temperature determine the rate of oxidation in
indirect oxidation. (Fıl et al. 2013)
Due to frequent presence of chloride ions in wastewater, the main used
electrochemical oxidant is most likely chlorine or hypochlorite because of their
effective action (Szpyrkowicz L. 2006). With existence of chloride ions in
treated solution during EO, several reactions involving indirect oxidation are
given in Eq.(2.19) to Eq.(2.24)(Fıl et al. 2013).
Anodic reactions:
2𝐶𝑙 − → 𝐶𝑙2 + 2𝑒 − (2.19)
2𝐻2 𝑂 → 𝑂2 + 4𝐻+ + 6𝑒 − (2.20)
Bulk reactions:
𝐶𝑙2 + 𝐻2 𝑂 → 𝐻𝑂𝐶𝑙 + 𝐻+ + 𝐶𝑙 − (2.21)
𝐻𝑂𝐶𝑙 → 𝐻+ + 𝑂𝐶𝑙 − (2.22)
Cathodic reactions:
2𝐻2 𝑂 + 2𝑒 − → 2𝑂𝐻− + 2𝐻2 (2.23)
𝑂𝐶𝑙 − + 𝐻2 𝑂 + 2𝑒 − → 𝐶𝑙 − + 2𝑂𝐻− (2.24)

If suitable amount of chloride ions are present in the wastewater, the

anodically generated Cl2 and OCl- in Eq.(2.19) and Eq.(2.22) respectively can be
used to destroy and eliminate oxidizable inorganic and organic pollutants.
(Martı´nez-Huitle and Ferro 2006)

2.5.2 The Electrode Material

The electrode substance is one of limiting factors that impact on
the electrochemical oxidation of organic pollutants. Conventional
insoluble anodic electrodes, such as platinum and graphite electrodes,
still obtain a broad scope of uses in wastewater treatment. In order to
enhance the performance of electrochemical treatment, researchers and
scientists started to create and think about anode materials which have
higher stability, catalytic activity and oxygen over potential. (Du X. 2015)
The anodic overpotential of oxygen evolution restrict the electrode
catalytic activity towards organic oxidation. Table (2.2) gives a
comparison of oxygen over potential of widely studied electrode
materials.
Pt, IrO2, and graphite have low values of overpotential for the oxygen
evolution reaction. This demonstrates that powerful oxidation of organics at
these anodes may happen just at low current density. Otherwise, critical decline
of the efficiency is normal at high current density, because of the oxygen
creation.
The titanium substrate-boron doped diamond film (Ti/BDD) electrode
have the highest value of oxygen overpotential and high efficiency even at
considerably high current in addition of minimal side reaction involvements
from the oxygen evolution. (Martınez-Huitle C. A. 2004)
Table (2.2) Potential for the oxygen evolution at different anodes
(anglada et al. 2009)

Anode Value Conditions

Pt 1.6 0.5M H2SO4
IrO2 1.6 0.5M H2SO4
Graphite 1.7 0.5M H2SO4
PbO2 1.9 1 M H2SO4
SnO2 1.9 0.5M H2SO4
TiO2 2.2 1 M H2SO4
Si/BDD 2.3 0.5M H2SO4
Ti/BDD 2.7 0.5M H2SO4

Distinctive anodes have been utilized for the treatment of industrial

wastewaters. These days, electrode graphite has been broadly utilized for the
decomposition of organic matter since it is cheap. Graphite has an extensive
surface area, this property can improve the rate of organic pollutes elimination
by adsorption and electrochemical oxidation. However relative short life of
graphite electrode due to surface corrosion is one of the general drawbacks
especially when electrooxidation happens at high current densities. (Dindarloo
et al. 2015)
Hydrogen peroxide can be formed on the cathode by reduction of oxygen.
It is a good oxidant regent for indirect electrolyses of organic matters. Carbon
based materials have been widely used for this purpose through couple electron
reduction of O2 as in Eq.(2.25) on the cathode surface. (Panizza M. 2010)
𝑂2 + 2𝐻+ + 2𝑒 − → 2𝐻2 𝑂2 (2.25)

Indeed, graphite and carbon show good electrochemical activities for

oxygen reduction. (Do and Chen 1994)
2.5.3 Operating Conditions Effects on the EO
 Among the variables that are generally adjusted in electrolytic process,
the current density may be the one most commonly used in electrochemical
oxidation treatments as it controls the reaction rate. The amount of reduced and
oxidized matters on anode surface is proportional with increasing of current
density. Also, the production of mediator oxidizing agents, like free chlorine,
will increase with the current density through indirect EO of pollutants. (Fıl et
al. 2013)
However, higher current density doesn't necessarily leads to greater
oxidation rate, since for particular anode material, the oxidation efficiency is
related to treated solution characteristics.(Asghar et al. 2015)
Opposite to current density, the effect of temperature on the removal
efficiency of the electrooxidation process hasn't been extensively investigated.
Generally the temperature has more powerful effect on mediated oxidation
process than direct oxidation process. An enhancement with rising temperature
of oxidation efficiency by different reagents has been reported by (Silva et al.
2013) and (Santos et al. 2006b)
Similar as temperature, the pH value impacts frequently mediated
electrooxidation. However, a survey of past publications doesn't permit a
definite conclusion if increasing or decreasing the pH value leads to pollutant
elimination in electrooxidation of wastewaters.
In chloride mediated reactions, chlorine generation occurs at the anode
surface. Chlorine is the main active species when the pH value is lower than 3.3
while further reaction tack places to produce HClO at pH lower than 7.5 and
ClO- at higher pH. Among chloro oxidant species, Cl2 is a strongest oxidant
followed by HClO, therefore, acidic medium mostly is preferred theoretically.
But practically the electrochemical system usually promotes Cl2 desorption,
consequently neutral pH would theoretically support the electrooxidation of
pollutants by HClO and ClO- (anglada et al. 2009).

2.5.4 Advantages and Disadvantages of EO

 Electrochemistry is regularly considered as an ecologically attractive
approach. The fundamental point of interest in the EO technology is that
chemicals are not utilized. In fact, just electrical energy is exploited for the
oxidation of organic substances, since the electron itself is considered as a safe,
clean and extremely powerful reagent.(Rajkumar and Palanivelu 2004)
The main advantages as often given in the literature are:
 Versatility: electrooxidation is usually not selective and can deal with
different pollutants and treat wide volumetric capacity range.
 Energy efficiency: the EO generally operates at ambient temperature, the
operational parameters can be planned to reduce energy loss and potential
can be readily adjusted.
 Amenability to automation: the electrical variable in the process are well
suitable for data collecting, process control and automation. So, the EO is
an extremely attractive and talented option in environmental engineering
for the solving the pollution troubles, particularly within water treatment.
(Muff J. 2010)

The primary disadvantage of EO process is its high working expense

because of the high energy utilization. Moreover, possibility for the production
of chlorinated organics through mediated oxidation by free chlorine should be
considered. Also, the effluent electrical conductivity has to be conducting.
Unluckily, not all wastewater will have adequate conductance and an electrolyte
may be needed. In addition, fouling problems may happen because of deposition
of contaminants on the electrode surface. (anglada et al. 2009)

2.6 Electrodialysis (ED)

In the medial of 20th century business equipment based on electrodialysis
(ED) innovation was created to remove mineral ions from brackish water. From
that time ED has progressed quickly due to enhanced ion exchange membrane
properties, advances in technology and better materials structure.
Electrodialysis Reversal (EDR) was created in the 1960s to prevent
organic fouling troubles. EDR is a membrane desalination process that operates
with reciprocal polarity mode of electrodes in reliably and economically on
surface water, reuse and specific wastewater. (Grebenyuk and Grebenyuk
2002)
Electrodialysis procedure is more cost effective than reverse osmosis for
desalination of the wastewater which contains TDS of 500 - 4000 ppm, thus,
ED is generally utilized for desalination of industrial wastewater containing
TDS of 500 ~ 1500 ppm (Sato et al. 1983).
The reclamation and reuse of wastewater by ED was widely reported in
publications like in almond industry (Valero et al. 2015), wastewater plant
(Broens et al. 2004) brine from a reverse osmosis (Badruzzaman et al. 2009)
and nuclear power plant (Yeon et al. 2007).
ED is an electrochemical separation process in which ions are traveled
through ion exchange membranes by effects of a direct current potential.
Potential driving force is utilized to transfer dissolved ions from the feed water
through cationic and anionic exchange membranes to form a concentrate and
dilute streams (Valero et al. 2011). The schematic diagram of the ED process is
illustrated in figure (2.7) where the terms cm, am and s refer to cation exchange
membrane, anion exchange membrane and spacer respectively.
 Figure (2.7) Schematic sketch of the ED process.(Němeček M.)

2.6.1 The Principle of Electrodialysis

The fundamentals of electrodialysis are represented in Figure (2.7). A
simple electrodialysis cell structure comprises of a sequence of cation and anion
exchange membranes set in an alternating style between a cathode and an anode
to frame singular cells.
When the electrolytic feed solution flows through the cells and a potential
driving force is set up between the electrodes, the negative anions transfer
towards the anode and the positive cations towards the cathode. The negative
anions can readily pass through the anion exchange membrane but are prevented
by the cation exchange membrane while opposite act occurs for the positive
cations. As a result, low and high ion concentration solutions are yielded which
referred to as dilute and the concentrated solution respectively
A cell pair consists of the whole space of the concentrate and dilute
compartments and the adjacent cation and anion exchange membranes. While an
ED stack consists of repeating cell pair unit. (Strathmann H. 2000)
Generally, several factors can affect the ED process performance such as
stack design, length of the solution path in the stack, number of cells, feed
concentration, flow rate and applied voltage, etc. (Kaňavova et al. 2014) and
(Moheb et al. 2010)

2.6.2 Membrane Stack

The design of membrane stack determines the amount of removed ions. A
membrane stack can be designed in either a vertical or horizontal position. A
schematic sheet-flow of an electrodialysis stack is shown in the Figure (2.8)
where the cell pairs form the essential unit of an ED stack.
Each stack has two electrodes and numbers of cell pairs. ED membrane
stack can be assembled with more than six hundreds cell pairs for industrial
applications. The number of cell pairs need to get a specific water quality and is
mainly dependent on the source water properties (Valero et al. 2011).

Figure (2.8) Schematic of a sheet-flow electrodialysis stack. (Strathmann H.

2012)

Any leakage between all compartments should be prevented. To reduce

the concentration polarization, The spacer screen supposed to offer greatest
mixing of the solutions at the membrane surfaces with pressure drop as small as
possible (Strathmann H. 2000).
 In industrial ED stack, two different spacer designs are used: tortuous and
the sheet-flow path flow design. In the tortuous type, the spacer has a long
narrow channel for the fluid flow which provides high solution flow velocity. A
tortuous path flow spacer gasket is shown schematically in Figure (2.9 a).
In a sheet-flow design the solution flows straightly from the entrance to
the exit ports, which prevent an excessive pressure drop as shown in Figure
(2.9.b) (Baker R. W. 2004)

Figure (2.9) Spacers used in the electrodialysis unit; (a) tortuous path spacer, (b)
sheet flow spacer. Richard W. (Baker R.W. 2004)
The cell thickness should be as small as possible to reduce the electrical
resistance of the solutions. Consequently, lower energy is consumed.
Industrially, the cell thickness is usually between 0.3 and 2 mm. A spacer is
fixed between each ionic membrane to keep distance between the membranes
and to maintain the solution flow distribution. Solution flow velocities in
tortuous path flow stacks are normally15 to 50 cm/s, while in sheet flow stacks
the flow velocities are about 3 – 10 cm/s. (Strathmann H. 2012)

2.6.3 The Electrode and Electrode Chamber

Graphite, platinum or magnetite is utilized for anode electrode material
and iron or stainless is utilized for cathode electrode material. The electrodes
can be formed in flat, bar or net shape. Both electrode chambers are separated
from a stack using a partition to prevent mixing of solution.
A partition is inserted between an electrode chamber and a stack for
preventing the mixing of solutions. A feed or a concentrated solution can be
used in the electrode chamber as electrolyte solution. Sometimes, Na2SO4
solution is used as electrolyte solution with mixing the effluent from anode and
cathode chambers to achieve the neutralization. (Tanaka Y. 2015)

2.6.4 Membranes
The electrically conductive membranes are manufactured in the layers
form consist of tiny polymeric particles which have ion exchange groups fixed
by polymer structure. The membranes are impermeable for water and have good
mechanical properties even under pressure.(AWWA 1995)
In ED stack, two kinds of ion exchange membranes are used:
• Cation membranes which allow just positively charged ions to pass through. It
is composed of sulfonated polystyrene matrix which has -SO3H groups linked to
the polymer. The sulfonated group ionizes in water generating a movable ion H+
and unchangeable charge (-SO3-).
• Anion membranes allow only negatively charged ions to pass through. The
membrane matrix has ammonium positively charged groups (-NR3+OH-) which
prevent cations.
The two kinds of membranes have general characteristics: insoluble in
water, hand washable, and low electrical resistance. Also, the membranes should
be resistant to fouling, change in pH (1-10), temperatures (up to 46ºC) and have
long working life. (Valero et al. 2011)
2.6.5 Operating Regimes of the Electrodialysis
2.6.5.1 Potentiostatic vs. Galvanostatic Mode
The ED unit can be operated in two electrical mode: potentiostatic mode
(constant voltage) or galvanostatic mode (constant current). Usually, the ED
stack is preferred to operate at constant voltage due to safety reasons.
 Throughout the ED operation the ions concentration and electric
conductivity of the solution decreases resulting in the raise of electrical
resistance of the system. If the ED system operates at constant current, it could
cause an uncontrolled raise of applied voltage resulting in potential collapse of
electric power supply and damage of membrane stack. (Němeček M.)

2.6.5.2 Batch vs. Flow-through (continuous) Setup

Based on the volume of treated solutions and the ED process application,
two operating regimes can be used: batch regime or flow-through (continuous)
regime.
In batch regime, the product solution is re-circulated during the ED
process until targeted concentration of salts in the corresponding tank is
achieved. In continuous regime, the product solution is concentrated or
desalinated during unidirectional flow through the ED stack. (AWWA 1995)
The essential contrast between these two regimes is clear from Figure
(2.10) which represents a laboratory scheme of the batch and flow-through
regime. However in industrial scale, the scheme can slightly differ due to
continuous provide of the feed solution. In Figure (2.10.A) both concentrate and
dilute solutions recycle in divided circuits resulting in a continuous increase of
ions concentration in tank C and concentration decrease in tank D. Conversely,
in Figure (2.10.B) the feed solution is identical for both inlet streams. The
outlets streams from concentrated concentrations (CCs) and diluted
concentrations (DCs) are continuously mixed keeping the feed solution
composition unchanged in the collecting tank during the process. (Němeček M.)
 Figure (2.10) Operational regimes of the ED process: (A) batch (B) flow-
through. (Němeček M.)

2.7 Previous Work on Combined and Hybrid EC and EO Process

The elimination performance of organic compounds in industrial
wastewater utilizing two step technique combining electrocoagulation followed
by electrooxidation was addressed by Linares-Hernández et al. (2010). Iron
and BDD (boron-doped diamond) electrodes were used in electrocoagulation
and electrooxidation respectively. The industrial wastewater samples were
gathered from the exit of a biological activated sludge plant.. The COD values
of the industrial wastewater were between 800-1200 (ppm) and the turbidity was
900 NTU. The effluent after electrocoagulation process was sequentially treated
by electrooxidation. At a current density of 80 mA/cm2 and pH 8, just 90 min. of
coupled process time required to completely eliminate the COD while 21 hours
needed when using electrooxidation alone. also the turbidity and the BOD were
completely removed. They mentioned that EC is a rather fast process and
effective in removing suspended and colloidal particles but not all organic
materials. While EO is effective in destroying organic compounds by oxidation,
but requires a lot of time, especially when high TSS are present.
 A synergistic combination of electrocoagulation and electrooxidation has
been applied by Hu and Li (2011) for the treatment of pulp industry effluent
loaded with COD (33000 ppm) and color (48,000 CU). In EC process, a
stainless steel was used as anode whereas graphite electrode was used as
cathode. The COD and color could be optimally diminished about 40% and
90%, respectively, while applying a reaction time of 60 min and a current of 0.6
A. after electrocoagulation the electrooxidation reduced the COD above 80%
under current density 8 mA/cm2, pH 5 and room temperature for 80 min of
treatment. They mentioned that the coupled process of EC followed by EO was
operated in which the major of charged and colloid species have been firstly
separated by EC according to highly color removal, then small organic could be
destroyed by EO reflected by COD reducing efficiently.

Ma et al. (2015) examined the performance of integrated process consist

of electrocoagulation (EC) combined with electrochemical oxidation for
treatment of papermaking tobacco sheet wastewater, which has the total COD
(6715 ppm), turbidity (1750 NTU), high content of suspended solids (SS=1860
ppm) and low biodegradability. In EC process, stainless steel net cathode and
aluminum (Al) anode were used while for electrochemical oxidation, a β-PbO2
or a mixed metal oxide (MMO) as anode was used. The wastewater was initially
treated by EC process under 40 mA/cm2 of current density, the pH (6.8) and 2.5
g/L of NaCl. The COD, turbidity and SS removal were 65% , 99.9% and 96.5%
respectively after 6 minutes of EC process. The effluent was further treated by
electrochemical oxidation under 20 mA/cm2 of current density and pH 5 with a
β-PbO2 anode or under 30 mA/cm2 of current density and pH 6.7 in case of
using (MMO) anode. 83.9% and 82.8% of COD removal could be achieved on
the β-PbO2 and MMO anodes, respectively. the authors concluded that The
removal of SS in the EC process was very useful to mass transfer of organic
compounds during electrooxidation process. The results proved that the
integrated process is a hopeful choice for pretreatment of papermaking tobacco
sheet wastewater before biological treatment since the major materials of the
ending effluent were biodegradable organic acids

A combined electrochemical technique was also studied for the treatment

of wastewater from a textile industry that produces synthetic polyester fabric.
The wastewater sample characteristics were COD (1316 ppm), the original pH
7.3, suspended solids (830 ppm). In the first treatment stage, the sample was
treated by electrocoagulation to remove suspended solids and followed by
electrooxidation stage. Both Aluminum and Mild steel electrodes were studied
in EC process. Based on the results, the aluminum was preferred for the
eliminate of suspended solids with about 99% removal and the COD reduced by
67.4% from its initial value. following EC, the electrocoagulated effluent was
additional subjected to electrooxidation using RuO2/IrO2/TaO2 coated titanium
and graphite electrodes. In this stage the COD removal was 18.7% and 88.8% in
case of RuO2/IrO2/TaO2 coated titanium and graphite respectively.
Graphite was found to be more competent for anodic incineration of organics
contrasted to RuO2/IrO2/TaO2 covered titanium, since the depletion of Cl− ion

concentration was relatively high in the existence of graphite electrode.(Raju et

al. 2008)

A carwash service wastewater was treated using a combined

electrocoagulation and electrooxidation process. The characterization of
wastewater presented COD (1295 ppm), turbidity (898 NTU), oil (369 ppm)
and total solids (1299 ppm). Electrocoagulation was investigated using iron and
aluminum electrodes. It was found that both types of electrodes produced alike
results, however, Al electrode was preferred and applied for a combined system
since the iron electrode imparted yellowish green color to the solution.
Electrocoagulation for 60 min of operation at pH 7 with a current density of 10.5
mA/cm2 reduced COD by 76%, turbidity by 98%, oils by 92%. After EC, The
effluent was further subjected by electrooxidation using BDD electrodes under
15 mA/cm2 for 120 min. The combined process was very effective in reducing
COD 96%, turbidity 98.4% and oils 100%. The authors reported that the
combined system is very effective on reducing organics like (oils, detergents,
soaps, etc.), but less effective on inorganics since the total solids removal was
46% and the conductivity was only reduced by 11%.(Rubí-Juárez et al. 2015)

Daghrir et al. (2012) examined the electrocoagulation-electrooxidation

(EC-EO) process for the remediation of restaurant wastewater loaded with
inorganic and organic matter, oil and suspensions solids. An coagulant and
oxidant agents were simultaneously produced by utilizing either aluminum or
iron plat electrodes set in a bipolar arrangement or graphite electrodes set in a
monopolar arrangement in the same electrolytic reactor. Relatively high
concentrations of iron (40–60ppm) or aluminum (20–40 ppm) and active
chlorine (9.6 mg/A. min) were produced in situ. The excellent performance for
wastewater treatment was resulted by using graphite and aluminum plates
alternated in the electrolytic cell and operated at current density of 3.64 mA/cm2
for 90 min of operation with pH adjusted to about 7. At these treatment
conditions, the Oil, COD and BOD removal reached more than 98%, 90% and
86%, respectively. the workers reported that the EC-EO process was a
practicable technology for the remediation of restaurant wastewater
characterized by high Oil, COD, BOD, and total suspended solids
concentrations. the process was effective in reducing both suspended solids and
turbidity to (98%).

Mahvi et al. (2011) studied the performance of a continuous bipolar

electrocoagulation-electrooxidation and electroflotation ECEO–EF reactor
designed for simultaneous separate of phosphate and ammonia from synthetic
and actual an anaerobic reactor wastewater effluent. The characteristics of the
wastewater were as a phosphate concentration of (48.3 ppm), an ammonia
concentration of (28 ppm) and COD (35 ppm). the electrochemical unit was
consist of a two pairs of RuO2/Ti and stainless steel plates set with nine plats of
Al arranged in bipolar configuration. The actual wastewater was treated at
current density of 16.6 mA/cm2, a pH 7 and residence time of 60 min in the
reactor. Under these operating conditions the electrochemical reactor was able to
reduce the concentrations of ammonia, phosphate and COD by 98%, 98%, and
72%, respectively. It was concluded that increasing the detention time and
current density had good effects on the overall performance of the reactor at a
neutral pH solution.

Ge et al. (2004) developed a single continuous reactor for simultaneously

electrocoagulation/electroflotation process to treat laundry wastewater. Eight
pieces of monopolar titanium and 21 pieces of bipolar aluminum plates were
used as electrodes with an affective area 50 cm2 of each one. The operating
parameters such as current density, hydraulic residence time (HRT) and initial
pH were investigated. The design of the electrochemical unit made it possible
for the effective removal of COD, turbidity, surfactant and phosphate in a wide
pH range (5–9) at a short HRT (5–10 min).
It was found that the removal of COD, turbidity and surfactant was increased
with increasing current and HRT. The authors reported that the pH
neutralization impact allowed this process to be suitable in a larger range of pH,
which made it better than traditional chemical coagulation. Although, the
indirect electrooxidation reactions on the anodic electrode were mentioned, the
impact of these reactions on the COD removal was not farther discussed. For
pilot scale, electrochemical units with a capacity of (1.5 m3/h) were carried out
successfully to treatment of and it demonstrated laundry wastewater.

The performance of a hybrid process combining electrocoagulation and

electrooxidation (EO) was examined for the batch treatment of domestic
wastewater (DWW) loaded with COD (420 ppm), turbidity (202 NTU) and TSS
(399 ppm) (Daghrir et al. 2013). At the first, The process was estimated in
terms of its ability of producing a coagulant and an oxidant agents
simultaneously in the same reactor. aluminum or iron plats were used as
sacrificial electrodes in a bipolar arrangement, whereas flat graphite sheets were
used as monopolar electrodes. To characterize the optimum experimental
conditions for COD removal from the wastewater, the statistical factorial and
central composite design methodologies were sequentially applied.
The influence of current intensity, electrolysis time and type of electrode on the
COD removal as a evaluating response have been investigated. It was found that
the current intensity and treatment time were very significant for COD removal.
The impact of these coupled key parameters was approximately 90% on the
response, while the type of sacrificial electrode influenced only 10%. By using
aluminum electrode, 78% of COD removal can be achieved under optimal
conditions of (0.7 A) current intensity and (39 min) treatment time. The workers
notified that the hybrid process joining electrocoagulation and electrooxidation
could form the basis of a suitable procedure for eliminating COD from
municipal, domestic and industrial effluents.

Esfandyari et al. (2014) studied the removal of pollutants from olive oil
mill wastewater by peroxi-electrocoagulation/electrooxidation-electroflotation
process using a pilot continuous reactor. the olive mill wastewater was diluted
four times and then characterized as COD (28500 ppm), BOD (8300 ppm),
turbidity (320 NTU), oil (5320 ppm) and SS (13800 ppm). The electrochemical
reactor was consist of a two pairs of RuO2/Ti and stainless steel plates set with
nine plats of Al arranged in bipolar configuration. The effects of current density,
hydrogen peroxide doses, initial pH, NaCl concentrations, and reaction times
were studied. The peroxielectrochemical method was found especially efficient
in removal of organic pollution from the wastewater at optimal conditions of
current density of 40 mA/cm2, initial pH 4, reaction time (30 min.) and
concentration of (1000 ppm) for each H2O2 and NaCl. The treatment process
eliminated COD by 96 %, BOD5 by 93.6 %, turbidity by 88.7%, SS by 97% and
oil by 97.1 %. Since the biodegradability index (BOD5/COD) increased about
one half times, it was reported that the peroxi-
electrocoagulation/electrooxidation-electroflotation method using aluminum
electrodes could extensively increase the biodegradability and it possible used as
post treatment of the effluent before a biological system.

Based on literature reviews, the integrated electrochemical system of

combined electrocoagulation and electrodialysis was rarely developed or
investigated. Deghles and Kurt (2016) studied the performance of a hybrid
EC/ED system to remove COD (2800 ppm), Chromium (Cr), NH3-N and color
from tannery wastewater. In EC, effects of current density (7 or 14 mA/cm2) and
electrolysis time were analyzed to optimize the process with 5 pair electrodes of
iron or aluminum. Subsequently, the optimized electrocoagulated effluent was
integrated with ED. It was found that aluminum electrodes were more effective
since the removal efficiency of COD was 73% under optimized conditions
current density (14 mA/cm2), pH (6), electrolysis time (125 min.) and 6.75 KW
h/m3. Using ED cell consist of just one pair membrane, the process was able to
promote the quality of the treated wastewater corresponding to reduce
conductivity value from 22 to 0.371 mS/cm at 45 minute and 24 applied
voltages.

According to literature survey, It is clearly recognized that an integrated

system of combining EC-EO with ED has not been investigated yet. However as
like this electrochemical system will develop, highly performance can be
expected for organic and inorganic pollutes removal from Fuel washing
wastewater (FWW).
3.1 Introduction
The present study involves the treatment of heavy fuel washing
wastewater (FWW) effluents using simultaneous in situ electrocoagulation-
electrooxidation (EC-EO) process, followed by electrodialysis (ED) in order to
study and assess the performance of the integrated approach to eliminate organic
and inorganic pollutant load.
This chapter presents the characterization of the wastewaters used in the study.
The materials, experimental setup, procedures, and conditions used to treat the
effluents by electrochemical process are presented. The approaches followed,
the analytical techniques, and the experimental parameters used in this work, are
also introduced in this chapter. Taguchi as an experimental design method was
also mentioned here.

3.2 Materials and Methods

3.2.1 Effluents
The FWW used in this study was obtained from the South Baghdad Gas
Power Station/2. The samples were collected from the discharge effluent pipe to
the Tigers River. A settling tank represent the final stage of heavy fuel treatment
plant which called (Westfalia Unit) before FWW discharge. They were collected
in closed plastic containers and stored until use. The main characteristics of
FWW are presented in Table (3.1).
Table (3.1) Analysis of the FWW.
Parameter Value Permissible limit*
pH 6.5~7.3 6~9.5a
Turbidity (NTU) 785 5b
TSS (mg/L) 488 60a
Oil content (mg/L) 586 40b
E conductivity( µS/cm) 2350~2550 2000b
COD (mg/L) 753~760 < 100a
TDS (mg/L) 1370 1000b
* (a & b) subscript means the value based on: a (Iraqi regulation 2001), b (U.S.EPA 2002)

3.2.2 Apparatus
A. The following apparatus were used in the experiments of EC-EO:
1. DC power supply: a laboratory digital DC power supply (UNI-T, model:
UTP3315FT-L) with a voltage ranged from 0-30 V and current ranged
from 0-5A, was used in the experiments.
2. Digital pH (JENWAY Model 350, UK) was used to measure the pH of
the solution during the experiments.
3. Conductivity meter: ion conductivity meter(CRISON Basic-30, Spain),
was used to measure the ionic concentration and conductivity of the
solution during the experiments.
4. Water bath to keep the homogeneity and constant temperature of the
solution while treatment process in progress.
5. Glass Microfiber Filters: Whatman company 934-AH glass microfiber
filter was used to filter the samples taken from the reactor.
6. Electrical balance: an electrical balance (4 digits) product was used to
weigh the materials used in the work.
7. Glass ware: some glass wares were used in this work such as pipette,
beakers, volumetric flasks and others.
8. Electrocoagulation cell reactor: the cell was made of glass with inner
dimensions of(12cm width x 12cm length x 18cm height), with draining
valve at 2.5 cm from the bottom of the reactor. Upper Teflon cover (256
cm2 area and 2.8cm height) contains five slots distance 1 cm of each other
for electrodes fixation. Three holes were made to enter thermometer, pH
and electrical conductivity probs.
9. The electrodes: two kinds of electrodes were used aluminum and graphite
flat plats with same dimensions (10cm width x 20 cm length x 0.3 cm
thickness)
10. Avometer: current passing through the circuit was measured by means of
two Pros Kit MT 1210 avometer connected to the anodic lines.
11. Thermometer was used to measure the solution temperature.
B. The following apparatus were used in the experiments of ED.
1. DC power supply (as mentioned in section A above) was used in the
experiments.
2. Avometer (as mentioned in section A above) was used to measure current
passing through the ED stack circuit.
3. Three diaphragm pumps (Max. 1.8 L/min)
4. Two flow meter (0.5-4 L/min.)
5. Three pressure meters (0- 2.5 bar)
6. Set of connections pipes and valves.
7. Electro-dialysis stack reactor.

3.2.3 Chemicals
The following chemicals were used in the experiments:
1. Hydrochloric acid (HCl, 37%, Sigma-Aldrich) was used to prepare 1
Molarity and 0.1 Molarity. solution in order to adjust initial pH of the
treated FWW effluent.
2. Sodium hydroxide (NaOH, ≥97.0%, pellets, Sigma-Aldrich) was used to
prepare 1 Molarity and 0.1 Molarity solution.
3. N- Hexane 95%Fluka. AG
4. Sodium chloride (NaCl), with purity of 99.5 % by weight, product of
Fisher Chemicals (USA) was used to prepare concentrate solution at
appropriate electrical conductivity.
5. Sodium sulphate (Na2SO4), purity equal to 99.5 % by weight, product of
Fisher Chemicals (USA) was used to prepare rinse 0.5 Molarity solution.
6. Distilled water.

3.3 The EC-EO Experimental Lab Unit

The electrode sets consisted of two aluminum plate electrodes and three
graphite electrodes, each having an effective anodic surface area of 110 cm2 (10
cm width × 11 cm height) with an enter electrode distance of 1 cm. Aluminum
and graphite plates alternated in the cell reactor Teflon cover and were vertically
submerged in the effluent. They were placed at 2.0 cm from the bottom of the
cell. Only graphite electrodes were connected to the power supply (2 anodes and
a cathode). The aluminum electrodes situated between two graphite electrodes
were not electrically connected to the power supply as shown in the figure
(3.1). The two inner aluminum electrodes were operated as bipolar and
sacrificial electrodes. The cell reactor was placed in water bath to uphold
appropriate temperature. Figure (3.2) shows a photo of EC-EO unit and reactor
cell.

Figure (3.1) Schematic diagram of the EC-EO experimental setup.

 (a)

(b)
Figure (3.2) The EC-EO unit (a).The reactor cell (b).
3.4 The EC-EO Experimental Procedure
 1. The aluminum electrodes were weighed before and after each experiment
to determine the amount of aluminum loss of each experiment.
2. For all tests, a total volume of 1.87 L of effluent was used.
3. The pH of the electrolyte was adjusted with HCL or NaOH solution
before each experiment.
4. The anode and cathode sets were connected to the positive and negative
outlets, respectively.
5. Each run was timed starting with the DC power supply switching on.
During the experiments, anodic dissolution occurred and hydrogen gas
was produced at the cathode.
6. At the end of each experiment the treated effluent was left to settle for 30
minutes. 1.5 L for analysis from the middle suction through the cell valve
was withdrawn.
7. After each test, the electrolytic cell (including the electrodes) was cleaned
with 0.1 M hydrochloric acid solution for at least 5 minutes and then
rubbed with a sponge and rinsed with tap water.

3.5 Taguchi Design of the Experiment

The Taguchi design method applies fractional factorial test designs called
orthogonal arrays (OAs), which is provided to reduce the number of
experiments. The choice of a suitable OA depends on the number of control
parameters and their levels. Using OA design can estimate multiple process
variables which are simultaneously affecting the performance characteristic,
while minimizing the number of test runs (Shahavi et al. 2015). As example, for
four parameters at four levels, the traditional full factorial design would require
256 experiments. In the Taguchi L16 OA, however, the required experiments are
only 16. To accomplish such goal, Taguchi L16 OA design (four factors with 4-
level design) was used to determine and optimize the instrumental parameters to
consider higher removal of COD. As shown in table (3.2) the set of experiments
were designed to test successively different operating parameters such as current
density(3.64 to 14.55mA/cm2), initial pH (5 to 8), treatment times (20 to 80
min), temperature ( 30 to 60 °C) to determine the best conditions (maximum
COD removal) for FWW treatment. The design of experiment (DOE) using the
Taguchi method provides a simple, efficient, and systematic approach to
determine the optimum conditions. Table (3.3) shows the Taguchi L16 OA for
the COD removal.

Table (3.2) the experimental parameters and their levels

Parameters Level
1 2 3 4
2
Current density (mA/cm ) 3.64 7.27 10.91 14.55
pH 5 6 7 8
Time (min.) 20 40 60 80
Temperature (°C) 30 40 50 60

Table (3.3) Taguchi L16 Orthogonal Array for the COD removal.
CODED VALUE REAL VALUE
Current
initial Temp.
Run X1 X2 X3 X4 density Time (min)
PH C°
(mA/cm2)
1 1 1 1 1 3.64 5 20 30
2 1 2 2 2 3.64 6 40 40
3 1 3 3 3 3.64 7 60 50
4 1 4 4 4 3.64 8 80 60
5 2 1 2 3 7.27 5 40 50
6 2 2 1 4 7.27 6 20 60
7 2 3 4 1 7.27 7 80 30
8 2 4 3 2 7.27 8 60 40
9 3 1 3 4 10.91 5 60 60
10 3 2 4 3 10.91 6 80 50
11 3 3 1 2 10.91 7 20 40
12 3 4 2 1 10.91 8 40 30
13 4 1 4 2 14.55 5 80 40
14 4 2 3 1 14.55 6 60 30
15 4 3 2 4 14.55 7 40 60
16 4 4 1 3 14.55 8 20 50

3.6 Kinetic Models Experiments

The kinetic studies describe the rate of adsorption /oxidation of
organic contaminations taking place for EC, EC-EO and EO separately.
Their reaction rate constants were determined for the equilibrium time of
120 minutes. These kinetic models are useful for the design and
optimization of effluent treatment models. Similarly, anodic active area
was maintained using three different electrodes configurations as shown
in the figure (3.3). For all tests, a total volume of 1.87 L of FWW was used and
treated with the best investigated conditions based on EC-EO process. COD
reduction, pH, conductivity and cell voltage were examined with time.

- + - + - + + - +

Aluminum
electrode
Graphite
electrode

a b c

Figure (3.3) Various electrodes configurations for EC (a), EC-EO (b) and
EO (c) processes.

3.7 The Electrodialysis Setup

The ED setup consisted of: power DC, concentrate tank of 2 liters volume, feed
(dilute) tank of 2 liters volume, an electrode rinse tank of 2 liters volume, three
diaphragm pumps equipped each with a flow meter, three pressure gauges to
maintain the similar pressure drop across compartments. Three valves were used
to control solutions flow rate in the concentrate, dilute and electrodes
compartments of ED cell. Figure (3.4) Simplified diagram of the ED setup and
figure (3.5) shows a photo of ED setup.
Figure (3.4) Simplified diagram of the ED setup working in batch recirculation
mode.

Figure (3.5) A photo of ED setup.

3.8 Electrodialysis Cell
 The electro-dialysis cell employed at this stage of the work was designed
and manufactured based on the research studies in the field of lab electro-
membrane processes. The ED stackwas packed with five pair cells of cation and
anion exchange membranes. Diagonal net plastic separators with 0.5 mm were
placed between the membranes to form the flow paths of the dilute and
concentrate streams.
These spacers are designed to minimize boundary layer effects and are
arranged in the stack so that all the dilute and concentrate streams were manifold
separately. In this way a repeating section called a cell pair is formed; it
consisted of a cation exchange membrane, a dilute flow spacer, an anion-
exchange membrane, and a concentrate flow spacer. In this work, experiments
were carried out by this stack equipped with six cation exchange membranes
(CEM) and five anion exchange membranes (AEM) arranged as illustrated in
figure (3.6). A photo of the developed electrodialysis stack was shown in figure
(3.7).

Figure (3.6) The ED stack configuration.

 Figure (3.7) A photo of the electrodialysis stack.

It is essential to minimize the internal liquid leakage, which occurs

through gaps or pinholes due to the membrane deformation at the slot as shown
in figure (3.8). Usually, to prevent these troubles, many tricks are proposed like
bend the slot, decrease the width of the slot, or insert the support in the slot
(Tanaka Y. 2015). Which all these ideas may cause increasing the pressure drop
through the ED stack. In this work an innovative idea successfully was applied
using supportable gasket for the anionic membrane side as shown in figure (3.9)
 Figure(3.8) Deformation of an ion-exchange membrane. (Tanaka Y. 2015)

Anion membrane
Gasket
Cation membrane

Slot
Figure (3.9) Supportable gasket for the anionic membrane side.

Membranes used in these experiments are (anion AR204SXR412) and

(cation CR67,MK111) manufactured by Ionics, Watertown, MA, USA. Table
(3.4) shows the main characteristics of the membranes, according to the data
provided by the supplier (membranes were supplied from Aldora refinery, Iraq).

The active membrane area was 60cm2 per cell, thus the total active area
of the stack was 300cm2. Stainless steel (316 L) and graphite were selected as
cathode and anode electrodes respectively. Area of each electrode was 6 cm×10
cm. Thickness of dilution and concentrate cell are1.5 mm with 0.6 cm2 cross
sectional area of flow for each. Cathode and anode distances were 4 mm from
membrane in catholyte and anolyte compartments.

Table (3.4) Characteristics of the membranes

property membrane
 AR204SXR412 CR67,MK111
Reinforcing fabric Acrylic Acrylic
Specific weight mg/cm2 13.7 13.7
Thickness mm 0.5 0.56-0.58
Burst strength kg/cm2 7 7
Capacity meq/g 2.8 2.4
Chemical stability pH 1-10 1-10

3.9 The ED Experimental Procedure

1. The source of waste water for the ED was the treated FWW which was
produced from EC-EO based on the best investigated conditions. About 20
liters of treated FWW were produced and collected to be used later as waste
water in ED experiments.
2. In each experiment, the solutions employed were 1L of the wastewater
(treated FWW by EC-EO at best conditions) as a diluate, 1L of NaCl 895
mg/L (about 1700 µS/cm electrical conductivity) as a concentrate and 2L of
Na2SO4 0.5 M as the electrolyte solution.
3. In order to study the voltage effect on the ED process, a series of
potentiostatic experiments with voltage range of (6, 9, 12, 15 and 18) were
carried out with fixed flow rate of 0.5 L/min for dilute and concentrate
solutions.
4. In order to study the flow rate effect on the ED process, several tests at the
best selected voltage were approved with a flow rate range (0.5, 0.8, 1.1, 1.4
and 1.7 L/min.)
5. The ionic concentration of salts (as well as conductivity) of dilute and
concentrate solutions were measured at10 min. intervals. Also, the electrical
current of the ED stack was recorded during the electro-dialysis time.
6. The time of treatment for each experiment was 60 minutes.
7. The flow rate of the electrolyte solution was fixed at 1.2 L/min for all
experiments as well as pressure drop was maintained the same for all solution
streams in each case.
8. In this study, the characteristic quality was the removal efficiency percentage
which was calculated as follows:
Cout
𝑅𝑒𝑚𝑜𝑣𝑎𝑙 (%) = (1 − ) × 100 (3.1)
Cin

Where, Cout and Cin are outlet and inlet ionic salts concentrations,
respectively.
9. Specific power consumption (SPC) is an important parameter from the
economical point of view, as it can be described as the energy consumed for
desalting one liter of feed solution and it is calculated here as electrical
energy consumed only in the cells (kWh/m3)
𝑡
𝑈 ∫0 𝐼𝑑𝑡
𝑆𝑃𝐶 = (3.2)
1000 ∗ 𝑉d
where U is the applied potential (volte), I is the current intensity (ampere), Vd is
the dilute stream volume (m3), and t is the time (hour) (Kabay N. 2007)

3.10 Analysis Tests

3.10.1 COD Analysis
Organic compounds in water are normally measured as chemical oxygen
demand (COD). The COD is a measure of the amount of oxygen needed to
chemically oxidize the wastes in a specific time and temperature by a specific
oxidizer. The COD does not distinguish between ability of microorganisms to
degrade the waste and the chemical oxidation of inert organic matter. The COD
was measured as follows:
1. Two ml of filtered FWW sample were added to analysis oxidizer vial (0-
1500 mg/l) and digestion of organic take place in the reactor at 150 °C for
120 minutes.
 2. Remove the vials from the reactor and allow them to cool down to
ambient temperature before measuring.
3. Lovibond MD 200, Germany Photometers providing photometric
detection was used to measure the COD concentration in mg/l O2.

3.10.2 Oil Content Analysis

The oil content in FWW was measured using the Handheld Oil-in-Water
Meter. The test method was as follows:
1. 100 mL of contaminated water was collected in a clean, suitable graduated
glass mixing cylinder.
2. 6 N hydrochloric acid was added until the pH of the water sample was < 2.
3. 10 mL of extraction solvent (hexane) was added and securely cap the
cylinder.
4. Oil from the water was extracted by vigorously shaking the cylinder for 2
minutes.
5. The extracted solvent was allowed to separate from the water for
approximately 1 minute. The solvent extract will be floating on top of the
water.
6. The appropriate cuvette was filled (mini-cell cuvette) with the solvent
extract.
7. The cuvette was inserted into the Handheld Oil-in-Water Meter (TD-
500DTM, USA) then the oil content was recorded in mg/l.

3.10.3 Turbidity
Turbidity was measured using optoelectronic meter (TurbiDirect
Lovibond, TB 300 IR, Germany). In this digital meter, an artificial light source
emits a known intensity of light through a sample. The suspended particles
scatter or absorb the light. The scattered light is then recorded on a photo
detector. Scattered light is generally measured at an angle of 90o. This
measurement principle is known as nephelometry. The results are expressed in
terms of NTU (Nephelometric Turbidity Units). Turbidity measurement does not
require any sample preparation, other than shaking the sample bottle well before
analysis.

3.10.4 Total Suspended Solids

Total suspended solids (TSS) are that portion of the total solids that are
retained on a filter paper (Whatman company 934-AHglass microfiber filter).
Before sampling, filter papers were prepared by first soaking them in distilled
water, drying them at 100oC, weighing and recording their weights. Now, a
measured volume (250 ml) of treated FWW is passed through the filter. The
filter containing the residue is then dried in an oven for one hour at 100oC. The
sample is then cooled and weighed. The increase in weight represents TSS.
Finally, TSS was calculated by using the following equation (Hussein, 2014).

mg (A−B)
TSS ( )= × 1000 (3.3)
L Cw

where A = end weight of the filter (mg), B = initial weight of the filter (mg), and
Cw = volume of filtered sample (ml). This inexpensive TSS tells much about the
produced water character and can be run in less than two hours with fairly
inexpensive equipment.
Introduction
This chapter summarizes the results of the experimental work conducted
in three main sections. In the first section, the hybrid EC-EO in situ experiments
performed according to Taguchi design of experiment (DOE). By using Minitab
17.0 software, The effect and optimization of parameters on the process were
determined. Based on the COD removal efficiency, mean of means, signal to
noise ratio (S/N), analysis of variance (ANOVA) and regression equation were
calculated. Also, the multiple regression analysis was used to model the oil and
TDS removal. Moreover, current efficiency and specific power consumption
(SPC) were estimated. Results of EC-EO process experiments are cited in tables
A.1 to A.3, Appendix A.
Next section was focused on the dynamic behavior of the EO, EC, and
EC-EO in situ processes separately. For each of these processes, the change in
pH solution, conductivity, normalized voltage drop of the system and the
reaction kinetics were estimated. In addition, modeling of EC through
adsorption isotherm was conducted. Results of individual experimental are
shown in tables B.1 to B.4, Appendix B. and the electrocoagulation adsorption
calculation results are listed in tables C.1 to C.3, Appendix C.
In the last section, a batch recirculation electrodialysis study using locally
designed ED stack was performed to reduce TDS and solution conductivity from
pretreated wastewater by EC-EO process. The effect of applied potential and
flow rate on the TDS removal were investigated. The best operation conditions
of the ED stack and the specific power consumption (SPC) were estimated.
results of electrodialysis experiments are listed in tables D.1 to D.9, Appendix
D.

4.1 The EC-EO in Situ Experiments

Table (4.1) shows the obtained removal results of the EC-EO in situ
experiments performed according to Taguchi design of experiment (DOE). In
this table, experimental analysis are expressed as percentage of removal
efficiency (RE) for COD, oil, turbidity, total solid suspension, total and
dissolved solids were calculated based on the following general equation:
(𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑣𝑎𝑙𝑢𝑒−𝐹𝑖𝑛𝑎𝑙 𝑣𝑎𝑙𝑢𝑒)
𝑅𝐸 % = × 100 (4.1)
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑣𝑎𝑙𝑢𝑒

Table (4.1) Experimental plan of L16 and removal efficiency percentage.

Run COD/RE Oil/RE Turbidity/RE TSS/RE TDS/RE
no. % % % % %
1 65.0 64.5 58.6 57.4 16.1
2 77.2 97.4 97.2 92.3 8.0
3 73.9 99.6 98.5 94.5 17.3
4 73.8 99.7 98.8 95.8 22.8
5 83.0 98.3 99.1 93.4 9.9
6 78.9 80.0 98.5 96.2 23.1
7 84.7 90.0 91.3 90.8 29.2
8 84.5 99.3 98.5 94.3 27.7
9 77.0 97.0 90.3 85.0 22.1
10 90.0 99.9 84.5 80.2 27.7
11 84.9 85.2 89.0 88.8 27.9
12 83.2 86.3 89.1 90.3 26.4
13 84.3 99.8 72.0 70.8 26.4
14 89.1 99.6 81.0 79.6 42.1
15 80.0 99.2 99.0 95.7 32.4
16 82.7 87.6 98.7 96.2 16.1

The data of the COD removal efficiency were analyzed using Minitab
17.0 software to determine the effects of each parameter on COD removal as a
targeted characteristically performance response, since each of mean of means,
signal to noise ratio (S/N) and analysis of variance (ANOVA) were calculated
based on the COD removal efficiency.
4.1.1 Effect of Parameters on COD Removal Efficiency
Figure (4.1) shows the effect of current density, pH, treatment time and
temperature on the mean of means of COD removal. Each point in this figure
represent the mean value of four experiments which conducted at the same level
of the particular parameter. Through all parameter levels, different behaviors of
the removal efficiency were observed for each parameter.
Figure (4.1) Effect of each parameter on COD removal efficiency for Taguchi's
OA Experiments.
It is clear that increasing current density leads to increase the COD
removal considerably. Significant improvement in COD removal efficiency is
noted when the current density changed from first level (3.64 mA/cm2) to
second level (7.27 mA/cm2) while slightly removal development is observed
with higher than 7.27 (mA/cm2).
In fact, increasing current density will give rise to increase in charge
loading according to Faraday's law (Eq. 2.9) which will lead to higher amount of
dissolved aluminum and consequently enhance removal of pollutants.
The present results are in agreement with Ge et al. (2004) who
investigated a new bipolar aluminum electrocoagulation – electroflotation for
the treatment of laundry waste water using titanium as mono electrodes.
Similar behavior was observed for EC treatment of oily waste water with
highly COD (4000 ppm) content from gas refinery. It was found that under
different applied current density from 25 to 40 mA/cm2, the COD removal
efficiency was changed from 70 to 92%. It was mentioned that the effect of
current density on increasing removal efficiency slows down at higher current
densities. (Saeedi and Fahlyani 2011)
Solution pH is another important parameter affecting removal efficiency
of COD. So, pH was adjusted in the narrow range from 5 to 8 to investigate its
effect on the process. As shown from the figure (4.1) the COD removal is
drastically rising by changing pH from 5 to 6 and then decreasing with further
pH increasing, however closer COD removal could be obtained at both 7 and 8
pH value. The lower COD removal at law pH value is in agreement with
aluminum hydroxide amphotric chart (Figure 2.5) where the higher precipitation
of Al(OH)3 at pH of 6.3 and its solubility increases as the solution becomes
more acidic or alkaline.
The effect of solution pH was examined on the removal of COD from
textile industry waste water. A combination of EC-EO treatment process was
applied using bipolar either aluminum or iron electrodes. Starting with initial
COD (985 mg/l), it was recorded that COD removal reached its highest value
(90%) at initial pH of 6. ( Naje and Abbas 2013)
As seen in figure (4.1), the COD removal efficiency increased with
increasing operation time and it is clear that at least 40 minute of electrolysis is
required to generate adequate amount of Al+3 ions and aggregated flocs need the
time to be formed. It is well known that the electrolysis time is proportional with
coagulant concentration in the reaction medium which leads to higher pollutant
removal. In literature it was found that the time in range 5~60 min. (Kuokkanen
et al. 2013). On other hand, further time consumption means extra organic
substance removal by indirect electrooxidation reaction. This result is in
agreement with (El-Naas et al. 2009) and their assessment of electrocoagulation
for the treatment of petroleum refinery wastewater.
Few studies showed the observations about the effect of temperature on
the removal of contaminants. However, it seemed that increasing temperature
can have negative and positive effects on the removal efficiency. Figure (4.1)
shows inversely performance of COD removal with temperature. The removal
efficiency increases from first to second level and then decreases drastically
with advance temperature rising.
The improvement of performance at second level (40 °C) could be the
result of faster moving and better collision of molecules and ions which leads to
higher rate of indirect electrooxidation reaction in the bulk region especially,
with the absence of mechanical mixing in the testing reactor. The mixing of
solution depends absolutely on the hydrodynamics of bubbles production. On
the other side, the low removal of COD at end level (60 °C) may be caused by
shrinkage of the large pores of polymeric aluminum hydroxide gel, which results
in separate dense flocs with lower adsorption capacity. In addition when
temperature is too high, the solubility of both aluminum ions and oil emulsion
are increased leading to complicate the separation process. The same behavior of
temperature on COD removal was confirmed by Ghalwa and Farhat (2015)
Positive effect of temperature on the COD removal was observed in EC
and EO by Martinez-Delgadillo et al. (2010) and Dermentzis. et al. (2014)
respectively, while negative effect was reported by El-Naas et al. (2013 )

4.1.2 Signal to Noise ratio (S/N) and Optimization of Parameters

In Taguchi method, the S/N ratio is used to determine the optimum
conditions based on the results obtained from experiments designed by
orthogonal array (Mohammadi et al. 2004).
The commonly S/N ratio functions, "larger is better" was used to evaluate
the system performance based on COD removal efficiency. This function is
expressed mathematically as:
𝑆 2
(𝑁) L = −10 𝑙𝑜𝑔10 ( 𝑛1 ∑𝑛𝑖=11𝑌 ) i
(4.2)

where n is the number of repetition done for an experimental combination and

Yi is the performance value of the ith experiment. The S/N ratio was calculated
by equation (4.2) and represented in the figure (4.2).
 Figure (4.2) the S/N ratio of each parameter on the COD removal efficiency.
The S/N ratio in figure (4.2) is analogous with the mean of means
presented in figure (4.1). The peak of S/N ratios are the most favored for
performance measurements and according to equation (4.2) the preferred output
for the optimized process is the maximum value (Ozyonar F. 2015).
It is clear from figure (4.2) that the best conditions for treatment of FWW
are: current density (14.55 mA/cm2), pH (6), reaction time (80 min) and
temperature (40 °C). Since these conditions are not present at any run in the
experimental design OA, therefore it should be confirmed experimentally.
The analysis of variance (ANOVA) is usually used to find out the
percentage contributions of individual parameters (Tir et al. 2014). ANOVA
was conducted to determine whether the process parameters were significant or
not. Results of ANOVA for the COD removal efficiency are listed in table (4.2).

Table (4.2) Results of ANOVA of COD removal efficiency of FWW.

Seq Adj F- P- Contribution
Source DF Adj MS
SS SS Value Value Cr
Current density
3 369.81 369.81 123.269 17.97 0.020 61.27%
(mA/cm2)
 pH 3 84.55 84.55 28.184 4.11 0.138 14.01%
Time (min) 3 57.67 57.67 19.224 2.80 0.210 9.56%
0.168
Temperature(C) 3 70.96 70.96 23.654 3.45 11.76%

Error 3 20.58 20.58 6.861 3.41%

100.00%
Total 15 603.58

In general, P value points out which parameter has a significant effect on

the process. The parameter is considered important if its P value is smaller than
(0.05) with confidence 95% (Ghanizadeh. et al. 2015). So, From table (4.2) it
can be seen that only the current density has a major effect on the COD removal
for the EC-EO process where the P value was smaller than (0.05).
Quantitative evaluation was achieved using percentage contribution (Cr)
of all parameters by equation (4.3) (Gokkus and Yıldız 2015 ).

𝑆𝑒𝑞 𝑆𝑆−(𝐷𝐹 ×𝐴𝑑𝑗 𝑀𝑆 )

𝐶𝑟 = (4.3)
𝑆𝑒𝑞 𝑆𝑆total

Table (4.2) illustrated that the biggest contribution percentage was

that of current density with (61.27%) followed by pH (14.01%). Less influence
factors on the system were temperature (11.76%) and time (9.56%).Similar
current density contribution value on the COD removal was reported for
treatment of raw tannery wastewater by electrocoagulation technique (Deghles
and Kurt 2015).

4.1.3 Regression Equation

Based on the COD removal efficiency listed in table (4.1) Minitab 17.0
software was used to fit the data to linearization model which included the
coefficients of all parameters levels. The regression square value (R2) of the
model was (96.59%) and the general coded expression of the model equation
with all parameter coefficients were reported in table (4.3).
Table (4.3) Parametric coefficients and general model equation.
Levels
parameters

Code 1 2 3 4
X1 -8.29 2.01 3.01 3.26
X2 -3.44 3.04 0.11 0.29
X3 -2.89 0.09 0.36 2.44
X4 -0.26 1.96 1.64 -3.34
COD removal(%) = 80.763+x1+ x2+ x3+ x4

The model equation in Table (4.3) is useful to predict the COD removal
efficiency value of the full factorial experiments where: x1, x2, x3 and x4
represent the coefficients of particular parameters for selected level. Using the
model equation, the predicted COD removal efficiency value of L16 OA
experiments were calculated and plotted against the experimentally observed
COD removal responses in figure (4.3)

95.0

90.0
R² = 0.9661
85.0
RE (%) observed

80.0

75.0

70.0

65.0

60.0
60 65 70 75 80 85 90 95
RE (%) predicted

Figure (4.3) Observed response against predicted response for COD removal
efficiency.
 It is obviously noticed from figure (4.3) that the predicted values are
closer to experimental response for all L16 runs. Also the R2 value is (0.966)
which confirms a high-quality agreement between the observed and the
predicted values in all cases.
Moreover, the confirmation of the model under the detected optimum
experimental condition was implemented. Two experiments were proceeding
and the COD removal efficacy was calculated. The obtained verification
experiment results at the optimal parametric levels are given in table (4.4).

Table (4.4) Observed and predicted COD removal efficiency values at optimum
experimental conditions.
Run Current pH Time Temperature Observed Predicted Error
no. density (min.) (°C) COD COD %
(mA/cm2) removal% removal%
1 14.55 6 80 40 89.6 91.46 2.03
2 14.55 6 80 40 90.5 91.46 1.05

From table (4.4) it is noted that the verification experiments shows a good
conformity between the observed and predicted results within less than 5%
error. By analysis of the other pollutants, highly removal of oil by 99.7%,
turbidity by 96.8%, TSS by 88% were recorded except for TDS since only 33%
was removed.

4.1.4 Oil Removal

Oil content is another important contaminant involved in FWW . Based
on the oil removal results of OA in table (4.1) the multiple regression analysis
was used to model the relationship between the affected parameters and the oil
removal as a response. The response goal was to maximize the oil removal with
95% confidence. The final model equation, predicted response, optimal solution
and top five alternative solutions were tabulated in table (4.5) and the related
software graph for oil (E.1) is shown in appendix E.
Table (4.5) Multiple regression analysis solutions for oil removal
 Parameters Predicted
X1 X2 X3 X4 response %
Optimal Not
14.55 63 49.4 107.5
solution affected
10.91 80 50 102.510
Top five 10.91 60 60 101.882
alternative 3.64 60 50 101.676
solution 14.55 80 40 101.657
7.27 60 40 100.818
Final model
Oil removal (%) = -21.0 + 0.523 X1 + 1.381 X3 + 3.132 X4
equation
- 0.01092 (X3)2 - 0.03174 (X4)2
R2= 90.93

It can be noticed from table (4.5) that all predicted response values for oil
removal were higher than 100% which indicates that EC-EO process was
efficient treatment method for oil separation from FWW. The optimal conditions
of oil removal showed a small departure from optimal COD removal conditions,
however complete oil separation was also predicted under optimal COD removal
conditions. The model equation fitted the data with high regression coefficient
(R2= 90.93) while the pH parameter (X2) did not affect on the oil separation. For
EC process, highly oil removal exceeded than 95% were reported by Xu and
Zhu (2004) and Gilpavas et al. (2009).

4.1.5 TDS Removal

Since the EC-EO treated wastewater will post-reform by electrodialysis to
be reused in the washing fuel process, the total dissolved solids (TDS)
separation was considered as a useful step in reducing the burden on the
electrodialysis process. As in oil removal, the multiple regression analysis was
used to model the relationship between the affected parameters and the TDS
removal.
According to TDS removal data in table (4.1), the final model equation,
predicted response, optimal solution and top five alternative solutions were
tabulated in table (4.6) and the related software graph for TDS (E.2) is shown in
appendix E.
 From Table (4.6) the predicted TDS removal values were low and it can
be concluded that the EC-EO process was not capable to eliminate large amount
of TDS in solution. The model equation fitted the data with regression
coefficient (R2= 87.91) while the temperature parameter (X4) did not affect the
TDS removal. Generally the EC process is not efficient in TDS removal.

Table (4.6) The multiple regression analysis solutions for TDS removal
Parameters Predicted
TDS
X1 X2 X3 X4
removal %
Optimal Not
14.55 8 80 63.17
solution affected
14.55 6 60 39.6602
Top five 14.55 7 40 36.8891
alternative 10.91 6 80 30.4530
solution 7.27 7 80 29.0923
7.27 8 60 27.1508
final model
TDS removal (%) = -31.0 + 0.493 X1 + 23.5 X2 - 1.963 X3 -
equation
2.508 (X2)2 + 0.0401 (X1)(X3) + 0.2654 (X2)(X3)
R2= 87.91

For instance, TDS separation at range (50-44%) was observed by

Kongjao et al. (2008) for treatment of tannery wastewater using
electrocoagulation technique and by Khansorthong and Hunsom (2009) for
remediation of wastewater from pulp and paper mill industry.

4.1.6 Current Efficiency and Specific Power Consumption (SPC)

Table (4.7) shows the calculated results for experimentally consumed
aluminum weight, current efficiency and specific power consumption of the EC-
EO in situ runs performed according to Taguchi design of experiment (DOE).
The data of consumed aluminum electrodes in table (4.7) illustrated that
the weights were proportional to current density and time of the experiment so
the charge loading considered a dominant factor on electrodes consumption. The
greatest weight of dissolved aluminum was recorded in run 13 which was
carried out under upper level of both current density and time.

Table (4.7) Aluminum and specific power consumption experimentally and

process current efficiency.
Run no. Al wt. (gm) Current efficiency % SPC (Kw h/m3)
1 0.041 90.7 0.41
2 0.086 95.8 0.83
3 0.125 93.1 1.27
4 0.162 90.7 1.57
5 0.175 97.6 2.49
6 0.084 94.1 1.00
7 0.338 94.6 4.86
8 0.247 92.0 3.35
9 0.397 98.6 4.95
10 0.509 94.8 6.78
11 0.121 90.1 1.91
12 0.245 91.4 4.25
13 0.731 102.1 10.87
14 0.559 104.1 9.18
15 0.324 90.5 5.78
16 0.171 95.5 3.03

It is worth mentioning that the amounts of aluminum ions dissolved were

large in the trials 14, 13 and 10 where it was observed by the unclear solution
and its tendency to white color. This may be the reason of low turbidity and TSS
removal efficiency which were recorded in table (4.1) for particular relative
runs.
The current efficiency is defined as the ratio of the actual aluminum
consumption to the theoretical value. In EC, lifetime of the electrodes is an
economical factor which is affected by the current efficiency of the
electrochemical process (Chen et al. 2000).
 Table (4.7) showed that the current efficiency values were high and
exceeded 100% in experiments 13 and 14, which indicate the economical
applicability of EC-EO process in industry. Overcoming the theoretical current
efficiency value may be as a result of chemical side reactions which contribute
slightly to the dissolution of aluminum electrodes (as in Eq. 2.10). The current
efficiency at EC process higher than 100% was also reported by Mouedhen et
al. ( 2008) ; Terrazas et al. (2010) and Kobya et al. (2011).

In electrochemical treatment methods, the energy consumption is

considered cost limiting criterion which determines the feasibility of the process.
For galvanostatic EC-EO process, the specific power consumption (SPC),
KWh/m3 was estimated based on the equation (4.4). (Kalash et al. 2015)

𝑈𝐼𝑡
𝑆𝑃𝐶 = (4.4)
1000∗ 𝑉
Where U is the average voltage (volte), I is the current intensity (ampere),
t is the time (hour) and V is the solution volume (m3).

From table (4.7) the SPC was increased with the current density and
process time while both temperature and pH hadn't significant effect. SPC
ranged between 0.41 and 10.87 (KWh/m3). The SPC results were in agreement
with (Panizza and Cerisola 2010) who used the electrocoagulation and anodic
oxidation integrated process as an electrochemical methods to treatment and
reuse of carwash wastewaters. It should be noted that the SPC estimated at
maximum COD removal (under optimum conditions) was 10.93 (KWh/m3).
Economically, lower current density and operation time levels can be used with
high COD removal efficiency as in run 10 and 14. Thus from economic point of
view and based on SPC results, the conditions of run 10 can be adapted as the
best operating conditions because it gives both environmentally allowable COD
concentration and lower power consumptions.
 According to EC process literature review, the electrical energy
consumption values was found to differ greatly depending on the kind of
solution used, being typically between (0.4 - 4.0 kWh/m3). (Kuokkanen et al.
2013).

4.2 Dynamic Behavior and Kinetics

4.2.1 Reaction kinetics

In the hybrid EC-EO in situ process, both EC and EO processes

synergistically work to eliminate the pollutants. To better highlight the role of
individually EC and EO on the COD removal, separated experiments were
carried out under the optimal conditions of COD removal, (conditions in table
4.4), to evaluate the kinetics behavior and the reaction rate constants of either
process separately. The same anodic area in each process was maintained using
different electrode arrangement as shown in figure(3.3).
The decreasing of COD with time for the EO, EC and EC-EO in situ
process is shown in figure (4.4)

800

700

600

500
COD (ppm)

400 EO
EC
300
EC-EO
200

100

0
0 20 40 60 80 100 120 140
Time (min.)

Figure (4.4) The degradation of COD with time for the EO, EC and EC-EO
processes.
 It can be noticed from the figure(4.4) that at any time of reaction, the
COD concentrations of EO process were the highest values compared with the
other two processes. After 120 minutes of the EO process the COD
concentration just decreased to 58% of its initial value and it was larger about
six times than the COD value in the EC-EO process. This indicates that the EO
process is a slow treatment so it is insufficient to be adopted alone in this
particular case.
Figure (4.4) also shows that the EO process has slow reaction rate with
time comparable with EC or EC-EO processes. The COD concentrations in both
EC and EC-EO processes decreased sharply and the COD removals reached
about (75-80%) within the initial 20 minutes.
The EC and EC-EO curves take similar analogues with time, this may
confirm the foremost contribution role of EC process in the FWW treatment,
however with further reaction time small divergence between the two curves
was observed in the last part of the process and the EC-EO curve continued to
decrease slightly.
In EC process, the amount of aluminum produced is influenced by the
process time and consequently leads to increase Al+3 ions released into the
reaction volume. With exceeding the adequate ions quantity, the removal
efficiency remained constant due to saturation of ions. The slow-moving
behavior of EC curve is in agreement with (Benaissa et al. 2014) and
(Muthukumar et al. 2011). Since the EC process depends on adsorption
mechanism, it should be mentioned that the EC process cannot remove all kinds
of organic contaminants and some soluble organic matter such as phenols still
cannot be treated. (Martinez-Delgadillo et al. 2010)
In EC-EO treatment reactor, both EO and EC process were synergistically
contribution to eliminate pollutants. Even though the EC process played the
major function in treatment, the EO process was still required to achieve 90% of
the COD removal so as to be within the allowable local environmental limits.
 The kinetics were evaluated for the experimental data by plotting the
abatement of COD concentration with time to fit the pseudo-first- and pseudo-
second order reaction according to equations (4.5) and (4.6) respectively:

ln 𝐶𝑂𝐷t = ln 𝐶𝑂𝐷i − 𝑘1 𝑡 (4.5)

1 1
= 𝑘2 𝑡 + (4.6)
𝐶𝑂𝐷t 𝐶𝑂𝐷i

Where CODi and CODt represent the concentrations at the beginning and after
time t of the reaction, respectively. k1 and k2 represent the pseudo first and
second order reaction constant respectively.

Values of k1 were determined from the slop of the plots ln CODt verses (t)

while k2 were calculated from the slop of the 1/CODt against time. The related
plots of EO, EC and EC-EO processes are shown in figures (4.5),(4.6) and (4.7)
respectively. The rate constants and the squared regression R2were tabulated in
table (4.8).
 Pseudo 1st order-oxd.
Time (min.)

0 20 40 60 80 100 120 140

0
-0.1
-0.2
y = -0.0068x - 0.0314
ln(COD/CODi) -0.3
R² = 0.9925
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1

(a)

Pseudo 2nd order-oxd.

2

1.5
(1/COD)-(1/CODi) (L/gm)

1
y = 0.0139x - 0.0216
R² = 0.9786
0.5

0
0 20 40 60 80 100 120 140

-0.5
Time (min.)

(b)
Figure (4.5) The plots of pseudo first order(a) pseudo second order (b) For EO
process.
 Pseudo 1st order-cog.
Time (min.)

0 20 40 60 80 100 120 140

0

-0.5
y = -0.0131x - 0.7796
ln(COD/CODi)

-1 R² = 0.7192

-1.5

-2

-2.5

(a)

Pseudo 2nd order-cog.

12

10
(1/COD)-(1/CODi) (L/gm)

4 y = 0.0698x + 1.7053
R² = 0.9082
2

0
0 20 40 60 80 100 120 140
Time (min.)

(b)
Figure (4.6) The plots of pseudo first order (a) pseudo second order (b) For EC
process.
 Pseudo 1st order -in situ
Time (min.)

0 20 40 60 80 100 120 140

0

-0.5

-1 y = -0.0179x - 0.8412
R² = 0.784
ln(COD/CODi)

-1.5

-2

-2.5

-3

-3.5

(a)

Pseudo 2nd order-in situ

20
18
16
(1/COD)-(1/CODi) (L/gm)

14 y = 0.1374x + 1.6084
12 R² = 0.9704
10
8
6
4
2
0
0 20 40 60 80 100 120 140
Time (min.)

(b)
Figure (4.7) the plots of pseudo first order (a) pseudo second order
(b) For EC-EO process.

Table (4.8) Rate constants and the squared regression R2 of pseudo first order
and pseudo second order for all processes.
 pseudo first order pseudo second order
process
k1 (1/min.) R2 k2 (L/gm . min.) R2
EO 0.006 0.992 0.013 0.978
EC 0.013 0.719 0.069 0.908
EC-EO 0.017 0.784 0.137 0.970

From Table (4.8) it was clearly noticed that the EO process fits the pseudo
first order reaction with higher value of regression coefficient (0.992) and the
rate constant was (0.006 min.-1).
For EO treatment processes, it was also reported in literature that COD
removal generally obeys the first order reaction kinetics. Souza and Ruotolo
(2013) studied the electrochemical treatment of oil refinery effluent using
boron-doped diamond anodes. They found that the kinetics of COD removal
followed the pseudo first order model.
Electrochemical oil/water demulsification and purification of bilge water
using Pt/Ir electrodes were investigated by Körbahti and Artut (2010). Kinetic
studies resulted in first order overall electrochemical conversion rate of
pollutants based on COD concentration.
For the EC and the EC-EO processes table (4.8) shows that the kinetics
fits the pseudo second order reaction with rate constants (0.069 L/gm min.) and
(0.137 L/gm min.) respectively.
The EC results are in agreement with many EC kinetics studies,
(Moussavi et al. 2011); (Saeedi and Fahlyani 2011) and (Sakthipriya et al.
2011). However no kinetics studies have been reported for EC-EO process. The
reaction rate constant for EC-EO was higher than EC alone which confirms the
mutual cooperative contribution of two different electrochemical treatment
methods in a single stage.

4.2.2 Dynamic pH Response

 It is well known that the pH of solution changes with electrochemical
treatment time. The dynamic response of the pH means the variation of pH
parameter with time during the operation. To compare the dynamic responses of
pH of the EC, EO and EC-EO, the pH value of the three different processes
were measured with time for 80 minutes at 5 minutes intervals. The experiments
were carried out under current density of 14.55 (mA/cm2), temperature of 40 °C
and initial pH of 6. The measured pH value against process time were plotted in
figure (4.8)

EC pH EC-EO pH EO pH

6
PH

2
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Time (min.)

Figure (4.8) Dynamic pH response obtained in EC, EO and EC-EO.

It was shown from figure (4.8) that the variation of pH with time is different in
the three processes. In EC process the pH began to increase with time beyond
50 minutes of starting the reaction. This increasing may be resulted from
increasing the OH- concentration due to cathodic water reduction. The pH
increasing with time was also reported for EC process by Canizares et al.
(2008) and Gokkus and Yıldız (2015). Demirci et al. (2015) mentioned that the
dynamic increasing behavior of pH showed the necessity for a pH control
process and they suggested a computerized system using H2SO4 solution as
another variable in order to keep the pH constant.

For EO in figure (4.8) , the pH decreased with increasing the time. This is
a common trend as a result of the hypochlorous acid and hypochlorite formation
which leads to increase in proton ion concentration in the bulk solution with
time of the process reaction.

It can be clearly seen from Figure (4.8) that the EC-EO process has a
stable pH tendency with time and this behavior could be caused by combination
of cathodic reduction of water and generation of hypochlorous ion in the
solution. This unique phenomenon could be considered as remarkable advantage
of combined EC and EO together in situ. Since the EC-EO includes
sophisticated reactions, the dynamic pH performance is sensitive and the upset
balance of related reactions may be effected by many different parameters.

4.2.3 Conductivity and Voltage Response

Figure (4.9) shows the variation of conductivity of cell with time for the
three different processes. It can be seen that conductivity decreased with time
for EC and EC-OE while it slightly decreased then increased beyond 50min for
EO only. This may be interpreted as the total dissolved salt decreased in the
system due to their interaction with flocs in electrocoagulation. Demirci y.
(2015) reported that without control in EC, conductivity of wastewater decreases
and this causes increase in the power consumption. However in electrooxidation,
the generation of hypochlorous ions and its complexion with other positive ions
present in the solution led to increase the conductivity.
These behaviors where confirmed by the changing in the ratio of voltage
drop with time shown in figure (4.10).
 EC-EO conductivity EC conductivity. EO conductivity.
2700

2500
conductivity (µS/cm)
2300

2100

1900

1700

1500
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Time (min.)

Figure (4.9) The conductivity of cell solution with time for the three different
process.

EC-EO EC EO

1.5
1.4
1.3
1.2
1.1
U/U°

1
0.9
0.8
0.7
0.6
0.5
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Time (min.)

Figure (4.10) Ratio of voltage drop with time for the three different process.

4.2.4 Modeling EC through Adsorption Isotherm

Since the pollutants are negatively charged, it can act as electron donors
attracted to the metal ions in situ and formed gelatinous precipitate. Adsorption
isotherm models for pollutant removal like Langmuir, Freundlich and Timkin
can be used to describe the EC process. (Carmona et al. 2006) and (Adeogun
and Balakrishnan 2016)
To extend the adsorption isotherm models for EC process the amount of
aluminum electrochemically released based on Faraday's law and the reduced
COD concentration with time were calculated. The applied current density was
14.55 (mA/cm2) for the time of reaction (120 min.) and initial pH was 6.
All isotherms in this work are in their linearized form, to find out the best
fit isotherm model with the experimental equilibrium data. According to the
adsorption isotherm equations (2.13,15 &16) mentioned in chapter two, the
isotherm relations were plotted in figure (4.11) and the values of all parameters
of the adsorption isotherm models along with the linear regression coefficient R2
for the present experimental conditions were obtained and listed in table (4.9)

Table (4.9) Characteristic constant for adsorption isotherm model

Langmuir Isotherm Freundlich Isotherm Temkin Isotherm
KL= -0.00344 (L/mg) KF= 0.031 (mg/g)(L/mg)1/n KT= 0.0108 (L/mg)
qmax= -2632 (mg/g) n= 0.433 b= 9402 (mg/g)
R2= 0.868 R2= 0.983 R2= 0.898

0.0900
0.0800
0.0700
y = -0.0004x + 0.1065
0.0600
Ce/qe (g/L)

R² = 0.8634
0.0500
0.0400
0.0300
0.0200
0.0100
0.0000
0 50 100 150 200 250 300
Ce (mg/L)

(a)
 10.000

8.000

ln qe (mg/g)
6.000

4.000
y = 2.3127x - 3.4767
2.000 R² = 0.9833

0.000
4.400 4.600 4.800 5.000 5.200 5.400 5.600
ln Ce (mg/L)

(b)
12000.00
10000.00
8000.00
qe (mg/g)

6000.00
4000.00
y = 9402.1x - 42578
2000.00 R² = 0.8986
0.00
4.4000 4.6000 4.8000 5.0000 5.2000 5.4000 5.6000
ln Ce (mg/L)

(c)
Figure (4.11) Adsorption isotherm of COD for (a) Langmuir(b) Freundlich
(c) Temkin
Figure (4.11) shows that the Freundlich model plots fit satisfactorily with
the experimental data obtained. In addition, from table (4.9) It can be noticed
that the Freundlich model have a greater regression coefficient (0.983). The
negative value of qmax in Langmuir model reflects the inaptitude of this model
for interpreting adsorption isotherm in this experiment. (Alshabanat et al. 2013)
and (Alsenani G. 2013)
The applicability of Freundlich model has been confirmed in several
researches on the EC process, (Chithra and Balasubramanian 2010);
(Kermet-Said and Moulai-Mostefa 2015) and (Chou et al. 2010)
4.3 Electrodialysis
The treated FWW by EC-EO at the best investigated conditions was
further reclaimed by electrodialysis (ED) process in order to recycle and reuse
water in the washing fuel system again. About 20 liters of pretreated FWW were
produced and collected to be post treated by desalination in ED experiments.
The main characteristics of pretreated FWW are shown in Table (4.10).

Table (4.10) Characteristics of pretreated FWW

Parameter Value
pH 6.15
Turbidity (NTU) 24.3
TSS (mg/L) 34
Oil content (mg/L) 1.1
E conductivity( µS/cm) 1722~1751
COD (mg/L) 72~79
TDS (mg/L) 907~923

4.3.1 Effect of Applied Voltage

The separation performance of dissolved salts from the treated FWW was
investigated at constant voltage electrodialysis experimental studies through an
unsteady state batch recycled run of the ED system. At time intervals of 10 min,
the TDS concentrations and electrical conductivity of both concentrate stream
(C) and dilute stream (D) were measured. The operating time for each run was
fixed at a time of 60 minutes. The flow rate was set at (0.5 L/min) which is
approximately correspond (2.8 cm/s) liner flow velocity across the membrane
surface. Different voltages values (6, 9, 12, 15 and 18 V) were tested. The
conductivity of concentrate and dilute streams versus time at different voltages
was plotted in figure (4.12).
 3100
2900
2700
C 18
2500
2300 C 15
conductivity µs/cm
2100 C 12
1900 C9
1700
C6
1500
1300 D6
1100 D9
900 D 12
700
D 15
500
300 D 18
0 10 20 30 40 50 60
Time (min)

Figure (4.12) Curves of conductivity of dilute (D) and concentrate (C) vs. time
at different voltages and constant flow rate (0.5 L/min.).
It can be noticed from figure (4.12) that the conductivity of both dilute
and concentrate streams were varied with different voltages. The conductivity of
dilute stream decreased faster with increasing applied voltages. This means
higher transfer rate and lower duration time was needed to achieve a particular
target at greater potential driving force. On the other hand, the slop of
conductivity curves for concentrate stream was increased with increasing the
applied voltage as consequence of mass balance of the transferred salts. Same
conductivity behavior were illustrated by (Valero et al. 2015) who studied the
application of electrodialysis for the treatment of almond industry wastewater.
The TDS removal efficiency percentage of the dilute stream is calculated based
on Eq.(3.1) at different voltages and plotted against time in figure (4.13)
 80.0

70.0

60.0

50.0
18 V
Removal %

40.0 15 V
12 V
30.0
9V
20.0 6V

10.0

0.0
0 20 40 60 80
Time (min)

Figure (4.13) TDS removal efficiency of dilute stream against time at flow rate
0.5 L/min. and different voltages range.
It can be shown from figure (4.13) that the TDS removal efficiency was
increased with increase of electrical potential. After 60 minutes of the process,
the removal was 45.8% at 6 volte while it achieved 74.93 % and 75.2 at 15 and
18 voltages respectively. The convergence between two last curves may be
attributed to close approaching of the limiting current density of the ED process.
With rapidly depletion rate of ions the electrical resistance of the stack increased
and the system leaved the ohm's law region, therefore more curvature of plotted
lines were revealed (Farrell et al. 2003). The convergence of TDS removal
curves from each other at increasing voltages was also noticed by Jing et al.
(2009).

4.3.2 Effect of Flow Rate

From economical point view, applied voltage (15 V) was selected to
examine the effect of flow rate on the separation performance. At constant
voltage, various flow rates (0.5, 0.8, 1.1, 1.4 and 1.7 L/min.) were tested. The
conductivity of concentrate and dilute streams versus time at different flow rates
was plotted in figure (4.14)
 3600
3400
3200
3000 C 1.7
2800
2600 C 1.4
conductivity µs/cm

2400 C 1.1
2200
2000 C 0.8
1800
1600 C 0.5
1400 D 0.5
1200
1000 D 0.8
800
600 D 1.1
400
D 1.4
200
0 D 1.7
0 10 20 30 40 50 60
Time (min)

Figure (4.14) Curves of conductivity of dilute (D) and concentrate (C) vs. time
at different flow rates and constant voltage (15 V).
Figure (4.14) shows that the conductivity of dilute decreased while the
conductivity of concentrate increased with the increasing flow rate. The TDS
removal efficiency of the dilute stream against time at different flow rates were
plotted in figure (4.15)
100

90

80

70

60 1.7
Removal %

50 1.4
1.1
40
0.8
30
0.5
20

10

0
0 20 40 60 80
Time (min)
 Figure (4.15) The TDS removal efficiency of dilute stream against time at
applied voltage (15 V) and different flow rates range.

It can be shown from figure (4.15) that the TDS removal efficiency was
increased with increase inflow rate. After 60 minutes of the process, the removal
was 74.9% at flow rate of 0.5 L/min., while it achieved approximately 93 % at
both 1.4 and 1.7 L/min. Increasing the flow rate leads to increase in the linear
velocity of solution across the membrane surface, which results in decreasing
the boundary layer thickness and improve the mass transfer coefficient. Unless,
in high flow rate the decrease of residence time in cells offsets the positive effect
of layer thickness decrease. This behavior was reported as well by Lee G.
(2011)

4.3.3 Specific Power Consumption

For each set of potential and flow rate experiments in previous sections
(4.3.1 & 4.3.2), the electrical current variation was measured and it plots in
Figure (4.16)
160.0

140.0

120.0

100.0
15 V
current mA

80.0 18 V
12 V
60.0
9V
40.0 6V

20.0

0.0
0 20 40 60
Time (min)

(a)
 200

180

160

140

current mA 120 0.5

100 0.8

80 1.1
1.4
60
1.7
40

20

0
0 10 20 30 40 50 60
Time (min)

(b)
Figure (4.16) Electrical current variation (a) different voltages (flow rate,
0.5 L/min).(b) different flow rates (applied voltage, 15 V)
it can be noted from Figure (4.16.a) that increasing applied potential
increases current and therefore leads faster ion transport. Along with process
time, depletion of ions increased the electrical resistance of the stack
consequently, the current value was continually decreased as the voltage was
remained constant and the same explanation can apply on the Figure (4.16.b)
The specific power consumption (kWh/m3) were estimated according to
Eq.(3.2). The calculated SPC were plotted in figure (4.17) for both potential and
flow rate experiments.
 voltage flow rate

20 1.8
18 1.6
16 1.4

flow rate L/min.

14 1.2
voltage V
12
1
10
0.8
8
6 0.6
4 0.4
2 0.2
0 0
0 0.5 1 1.5 2 2.5
SPC Kw h/m3

Figure (4.17) The SPC for different potential (flow rate, 0.5L/min.) and different
flow rate (potential, 15 volte)

It can be seen form figure (4.17) that the SPC was drastically affected by
the change in the applied potential force and the voltage line was extended for a
wide range of SPC (0.287-1.94 KWh/m3).
In contrast, the SPC has negligible changes with flow rate chosen and the
flow rate line has small range (1.39-1.69KWh/m3) in SPC scale. Therefore it can
be concluded that voltage has the higher effect on the SPC rather than the flow
rate. This behavior was also observed by Demircioglu et al. (2001) and Kabay
et al. (2002).
Based on figure (4.17) it can be seen that the best conditions of ED
process which gave convergent SPC with relatively high TDS removal were 15
V and 1.4 L/min.
To investigate the possibility of achieving higher removal with increasing
time an experiment was conducted at the optimum conditions for different
electrolysis time as shown in figure (4.18)
 100
90
80
70
Removal %
60
50
40
30
20
10
0
0 20 40 60 80 100 120 140 160
Time (min.)

Figure (4.18) TDS removal at voltage (15V) , flow rate (1.4) against time.

The ED stack operated under potential of (15 V) and the flow rate of (1.4
L/min) was able to remove about 95% of TDS and reduces the dilute solution
conductivity value from (1538 µS/cm) to (67 µS/cm) during 80 min of operation
time.
It is clear that increasing time higher than (80 min) had no effect on the
removal efficiency and led to dissipate the energy used for the system to get the
required efficiency.
Conclusions
This work studied batch treatment of FWW using graphite electrodes as
monopolar electrodes whereas aluminum were used as sacrificial bipolar
electrodes. Taguchi experimental design methodology has been applied to
determine the optimal experimental conditions. Several operation parameters
have been evaluated. Subsequently, a laboratory study was conducted to
investigate the feasibility of electrodialysis process for treating the
electrochemically pretreated FWW containing TDS. The performance was
evaluated by measuring of the effects of the operating parameters such as
applied potential and flow rate on the TDS removal efficiency using five cell
locally developed ED stack. The following conclusions were reached as a result
of this research project:
1. Increasing current density and treatment time were found to be positively
effect on the COD removal while increasing temperature was inversely
performed.
2. The S/N ratio was employed to define the optimal operating conditions
for COD removal. It was found that the best conditions for treatment of
FWW are: current density (14.55 mA/cm2), pH (6), reaction time (80 min)
and temperature (40 °C). At these conditions approximately 90% of COD
removal was achieved.
3. The ANOVA verified that the current density is the most influent
parameters on the electrochemical removal of COD. The effect of current
density factors is around 61% on the investigated COD removal efficiency
as a response, followed by pH 14% whereas less influence factors on the
system were temperature (11.76%) and time (9.56%).
4. The EC-EO process presented high performance to eliminate the oil,
turbidity and TSS but it was not efficient in TDS removal. The multiple
regression analysis shown that pH and Temperature have not impact on
the removal of oil and TDS respectively.
5. The best operation condition in terms of cost/effectiveness (minimized
specific power consumption and maximize COD removal) were
recommended as current density (10.91 mA/cm2), pH (6), reaction time
(80 min) and temperature (50 °C). At these conditions 90% of COD
removal was experimentally recorded.
6. It was noticed that the decreasing of COD concentration in EO process
followed the pseudo first order reaction with the rate constant (0.006 min. -
1
). Whereas for the EC and the EC-EO processes the kinetics fits the
pseudo second order reaction with rate constants (0.069 L/gm min.) and
(0.137 L/gm min.) respectively. The higher reaction rate constant in EC-
EO confirmed the synergistically contribution of two different
electrochemical treatment methods in a single stage.
7. The EC-EO process has a stable pH tendency with time due to combine
effect of cathodic water reduction and hypochlorous ion generation in the
solution. This unique phenomenon could be considered as remarkable
advantage of combined EC and EO together to keep pH solution
controlled during treatment.
8. The EC process was modeled using adsorption isotherm kinetics and from
the present research it has been observed that Freundlich isotherm model
fit satisfactorily with the experimental data.
9. The hybrid EC-EO in situ process could be effectively treat the FWW in
particular for removing of organic compounds and suspension solids.
10. Removal efficiency was increased with the applied potential in the range
(6~18 V) due to strength of electrical current as driving force for mass
transfer. However, the increment of removal efficiency was diminished as
the applied potential increases.
11. Removal efficiency in dilute was enhanced with flow rate in the range of
(0.5~1.7 L/min) due to the positive effect on removal rate of salts ion as a
result of reducing the boundary layer thickness and improving the mass
transfer coefficient. The inconsequential increment of removal rate higher
 than (1.4 L/min) was come about because of the decline of residence time
in cells.
12. Based on the operation of the electrodialysis stack used in this work, the
applied voltage (15 V) and the flow rate of (1.4 L/min) are recommended
as suitable operating conditions for wastewater solutions which
corresponds to about 95% of TDS removal and reduces the dilute solution
conductivity around 23 times in 80 min of operation time.
13. It was obtained that the specific power consumption (SPC) was
influenced by the potential applied. While it was not intensely responsive
to the change in flow rate.

Recommendations

1. The treatment of the fuel washing wastewater FWW effluent using

advanced oxidation process like Electrofenton process. Develop system
consisted of Iron sacrificial anodes and graphite as cathodic electrodes is
expecting to generate highly oxidising species, and this can be compared
with the electrooxidation and electrocoagulation processes.
2. Develop a pilot plate scale of continuous process for treatment the FWW
and study the efficiency of pollutants removal with minimum economical
cost.
1. Abdel-Gawad S. A., Baraka M. A., Omran K. A. and Mokhtar M. M.,
(2012)," Removal of Some Pesticides from the Simulated Waste Water by
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