A

PROJECT REPORT

ON

WASTE WATER TREATMENT USING

ADVANCED OXIDATION PROCESSES

Submitted by: Guided by:

Mayank Desai (17BCH011) Dr. Jayesh Ruparelia
Dhananjay Boda (17BCH012) Professor, ITNU

CHEMICAL ENGINEERING DEPARTMENT

INSTITUTE OF TECHNOLOGY
NIRMA UNIVERSITY

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 CERTIFICATE

This is to certify that Mr. Mayank Desai(17bch011) and Mr. Dhananjay

Boda(17bch012), students of Chemical Engineering, 6th semester, of Institute of
Technology, Nirma University, have satisfactorily completed the mini project on
Waste Water Treatment Using Advanced Oxidation Processes as a partial
fulfilment towards the degree of B. Tech in Chemical Engineering.

Date:

Place: ITNU, Ahmedabad

Dr. Jayesh Ruparelia

Professor, ITNU

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 CONTENT

Page No.
Acknowledgement I
Abstract II
List of Tables III
List of Figures IV

Acknowledgement

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Our sincere thanks to all those who provided us the opportunity to work upon this project report.
We would like to express our deepest gratitude to our Director of the Institute, Dr. Rajesh Patel
and Head of the Chemical Department, Dr. Sanjay Patel for introducing this project work in our
curriculum for this semester.

We would like to express our deepest appreciation to our guide, Dr. Jayesh Ruparelia, Professor,
Chemical Department, ITNU, whose contribution in stimulating suggestions and encouragement
helped us in coordinating our project especially while preparing this report. We would like to
appreciate the guidance as given by other faculties and all the members who have helped directly
or indirectly for this project work. Lastly, thanking our dear friends who helped us in giving
valuable suggestions without which this work would not have been completed successfully.

Thanking God, we would like to express our gratitude to all those who have helped in successful
completion of this project work.

Abstract

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In these years, due to the increasing presence of molecules in industrial waste water from
factories and refineries, the conventional biological methods cannot be used for complete
treatment of the effluent. Advanced oxidation processes (AOPs) constitute a promising
technology for the treatment of wastewaters. s advanced oxidation processes (AOPs) in
wastewater treatment established. AOP's are one of the promising advanced technologies used to
destroy the total organic content, toxic pollutants etc. Number of attempts has been made from
the past two decades on the waste water treatment using various advanced oxidation treatment
techniques. We focus electro fenton process in our paper. It is one type of advance oxidation
process. It is the best and easy process for waste water treatment. The applicability of electro-
Fenton technology to remediation of wastewater contaminated by several organic pollutants such
as dyes and polycyclic aromatic hydrocarbons has been evaluated using iron-enriched zeolite as
heterogeneous catalyst. The electro-Fenton technology is an advanced oxidation process that is
efficient for the degradation of organic pollutants.

Chapter Title Page

No. No.

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1. Introduction 9-11
2. Classification of AOPs 11-16
2.1 Ozonation
2.2 AOP using hydrogen peroxide
2.3 AOP using Fenton’s Reagent, Fenton-Like and Photo Fenton
Processes
2.4 AOP using titanium dioxide (TiO2)
3. Fenton Process 16-18
4. Parameters that affects the Fenton process 18-20
5. Electro Fenton Process 20-23
6. Experimental Work 23-24
6.1 Experiment 1
6.2 Experiment 2

List of Tables
Table Title Page
No. No.
2.1 Relative oxidation power 11

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5.1 Advantages and limitations of electro-fenton process 23

List of Figures
Figure Title Page
No. No.

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 2.1 Classification of AOPs 12
3.1 Schematic Diagram of Fenton Process 17
4.1 The effect of pH on reaction efficiency 19
14.2 pH shifts as the reaction progresses 19
5.1 Types of electro Fenton 22

1. Introduction
With the growing industrialization and materialistic world, there is an increment in the
demanding water quality regulations due to environmental pollution. Immense research has
focused on upgrading present water treatment methods and technologies and developing the

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processes that can be economically viable, dealing with the highly toxic and refractory
contaminants especially organic impurities in various wastewaters. [ CITATION Paw15 \l 1033 ].
Many institutions and organizations have supported researches keeping the prime objective to
establish wastewater treatment technologies for the economical and practical disposal of waste
chemicals. This is done in context to avoid and mitigate the unfavorable health, safety and
environmental issues faced by the living beings on this planet [ CITATION Clá \l 1033 ] . One of the
severe environmental issues today refers to the impacts with the disposal of industrial wastewater
and other liquids into superficial and ground/underground water bodies[ CITATION Paw15 \l 1033 ].

Water is critical to many industrial processes for several purposes which includes heating and
cooling, generation of steam, and washing and cleaning, and as a constituent part of some
products. Poor quality water may compel the industries to relocate, find a new source of water,
or halt the production or the decrement in the quality of desired products. Large amounts of
industrial wastewater are discarded into open sources without being treated, reducing the quality
of large volumes of water. World widely, it is the estimation that industrialization is responsible
for dumping around 300-400 million tons of heavy metals, solvents, toxic sludge, and other
wastes into the waters each year (UNEP, 2010). Although there are significant measures been
made in many developed countries to reduce the direct discharge of pollutants into water bodies,
more than 70% pf industrial wastes are dumped untreated into waters [ CITATION DrK03 \l 1033 ].
According to India's Central Pollution Control Board, the country has an installed capacity to
treat only about 30% of the household waste it generates – the rest is released into open drains or
straight into the ground. And just two cities, Delhi and Mumbai, which generate around 17% of
the country's sewage, have nearly 40% of its installed capacity. According to Asit K Biswas and
Peter Brabeck-Letmathe, while 90% of households in Delhi are considered to have adequate
sanitation because they have indoor toilets, almost all of Delhi's untreated wastewater flows into
the Yamuna River, a source of drinking water for cities downstream [ CITATION Sup14 \l 1033 ].
Solutions to this issue require combined approaches, concerning generation, treatment, and
disposal into the environment not only of effluents but passive residues produced by specific
treatments: physical (resulting primarily from the formation of low-solubility solids and auxiliary
reagent for flocculation and precipitation); chemical (promising, but still undergoing up-scaling
as emergent processes); microbiological (the most commonly used on industrial scale in terms of

9
versatility and cost); or combined hybrid process. Several techniques are available for
wastewater treatment (as mentioned before, chemical, physical and biological processes) as well
as the use of combinations of these techniques to an optimal result. When organic compounds in
wastewaters present recalcitrant characteristics precluding treatments by conventional biological
methods, chemical oxidation can be used as pre- or post-treatment, decreasing toxicity before
applying a conventional biological process or conditioning the effluent to required maximum
concentrations (i.e., oxidize non- biodegradable residues).

Nowadays treatment of highly toxic organics in wastewaters attracts more attention due to their
harmful effects to the environment. During the last decades, Fenton’s process has been studied in
order to optimize its efficiency in the depuration of liquid effluents. These Advanced Oxidation
Process (AOP) are able to react and remove the organic matter by generating the strong oxidant
hydroxyl 1 from the decomposition of hydrogen peroxide in the presence of iron ions at acidic
conditions. Additionally, the catalytic decomposition of hydrogen peroxide follows a radical
mechanism involving hydroperoxyl radicals. Radical chain oxidations will be then initiated by
the hydroxyl radicals that will react non-selectively with the organic matter present in the
wastewater. The main advantage of this method is related with the fact that the reaction took
place at room conditions of pressure and temperature which makes the treatment less expensive.
Moreover, short reaction times are necessary thus it required easy-to-use reagents. The Fenton’s
process has an important role, either to promote the wastewater treatment in order to accomplish
the parameters standard to a safe discharge into the natural water courses, or to minimize the
effluent toxicity and enhance its biodegradability to allow an efficient post-biological depuration
in municipal wastewater treatment plants. The wastewater toxicity and biodegradability were
also measured in order to predict the possibility of using this chemical oxidation as a pre-
treatment to obtain an effluent suitable to be further biologically depurated.

AOPs typically operate with less energy requirement than direct oxidation. AOPs are near
ambient temperature water treatment processes which involve the generation of hydroxyl
radicals in sufficient quantity to affect water purification. The hydroxyl radicals are
extraordinarily reactive species, which attack the most part of organic molecules[ CITATION
Nor03 \l 1033 ]. A goal of the wastewater purification by means of AOP methods is the
reduction of the chemical contaminants [ CITATION Bha16 \l 1033 ].

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2. Classification of AOPs
There are several methods that are classified under the broad definition of advanced oxidation
processes. Most of these methods combine a strong oxidizing agent such as H 2O2 or O3 with a
catalyst such as transition metal ions and irradiation such UV. Evidence from literature shows
titanium dioxide/UV light process, Fenton’s reactions and hydrogen peroxide/UV light as the
most popular AOP producing hydroxyl radicals.

They can be classified under two categories: Homogenous processes and Heterogeneous
processes respectively. The homogenous processes include processes involving ultraviolet
radiation, ultrasound energy and electrical energy while the heterogeneous processes involve
photo catalysis, catalytic ozonation, and processes using heterogeneous catalysts.

Figure 2.1 Classification of AOPs[ CITATION Ahm18 \l 1033 ]

AOPs such as ozonation (O3), ozone combined with hydrogen peroxide (O3/H2O2) and UV
irradiation (O3/UV) or both (O3/H2O2/UV), ozone combined with catalysts (O3/catalysts),

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UV/H2O2, Fenton and Photo-Fenton processes (Fe 2+/H2O2 and Fe2+/H2O2/UV), and the ultrasonic
process and photo catalysis have been successfully used for wastewater treatment.
The advantages of the AOPs are due to the fast reaction rates and non-selective oxidation,
allowing
the simultaneous treatment of multiple contaminants. Table 1 shows the relative oxidation power
of the different oxidizing species, and it can be established that the oxidation power of HO• is
relatively higher. Generally, the rate constant for the reaction of the contaminant with HO•
determines the rate of destruction of a contaminant.
Table 2.1 Relative oxidation power

OXIDISING GROUPS RELATIVE OXIDATION POWER

Chlorine 1.00
Hypochlorous Acid 1.10
Permanganate 1.24
Hydrogen peroxide 1.31
Ozone 1.52
Atomic Oxygen 1.78
Hydroxyl Radical 2.05
Titanium dioxide 2.35

The brief description of different types of AOPs are given below:

2.1. Ozonation
The formation of radicals such as the hydroxyl radical (HO•) and superoxide radical (O 2-•)
occurs when ozone is added to water, through a complex series of reactions. The disintegration
rate of ozone in water is better at higher pH levels. A combination of reactions with molecular
ozone and reactions with HO• causes the oxidation of organic species.
3O3 + OH- + H+ → 2HO• + 4O2 (2)
The decomposition cycle of ozone can be enhanced by the addition of hydrogen peroxide to
result in the formation of HO•. Hydrogen peroxide partially dissociates in water to produce the
HO2-. This hydroperoxide ion reacts with the ozone rapidly producing the HO•. In summary, the
combination of reactions leads to the following:
2O3 + H2O2 → 2HO• + 3O2 (3)
Contact time, alkalinity of water, and the dose of ozone determine the performance of the
process. By introducing the dose of hydrogen peroxide once the oxidation of highly reactive
substances with ozone takes place, it enhances the degradation achieved. The process of

12
ozonation by H2O2/O3 systems seem to be the most established AOP in remediation for water as
compared to other AOPs.
Thus, there is a field-proven history of operation in the implementation of H2O2/O3 systems.
The second way to speed up ozonation is by the use of homogenous or heterogeneous catalysts.
Studies have been carried out with various metal oxides and metal ions, and have shown
significant changes in decomposition, however only in some cases. The concentration of ozone
in the inlet gas and the ozonation time has been considered as predominant factors to the
enhancement of the degradation rate. Oxidation studies have been carried out on various organic
contaminants using Fe2O3, MnO2, TiO2–Me, Fe2+, Fe3+, and Mn2+. The ozone/catalyst system
appears to be more effective for the reduction of chemical oxygen demand (COD) and total
organic carbon (TOC), than oxidation with ozone alone at higher pH values. In experiments
carried out by Horáková et al. it was observed that decomposition of the chemicals is effectively
improved by the synergistic effect of photo catalytic reactions occurring on TiO2-photocatalyst.
2.2. AOP using hydrogen peroxide
Hydroxyl radicals are formed by the photolytic dissociation of hydrogen peroxide in water by
UV
irradiation at a wavelength of 254nm. This formation is indicated in Equation 6 [13]. Medium
Pressure UV lamps produce a higher radical generation.
H2O2 + hυ → 2 HO• (hυ : λ <300 nm)
As with the UV/Ozone system, interfering compounds and turbidity can absorb the UV light,
thus reducing the efficiency of the system. Hydrogen peroxide can be introduced into the system
as a single dose or at many points in the system. Each water source requires optimization based
on lab scale testing, in order to ascertain the ideal dose of hydrogen peroxide. UV/H 2O2 system is
seen as a beneficial method for AOP, as it has high reaction rates, and is flexible in the design of
reactors, which leads to a lesser footprint in the treatment plant. The use of ultraviolet lamps also
provides disinfection of the water.
Phenolic complexes that are usually found in olive mill wastewater have been treated using
UV/H2O2 method. UV/H2O2 has also been successfully used for removal of dyes from textile
industry effluents. Various studies on textile effluent treatment show that increase in UV dosage
and H2O2 concentration increases the rate of decolorization. Furthermore, there are a number of

13
H2O2/UV industrial applications for remediation of drinking water. For example, Calgon Carbon
runs two industrial AOP applications for drinking water treatment. This method is the only AOP
that is used in drinking water remediation.
2.3. AOP using Fenton’s Reagent, Fenton-Like and Photo Fenton Processes
Radicals are produced when iron (II) reacts with hydrogen peroxide, where Fe 2+ ion acts as a
catalyst for this reaction. Fenton’s Process is a simple method to produce HO• without the need
for neither special apparatus nor chemicals, and takes place at ambient temperature and pressure.
This method is an attractive way for oxidation, as hydrogen peroxide and iron salts are easily
available, easy to handle and environmentally safe. The destruction of organic compounds takes
places by reacting with the HO•. Equation 7 shows how the HO• are formed:

Fe2+ + H2O2 → Fe3+ + OH- + HO• (7)

The rate of degradation of organic pollutants with Fenton–Fenton like reagents is strongly
accelerated by irradiation with UV-VIS light at wavelengths greater than 300nm. The photolysis
of Fe3+ complexes allow Fe2+ to be regenerated. The occurrence of Fenton reactions in the
presence of hydrogen peroxide is shown in equation 8.
Fe(OH) 2+ hν → Fe2+ + HO• + OH⁻ (8)
This process, like the other AOPs, is initiated by the hydroxyl radical for the degradation of
organic compounds, mainly by oxidation reactions. However, the Fenton process is strict and
requires pH control [2, 14], so as to prevent precipitation of the iron. For this method, the reactor
must be constructed so as to allow proper mixing of the Fe(II) and H2O2. This allows for
optimum hydroxyl radical formation, and degradation of the contaminants. The extraction of iron
from the effluent water could possibly raise the costs of using this system.
For Fenton-like processes, elements with several redox states such as chromium, copper, and can
be used to decompose H2O2 into HO• through conventional ways. However, the Fenton-like
system, each non-ferrous catalyst could counterbalance the practical gains of better catalyst
stability and working at neutral pH. Therefore, the activation process for H 2O2 is specific to the
nature of the catalyst and is influenced by its composition.

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2.4. AOP using titanium dioxide (TiO2)
Heterogeneous photocatalysis using titanium dioxide (TiO2) is an efficient advanced oxidation
method in industrial effluent treatment process. When the TiO 2 is illuminated by UV, it generates
a conduction band of electrons (ecb) and valence band holes (h⁺) (Eq. 9-11). These band
electrons interact with surface adsorbed oxygen to produce superoxide radical anions. The
hydroxyl radicals are produced when the band holes interact with water.
TiO2+ hν → ecb + h⁺ (9)
ecb + O2 → O2‾• (10)
h⁺ + H2O → H+ + HO• (11)
It has been shown that many organic complexes can be degraded by oxidation in the presence of
UV/TiO2. As with all the other processes in AOP, the degradation of organic compounds
takes place by reacting with the hydroxyl radicals.
Furthermore, TiO2 nanoparticles are deemed suitable for wastewater treatment, because they are
non-toxic, chemically and biologically inert, and inexpensive.
Out of these processes applicable, the Fenton or Fenton like processes are in great demand since
they are easy methods and inexpensive as compared to other processes[ CITATION NiR17 \l 1033 ].

3. Fenton Process
The reaction of the Fenton Process involves the decomposition of the H 2O2 resulting in the
formation of the OH ¿ radical which has the ability to oxidize the organic compounds (-RH or
-R) present in the effluent by abstraction of hydrogen ( ¿ R) or by the addition of the hydroxyl(
¿ ROH). The molecules formed ( ¿ R and ¿ ROH) are highly reactive and further oxidized.

Also in addition the newly formed ferric ion (Fe3+) catalyzes H2O2. ¿ OH2 is known as the
hydro peroxyl radical. ¿ OH 2 alone are less effective as compared to ¿ OH radical but they
also have the ability to attack organic compounds.
Fenton process is carried out at the ambient temperature and pressure, but it is also dependent on
the pH because of the presence of the iron ions (Fe2+ and Fe3+) and H2O2. However, from the
research studies it is found that the optimum pH should be around 3-4, a minor change in the pH
can sharply reduce then efficiency of the system. When the pH reaches lower than 3, H2O2
solvates the proton leading to the formation of the oxonium ions (H3O+), which can enhance the
stability of the H2O2 and lower the reactivity of it with the ferrous ion. And on the other end if
the pH rises above 4, the dissolved iron species can decrease the colloidal ferric species

15
appearance. There are also the side reaction occurring which produces the sulfate ions (SO42-)
influencing the yield of the hydroxyl radicals, acting as a radical scavenger.
The rate constant for the reaction of ferrous ion with hydrogen peroxide is high and Fe2+ oxidizes
to Fe3+ in a few seconds to minute in the presence of excess amounts of hydrogen peroxide.
Fe2+ + H2O2 → Fe3+ + OH- + ¿ OH
Hydrogen peroxide decomposes catalytically by Fe3+ and generates again hydroxyl radicals
according to following reactions:
Fe3+ + H2O2 → H+ + Fe – OOH2+
Fe – OOH2+ → HO2 ¿ + Fe2+
Fe2+ + H2O2 → Fe3+ + OH− + ¿ OH
For this reason, it is believed that most waste destruction catalyzed by Fenton’s reagent is
simply a Fe3+–H2O2 system catalyzed destruction process, and Fenton’s reagent with an excess of
hydrogen peroxide is essentially a Fe3+–H2O2 process (known as a Fenton-like reagent). Thus, the
ferrous ion in Fenton’s reagent can be replaced with the ferric ion. Iron salts act as a catalyst for
hydrogen peroxide decomposition, further reactions regenerate iron Fe2+.
It has been demonstrated by various researchers that:
1. Fenton’s reagent is able to destroy different phenols, nitrobenzene, and herbicides in water
media as well as to reduce COD in municipal wastewater.
2. The Fe2+/H2O2 system acts as a potential oxidant for soil contaminants can also been
investigated.
3.Pentachlorophenol (PCP) and trifluralin are extensively degraded while hexadecane and
dieldrin can partially transformed in a soil suspension at acidic pH.
The use of Fe2+/H2O2 as an oxidant for wastewater treatment is attractive due to:
(1) Iron is a highly abundant and non-toxic element,
(2) H2O2 is easy to handle and environmental friendly substance.
Thus, the Fenton process is very effective for ¿ OH Hydroxyl radicals generation; however, it
involves consumption of one molecule of Fe2+ for each ¿ OH radical produced, demanding a
high concentration of Fe2+.

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 Figure 3.1 Schematic Diagram of Fenton Process [ CITATION Dan16 \l 1033 ]
Oxidation of impurity molecules by Hydroxyl radical ( ¿ OH) Depending upon the nature of
the organic impurity, following types of reactions are possible:
1. By radical addition: The addition of the hydroxyl radical to an unsaturated aliphatic or
aromatic organic compound (e.g.,C6H6) results in the production of a radical organic compound
that can be oxidized further. It can add itself to the contaminant, as in the case of olefins or
aromatic compounds.
R + ¿ OH → ROH
2. By hydrogen abstraction: The hydroxyl radical can abstract a hydrogen atom from water, as
with alkanes or alcohols, The removal of a hydrogen atom results in the formation of a radical
organic compound, initiating a chain reaction where the radical organic compound reacts with
oxygen, producing a peroxyl radical, which can react with another compound and so on.
R + ¿ OH → R ¿ + H2O
3. By electron transfer: Electron transfer results in the formation of ions of a higher valence.
Oxidation of a monovalent negative ion will result in the formation of an atom or a free radical.
Rn + ¿ OH → R n-1 + OH ¿

4.By radical combination: Two radicals can combine to form a stable product. See reaction.
¿ OH + ¿ OH → H2O2 [ CITATION Ank141 \l 1033 ]

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4. Parameters that affects the Fenton process
A. Effect of Iron Concentration: In the absence of iron, there is no evidence of hydroxyl
radical formation when H2O2 is added to wastewater. As the concentration of iron is increased,
impurity removal accelerates until a point is reached where further addition of iron becomes
inefficient. The optimal dose range for iron catalyst is characteristic of Fenton’s Reagent and its
range varies with the type of contaminants in wastewater. Three factors, typically influence the
optimal dose are given below.
1. A minimal threshold concentration of Fe which allows the reaction to proceed within a
reasonable period of time regardless of the concentration of impurity material.
2. A constant ratio of Fe: substance above the minimal threshold, which produces the desired end
products. Note that the ratio of Fe: substance may affect the distribution of reaction products.
Iron dose may also be expressed as a ratio to H2O2 dose.
3. A supplemental quantity of Fe which saturates the chelating properties in the wastewater,
thereby availing un-sequestered iron to catalyze the formation of hydroxyl radicals.
B. Effect of Iron Type (Ferrous or Ferric): For most applications, it does not matter whether
Fe2+ or Fe3+ salts are used to catalyze the reaction. The catalytic cycle begins quickly if H2O2 and
organic material are in sufficient amount. However, if low doses of Fenton’s Reagent are being
used, some researchers suggest ferrous iron may be preferred. Neither does it matter whether a
chloride or sulfate salt of the iron is used, although with the former, chlorine may be generated at
high rates.
C. Effect of H2O2 Concentration: Because of the indiscriminate nature by which hydroxyl
radicals oxidize organic materials, it is important to profile the reaction in the laboratory for each
waste to be treated. Each transformation in this series has its own reaction rate. In case of
phenolic contaminants, there may generate undesirable intermediate (quinones), if insufficient
amount of H2O2 is added. In pretreatment of a complex organic wastewater for toxicity
reduction, as the H2O2 dose is increased, a steady reduction in COD may occur with little or no
change in toxicity until a threshold is attained, whereupon further addition of H2O2 results in a
rapid decrease in wastewater toxicity.
D. Effect of Temperature: The rate of reaction with Fenton’s reagent increases with increasing
temperature, with the effect more pronounced at temperatures less than 20 ℃. However, as
temperatures increase above 40-50 ℃., the efficiency of h2o2 utilization declines. This is due to
the accelerated decomposition of h2o2 into oxygen and water. As a practical matter, most
commercial applications of Fenton’s reagent occur at temperatures between 20-40 ℃..
Moderating the temperature is important not only for economic reasons, but for safety reasons as
well.
E. Effect of pH: The effect of pH on reaction efficiency is shown in figure. The optimal pH
occurs between 3 and 6. The drop in efficiency on the basic side is attributed to the transition of
iron from a hydrated ferrous ion to a colloidal ferric species. In the latter form, iron catalytically
decomposes the H2O2 into oxygen and water, without forming hydroxyl radicals.

18
 Figure 4.1 The effect of pH on reaction efficiency [ CITATION Ank141 \l 1033 ].
A second aspect of pH deals with its shift as the reaction progresses. Provided an initial
wastewater pH of 6.0, the following profile is typical of Fenton reactions. The first inflection is
caused by the addition of Fe salt catalyst having acidic pH. A second, more pronounced drop in
pH occurs when the H2O2 is added, and continues gradually at a rate which is attributed to the
fragmenting of organic material into organic acids. The absence of such a pH decrease may mean
that the reaction is inhibited and that a potentially hazardous build-up of H2O2 is occurring within
the reaction mixture.

Figure 4.2 pH shifts as the reaction progresses [ CITATION Ank141 \l 1033 ].

F. Effect of Reaction Time: The time needed to complete a Fenton reaction will depend on the
many variables discussed above, most notably catalyst dose and wastewater strength. For simple
phenol oxidation (less than ca. 250 mg/L), typical reaction times are 30 - 60 minutes. For more
complex or more concentrated wastes, the reaction may take several hours. In such cases,
performing the reaction in steps (adding both iron and H2O2) may be more effective than
increasing the initial charges. Determining the completion of the reaction may prove
troublesome. The presence of residual H2O2 will interfere with many wastewater analyses.
Residual H2O2 may be removed by raising the pH to 7 - 10, or by neutralizing with bisulfite

19
solution. Often, observing color changes can use to assess the reaction progression. Wastewaters
will typically darken upon H2O2 addition and clear up as the reaction reaches completion

[ CITATION Ank141 \l 1033 ].

5. Electro Fenton Process:

Electro-Fenton process has been developed to overcome the limitations of classical Fenton
process: the accumulation of iron sludge and the high costs and risks associated with handling,
transportation and storage of reagents. Conventional Fenton process can be especially improved
by electrochemistry because of its advantages such as versatility, high energy efficiency,
amenability of automation, and its environmental compatibility. Therefore, the combination of
conventional Fenton process with electrochemistry gives rise to the so-called electro Fenton
process. Its essence is that H2O2 is in situ generated via the electrochemical reduction of O2 on the
cathode, which can avoid the costs and risks associated with handling, transportation and storage
of H2O2. And Fe3+ generated by Fenton reaction is reduced to Fe2+ on the cathode, which can
achieve the regeneration of Fe2+ and reduce the iron sludge production. Electro Fenton process is
classified into four categories depending on Fenton reagents addition or formation: cathode
electro-Fenton process (EFH2O2), sacrificial anode electro-Fenton process (EF-Feox), Fe2+
cycling electro-Fenton process (EF-Fere), cathode and Fe2+ cycling electro Fenton process (EF-
H2O2-Fere).

In the EF-H2O2 process, Fe2+ is externally added while H2O2 is in situ generated via the
electrochemical reduction of O2 on the cathode (Eq. 1), which can avoid the costs and risks
associated with handling, transportation and storage of H2O2. In the EF-Feox process, H2O2 is
externally added while Fe2+ is electro-generated using a sacrificial anode (Eq. 2), which can avoid
the addition of Fe2+. However, EF-Feox process has some disadvantages such as serious
consumption of anode and a large amount of iron sludge production. In the EF-Fere process,
H2O2 and Fe2+ are both externally added, but Fe3+ generated by Fenton reaction is reduced to Fe 2+
on the cathode (Eq. 3), which can reduce the iron sludge production and the initial Fe2+
concentration input. EF-H2O2-Fere process is the combination of EFH2O2 process with EF-Fere
process. In the EF-H2O2-Fere process, H2O2 is in situ generated via cathodic reduction of O 2 and
Fe2+ is regenerated through the reduction of Fe3+ on the cathode, which can avoid the addition of
H2O2 and reduce the iron sludge production and the initial Fe2+ concentration input.

20
Figure 5.1 Types of electro fenton

O2 + 2H+ + 2e- → H2O2 (1)

21
 Fe → Fe2+ + 2e- (2)

Fe3+ → Fe2+ + e- (3)

The advantages of electro-Fenton process compared with conventional Fenton process are as
follows: (1) the on-site production of H2O2, which can avoid the risks related to its transport,
storage, and handling; (2) the continuous regeneration of Fe2+ on the cathode, which can
minimize the iron sludge production and improve the degradation efficiency of organic
pollutants [ CITATION Men19 \l 1033 ].

Table 5.1 Advantages and limitations of electro-fenton process [ CITATION Men19 \l 1033 ]

Advantages Limitations
The on-site production of H2O2 The low H2O2 yield
Handling, transportation and storage of H2O2 The low unit cell body throughput
The continuous regeneration of Fe2+ on the The low current density
cathode
The low iron sludge production. The low conductivity

6.Experimental Work
6.1 Experiment 1:
Aim: To study the Electro-Fenton process to remove the benzene, toluene and p-xylene from the
wastewater sample
Materials: BTX, Methanol, Ferrous sulphate, hydrochloric acid, wastewater, pH meter, filter
paper, beakers, electrodes, stirrer.
Method:
 In a beaker of around 1000 ml, 650 ml of wastewater is added along with the benzene,
toluene, and xylene if not present.
 The carbon felt piece used as a cathode (30 x13.5x0.5 cm) that can cover the inner
cylindrical wall of the beaker.
 Anode can be used with different material say sacrificial iron plates or stainless steel, or
nickel plates (5 x 5 x 0.5 cm) and placed vertically in the center

22
  The solution is vigorously stirred using a magnetic stirrer and then if possible include O 2
using compressed air pump and continue till the end of the experiment.
 The pH is adjusted using HCl or sulfuric acid and recorded using pH meter.
 The electrodes are connected to a digital DC power supply and added the desired amount
of ferrous sulphate at the time of switching on the power supply.
 Sodium sulphate can be added to obtain the required conductivity of the EF process.
 Ammeter and voltmeter readings are also recorded and samples are taken periodically
during the process and filtered using the filter papers.
 The sludge formed is weighted out at the end of the experiment and analyze the effects of
sludge removal of EF process. [ CITATION Mah19 \l 1033 ]
6.2 Experiment 2:
Aim: To the Electro-Fenton process to remove the benzene, toluene and p-xylene from the
wastewater sample
Materials: TiO2 and Ti plates, Ferrous sulphate, hydrochloric acid, wastewater, pH meter, filter
paper, beakers, electrodes, stirrer.
Method:
 In a beaker of around 1000 ml, the electrodes of TiO2 and Ti plates are placed inside it.
 Each plate had a geometric dimension of 10 cm × 10 cm × 0.1 cm, with 10 cm space
between two electrodes.
 The solution is vigorously stirred using a magnetic stirrer and the electrodes are
connected to a digital DC power supply and added the desired amount of ferrous sulphate
at the time of switching on the power supply.
 The desired amount of H2O2 is added to initiate the required reaction through EF process.
 The pH is adjusted using HCl or sulfuric acid and recorded using pH meter.
 Ammeter and voltmeter readings are also recorded and samples are taken periodically
during the process and filtered using the filter papers.
 The slurry mixed with the magnetic stirrer is transformed into the funnel through the
filter papers used.
 The sludge formed is weighted out at the end of the experiment and analyze the effects of
sludge removal of EF process. [ CITATION MCa19 \l 1033 ]

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