Print 2 Final Project Report

DISSERTATION REPORT
On
“INTENSIFICATION OF DEGRADATION OF EMERGING
CONTAMINANTS BY ADVANCED OXIDATION PROCESS ”
Is submitted in partial fulfillment of the requirements for the award of degree of
Master of Technology
In
Chemical Engineering
By
Ms. Priyanka C. Waghulade
( University PG Registration No – 2019016402610894 )
Under the guidance of
Dr. Manisha V. Bagal
SCHOOL OF ENGINEERING AND APPLIED SCIENCES

KALYAN - 421301
UNIVERSITY OF MUMBAI
Department of Chemical Engineering
Academic Year : (2020-21)
1
SCHOOL OF ENGINEERING AND APPLIED SCIENCES
KALYAN - 421301
UNIVERSITY OF MUMBAI
Academic Year : (2020-21)
Dissertation Approval For M.Tech

This dissertation report entitled “Intensification of Degradation of Emerging
Contaminants By Advanced Oxidation Process” by Ms.Priyanka C. Waghulade is
approved for the Degree Of Master of Technology In Chemical Engineering for
academic year 2020-2021.
Examiners
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2. ________________________
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SCHOOL OF ENGINEERING AND APPLIED SCIENCES ,
UNIVERSITY OF MUMBAI ( KALYAN SUB CENTER )
Declaration
I declare that this written submission represents my ideas in my own
words and where other’s ideas or words have been included. I have been
adequately cited and reference the original sources. I also declared that I have
adhere to all the principles of academic honesty and integrity and have not
misrepresented or fabricated or falsified any ideas, data, fact, source in my
submission.
Date : ___________
______________________________
Ms. Priyanka C. Waghulade
Reg .No. : 2019016402610894
SCHOOL OF ENGINEERING AND APPLIED SCIENCES,
UNIVERSITY OF MUMBAI (KALYAN SUB CENTER)
Department Of Chemical Engineering
(2020-2021)
CERTIFICATE
This is to certify that Ms. Priyanka C. Waghulade has successfully completed
Project Report entitled On “Intensification of degradation of emerging
contaminants by Advanced Oxidation Process” in semester IV and submitted
the work in partial fulfillment for the award of Master of Technology in
Chemical Engineering Of University of Mumbai( Kalyan Sub Center)
during academic year 2020-21.
Date:__________
Project Guide College Stamp

Internal Examiner External Examiner
Director
INTENSIFICATION OF DEGRADATION OF
EMERGING CONTAMINANTS BY ADVANCED
OXIDATION PROCESS
ACKNOWLEDGEMENT
I take this opportunity to express my deep gratitude and regards to my guide

Dr. Manisha V. Bagal her exemplary guidance, monitoring and constant encouragement
throughout the course of this thesis. The blessing, help and guidance given by her time to
time shall carry me a long way in the journey of life on which I am about to embark.
I also take this opportunity to express a deep sense of gratitude to our Head of
department, Dr. Kalpana S. Deshmukh , and our Director Dr. Adwait M. Vaidya, School
of Engineering and Applied Sciences, Mumbai University (Kalyan sub center ) for their
cordial support, valuable information and guidance, which helped me in completing this
task through various stages.
I am obliged to staff members of School of Engineering and Applied Sciences,

Mumbai University (Kalyan sub center ) for the valuable information provided by them in
their respective fields. I am grateful for them for their cooperation during the period of my
assignment .
Lastly, I thank almighty, my parents, brother, sisters and friends for their constant
encouragement without which this assignment would not be possible.
Ms. Priyanka Waghulade
i
CONTENTS
Acknowledgement ------------------------------------------------------------------------------- i
List of Abbreviation -------------------------------------------------------------------------------ii
List of Figure ---------------------------------------------------------------------------------------ii
List of Table ----------------------------------------------------------------------------------------iii
INDEX
1. Abstract -------------------------------------------------------------------------------------1
2. Motivation and Objective ----------------------------------------------------------------2
3. Significance and Technical novelty ---------------------------------------------------- 3
4. Outline of the report
• Introduction -------------------------------------------------------------------4
• Literature Survey ------------------------------------------------------------10
• Methodology ---------------------------------------------------------------- 19
• Case Study ------------------------------------------------------------------- 41
5. Conclusions and Future Scope ----------------------------------------------------------47
6. References -------------------------------------------------------------------------------- 49
List of Abbreviation
AOP Advanced Oxidation Process
PVA Polyvinyl Alcohol
UV Ultraviolet
US Ultrasound
COD Chemical Oxidation Demand
TOC Total Oxygen Carbon
Ecb Electron Conduction Bond
List of Figure
Figure 1 Unit Cell structure of PVA
Figure 2 Reaction scheme of PVA degradation
mechanism by AOP
Figure 3 PVA degradation mechanism,TiO2
based photocatalytic oxidation
Figure 4 Representation of equipment based
on photocatalytic oxidation
Figure 5 Reaction between PVA and Ozone
on ozonisation
Figure 7 Treatment flowsheet for Fenton
oxidation
Figure 8 Ultrasound Cavitation Mechanism.
on Acoustic Cavitation
Figure 10 PVA degradation by Photochemical
Reactor.
ii
List of Table
Table 1 Physical and chemical properties of

PVA
Table 3 Basic classification of Advanced
oxidation processes (AOPs)
Table 3 Application of some water-soluble
polymer
Table 3.1 Summary of Research studies in
which AOPs used for PVA
iii
ABSTRACT
Advanced oxidation processes (AOPs) constitute a promising technology to

treat wastewater containing organic pollutants that are not easily biodegradable. They have
received increasing attention in the research and development of wastewater treatment
technologies in recent decades for their removal or degradation of recalcitrant pollutants or
as pretreatments to convert pollutants into smaller compounds, which can be treated using
conventional biological methods. Polyvinyl alcohol (PVA) is a typical organic pollutant. It
has received special attention due to its low biodegradability and the large amount of PVA-
containing wastewater discharged from textile and paper mills. This work focuses on PVA
removal and PVA wastewater pretreatment by AOPs, which include ozonation, Fenton
oxidation, photocatalysis, ultrasound cavitation, photo-Fenton oxidation. The mechanistic
degradation steps of PVA by AOPs are also discussed. In addition, a new classification of
AOPs is also applied for PVA treatment. In AOP processes, The flow of oxidants must be
controlled to minimize the oxidants residuals in a post biological treatment and maximize
the total organic carbon removal and degradation .
Keywords : PVA, cavitation, Ozonisation , Photo Fenton oxidation , Fenton oxidation,

operating parameters
1
MOTIVATION AND OBJECTIVE
The uncontrolled release of polyvinyl alcohol (PVA) and structurally related

polymers from industrial plants into the environment causes many ecological problems.
An inexpensive and versatile solution, especially for wastewater discharged from desizing
processes in the textile industry, has not yet been developed. These highly polluted waste
waters contain amounts of dissolved organic carbon (DOC) as high as 10 g L—1 giving rise
to high chemical oxygen demand (COD). The oxidative degradation of PVA in municipal
and industrial wastewater treatment facilities is usually limited if specially adapted bacteria
strains are not employed.
Whereas some adapted bacteria showed promising results in biological model

plants , high salt contents prevailing in desizing waste waters prohibit their successful
application. The use of seawater in industrial processes may help to preserve freshwater
resources, and oxidation methods have to be developed which will function successfully
under these conditions. A further environmental problem arises from the enhanced
mobilization of heavy metals from the sediments of streams, lakes and oceans by PVA .
Therefore, methods for the removal of PVA from wastewater, preferentially by
mineralization, have to be developed.
Objective :
The objective of this study is to minimize degradation of contaminants in industry

like polymers PVA by using recent technique Advanced oxidation processes. This work is
based on following objectives,
2
1. To review fundamentals and recents advances in Advanced oxidation processes used
in waste water and degradation of polymers .
2. Treatment of real wastewater system containing mixture of pollutants.
3. To remove organic matters, traceable emerging contaminants in addition to certain

inorganic pollutants.
4. Optimization of operating parameter.

SIGNIFICANCE AND NOVELTY
Polyvinyl alcohol is a water-soluble polymer with high thermal stability,

high strength and excellent film-forming properties. PVA is widely used in textile resins,
grease-resistant paper coatings, and adhesives, and the global consumption is over one
million tons per year. Moreover, it is expected to increase at an overall rate of
approximately 3.5% annually. However, PVA is not a readily biodegradable organic
compound. The BOD5 (biochemical oxygen demand) /COD (chemical oxygen demand)
ratio of PVA wastewater usually is less than 0.1 . PVA, which is released from the
printing and dyeing wastewater of the textile industry, particularly from the desizing
process, can directly deteriorate the receiving body of water.
Due to its poor biodegradability, it is difficult for conventional biological
processes to degrade PVA. Many wastewater treatment plants have been seriously
challenged. When this wastewater discharges into the environment without efficient
treatment, the water surfaces are sealed by a large area of foam. Due to the absence of
oxygen, the activities of aerobic microorganisms will be inhibited, and the water viscosity
will increase. In addition, the mobilization of heavy metals from the sediments of streams,
oceans and lakes can be enhanced by PVA which causes accumulation of hazardous
substances.
There are many methods available for degradation like membrane separation,
coagulation , ion exchange method as PVA has very strong stability and strength this
process does not give complete degradation of PVA . Hence for more degradation
Advanced Oxidation processes are used as it give more degradation. In AOPs degradation
is carried out by means of hydroxyl radicals . There are many Advanced oxidation
processes available for degradation like ozonisation , photocatalysis , fenton oxidation ,
cavitation .
3
In recent years, various methods of photochemical degradation referred to as
advanced oxidation processes (AOP) have been proposed for the treatment of ground,
surface and wastewaters containing toxic or non-biodegradable organic compounds. AOP
are most often initiated by hydroxyl radicals which may be generated by various methods
(such as UV photolysis of hydrogen peroxide, TiO2 photocatalysis, vacuum ultraviolet
(VUV) photolysis of water). Among AOP, the Fenton reaction and especially the
photochemically enhanced Fenton reaction are considered most efficient for the
remediation of highly contaminated waste waters.
Sometimes, these processes are not enough or give complete degradation as
they have some barriers for that new Hybrid treatment processes are also useful which
also gives high degradation of polymers. Hybrid treatment processes are the combination
of AOP processes which are more efficient like photocatalysis and Fenton, cavitation and
photocatalysis ,cavitation and ozone etc .Sodium persulphate process is also gives good
efficiency nowadays which is a latest development in AOP.
Intensification of degradation of emerging contaminants by Advanced Oxidation Process
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OUTLINE OF REPORT
INTRODUCTION
The increasing turnover and consumption of water-soluble synthetic polymers

generate lots of wastes during production, use, and disposal. In addition, many materials in
the production are often non-biodegradable or toxic to micro-organisms and can have very
long half-life periods in the environment. For example, polyvinyl alcohol (PVA), which is
widely used in sizing process of the textile industry, is difficult to be degraded biologically.
The wastewater produced from the manufacturing of chemical compounds must

be well treated to eliminate any harmful impact in the ecosystem environment.
Conventional biological techniques using microbes and bacteria to degrade toxic chemicals
from wastewater systems, are not sufficient to degrade some organic materials. Many of
these complex compounds are resistant to conventional wastewater treatment and
biological degradation. Scientists and engineers understand the need for degradation of
such pollutants for that advanced oxidation processes (AOPs) is very useful to complement
and improve conventional biological wastewater treatment processes (Ardekani, 2015).
Polyvinyl alcohol (figure 1) is a water-soluble polymer with high thermal

stability, high strength and excellent film-forming properties. PVA is widely used in textile
resins, grease-resistant paper coatings, and adhesives, and the global consumption is over
one million tons per year. Moreover, it is expected to increase at an overall rate of
approximately 3.5 % annually . However, PVA is not a readily biodegradable organic
compound. The BOD (biochemical oxygen demand) /COD (chemical oxygen demand)
ratio of PVA wastewater is less than 0.1. PVA, which is released from the printing and
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Department of Chemical Engineering , School of Engineering and Applied Sciences

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dyeing wastewater of the textile industry, particularly from the desizing process, can
directly deteriorate the receiving body of water.
Due to its poor biodegradability, it is difficult for conventional biological

processes to degrade PVA. Many wastewater treatment plants have been seriously
challenged. When this wastewater discharges into the environment without efficient
treatment, the water surfaces are sealed by a large area of foam . Due to the absence of
oxygen, the activities of aerobic microorganisms will be inhibited, and the water viscosity
will increase. In addition, the mobilization of heavy metals from the sediments of streams,
oceans and lakes can be enhanced by PVA , which causes accumulation of hazardous
substances.
Table 1. Physical and chemical properties of polyvinyl alcohol is as follows,
Property Values
Molecular weight 100,000 g/mole
Molecular formula (𝐶𝐶2𝐻𝐻4𝑂𝑂)𝑛𝑛
Boiling point 228°𝐶𝐶
Melting point 150 − 190℃
Density at 25 ℃ 1.19-1.31 g/ml
Viscosity at 25 ℃ 0.9 𝑚𝑚𝑚𝑚𝑚𝑚. 𝑠𝑠
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Figure 1: The unit cell structure of PVA. (From Journal of Advanced Oxidation
Technologies , Weilhua sun ,2017-20170018 )
Because of the huge market for polymers such as PVA, PAM, PAA , it is
harmful to human beings, much attention has been paid to examining the extensive
treatment of polymers PVA-containing wastewater using different technologies, such as
membrane filtration , biological technology and advanced oxidation processes . Although
an appropriate membrane may remove most types of pollutants, e. g. dyes, a PVA film
forms on the membrane, and membrane blocking is a serious problem for filtrating PVA
wastewater. In addition, concentrated sludge production and costly membrane replacement
limit its wide spread application. A biological process with a long treatment period is
always affected by water quality fluctuation, e. g. food-to-microorganism ratios and
temperature . Moreover, industrial wastewater generally contains other toxic compounds
such as dyes, which are resistant to biodegradation. Further, several water-soluble
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polymers such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylamide
(PAM) are not degradable by biological treatments (Ghafoori et al., 2014). Also, many
pharmaceutical compounds are not easily degradable by means of conventional biological
treatments. Previous studies undertaken by Ghafoori (2013) and Hamad (2015) have
focused on experimental and theoretical investigations of polymer degradation. In
advanced oxidation processes active hydroxyl radicals are produced to degrade complex
organic compounds by attacking the long molecular chains (Tabrizi and Mehrvar, 2004;
Mohajerani et al., 2010).
As Compared with other technologies, advanced oxidation processes
(AOP ) are short treatment times, good removal efficiency and broad applications for the
removal of different pollutants. It has been proven to be effective for PVA wastewater
treatment. This work is devoted to summarizing the main aspects of the degradation and
mineralization of PVA in wastewater using AOP.
• Advanced Oxidation Processes:

AOPs are water treatment processes that can produce highly reactive radicals
and radical intermediates, particularly hydroxyl radical (•OH). Highly reactive •OH is
traditionally considered the active species for organic pollutant degradation. Almost all
organic pollutants can be oxidized to CO2 and H2O by the radical. The intermediates
include some of the simplest organic products, such as acetic acid, acetone . It is interesting
to note that these small organic compounds can be further degraded through conventional
biological treatment technologies. These small organic compounds can be generated via
chemical, photochemical or electrochemical reactions. Although AOPs show high
efficiencies on organic compound degradation, they are expensive for practical application.
From an economical viewpoint, coupled an AOP and a subsequent conventional biological
treatment process appears to be better .
Weihua Sun.et.al (2017) earlier reported that AOPs are classified into chemical-
based methods, energy-based methods and hybrid methods. Chemical-based methods use
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chemical substances (solid, liquid, gas) and their combinations as oxidants. Similarly,
energy-based methods use energy (light, electricity, sound, wave, heat, magnetism and
mechanical energy) or their combinations as reaction powers to produce •OH and other
radical species. The combination of these two groups composes hybrid methods.
Table 2 shows the basic classification of Advanced Oxidation Processes.
Table 2 : Basic classification of advanced oxidation processes.
AOPs Single methods Combined methods

Chemical-based Ozone (O3), Persulfate (PS), O3/H2O2
Fenton agent, Fenton-like
agents
Energy-based Photocatalytic oxidation, Sono-

Electrochemical oxidation, photochemical
Ultrasound (US) cavitation, oxidation,Sono-
Microwave(MW),Ionizing photocatalytic
radiation (IR) oxidation
Hybrid method UV/O3, US/O3, UV/H2O2, Wet air oxidation

US/H2O2, (WAO), WAO/US,
Electro/Fenton, Photo/Fenton, Supercritical water
US/Fenton, IR/O3, IR/H2O2 oxidation,
O3/H2O2/UV
As shown in Figure 2 chemical-based AOPs (such as ozonation, Fenton

reagent, persulfate), and hybrid AOPs (such as wet air oxidation (WAO) and wet peroxide
oxidation (WPO)) are efficient to degrade PVA. Moreover, energy-based AOPs, such as
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photocatalytic oxidation, electrochemical oxidation, ultrasonic oxidation and ionizing

radiation, are also applied in degradation of PVA .
Generally, •OH acts with high efficiency to destroy pollutants in aqueous

solutions. Furthermore, PVA is sensitive to oxidants. Therefore, most AOPs are designed
to produce •OH to enhance PVA removal efficiency.
The reaction scheme for PVA mechanism is shown as below ,
Figure 2: The reaction scheme of PVA degradation mechanism by AOPs .( Sun.et.al ,

2019)
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LITERATURE REVIEW
Open literature shows that many studies have been conducted to

degradation of many pollutants such as pharmaceutical products, detergents,
polymers and disinfecting processes in wastewater streams. Conventional
biological techniques using microbes and bacteria to degrade toxic chemicals from
wastewater systems are not sufficient to degrade new complex materials (Harimurti
et al.,2014). However, advanced oxidation processes(AOP) are efficient techniques
to treat wastewater effluents.
For instance, Fernanbo et al. (2009) studied the degradation of Poly Vinyl
Alcohol , poly ethylene glycol were determined by the oxidation process (Santos
et al., 2009). The mechanisms were determined by studying different methods of
AOP for degradation of polymers .
Water-soluble polymers such as Polyphthalamide (PPA), polyvinyl

alcohol (PVA), and polyacrylamide (PAM), and other polymers listed in Table 2
are frequently utilized in several commodity and industrial applications such as
textile industry, oil field products, detergent-based industry and cosmetics (Aarthi
et al., 2007). The degradation of these polymers gave rise to smaller carboxylic
acids such as formic, glycolic and oxalic acids (Santos et al., 2009).
In hydrocarbon industries, Harimurti et al. (2014) investigated a UV/H2O2

process to degrade alkanolamine in effluents of a refinery of sweetening processes.
Alkanolamine is used in the formulation of cosmetic and pharmaceutical products,
and also are used as solvents. During the scheduling maintenance of adsorption and
desorption columns, effluent with high concentrations of alkanolamine are
generated from sweeting process at refineries. Harimurti et al. (2014) reported that
this particular effluent cannot be treated in a biological process. Therefore, AOP
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processes are promising techniques in the treatment of toxic organic compounds.

However, most methods used in the pre-treatment of refinery effluents are Fenton
reagents, UV/Ozone and UV/H2O2. As a result of no sludge production, the high
efficiency in the production of hydroxyl radicals for the brakeage of organic
compounds.
Table 3 illustrates some common water-soluble polymers that may be found
in industrial wastewater effluents.
Table 3 . Applications of some Water-Soluble Polymers
Soluble Polymers in water Applications

Polyvinyl alcohol (PVA) Detergent, dissolvable laundry
packages, paper and textile coatings.
Polyacrylamide (PAM) Flocculants, adhesive, lubricant,
paint and pigment dispersant.
Polyacrylic acid (PAA) Detergent, thickener, super
absorbent.
Polyaspartic acid (PASP) Detergent, paint, fertilizer, cosmetics,
biomedical (drug delivery, artificial
skin, dialysis membranes).
Polyethylene glycol (PEG) Tissue engineering, drug delivery,
cosmetic.
Polyethylene oxide (PEO) Tissue engineering, drug delivery,
cosmetic.
Polycarboxylates (PAA-PMA) Pharmaceutical compound (vaccine).
Galactomannan (Guar) Food additives, Rheology modifier.
Polyethyleneimines (PEI) Detergent, lubricant, binder.
Polyvinylpyrrolidone (PVP) Pharmaceutical compound
(disinfectant), emulsifier, adhesive.
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Ghafoori (2013) and Hamad (2015) have done very interesting and original studies
on modeling polymer degradation in photochemical reactor using photochemical kinetic
approach. Alternatively, process identification is another important approach to describe
the industrial processes form input and output measured signals of a process such as the
identification of a bioreactor (Pramod and Chidambaram, 2000), pulp and paper process .
The following Table 3.1 shows a summary of research studies in which AOP were
used for PVA degradation .
Table 3.1: A summary of research studies in which AOPs were used for PVA degradation.
Researcher Methodology Research System Reaction Result

’s Name Condition
Weihua Ozonisation O3 + 50-200 mg/L PVA 10 mg/min PVA was

Sun.et.al aqueous solution O3, pH 5-12 removed
(2017) completely
within
20 min.
Ozonation
efficiency of
PVA
increased as
pH increasing.
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O3 + 8–15 g/L PVA 90 mg/L O3, Ratio of O3

aqueous Solution magnetic /PVA <0.05 was
stirring, found to
12 h, acidic decrease the
conditions, viscosity
170C
Yingxu Photocatalytic Photocatalytic oxidation 2 UV lamps PVA could be

Chen.et.al Oxidation + (6 W/lamp, degraded
(2001) 365 nm), pH completely in
20–40 mg/L PVA
4–11, 120 min when
(MW=80000) aqueous
0–8 mmol/L the TOC
solution.
H2O2, TiO2 removal rate
1:1.0, g/L, was only 2 %.
constant The optimal
stirring concentration
value of H2O2
and TiO2 were
found to be
5 mmol/L and
2.0 g/L.
Ye Yang Fenton Fenton + 0.5 % PVA PVA The chemical

.et.al (2001) Oxidation (MW=79200) aqueous pretreatmen pretreatment
solution + biological t with resulted in
treatment Fenton greater PVA
reagent degradation
than the
degradation
observed when
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biological
degradation
alone was
used.
More than
70 % COD
Fenton + 5 % PVA 1.56 mol/L and 60 %
(MW=26400 or 79200) H2O2 and TOC was
aqueous solution + 0.056 mol/ removed.
biological treatment. L FeSO4;
pH 6, 7
days at
370C with
Shaking
Lei Ch .et Photo-Fenton Photo-Fenton + 200 mg UV, mole Approximate
al.(1998) Oxidation /L of PVA ratio of 90 % of DOC
(MW=15000,49000, Fe2+ / PVA removed
100000) pH 4 , 40℃ within 0.5 hr.
aqueous solution. PVA may

form
complexes
with ferrous
ions.
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Photo-Fenton+200 mg/L Fe++ / PVA The

PVA PH =4 , 120 formation of
(MW=15000,49000, min , 400C super macro
100000)aqueous molecules
solution was found to
be consisted
of Fe3+ and
Oxidized
PVA
Gronroos A Ultrasound The study A Cavitation

US + 1 – 3 % PVA
.et.al (2001) Cavitation based on 3 threshold of
(MW=115000) aqueous
reactors input power
solution
with for PVA
different degradation
frequencies was found to
,ultrasonic be 23 KHZ
input power when PVA
0–350 W, 0– concentration
120 min was 1%
US + Simulated waste
water contained50 – 300 3 MHz , 20- The
0
mg/L PVA (Mw = 86000 50 C interaction and
and dextran the
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compatibility
of PVA and
dextran were
found due to
cross link via
H bonding
involving OH
group of both
the biomacro
molecules
Hung Suck Persulphate 250 mg/L PVA could
PS + 50 mg/L PVA
Park.et.al Cavitation PS, Fe2+ or be removed
(MW=66000) aqueous
(2009) Fe(0) to PS 95 % at 80℃
solution
molar within
ratios=0.25– 120 min. Due
5.0, 20– to the
80℃ addition of
Fe2+ or Fe(0),
PVA was
degraded
completely
within 30 min
at the ratio of
1:1
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60
W Sun.et.al Ionising IR + 0–500 mg/L PVA A Co-γ- An optimal
(2017) Radiation (74800<MW<79200) source,dose dosages of
aqueous solution rate 5- H2O2 was
100Gy/min found .A
,PH= 1-12 proposed
,radiation degradation
time 0-150 pathway of
min,H2O2 0- PVA was
20 mmol /L, built.
air or
nitrogen
saturated.
60 OH and H
A Co-γ-
initiated PVA
source,dos
degradation .
e rate 10–
70 Gy
IR + 0-500 mg/L PVA
/min,
(74800<MW<79200)
absorbed
aqueous solution
dose 0–
16 kGy,
pH 0 to 14
radiation
time 30 or
60 min,
H2O2
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10 mmol/L,
O2 or N2
saturated
Chen Wet Air WAO + 200-500mg/L 175- 250 0C, 90% PVA
GH.et.al Oxidation PVA [Mw = 66000] 0.53 – 2.11 removed in 90
(2000) aqueous solution MPa , excess min at 2000C,
oxygen 0- no excess
300% oxygen,
0.7MPa
oxygen partial
pressure
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METHODOLOGY
 Various Advanced Oxidation processes Available for

degradation of PVA
1. Photocatalysis Oxidation process:
Photo-catalytic oxidation is evolved from ultraviolet (UV, expressed as

“hν”) photo oxidation. Because of the low reaction rate of photo oxidation,
photocatalytic oxidation is used to accelerate the reaction rate and enhance the yield
and energy efficiency. With high photocatalytic activity, biological and chemical
inertness, resistance to photo corrosion, and non-toxicity, the form of TiO2 is the
most popular semiconductor catalyst.
The dosage of UV and TiO2 obviously affects PVA degradation.
• Mechanism :
PVA degradation mechanism of the TiO2-based photocatalytic process was
shown in Figure 3.
The generated •OH radicals can attack PVA by hydrogen abstraction, which
forms carbonyl bonds. Then, short-chain compounds are formed by scissoring carbon-
carbon bonds. PVA can be oxidized to oligomers (Mw < 1000 g/mol) by photocatalytic
oxidation. Furthermore, the intermediates can be degraded with prolonged reactions. The
mineralization stages occur after the initial PVA is degraded. The reaction mechanism is
as follows,
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Photocatalysis using titanium dioxide (TiO2) is an efficient advanced

oxidation method in industrial effluent treatment process. When the TiO2 is illuminated
by UV, it generates a conduction band of electrons (ecb) and valence band holes (h+) (Eq.
1-3) 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 (1)
ecb + O2 → O2‾• (2)
h + H2O → H+ + HO• (3)
It has been shown that many organic complexes can be degraded by oxidation
in the presence of UV/TiO2 . PVA can be removed from aqueous solutions through
photocatalytic degradation and smaller TiO2 adsorption . Both UV irradiation and smaller
TiO2 (average particle size 25 nm) are required to ensure the effective removal of PVA.
However, this behavior was not observed in the photocatalytic degradation of PVA using
larger TiO2 particles.( Chen et.al ) found that only 1.2 % of PVA was adsorbed by the
surface of larger TiO2 particles (average particle size 950 nm).
Figure 3. PVA degradation mechanism of the TiO2-based photocatalytic

process.(Weilhua Sun et.al ,2017)
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• Reactors used for degradation of PVA using Photocatalytic

Oxidation.
The photocatalytic oxidation process can be carried out by simply using

slurry of the fine particles of the solid semiconductor dispersed in the liquid phase
in a reactor irradiated with UV light either directly or indirectly. The proper
dispersion of the catalyst in the liquid phase can be achieved using either
mechanical or magnetic stirrers.
Figure 4. Schematic representation of equipments based on photocatalytic

oxidation.(P.R .gogate 2004 ,550-551)
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• Effect of operating Parameters on degradation of PVA
1. Effect of TiO2 and UV on degradation of PVA :
Yang et al., reported ,in presence of both TiO2 and light , PVA was
found to be degrade after 1 hr. This was in contrast with degradation for the
same experiment performed in the absence of TiO2 , and only the UV lamps
had switched off and reaction was allowed to occur in the darkness (Ye Yang
et al 2001). These experiments suggested that PVA had negligible photo
activity , both light and TiO2 were needed for the effective degradation of PVA.
It had been proved that photo generated holes oxidized water or absorbed •OH
at the surface of semiconductor to hydroxyl radicals.These highly reactive
radicals could then be used to mineralize or atleast partially degrade most
organic pollutants. Earlier (Ye Chang et al 2001) rerported , the optimum
dosage of TiO2 in the photo degradation of PVA , the degradation rates were
lower because that the limiting factor for the low rate was the lack of required
amount of the catalyst. In superfluous TiO2, the UV was diffused by TiO2
particles.
2. Effect of initial concentration :
The effect of initial PVA concentration on degradation rate increases

with increasing PVA concentration .
3. Effect of PH :
According to some literatures , pH value was one of the major factors

influencing the rate of degradation of some organic compounds in the
photocatalytic process. It was also an important operation variable in
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wastewater treatment. PVA degradation is more effective under acidic or

alkaline than neutral condition . At different pH levels, the •OH production
pathway likely varies. In alkaline solutions, OH− ions can form •OH radicals at
the surface of TiO2 by trapping photo produced holes In acidic solutions, •OH
formation is mainly generated according to mechanism reaction.
4. Effect of temperature:
Usually photocatalytic systems are operated at room temperature, but with the
release of energy in the destruction process due to recombination of electron-
hole pairs, temperature might increase .
2. Ozonisation Process :
With the development of large-scale O3 generators in recent decades,

ozone (O3) has drawn increasing attention in treating wastewater that contains refractory
organic pollutants. Because of its powerful oxidizing capability, O3 is efficient in
removing organic compound and is friendly to most organisms because no other
substances are added to the treated wastewaters.
• Mechanism :
Ozone is a very powerful oxidizing agent that can react with most
species containing multiple bonds (such as C_C, C_N, N_N, etc.), but not with
singly bonded functionality such as C–C, C–O, O–H at high rates. This is
mainly due to the fact that there is no easy chemical pathway for the oxidation
to take place.
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These oxidations are simple and the mechanisms only require contact of ozone
with the ion. Consequently, the oxidation of these ions by ozone occurs rapidly.
The mechanism reactions are as follows, The formation of radicals are,
O3 + OH− → HO2• + •O2 (1)

•O3 + H+ → HO3• (2)
HO3• → HO• + O2 (3)
Due to the affinity of oxygen atom to electrons or protons, the oxidation ability
Of O3 is strong. The fresh oxygen molecule produced by O3 decomposition is also Strongly
oxidative . O3 reacts with OH− to yield •OH radicals. They react with inorganic or organic
pollutants in aqueous solutions in a non-selective manner.
Cataldo and Angelini(2006), documented that the addition of PVA enhanced
the dispersion and solubilization of O3 into the substrate by forming featured foam. The
ability traps ozone into the wastewater system, which prolongs the ozonation. As shown
in Figure 5 a complex with hydrogen bonds between PVA and ozone was described.
Figure 5: Reaction between PVA and ozone.( Weilhua sun.et.al. 2019)
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PVA degradation is more efficient under alkaline conditions rather than under
the acidic conditions which indicates that •OH radicals play a more important role than
O3 in the PVA decomposition. Importantly, micro-bubble technology is another method
to degrade PVA by enhancing the •OH yield. (Takahashi et al.) demonstrated that a large
quantity of •OH radicals was generated when O3 micro-bubbles collapsed.
• Reactors used for degradation of PVA using Ozonisation

Process .
A number of devices can be used to transfer the generated ozone into

water such as countercurrent bubble column, packed and plate columns, static
mixers, jet reactors and agitated vessels (Bowers et al., 1973; Glaze, 1987; Munter
et al., 1993; Martin and Galey, 1994). Fig. 6 shows some of the commonly used
equipments for transferring ozone in water. Ozone transfer efficiency should be
maximized by increasing the interfacial area of contact (reducing the bubble size
by using small size ozone diffusers such as porous disks, porous glass diffusers
(Ledakowicz et al. 2001), ceramic membranes (Janknecht et al., 2001; Ciardelli et
al., 2001; Ciardelli and Ranieril, 2001; Picard et al., 2001))
The schematic representation of equipment used for Ozonisation

process is as shown below,
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Figure 6 : Schematic representation of equipment used for ozonation.( (P.R .Gogate 2004
550-551)
• Effect of operating Parameters on degradation of PVA
1. Effect of PH on degradation of PVA:
The pH of the solution is a major factor that determines the

efficiency of O3 since it can change the pathways or kinetics of pollutant
degradation. Different oxidized products are generated by different reaction
pathways. Under acidic conditions (pH < 4), molecular ozone is stable.
Through dipolar addition reactions, nucleophilic or electrophilic reactions,
O3 can directly react with pollutants with specific functional groups. The
fresh oxygen molecule produced by O3 decomposition is also strongly
oxidative. At high pH (pH > 9), O3 reacts with OH− to yield •OH radical. In
addition, the direct ozonation and indirect pathway are both present in the
pH range of 4 – 9.
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Under acidic conditions, the main viscosity decrease is achieved at

the ratio of 1 molecule of O3 to >20 sub-units of PVA. The solution becomes
more acidic following the production of formic acid and the formation of
carboxylic end groups. In addition, ozone appears to directly attack PVA
chain randomly. However, PVA degradation is more efficient under alkaline
conditions rather than under the acidic conditions which indicates that •OH
radicals play a more important role than O3 in the PVA decomposition.
2. Effect of ozone partial pressure:
Increase in the ozone partial pressure increases the extent of

degradation (Beltran et al., 1992, 1993a); the extent of enhancement also
depends on the contaminant in pollutant. Increase in the ozone partial
pressure is usually associated with a substantial increase in the cost of
generation of ozone (Brink et al. 1991; Glaze, 1987). Thus, it is observed that
increase in the rates of degradation should be checked with the increase in
the costs before selection of operating conditions.
3. Effect of temperature:
The effect of temperature is the resultant of the two simultaneous

effects, increase in the rate constant of the reaction and the indirect effect
through the variation of ozone solubility with temperature. Due to an increase
in the temperature, ozone solubility decreases, thereby reducing the amount
of ozone available for the reaction, which may result in decreased
degradation (Beltran et al., 1994). However, Meijers et al. (1995) have
reported that degradation of polymers increased with an increase in the
temperature.
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4. Effect of presence of radial scavengers :
The effect depends on the mechanism of the degradation. If the

destruction is by direct attack of ozone on the chemical bonds, it not much
effect but if it is through the free radicals, presence of radical scavengers such
as HCO3 ions decreases the extent of degradation.
3. Fenton Oxidation Process:
The Fenton process is a reaction between H2O2 and a metal . The most
common metal is iron, which was first observed in 1894 . A mechanism of •OH generation
was revealed until the 1930s after. It treats various industrial pollutants that contain a
range of organic wastes such as phenols , formaldehyde , pesticides ,plastic additives ,
and rubber chemicals .
Fenton’s reagent has been widely used to treat textile wastewater that
contains PVA. Kang.et al. simulated textile wastewater that contained PVA and the dye.
• Mechanism :
The oxidation system based on the Fenton’s reagent (hydrogen peroxide

in the presence of a ferrous salt) has been used for the treatment of both organic
and inorganic substances under laboratory conditions as well as real effluents from
different resources like chemical manufacturers, refinery and fuel terminals, engine
and metal cleaning etc. (Bigda,1996). The process is based on the formation of
reactive oxidizing species, able to efficiently degrade the pollutants of the
wastewater stream.
Fenton’s reagent has been widely used in textile wastewater that
contained PVA . The results showed that the color removal was mainly due to
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Fenton oxidation, whereas the COD removal was mainly caused by Fenton
coagulation. Moreover, the decolorization of the textile wastewater was more
efficient than the COD removal using the Fenton process. The reactions are as
follows ;
H2O2 + Fe2+ → Fe3+ + HO− + HO• (1)
H2O2 + Fe3+ → Fe-OOH2+ + H+ (2)
Fe-OOH2+ → Fe2+ + HO2• (3)
HO2• + H2O2 → O2 + H2O + •OH (4)
RH + •OH → H2O + R• (5)
R• + Fe3+ → R + Fe2+ (6)
R + H2O → ROH + H+ (7)
Commonly, the degradation of PVA is first-order kinetics. In addition, PVA

competed for •OH, which reduces PVA removal efficiency. PVA can be degraded to small
molecules such as alcohols, aldehydes, ketones, and acids with small molecular weight in
Fenton system . Furthermore, O2 aeration can accelerate the oxidation reaction in the
Fenton system by converting HCOOH to HCOO• or •COOH/•COO− .
Recently, increasingly more Fenton-like systems, such as H2O2/Fe(0) and a

photocatalytic-Fenton system have been studied and used to remove PVA.
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• Reactors used for Degradation of PVA using Fenton Oxidation

Process .
A batch Fenton reactor essentially consists of a non- pressurized stirred
reactor with metering pumps for the addition of acid, base, a ferrous sulfate catalyst
solution and industrial strength (35–50%) hydrogen peroxide. It is recommended
that the reactor vessel be coated with an acid-resistant material, because the Fenton
reagent is very aggressive and corrosion can be a serious problem. pH of the
solution must be adjusted for maintaining the stability of catalyst .
A schematic representation of the Fenton oxidation treatment has

been shown in figure 7
Figure 7 : Treatment flowsheet for Fenton oxidation (P .R . Gogate (2004)
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• Effect of operating parameter on degradation of PVA
1. Effect of PH on degradation of PVA :
PH of the system has been observed to significantly affect the

degradation of pollutants. The optimal pH for •OH formation is 3 – 5(Venkatadri
and Peters, 1993; Tang Huang, 1996; Kwon et al., 1999; Benitez et al., 2001a)
and hence is recommended as the operating pH. At lower pH (pH-2.5), the actual
formation of ( Fe (II) ( H2 O2 )) occurs, which reacts more slowly with hydrogen
peroxide and, therefore, produces less amount of reactive hydroxyl radicals those
thereby reducing the degradation efficiency (Gallard et al., 1998).
2. Effect of Amount of Fe ions :
Usually the rate of degradation increases with an increase in the

concentration of Ferrous ions (Lin and Lo, 1997; Kwon et al., 1999; Benitez et
al., 2001a) so there should be optimum loading of ions
3. Effect of Concentration of hydrogen peroxide :
Concentration of hydrogen peroxide plays a more crucial role in deciding

the overall efficiency of the degradation process. Usually, it has been observed
that the percentage degradation of the pollutant increases with an increase in the
dosage of hydrogen peroxide (Lin and Peng, 1995; Lin and Lo, 1997; Kwon et
al., 1999.
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4. Effect of Operating temperature:
Not many studies are available for the effect of temperature on the
degradation rates and ambient conditions can safely be used with good efficiency.
In fact, Lin and Lo (1997) have reported an optimum temperature of 300C
whereas Rivas et al. (2001) reported that the degradation efficiency is unaffected
even when the temperature is increased from 10 to 40 8C.But for degradation of
PVA the temperature should kept at 300C .
4. Ultrasound Cavitation Process
Cavitation is the phenomena of the formation, growth and subsequent

collapse of microbubbles or cavities occurring in extremely small interval of time
(milliseconds), releasing large magnitudes of energy (Lorimer and Mason, 1987;
Mason and Lorimer, 1988; Suslick, 1990; Shah et al., 1999) . Ultrasound (US)
created in a liquid is reflected at standing waves, the interface of gas/liquid or
fluctuating areas where the sound nodes and antinodes generate. In the antinodes,
the pressure phases change with the frequency.
• Mechanism
The generation of growth and subsequent collapse of cavities formed in
liquid medium ,
H2O H + OH (8)
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Figure No. 8 : Ultrasound Cavitation Mechanism (Gronroos A.et.al,2001)
The •OH radicals were play an important role in water-soluble polymer

degradation . In addition, the scission of polymer chains preferentially occurs near
the middle of the chains. In the PVA solution, the shear forces that are generated
when cavitation bubbles collapse break the chemical bonds in the polymer. There
is a cavitation threshold for the input power. When it is exceeded, the degradation
of PVA occurs.
• Reactors used for degradation of PVA :
For Acoustic Cavitation

The sonochemical reactors are mostly used for acoustic cavitation
which is earlier reported by (Pandit and Moholkar, 1996; Shah et al. 1999;
Thompson and Doraiswamy,1999; Keil and Swamy, 1999; Gogate et al.,2001a,
2002b).
Fig. 8 gives the schematic representation of the commonly used
equipments based on acoustic cavitation.
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Typically, these equipment with higher dissipation area give larger energy
efficiency at similar levels of the supplied input energy (more amount of energy of
the total supplied electrical energy is converted for positive effects (Gogate et al.,
2001a, 2002b)). Also, the use of equipment based on multiple frequencies multiple
transducers (device used for converting supplied electrical energy into sound
energy and generate ultrasound with frequency in the range of 15 kHz–10 MHz)
has been reported to be more beneficial as compared to the equipments based on a
single frequency (Hua et al., 1995a; Thoma et al., 1997; Sivakumar et al., 2002;
Gogate et al., 2001a, 2002b).
Ultrasonic horns vibrating in radial directions, which also gives additional

advantage of better energy dissipation due to larger irradiating area (Dahlem et al.,
1998, 1999), is another new development with promising future for medium to
large-scale applications, but more work is required in terms of testing these
equipments for operation at high frequency and high power dissipation.
A schematic representation of equipments used for Acoustic Cavitation as
as shown below ,
Figure 9 : Schematic representation of the equipments based on acoustic

cavitation.(Gogate,2004,551-550)
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At low contribution of physical effects , the shear force formed after

cavitation collapse controls the breakage of PVA chains.
• Effect of operating parameters on degradation of PVA
1. Effect of sonication time on intrinsic viscosity :
It has been seen that as the sonication time increased there was reduction
in intrinsic viscosity of polymer solution permanently . After a certain point of
there was no reduction viscosity even through the polymer solution was further
subjected to ultrasonic energy , This point is known as limiting intrinsic of the
viscosity . Below the limiting intrinsic viscosity the PVA polymer chain has
becomes so short that it follows the ultrasonic vibrations flexibly. Hence there
is no further cleavage at the center of molecule, as reported by Mohod(2011).
The viscosity increases with the PVA concentration, which decreases
the velocity gradients of molecules around the collapsing bubbles. When the
PVA concentration increases, the cavitation point gradually become saturated,
decreases the PVA removal efficiency.
2. Effect of concentration on PVA polymer solution :
The extent of viscosity reduction decreases with increase in concentration

,this were earlier reported with (Bhatnagar.et.al.1994) that the extent of
degradation is higher for lower polymer concentration. As the concentration of
the PVA increases, there is increase in viscosity of the solution. Due to increase
in viscosity of the PVA solution the intensity of energy released during
cavitation becomes less .It has been shown that independent bubble dynamic
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that as viscosity of PVA solution increases, there is decrease in collapse

pressure generated due to cavitation.
3. Effect of depth of horn :
The effect of depth of horn on the viscosity reduction for solution of

PVA ,It has been observed that, during the initial stages of operation, the extent
of viscosity reduction is higher for the operation with low depth as (1-2 cm ).
However, the final extent of reduction in intrinsic viscosity is marginally higher
at a depth .It also depend on the PVA solution .The extent of viscosity
reduction was maximum for the depth of immersion over the entire range of
ultrasonic treatment. (Ashish mohod ,2011)
4. Effect of temperature :
Prince.et.al,(1994) suggests that the operating temperature increases for

ultrasound treatment the cavitational activity is lowered. This causes a decrease
in extent of degradation .
At low-temperature PVA solution has advantage over the ultrasonic
induced degradation of PVA. At high temperature would increase the vapor
pressure, which makes the vapor easily enter the cavitation bubbles and reduces
the cavitation intensity.
5. Effect of ultrasonic frequency :
When the PVA concentration (1 %) is low and the input power is more
the cavitation threshold ,the most extensive PVA decomposition occurs at very
lowest frequency (approx. 23KHz). On the other hand, viscosity reduction is
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36
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the very negligible a higher frequency operation (204 kHz and 694 kHz). This
result was possibly attributed to the low contribution of physical effects , in
which the has shear force formed after cavitation collapse controls the breakage
of PVA break chains.
5. Photo – Fenton Process (Hybrid AOPs)
The Photo-Fenton process is an important in the Fenton system hybrid

AOP. Both homogeneous and heterogeneous photo-Fenton processes were studied and
used for PVA degradation. Bossmann.et.al.(2001) found that the homogeneous photo-
Fenton process was advantageous for PVA degradation in comparison to the heterogeneous
photo-Fenton process, which consists of ferric ions-exchanged zeolite. In general,
homogeneous photo-Fenton processes follow reactions given below ,
• Mechanism :
Bossmann.et.al, (2001) during the homogeneous photo-Fenton process,

up to 90 % of the DOC is removed within 0.5 h at a ratio of 1 mole ferrous ions
per 20 moles of PVA subunits (C2H4O) and a stoichiometric H2O2/PVA-unit ratio
also the carrier gas, H2O2 and Fe2+ dosage can affect the photo-Fenton oxidation
process. However, the DOC removal efficiency is not directly linked with the
polymerization degree of PVA. The reactions are as follows,
H2O2 + Fe2+ → Fe3+ + HO− + HO• (9)
Fe3+ + H2O + hv → Fe2+ + H+ + HO• (10)
H2O2 + hv → 2•OH (11)
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Super macromolecules (MW 1-5×106 g/mol) which were formed by iron salt and PVA
during the oxidation process by the Fenton reagent and CO2 is directly released.
• Reactors used for degradation of PVA using Photo – Fenton
1- Photochemical reactor.
2- PVA solution influent tank.
3- Low flow PVA solution peristaltic pump.
4- Hydrogen peroxide peristaltic pump.
5- Hydrogen peroxide acrylic Jar.
6- Treated PVA solution effluent tank.
Figure 9 : PVA degradation photochemical reactor .(Hamad .et.al ,2016)

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• Effect of Operating parameters on Photo-Fenton Oxidation :
i) Effect of PH :
The PH of the system is very important factor in degradation of pollutants .

The optimal PH value for Photo Fenton degradation is usually 4-5 . At low PH
value the formation of ions occurs which leads to less degradation .
ii) Effect of Concentration :
At high PVA concentrations, in units of g/L, the formation of solid particles

during the photo-Fenton reactions, implies low iron and peroxide levels in most
cases, is an advantage for the remediation of PVA containing wastewater.
iii) Effect of Temperature :
Not many studies are available for the effect of temperature on the PVA
degradation rates and ambient conditions can safely be used with good effect
efficiency. Earlier it is reported , at optimum temperature up to 400C the PVA
degradation rate is very efficient .
iv) Amount of Fe ions and hydrogen peroxide :
Usually degradation increases with increase in concentration of

ferrous ions . H2O2 and Fe2+ dosage can affect the photo-Fenton oxidation
process. However, the DOC removal efficiency is not directly linked with
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the polymerization degree of PVA. Hence the amount of loading should be

minimum.
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• Case Study for Photochemical Enhanced Fenton Reaction

Process.
Nowadays various methods of photochemical degradation referred to as

advanced oxidation processes (AOP) have been proposed for the treatment of ground,
surface and waste waters containing toxic or non-biodegradable organic compounds . AOP
are most often initiated by hydroxyl radicals which may be generated by various methods
(such as UV photolysis of hydrogen peroxide, TiO2 photocatalysis, vacuum ultraviolet
(VUV) photolysis of water). Among AOP, the Fenton reaction and especially the
photochemically enhanced Fenton reaction are considered most efficient for the
remediation of highly contaminated waste waters. The Fenton reagent (a mixture of
hydrogen peroxide and iron(II)salt) is a powerful oxidant and a wide range of successful
studies and applications has been reported by Rigg T .et.al (1975), including the treatment
of industrial waste water on a large pilot scale (500 liters) by the photochemically enhanced
Fenton reaction .
The mechanism reaction for degradation of polyvinyl alcohol by photochemically
enhanced Fenton reaction has studied by (Stefan Bossmann.et.al (2001)).They observed
very fast and effective degradation in batch reactor by medium pressure mercury arc in a
Pyrex envelope and 80% of H2O2 used for total oxidation of PVA and concentration ratio
as low as 1 mol of Iron sulphate per 20 moles of PVA sub units (C2H4O) . PVA polymers of
three different molecular weights( 15,000, 49,000 and 100,000 g mol—1) were found
identical patterns for degradation . Low molecular weight polymers were not found
during PVA degradation such as formic acid ,oxalic acid or formaldehyde and during the
PVA degradation reactions CO2 was released directly .
Stefan Bossmann.et.al (2001) has reported that the mechanisms involved in the
photochemically enhanced Fenton Reaction is formation of hydroxyl radicals as primary
oxidizing species .However Earlier Bossmann (2001) also reported that the formation of
the hydroxyl radical as a reactive intermediate during the photochemically enhanced
Fenton degradation of 2,4-xylidine.As a synthesis of the literature and result Bossmann
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(2001) reported certain sequence of reactions leading to the oxidation of organic substrate
are as follows ,
(1) At PH values ranging from 2.5 to 4.5 and at low iron concentrations
[Fe(OH)(H2O)5]+ is the species prevailing in the system before H2O2 and all the
organic substrates are added . Upon H2O2 addition coordinated H2O is exchanged
against H2O2 (equation 1)
[Fe(OH) (H2O)5]+ + H2O2 → [Fe(OH) (H2O2) (H2O)4]+ + H2O (1)
(2) An inner sphere two electron transfer reaction within the iron - H2O2 complex leads to
the formation of ferrous ion [Fe(OH)3(H2O)4]+ from equation (2). This species is most
likely main oxidizing intermediate during the Fenton oxidation of organic compounds
in aqueous solution.
[Fe(OH) (H2O2) (H2O)4]+ → [Fe(OH)3 (H2O)4]+ (2)
The recycling of iron (II) involves the reduction of Fe3+aq by Fe3+aq by H2O2 in
following steps ,
i) Formation of hydrated iron and H2O2 complex .

ii) Transfer of electron reaction within the complex reaction .
[Fe(OH)(HO2) (H2O)4]+ + H2O → [Fe(OH) (H2O)5]+ + HO2• (3)
Similarly Lechang Lei.et.al (1998) has also reported PVA degradation by

photochemically enhanced Fenton reaction under standard conditions ,higher molecular
weight 49,000 g mol with different iron (II) concentrations. Giratto.et.al(2006) reported for
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higher molecular weight between 30,000 to 36,300 g mol under optimum condition gives
almost 90% PVA degradation .
Experimental section :
Stefan Bossmann.et.al (2001) used FeSO4 3 7 H2O, (Fe)2(SO4)3 3 11 H2O,

H2O2 (30 % w/w in H2O), H2SO4, Na3PO4, H3PO4, KMnO4, Na2SO3, Na2SO4, Na2HPO4,
TiO(SO4), oxalic acid, acetaldehyde, ethanol, formaldehyde (20 % w/w in H2O), 1,10-
phenanthroline, acetonitrile and acetic acid chemicals and hydrogen peroxide was analyzed
by KMnO4-titration. PVA of molecular weight (MW = 15,000, 49,000 and 10,0000) was
obtained from Sigma. Four additional PVA standards were also used (MW = 1,000, 2100,
5100 and 2,000,000). The PVA stock solutions were diluted by a factor of ten (to 8·325 x
10—3 M of polymer sub-units (C2H4O) corresponding to 200 mg C L—1) in the
photochemical equipment for a total volume of 0·50 L. Immediately before experiments
were started, iron(II) was added (standard concentration: 4·16 3 x 10—4 M corresponding
to a molar ratio of iron(II) to (C2H4O)-units of 1/20). The pH was adjusted to the initial
value of 4·0 using diluted H2SO4 .The reaction mixture was circulated for 15 min. A
defined amount (1·665 3 × 10—2 – 6·66 3 × 10—2 M) of H2O2 was added at once. All
experiments were carried out during 120 min. The temperature was maintained at 40 ±
2°C. Samples were taken at various irradiation time intervals and analyzed.
Best results are obtained when initial pH values ranges between 2 – 3 were
used for Fenton process but for PVA degradation earlier it was observed that no significant
degradation of reaction rates of PVA was between pH = 2.0 and 4.0 . Hence all
experiments were reported with initial pH value 4.0. Similar results were reported by Z.Sun
(2001) and Giratto.et.al(2006) .
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Result and Discussion :
i) Effect of various parameters on efficiency of PVA by photochemically

enhanced fenton reactions molecular weight of PVA :
The efficiency of PVA has been observed for three different molecular
weight (15000, 49,000 , 10,0000 ) and same concentration of PVA has been
used in all experiment reported by Stefan Bossmann (2001) .Similarly Lei
Ch .et.al(1998) reported for same result .
ii) Hydrogen Peroxide Concentration :

Based on an initial concentration of 8·33 3 10—3 M of (C2H4O) units,
the stoichiometric amount of H2O2 required for the total oxidation of PVA
[H2O2] is 4·16 3 10—2 M , which is a maximum amount required for
mineralization process according to Bossmann(2001) .
(4)
The concentration of H2O2 was varied between 40 and 200% of [H2O2]

while maintaining all other concentrations.
iii) Initial Iron (II) concentration :

Bossmann and Oliveros (2001) reported the initial PVA degradation
rate increases as molar ratio of Iron (II) to (C2H4O)- units increases. This
result correlate with those obtained from the degradation of low molecular
weight compounds, such as substituted benzene, phenols and 2,4-
dimethylaniline.
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iv) Temperature :
The photochemically enhanced fenton process consists of complex
series of thermal reactions therefore temperature were dependent , The
observed temperature range mostly in between 20 °C to 60 °C.
Conclusion :
The basic steps of the reaction mechanism of the PVA degradation, which has
great importance in many industrial applications. In the early stages the Photo Fenton for
PVA degradation , drastic changes were observed .These changes support the formation
of molecules with high molecular weight ( Super macro moleules) formed from oxidized
PVA chains and Iron (II) .
The fast and efficient degradation of PVA polymers of three different
molecular weights (15,000, 49,000 and 100,000) were found to follow identical, i.e.
molecular weight independent, degradation patterns. The results observed that the
degradation rates of PVA were affected by the initial concentrations, pH and addition of
H2O2 . It was more effective for PVA to be degraded under acidic or alkaline condition.
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• Need of Hybrid Technology
The AOPs used for degradation has some barriers as they does not
degrade completely. For example, in cavitation it has very high operating cost
and low efficiency, in photocatalysis recovery from mixture is not easy , in
Fenton oxidation chances of ion sludges is more . To overcome this problem
hybrid technology is develop nowadays.
Hybrid technology is require as ,

i) It has high effectively degrade
ii) It gives complete mineralization within one hour
iii) Sludge formation does not formed
iv) Potential option for biodegradability enhancement .
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CONCLUSION AND FUTURE SCOPE
Hydroxyl radicals are the main species for PVA degradation in advanced
oxidation processes .The efficiency of the process depends on the generation of hydroxyl
ions . PVA can be oxidized to small molecules or mineralized by hydroxyl radicals. It can
be expected that PVA decomposition follows pseudo first-order kinetics in the presence
of sufficient energy or oxidants. Due to intermediates and unoxidized PVA, the removal
rates are relatively slower than those of PVA. In addition, PVA structural features relate
to the propensity to degradation. However there is little research that focuses on the
relationship between PVA structural features and the propensity to degradation using
AOPs and further biodegradation.
There is an urgent need for the study and development of new methods of
wastewater treatment that use less energy, cost less and minimize chemical use and
environmental effects . AOPs with excellent performance in treating hundreds of
pollutants appear to be robust. Moreover, energy-based methods of AOPs are
environmentally friendly; they do not require the addition of chemicals and avoid
secondary pollution. However, some methods, such as ionizing radiation and ultrasound
oxidation, remain in their infancy in wastewater treatment. The intensive capital and low
energy conversion of the needed machines are common problems for the practical
application of these new methods. Fortunately, the pretreatment of PVA wastewater by
AOPs effectively enhances both biodegradability and coagulation.
For most reactive and efficient degradation of Polyvinyl Alcohol higher

molecular weight polymers are used . Higher molecular weight polymers gives almost
90% of degradation .
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FUTURE SCOPE
i) Treatment of real wastewater systems containing mixtures of pollutants are

more efficient .
ii) Development of novel catalytic materials. (Modification of the shape of nano
sphere TiO2 to form nanorods, nanotubes, nanofibers).
iii) Development of photo catalysts using solar irradiations as the energy source
that can reduce treatment cost.
iv) Use of solid iron containing catalysts in combination with oxygen instead of
H2O2 .
v) Optimization of operating parameters and scale up of the sonochemical
processes to treat the real wastewater systems.
vi) Use of chelating agents to increase the efficiency of operation near neutral pH
range.
vii) Use of sulfate radical based operation.
________________________________________________________________________
48
____________________________________________________________________________________
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________________________________________________________________________
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DISSERTATION REPORT

Is submitted in partial fulfillment of the requirements for the award of degree of

SCHOOL OF ENGINEERING AND APPLIED SCIENCES

Dissertation Approval For M.Tech

Project Guide College Stamp

Internal Examiner External Examiner

I take this opportunity to express my deep gratitude and regards to my guide

I am obliged to staff members of School of Engineering and Applied Sciences,

Ms. Priyanka Waghulade

Table 1 Physical and chemical properties of

Advanced oxidation processes (AOPs) constitute a promising technology to

Keywords : PVA, cavitation, Ozonisation , Photo Fenton oxidation , Fenton oxidation,

The uncontrolled release of polyvinyl alcohol (PVA) and structurally related

Whereas some adapted bacteria showed promising results in biological model

The objective of this study is to minimize degradation of contaminants in industry

2. Treatment of real wastewater system containing mixture of pollutants.

3. To remove organic matters, traceable emerging contaminants in addition to certain

4. Optimization of operating parameter.

Polyvinyl alcohol is a water-soluble polymer with high thermal stability,

The increasing turnover and consumption of water-soluble synthetic polymers

The wastewater produced from the manufacturing of chemical compounds must

Polyvinyl alcohol (figure 1) is a water-soluble polymer with high thermal

Department of Chemical Engineering , School of Engineering and Applied Sciences

Due to its poor biodegradability, it is difficult for conventional biological

Table 1. Physical and chemical properties of polyvinyl alcohol is as follows,

Molecular weight 100,000 g/mole

Molecular formula (𝐶𝐶2𝐻𝐻4𝑂𝑂)𝑛𝑛

Boiling point 228°𝐶𝐶

Melting point 150 − 190℃

Density at 25 ℃ 1.19-1.31 g/ml

Viscosity at 25 ℃ 0.9 𝑚𝑚𝑚𝑚𝑚𝑚. 𝑠𝑠

• Advanced Oxidation Processes:

Table 2 : Basic classification of advanced oxidation processes.

AOPs Single methods Combined methods

Energy-based Photocatalytic oxidation, Sono-

Hybrid method UV/O3, US/O3, UV/H2O2, Wet air oxidation

As shown in Figure 2 chemical-based AOPs (such as ozonation, Fenton

photocatalytic oxidation, electrochemical oxidation, ultrasonic oxidation and ionizing

Generally, •OH acts with high efficiency to destroy pollutants in aqueous

The reaction scheme for PVA mechanism is shown as below ,

Figure 2: The reaction scheme of PVA degradation mechanism by AOPs .( Sun.et.al ,

Open literature shows that many studies have been conducted to

Water-soluble polymers such as Polyphthalamide (PPA), polyvinyl

In hydrocarbon industries, Harimurti et al. (2014) investigated a UV/H2O2

processes are promising techniques in the treatment of toxic organic compounds.

Soluble Polymers in water Applications

Researcher Methodology Research System Reaction Result

Weihua Ozonisation O3 + 50-200 mg/L PVA 10 mg/min PVA was

O3 + 8–15 g/L PVA 90 mg/L O3, Ratio of O3

Yingxu Photocatalytic Photocatalytic oxidation 2 UV lamps PVA could be

Ye Yang Fenton Fenton + 0.5 % PVA PVA The chemical

(MW=15000,49000, Fe2+ / PVA removed

100000) pH 4 , 40℃ within 0.5 hr.

aqueous solution. PVA may

Photo-Fenton+200 mg/L Fe++ / PVA The

Gronroos A Ultrasound The study A Cavitation

 Various Advanced Oxidation processes Available for

1. Photocatalysis Oxidation process:

Photo-catalytic oxidation is evolved from ultraviolet (UV, expressed as

Photocatalysis using titanium dioxide (TiO2) is an efficient advanced

Figure 3. PVA degradation mechanism of the TiO2-based photocatalytic

• Reactors used for degradation of PVA using Photocatalytic

The photocatalytic oxidation process can be carried out by simply using

Figure 4. Schematic representation of equipments based on photocatalytic