CONTENTS

Page
No.
Title page
Approval of supervisor and external examiner
Certificate by the supervisor
Dedication
Acknowledgements
Declaration by the student
List of publications based on the present work 1

List of figures 3
List of tables 9
List of symbols 13
List of abbreviations 14
Abstract and keywords 15
content 17
Chapter 1 Introduction 25

1.1.Advanced oxidation processes 27

1.2.Cavitation 28

1.2.1: Types of Cavitation 29

1.3. Acoustic cavitation 31

1.3.1. Hot-Spot Theory 32

1.3.2. Sonochemical reaction sites 32

1.3.3. Sonochemical Reactors 34

 1.4. Hydrodynamic cavitation 35

1.4.1. Design Aspects 37

1.5. Photocatalytic Oxidation 39

1.6. Chemical oxidation using hydrogen peroxide 42

1.7. Fenton process 42

1.8. Limitations of individual operations 44

1.9.Hybrid treatment strategy 46

1.10. Selection of model pollutants 49

1.10.1. Alachlor 49

1.10.2. 2,4- dinitrophenol (DNP) 50

1.10.3: Diclofenac sodium 51

1.11. Aims and Objectives of the research work 52

Chapter 2 Literature Survey 53

2.1. Sono-Fenton Process 54

2.2. Hydrodynamic cavitation coupled with Fenton

60
oxidation

2.3. Sonophotocatalysis 63

2.4. Combined process of Hydrodynamic cavitation and

67
photocatalysis

2.5. Degradation of Pesticides 67

2.5.1. Degradation of Alachlor 69

 2.6. Degradation of Pharmaceutical components 70

2.6.1. Degradation of diclofenac sodium 74

2.7. Phenolic Waste Degradation 76

2.7.1. Degradation of 2,4-dinitrophenol 78

2.8. Overall findings of the literature review 80

Chapter 3 Materials and Methods 82

3.1. Materials 83

3.2. Experimental setup 83

3.2.1. Sonochemical reactors 83

3.2.2. Hydrodynamic cavitational (HC) reactor 86

3.2.3. Photocatalytic reactors 89

3.2.4. Calorimetric Investigations for Cavitational Reactors 90

3.3. Analytical Procedure 92

3.3.1 Calibration plot for alachlor 93

3.3.2. Calibration plot for diclofenac sodium 95

3.3.3. Calibration plot for 2,4-dinitrophenol 96

3.4.Methodology 98

3.4.1. Experimental Procedure for Sonolysis 98

3.4.1.1. Experimental Procedure for Sonolysis with

99
additives
 3.4.2. Experimental Procedure for degradation of alachlor
99
using Sonophotocatalysis / Photocatalysis

3.4.2.1. Experimental Procedure for Sonophotocatalysis

100
with different additives

3.5. Experimental Procedure for Hydrodynamic Cavitation

101
with different additives

3.5.1. Experimental Procedure for Hydrodynamic Cavitation

102
in combination with Photocatalysis

Chapter 4 Results and Discussion 104

4.1. Energy efficiency studies 105

4.1.1. Calorimetric study for conventional ultrasonic horn

105
(20 kHz)

4.1.2. Calorimetric study for ultrasonic longitudinal horn (25

106
kHz, 1 kW)

4.1.3. Calorimetric study for ultrasonic longitudinal horn (36

108
kHz, 150W)

4.2. Degradation of alachlor 109

4.2.1. Effect of initial pH on degradation of alachlor 109

4.2.2. Effect of addition of hydrogen peroxide 112

4.2.3. Degradation of alachlor using a combination of

118
ultrasound and Fenton process

4.2.4. Degradation of alachlor using a combination of

122
ultrasound and advanced Fenton process (AFP)
4.2.5. Effect of addition of CCl4 125

4.2.6. Degradation of alachlor using sonolysis(US),

129
photolysis (UV) and sonophotolysis (US/UV)

4.2.7. Degradation of alachlor using photocatalysis 131

4.2.8. Degradation of alachlor using sonophotocatalysis. 136

4.2.9. H2O2 assisted sonophotocatalytic degradation of

141
alachlor

4.2.10. Degradation of alachlor in the presence of radical

143
scavengers

4.2.10.1. Sonolytic degradation 143

4.2.10.2. Sonophotocatalytic degradation 146

4.2.11. Scale up study 148

4.2.12. Analysis of alachlor degradation products 150

4.2.12.1. Sonolytic degradation 150

4.2.12.2. Sonophotocatalytic process 151

4.3. Degradation of 2,4-dinitrophenol 153

4.3.1. Effect of operating parameter on degradation of 2, 4 153

dinitrophenol using acoustic cavitation
4.3.1.1 .Effect of initial pH on the degradation of DNP using
153
acoustic cavitation

4.3.1.2. Comparison of different configurations of the 156

sonochemical reactors
4.3.2. Effect of operating parameters on degradation of 2, 4 157
dinitrophenol using Hydrodynamic cavitation
4.3.2.1. Hydraulic Characteristics 157

4.3.2.2. Effect of inlet pressure on the degradation of DNP

158
using Hydrodynamic cavitation

4.3.2.3. Effect of temperature on the degradation of DNP

161
using Hydrodynamic cavitation

4.3.2.4. Effect of operating pH on the degradation of DNP

163
using Hydrodynamic cavitation

4.3.3. Effect of addition of hydrogen peroxide 165

4.3.3.1. Using acoustic cavitation (US/H 2O2 process) 165

4.3.3.2 Using Hydrodynamic cavitation (HC/H 2O2) 169

4.3.4.Effect of addition of CCl4 172

4.3.5. Degradation of DNP using cavitation combined with

174
Fenton process.

4.3.5.1. Using Acoustic cavitation 174

4.3.5.2. Using hydrodynamic cavitation reactor (HC/Fenton

179
process)

4.3.6. Degradation of DNP using cavitation combined with

183
advanced Fenton process.

4.3.6.1. Using acoustic cavitation (US/advanced Fenton

183
process)

4.3.6.2. Using Hydrodynamic cavitation (HC/Advanced

187
fenton process)
4.3.7. Degradation of DNP using combination of cavitation
189
and CuO/H2O2.

4.3.7.1 Using acoustic cavitation (US/CuO/H 2O2) 189

4.3.7.2 Using Hydrodynamic cavitation 191

4.3.8. Degradation of DNP using combined

193
Cavitation/Na2 S2O8/FeSO4 process

4.3.8.1. Ultrasonic longitudinal horn (25 kHz, 1kW) 194

4.3.8.2. Conventional ultrasonic horn (20 kHz, 100W) 197

4.3.8.2. Ultrasonic longitudinal horn (36 kHz, 150 W) 197

4.3.8.3. Hydrodynamic cavitation process 198

4.3.9. Analysis of the intermediates formed during removal

203
of 2,4-dinitrophenol

4.3.9.2. Analysis of intermediates formed during the

204
degradation process using hydrodynamic cavitation

4.3.10 .Conclusions 205

4.4. Degradation of diclofenac sodium 212

4.4.1. Effect of operating parameter on degradation of 212

diclofenac sodium using hydrodynamic cavitation

4.4.1.1. Effect of hydrodynamic parameters. 213

4.4.1.2.Effect of inlet pressure 215

4.4.1.2.1.Effect of pH 217

4.4.2.Comparison of HC, UV and HC/UV in absence of

219
photocatalyst
 4.4.3.Effect of TiO2 loading on the extent of degradation 221

4.4.4. Effect of addition of H2O2 225

4.4.5. Degradation of diclofenac sodium in the presence of 228

radical scavengers
4.4.6. Identification of intermediates 230

Chapter 5 Conclusions 231

5.1. Degradation of alachlor 232

5.2. Degradation of 2,4-dinitrophenol 234

5.3. Degradation of Diclofenac Sodium 236

5.4.Overall coclusions 238

Chapter 6 Scope for Future Work 239

Chapter 7 References 242