x

TABLE OF CONTENTS

CHAPTER NO. TITLE PAGE NO.

ABSTRACT v
LIST OF TABLES xvi
LIST OF FIGURES xx
LIST OF SYMBOLS AND ABBREVIATIONS xv

1 INTRODUCTION 1
1.1 WORLD WATER AVAILABILITY 1
1.2 WATER POLLUTION SOURCES 2
1.2.1 Major Water Consuming Industries 3
1.2.2 Status of Textile Industries in India 4
1.3 TEXTILE INDUSTRY OPERATIONS 5
1.4 EFFECTS OF TEXTILE EFFLUENT
ON ENVIRONMENT 11
1.5 DISCHARGE STANDARDS FOR TEXTILE
EFFLUENT IN INDIA 12
1.6 CONVENTIONAL WASTEWATER
TREATMENT 14
1.6.1 Preliminary Treatment 16
1.6.2 Primary Treatment 16
1.6.3 Chemical Treatment 16
1.6.3.1 Coagulation and flocculation 17
1.6.3.2 Advance oxidation process 17
1.6.4 Biological Treatment 21
1.6.4.1 Aerobic process 21
1.6.4.2 Anaerobic process 22
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CHAPTER NO. TITLE PAGE NO.

1.6.5 Tertiary Treatment 22

1.6.5.1 Adsorption 23
1.6.5.2 Ion exchange 24
1.6.5.3 Membrane operations 24
1.6.5.4 Multiple effect evaporator 25
1.6.5.5 Zero liquid discharge 26
1.7 SCOPE OF THE STUDY 26
1.8 OBJECTIVES OF THE PRESENT STUDY 27

2 LITERATURE REVIEW 29
2.1 ADSORPTION 29
2.1.1 Preparation of Activated Carbon using
Chemical Activation Method 30
2.1.2 Preparation of Activated Carbon using
Physical Activation Method 34
2.1.3 Preparation of Activated Carbon using
Physiochemical Activation Method 36
2.2 ELECTROSORPTION STUDIES 38
2.2.1 Monolayer Adsorption 39
2.2.2 Multilayer Adsorption 40
2.3 DESALINATION STUDIES 43
2.3.1 Electrode Materials 45

3 MATERIALS AND METHODS 55

3.1 BIOMASS SELECTION 55
3.1.1 Casuarina Tree Leaves 56
3.1.2 Groundnut Foliage and Groundnut Husk 58
3.1.3 Rice Husk and Rice Straw 60
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CHAPTER NO. TITLE PAGE NO.

3.2 PREPARATION OF ACTIVATED CARBON 63

3.2.1 Chemicals used 63
3.2.2 Activated Carbon Preparation 63
3.3 CHARACTERIZATION OF ACTIVATED
CARBON 65
3.3.1 Percentage of Yield 65
3.3.2 Methylene Blue Number 65
3.3.3 Iodine Number 66
3.3.4 pHPZC 67
3.3.5 Particle Size Determination 68
3.3.6 Bulk Density 68
3.3.7 Thermogravimetric Analysis (TGA) 69
3.3.8 Ultimate Analysis 69
3.3.9 Scanning Electron Microscopy (SEM) 69
3.3.10 Pore Size Distribution 69
3.3.11 Fourier Transform Infrared Spectroscopy
(FTIR) 70
3.3.12 Conductivity 70
3.4 PREPARATION OF ADSORBATES 70
3.5 BATCH ADSORPTION STUDIES 72
3.6 BATCH DESORPTION STUDY 73
3.7 PREPARATION OF ACTIVATED CARBON
ELECTRODE FOR ELECTROSORPTION
AND DESALINATION EXPERIMENTS 73
3.7.1 Fabrication of Electrodes 74
3.8 CHARACTERIZATION OF FABRICATED
ACTIVATED CARBON ELECTRODES 75
3.8.1 Electrochemical Characterization 75
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CHAPTER NO. TITLE PAGE NO.

3.8.1.1 Cyclic voltammetry 77

3.8.1.2 Galvanostatic charge-discharge
studies 77
3.8.1.3 Electrochemical impedance
spectroscopy 77
3.8.2 X-Ray Diffraction (XRD) Measurement 78
3.8.3 Scanning Electron Microscopy (SEM) 78
3.9 ELECTROSORPTION/DESORPTION OF
CATIONIC AND ANIONIC DYES 78
3.10 DESALINATION USING CAPACITIVE
DEIONIZATION CELL 79

4 RESULTS AND DISCUSSION 81

4.1 CHARACTERIZATION OF PREPARED
ACTIVATED CARBONS 82
4.1.1 Percentage Yield 82
4.1.2 Thermogravimetric Analysis (TGA) 83
4.1.3 Ultimate Analysis of Activated Carbon
Precursors 84
4.1.4 Point of Zero Charge 85
4.1.5 Conductivity 85
4.1.6 Methylene Blue Number 86
4.1.7 Iodine Number 86
4.1.8 Bulk Density 86
4.1.9 Particle Size Analysis 87
4.1.10 Surface Area and Pore Volume 87
4.1.11 Scanning Electron Microscopy (SEM) 90
4.1.12 Fourier Transform Infrared Spectroscopy
(FTIR) 93
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CHAPTER NO. TITLE PAGE NO.

4.2 BATCH ADSORPTION STUDIES 101

4.2.1 Effect of Time 101
4.2.2 Effect of Adsorbate Concentration 105
4.2.3 Effect of Solution pH 106
4.2.4 Effect of Adsorbent Dosage 108
4.2.5 Effect of Temperature and Thermodynamics 110
4.2.6 Adsorption Isotherm 115
4.2.6.1 The Langmuir model 116
4.2.6.2 The Freundlich model 117
4.2.6.3 The Dubinin-Radushkevich model 119
4.2.6.4 The Temkin model 122
4.2.7 Adsorption Kinetics 128
4.2.7.1 Lagergren’s pseudo first order
kinetic model 128
4.2.7.2 Mckay’s pseudo-second-order
kinetic model 129
4.2.7.3 Elovich model 131
4.2.7.4 Intraparticle diffusion model 138
4.2.7.5 Boyd’s film-diffusion model 139
4.3 BATCH DESORPTION STUDY 142
4.4 CHARACTERIZATION OF ACTIVATED
CARBON ELECTRODES 145
4.4.1 Cyclic Voltammetry 145
4.4.2 Galvanostatic Charge-Discharge
Measurements 147
4.4.3 EIS 148
4.4.4 X-Ray Diffraction 150
4.4.5 Scanning Electron Microscopy 152
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CHAPTER NO. TITLE PAGE NO.

4.5 ELECTROSORPTION STUDIES 153
4.5.1 Electrosorption of MB and DR Dyes
using Modified AC Electrodes 153
4.5.2 Multiple Electrosorption and Desorption
Cycles of MB and DR Dye Removal 155
4.5.3 Electrosorption Capacity of the
Modified Electrodes 155
4.5.4 Electrosorption Isotherm 159
4.5.5 Electrosorption Kinetics 162
4.5.6 Performance Comparison of Conventional
Adsorption and Electrosorption 165
4.6 DESALINATION PERFORMANCE OF
ELECTRODES 167
4.6.1 Effect of NaCl Concentration 167
4.6.2 Multiple Desalination Cycles 170
4.6.3 Electrosorption Isotherm 173
4.6.4 Electrosorption Kinetics 175
4.7 COMPARISON OF PERFORMANCE OF
ELECTRODE 178
4.8 COST ANALYSIS 179
4.9 DISPOSAL OF USED ELECTRODES 182

5 CONCLUSIONS 183
5.1 SUMMARY AND CONCLUSION 183
5.2 FUTURE WORK 192

APPENDIX 1 193
REFERENCES 194

LIST OF PUBLICATIONS 215

 xvi

LIST OF TABLES

TABLE NO. TITLE PAGE NO.

1.1 Water demand for large industries 4

1.2 Types of dyes, respective degree of fixation and
its characteristics on application 9
1.3 Effluent discharge standards for textile industries
in India 13
1.4 Wastewater generation limit for textile industry 13
2.1 List of Various Electrode materials reported In
CDI studies 53
3.1 Summary of selected precursor and its details 63
3.2 Activated carbon precursor and its abbreviation 64
4.1 Ultimate analysis of prepared Activated carbon 85
4.2 Characterization of Prepared Activated carbon 88
4.3 Comparison of surface area of the prepared
adsorbent with the reported low-cost adsorbents 89
4.4 Thermodynamic analysis for MB and DR dyes
removal on ACL 114
4.5 Thermodynamic analysis for MB and DR dyes
removal on AGF 114
4.6 Thermodynamic analysis for MB and DR dyes
removal on AGH 114
4.7 Thermodynamic analysis for MB and DR dyes
removal on ARH 115
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TABLE NO. TITLE PAGE NO.

4.8 Thermodynamic analysis for MB and DR dyes

removal on ARS 115
4.9 Separation factor conditions 117
4.10 Isotherm constants for cationic dye adsorption on
prepared AC 123
4.11 Isotherm constants for anionic dye adsorption on
prepared AC 124
4.12 Comparison of dye adsorption capacity on
adsorbents prepared from agricultural residues
reported in the literature 125
4.13 Comparison of adsorption kinetics models and its
constants for MB and DR dyes adsorption on
ACL 133
4.14 Comparison of adsorption kinetics models and its
constants for MB and DR dyes adsorption on
AGF 134
4.15 Comparison of adsorption kinetics models and its
constants for MB and DR dyes adsorption on
AGH 135
4.16 Comparison of adsorption kinetics models and its
constants for MB and DR dyes adsorption on
ARH 136
4.17 Comparison of adsorption kinetics models and its
constants for MB and DR dyes adsorption on
ARS 137
4.18 Intraparticle diffusion rate parameter and
coefficient for MB and DR dye adsorption on
prepared activated carbon 140
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TABLE NO. TITLE PAGE NO.

4.19 Specific capacitance of fabricated electrodes 145

4.20 Electrosorption capacity of the modified
electrodes 159
4.21 Isotherm constants for MB dye electrosorption 161
4.22 Isotherm constants for DR dye electrosorption 161
4.23 Comparison of adsorption kinetics models and its
constants for electrosorption of MB and DR dyes
on modified ACL electrode 163
4.24 Comparison of adsorption kinetics models and its
constants for electrosorption of MB and DR dyes
on modified AGF electrode 164
4.25 Comparison of adsorption kinetics models and its
constants for electrosorption of MB and DR dyes
on modified AGH electrode 165
4.26 Comparison of MB dye removal efficiency on
prepared adsorbents using adsorption and
electrosorption process 166
4.27 Comparison of DR dye removal efficiency on
prepared adsorbents using adsorption and
electrosorption process 166
4.28 Desalination performance and electrical energy
consumption for NaCl removal 173
4.29 Isotherm constants for desalination of NaCl
using modified carbon electrodes 175
4.30 Comparison of adsorption kinetics models and its
constants for desalination of NaCl on ACL 177
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TABLE NO. TITLE PAGE NO.

4.31 Comparison of adsorption kinetics models and its

constants for desalination of NaCl on AGF 177
4.32 Comparison of adsorption kinetics models and its
constants for desalination of NaCl on AGH 178
4.33 Comparison of desalination performance of
various electrode materials 179
4.34 Cost estimation for preparation of 1 kg of
adsorbent 180
4.35 Cost of adsorbent for removal of 1 g of selected
dyes from aqueous solution 181
 xx

LIST OF FIGURES

FIGURE NO. TITLE PAGE NO.

1.1 Total world water availability 2

1.2 Significant pollutants that emerge during wet
processing of cotton-based textile industry 6
1.3 Schematic diagram of commonly used
processes in textile effluent treatment system 15
2.1 Electrosorption of wastewater 45
3.1 Casuarina tree leaves 57
3.2 Groundnut foliage 59
3.3 Groundnut husk 59
3.4 Rice husk 61
3.5 Rice straw 61
3.6 Structure of Methylene blue 71
3.7 Structure of Direct Red 80 71
3.8 Electrode fabrication method 76
3.9 Electrosorption experimental setup 79
3.10 Desalination experimental setup 80
4.1 Percentage yield of char and activated carbon
of selected precursor’s 83
4.2 Thermogravimetric analysis of selected
precursor’s char 84
4.3 SEM images of prepared adsorbent 91
4.4 FTIR Spectra of CL 95
4.5 FTIR Spectra of GF 96
4.6 FTIR Spectra of GH 97
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FIGURE NO. TITLE PAGE NO.

4.7 FTIR Spectra of RH 98

4.8 FTIR Spectra of RS 99
4.9 Effect of contact time for MB and DR dye
adsorption on ACL 103
4.10 Effect of contact time for MB and DR dye
adsorption on AGF 104
4.11 Effect of contact time for MB and DR dye
adsorption on AGH 104
4.12 Effect of contact time for MB and DR dye
adsorption on ARH 104
4.13 Effect of contact time for MB and DR dye
adsorption on ARS 105
4.14 Comparison of effect of initial dye
concentration for the adsorption of MB and DR
dye on prepared AC’s 106
4.15 Comparison of effect of pH on adsorption of
MB and DR dyes on prepared AC’s 107
4.16 Effect of carbon dosage for the adsorption of
MB and DR dyes on prepared activated carbon 109
4.17 Comparison of temperature effect for MB and
DR dye adsorption on prepared AC’s 111
4.18 Van’t Hoff plot for the MB and DR dye
adsorption on prepared activated carbons 112
4.19 Comparison of Langmuir plots for the
adsorption of MB and DR dyes by prepared
activated carbon 119
4.20 Comparison of Freundlich plots for the
adsorption of MB and DR dyes by prepared
activated carbon 119
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FIGURE NO. TITLE PAGE NO.

4.21 Comparison of Dubinin - Radushkevich plots

for the adsorption of MB and DR dye by
prepared activated carbon 121
4.22 Comparison of Temkin plots for the adsorption
of MB and DR dyes by prepared activated
carbon 122
4.23 Comparison of Pseudo-first-order kinetics for
the adsorption of MB and DR dyes onto
prepared activated carbon 129
4.24 Comparison of Pseudo-second order model for
the adsorption of MB and DR dyes onto
prepared activated carbon 132
4.25 Comparison of Elovich model for the
adsorption of MB and DR dyes onto prepared
activated carbon 132
4.26 Weber–Morris intraparticle model plot for MB
and DR dye adsorption on prepared adsorbents 141
4.27 Boyd’s plot for MB and DR dye adsorption
onto the prepared adsorbents 141
4.28 Desorption studies on MB dye adsorbed spent
adsorbents 143
4.29 Desorption studies on DR dye adsorbed spent
adsorbents 144
4.30 Cyclic voltammograms of modified electrode 146
4.31 Galvanostatic charge-discharge curves of
modified electrodes 148
4.32 Nyquist plots of modified carbon electrodes 149
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FIGURE NO. TITLE PAGE NO.

4.33 XRD profile of modified carbon electrode 151

4.34 SEM image of modified carbon electrode 152
4.35 Electrosorption and desorption profiles of
cationic and anionic dye on modified electrodes 154
4.36 Multiple electrosorption and desorption cycles
of MB dye on ACL 156
4.37 Multiple electrosorption and desorption cycles
of DR dye on ACL 156
4.38 Multiple electrosorption and desorption cycles
of MB dye on AGF 157
4.39 Multiple electrosorption and desorption cycles
of DR dye on AGF 157
4.40 Multiple electrosorption and desorption cycles
of MB dye on AGH 158
4.41 Multiple electrosorption and desorption cycles
of DR dye on AGH 158
4.42 Comparison of Langmuir plot for MB and DR
dye electrosorption on modified electrodes 160
4.43 Comparison of Freundlich plot for MB and DR
dye electrosorption on modified electrodes 160
4.44 Comparison of Pseudo-first-order kinetics for
MB and DR dye electrosorption on modified
electrodes 162
4.45 Comparison of Pseudo-second-order kinetics
for MB and DR dye electrosorption on
modified electrodes 162
4.46 Electrosorption and desorption profiles of 1%
NaCl on modified carbon electrode 168
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FIGURE NO. TITLE PAGE NO.

4.47 Electrosorption and desorption profiles of 2%

NaCl on modified carbon electrode 168
4.48 Electrosorption and desorption profiles of 5%
NaCl on modified carbon electrode 169
4.49 Electrosorption and desorption profiles of 10%
NaCl on modified carbon electrode 169
4.50 Electrosorption and desorption profiles of 25%
NaCl on modified carbon electrode 170
4.51 Multiple electrosorption and desorption cycles
of 2% NaCl solution on modified ACL
electrode 171
4.52 Multiple electrosorption and desorption cycles
of 2% NaCl solution on modified AGF
electrode 171
4.53 Multiple electrosorption and desorption cycles
of 2% NaCl solution on modified AGH
electrode 172
4.54 Comparison of Langmuir plot for desalination
of NaCl on modified electrodes 174
4.55 Comparison of Freundlich plot for desalination
of NaCl on modified electrodes 174
4.56 Comparison of Pseudo-first-order kinetics for
desalination of NaCl on modified electrodes 176
4.57 Comparison of Pseudo-second-order kinetics
for desalination of NaCl on modified electrodes 176
4.58 Comparison of point of zero charge of prepared
adsorbents 193