advanced physicochemical treatment technologies volume 5 handbook of environmental engineering

Advanced Physicochemical Treatment Technologies
Advanced
Physicochemical
Treatment Technologies
Edited by
Lawrence K. Wang,
PhD, PE, DEE
Lenox Institute of Water Technology, Lenox, MA
Krofta Engineering Corporation, Lenox, MA
Zorex Corporation, Newtonville, NY
Yung-Tse Hung, PhD, PE, DEE
Department of Civil and Environmental Engineering
Cleveland State University, Cleveland, OH
Nazih K. Shammas, PhD
Lenox Institute of Water Technology, Lenox, MA
Krofta Engineering Corporation, Lenox, MA
VOLUME 5
HANDBOOK OF ENVIRONMENTAL ENGINEERING
Dedication
The Editors of the Handbook of Environmental Engineering series dedicate this volume
and all subsequent volumes to Thomas L. Lanigan (1938–2006), the founder and president
of Humana Press.
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Preface
v
The past thirty years have seen the emergence of a growing desire world-
wide that positive actions be taken to restore and protect the environment from
the degrading effects of all forms of pollution — air, water, soil, and noise.
Since pollution is a direct or indirect consequence of waste, the seemingly ide-
alistic demand for “zero discharge” can be construed as an unrealistic demand
for zero waste. However, as long as waste continues to exist, we can only at-
tempt to abate the subsequent pollution by converting it to a less noxious form.
Three major questions usually arise when a particular type of pollution has
been identified: (1) How serious is the pollution? (2) Is the technology to abate

it available? and (3) Do the costs of abatement justify the degree of abatement
achieved? This book is one of the volumes of the Handbook of Environmental
Engineering series. The principal intention of this series is to help readers for-
mulate answers to the last two questions above.
The traditional approach of applying tried-and-true solutions to specific
pollution problems has been a major contributing factor to the success of envi-
ronmental engineering, and has accounted in large measure for the establish-
ment of a “methodology of pollution control.” However, the realization of the
ever-increasing complexity and interrelated nature of current environmental
problems renders it imperative that intelligent planning of pollution abatement
systems be undertaken. Prerequisite to such planning is an understanding of
the performance, potential, and limitations of the various methods of pollution
abatement available for environmental scientists and engineers. In this series
of handbooks, we will review at a tutorial level a broad spectrum of engineer-
ing systems (processes, operations, and methods) currently being utilized, or
of potential utility, for pollution abatement. We believe that the unified inter-
disciplinary approach presented in these handbooks is a logical step in the evo-
lution of environmental engineering.
Treatment of the various engineering systems presented will show how an
engineering formulation of the subject flows naturally from the fundamental
principles and theories of chemistry, microbiology, physics, and mathematics.
This emphasis on fundamental science recognizes that engineering practice has
in recent years become more firmly based on scientific principles rather than
on its earlier dependency on empirical accumulation of facts. It is not intended,
though, to neglect empiricism where such data lead quickly to the most eco-
nomic design; certain engineering systems are not readily amenable to funda-
mental scientific analysis, and in these instances we have resorted to less science
in favor of more art and empiricism.
Since an environmental engineer must understand science within the con-
text of application, we first present the development of the scientific basis of a

particular subject, followed by exposition of the pertinent design concepts and
operations, and detailed explanations of their applications to environmental
quality control or remediation. Throughout the series, methods of practical
design and calculation are illustrated by numerical examples. These examples
clearly demonstrate how organized, analytical reasoning leads to the most di-
rect and clear solutions. Wherever possible, pertinent cost data have been pro-
vided.
Our treatment of pollution-abatement engineering is offered in the belief that
the trained engineer should more firmly understand fundamental principles,
be more aware of the similarities and/or differences among many of the engi-
neering systems, and exhibit greater flexibility and originality in the definition
and innovative solution of environmental pollution problems. In short, the en-
vironmental engineer should by conviction and practice be more readily adapt-
able to change and progress.
Coverage of the unusually broad field of environmental engineering has
demanded an expertise that could only be provided through multiple author-
ships. Each author (or group of authors) was permitted to employ, within rea-
sonable limits, the customary personal style in organizing and presenting a
particular subject area; consequently, it has been difficult to treat all subject
material in a homogeneous manner. Moreover, owing to limitations of space,
some of the authors’ favored topics could not be treated in great detail, and
many less important topics had to be merely mentioned or commented on
briefly. All authors have provided an excellent list of references at the end of
each chapter for the benefit of interested readers. As each chapter is meant to
be self-contained, some mild repetition among the various texts was unavoid-
able. In each case, all omissions or repetitions are the responsibility of the edi-
tors and not the individual authors. With the current trend toward metrication,
the question of using a consistent system of units has been a problem. Wher-
ever possible, the authors have used the British system (fps) along with the
metric equivalent (mks, cgs, or SIU) or vice versa. The editors sincerely hope

that this duplicity of units’ usage will prove to be useful rather than being dis-
ruptive to the readers.
The goals of the Handbook of Environmental Engineering series are: (1) to
cover entire environmental fields, including air and noise pollution control,
solid waste processing and resource recovery, physicochemical treatment pro-
cesses, biological treatment processes, biosolids management, water resources,
natural control processes, radioactive waste disposal and thermal pollution
control; and (2) to employ a multimedia approach to environmental pollution
control since air, water, soil and energy are all interrelated.
As can be seen from the above handbook coverage, the organization of the
handbook series has been based on the three basic forms in which pollutants
and waste are manifested: gas, solid, and liquid. In addition, noise pollution
control is included in the handbook series.
This particular book Volume 5 Advanced Physicochemical Treatment Technolo-
gies is a sister book to Volume 3 Physicochemical Treatment Processes and Vol-
ume 4 Advanced Physicochemical Treatment Processes. Volumes 3 and 4 have
already included the subjects of screening, comminution, equalization, neu-
vi Preface
tralization, mixing, coagulation, flocculation, chemical precipitation, recarbon-
ation, softening, oxidation, halogenation, chlorination, disinfection, ozonation,
electrolysis, sedimentation, dissolved air flotation, filtration, polymeric adsorp-
tion, granular activated carbon adsorption, membrane processes, sludge treat-
ment processes, potable water aeration, air stripping, dispersed air flotation,
powdered activated carbon adsorption, diatomaceous earth precoat filtration,
microscreening, membrane filtration, ion exchange, fluoridation, defluoridation,
ultraviolet radiation disinfection, chloramination, dechlorination, advanced oxi-
dation processes, chemical reduction/oxidation, oil water separation, evapora-
tion and solvent extraction. This book, Volume 5, includes the subjects of
pressurized ozonation, electrochemical processes, irradiation, nonthermal
plasma, thermal distillation, electrodialysis, reverse osmosis, biosorption, emerg-

ing adsorption, emerging ion exchange, emerging flotation, fine pore aeration,
endocrine disruptors, small filtration systems, chemical feeding systems, wet air
oxidation, and lime calcination. All three books have been designed to serve as
comprehensive physicochemical treatment textbooks as well as wide-ranging
reference books. We hope and expect that the books will prove of equal high
value to advanced undergraduate and graduate students, to designers of water
and wastewater treatment systems, and to scientists and researchers. The editors
welcome comments from readers in all of these categories.
The editors are pleased to acknowledge the encouragement and support re-
ceived from their colleagues and the publisher during the conceptual stages of
this endeavor. We wish to thank the contributing authors for their time and
effort, and for having patiently borne our reviews and numerous queries and
comments. We are very grateful to our respective families for their patience
and understanding during some rather trying times.
Lawrence K. Wang, Lenox, MA
Yung-Tse Hung, Cleveland, OH
Nazih K. Shammas, Lenox, MA
Preface vii
ix
Contents
Preface v
Contributors xvii
1 Pressurized Ozonation
Lawrence K. Wang and Nazih K. Shammas 1
1. Introduction 1
1.1. Oxyozosynthesis Sludge Management System 2
1.2. Oxyozosynthesis Wastewater Reclamation System 5
2. Description of Processes 7
2.1. Ozonation and Oxygenation Process 7
2.2. Flotation Process 9

2.3. Filter Belt Press 13
2.4. Performance of Oxyozosynthesis Sludge Management System 16
2.5. Performance of Oxyozosynthesis Wastewater Reclamation System 18
3. Formation and Generation of Ozone 18
3.1. Formation of Ozone 18
3.2. Generation of Ozone 19
4. Requirements for Ozonation Equipment 22
4.1. Feed Gas Equipment 23
4.2. Ozone Generators 24
4.3. Ozone Contactors 24
5. Properties of Ozone 26
6. Disinfection by Ozone 31
7. Oxidation by Ozone 35
7.1. Ozone Reaction with Inorganics 35
7.2. Ozone Reaction with Organic Material 38
8. Oxygenation and Ozonation Systems 43
8.1. Oxygenation Systems 43
8.2. Ozonation Systems 46
8.3. Removal of Pollutants from Waste by Ozonation 48
Nomenclature 50
Acknowledgments 50
References 50
2 Electrochemical Wastewater Treatment Processes
Guohua Chen and Yung-Tse Hung 57
1. Introduction 57
2. Electrochemical Reactors for Metal Recovery 58
2.1. Typical Reactors Applied 58
2.2. Electrode Materials 64
2.3. Application Areas 64
3. Electrocoagulation 64

3.1. Factors Affecting Electrocoagulation 66
3.2. Electrode Materials 69
3.3. Typical Design 69
3.4. Effluents Treated by EC 70
4. Electroflotation 70
4.1. Factors Affecting EF 71
4.2. Comparison with Other Flotation Technologies 76
4.3. Oxygen Evolution Electrodes 76
4 4 Typical Designs 77
4.5. Wastewaters Treated by EF 80
5. Electro-oxidation 80
5.1. Indirect EO Processes 82
5.2. Direct Anodic Oxidation 82
5.3. Typical Designs 93
6. Summary 93
Nomenclature 95
References 95
3 Irradiation
Lawrence K. Wang, J. Paul Chen, and Robert C. Ziegler 107
1. Introduction 107
1.1. Disinfection and Irradiation 107
1.2. Pathogenic Organisms 108
1.3. Pathogen Occurrence in the United States 108
1.4. Potential Human Exposure to Pathogens 108
2. Pathogens and Thier Characteristics 109
2.1. Viruses 109
2.2. Bacteria 110
2.3. Parasites 110
2.4. Fungi 112
3. Solid Substances Disinfection 112

3.1. Long-Term Storage 112
3.2. Chemical Disinfection 112
3.3. Low-Temperature Thermal Processes for Disinfection 113
3.4. High-Temperature Thermal Processes for Disinfection 114
3.5. Composting 114
3.6. High-Energy Radiation 115
4. Disinfection with Electron Irradiation 115
4.1. Electron Irradiation Systems and Process Description 115
4.2. Electron Irradiation Design Considerations 117
4.3. Electron Irradiation Operational Considerations 118
4.4. Electron Irradiation Performance 118
5. Disinfection with L-Irradiation 119
5.1. L-Irradiation Systems and Process Description 119
5.2. L-Irradiation Design Considerations 122
5.3. L-Irradiation Operational Considerations 124
6. X-Ray Facilities 126
7. New Applications 126
7.1. Food Disinfection by Irradiation 126
7.2. Hospital Waste Treatment by Irradiation 128
7.3. Mail Irradiation 130
8. Glossary 131
References 132
4 Nonthermal Plasma Technology
Toshiaki Yamamoto and Masaaki Okubo 135
1. Fundamental Characteristics of Nonthermal Plasma 135
1.1. Definition and Characteristics of Plasma 135
1.2. Generation of Plasma 145
1.3. Analysis and Diagnosis of Nonthermal Plasma 165
2. Environmental Improvement 173
2.1. Electrostatic Precipitator 173

2.2. Combustion Flue Gas Treatment from Power Plant 183
2.3. Nonthermal Plasma Application for Detoxification 196
2.4. Air Cleaner for Odor Control 199
x Contents
2.5. Ozone Synthesis and Applications 206
2.6. Decomposition of Freon and VOC 212
2.7. Diesel Engine Exhaust Gas Treatment 215
2.8. Gas Concentration Using Nonthermal Plasma Desorption 239
2.9. Emission Gas Decomposition in Semiconductor Manufacturing Process 248
3. Surface Modification 256
3.1. RF Plasma CVD 256
3.2. Surface Modification for Substrate 257
3.3. Surface Modification for Glass 261
3.4. Surface Modification for Polymer or Cloth 266
3.5. Surface Modification for Metal 271
Nomenclature 277
References 280
5 Thermal Distillation and Electrodialysis Technologies for Desalination
J. Paul Chen, Lawrence K. Wang, and Lei Yang 295
1. Introduction 295
2. Thermal Distillation 301
2.1. Introduction 301
2.2 Working Mechanisms 302
2.3. Multistage Flash Distillation 304
2.4. Multieffect Distillation 304
2.5. Vapor Compression 307
2.6. Solar Desalination 307
2.7. Important Issues in Design (O&M) 311
3. Electrodialysis 312
3.1. Introduction 312

3.2. Mechanisms 312
3.3. Important Issues in Design 314
3.4. Electrodialysis Reversal 317
3.5. Electrodeionization 319
4. Reverse Osmosis 321
5. Energy 322
6. Environmental Aspect of Desalination 324
Nomenclature 325
References 326
6 Reverse Osmosis Technology for Desalination
Edward S.K. Chian, J. Paul Chen, Ping-Xin Sheng,
Yen-Peng Ting, and Lawrence K. Wang 329
1. Introduction 329
2. Membrane Filtration Theory 330
2.1. Osmosis and RO 330
2.2 Membranes 332
2.3. Membrane Filtration Theory 334
2.4. Concentration Polarization 338
2.5. Compaction 339
3. Membrane Modules and Plant Configuration 340
3.1. Membrane Modules 340
3.2. Plant Configuration of Membrane Modules 343
4. Pretreatment and Cleaning of Membrane 346
4.1. Mechanisms of Membrane Fouling 346
4.2. Feed Pretreatment 349
4.3. Membrane Cleaning and Regeneration 354
5. Case Study 359
5.1. Acidification and Scale Prevention for Pretreatment 359
5.2. Cartridge Filters for Prefiltration 359
5.3. Reverse Osmosis 359

Contents xi
5.4 Neutralization and Posttreatment 361
5.5. Total Water Production Cost and Grand Total Costs 362
Nomenclature 362
References 363
7 Emerging Biosorption, Adsorption, Ion Exchange,
and Membrane Technologies
J. Paul Chen, Lawrence K. Wang, Lei Yang, and Soh-Fong Lim 367
1. Introduction 367
2. Emerging Biosorption for Heavy Metals 367
2.1. Biosorption Chemistry 368
2.2 Biosorption Process 369
2.3. Biosorption Mathematical Modeling 372
3. Magnetic Ion Exchange Process 374
4. Liquid Membrane Process 377
4.1. Introduction 377
4.2. Mechanism 377
4.3. Applications 378
5. Emerging Technologies for Arsenic Removal 380
5.1. Precipitation–Coagulation, Sedimentation, and Flotation 380
5.2. Electrocoagulation 381
5.3. Adsorption 382
5.4. Ion Exchange 386
5.5. Membrane Filtration 386
Nomenclature 387
References 387
8 Fine Pore Aeration of Water and Wastewater
Nazih K. Shammas 391
1. Introduction 391
2. Description 392

3. Types of Fine Pore Media 393
3.1. Ceramics 394
3.2. Porous Plastics 395
3.3. Perforated Membranes 396
4. Types of Fine Pore Diffusers 398
4.1. Plate Diffusers 398
4.2. Tube Diffusers 400
4.3. Dome Diffusers 402
4.4. Disc Diffusers 403
5. Diffuser Layout 407
5.1. Plate Diffusers 408
5.2. Tube Diffusers 409
5.3. Disc and Dome Diffusers 410
6. Characteristics of Fine Pore Media 411
6.1. Physical Description 411
6.2. Dimensions 411
6.3. Weight and Specific Weight 412
6.4. Permeability 412
6.5. Perforation Pattern 413
6.6. Strength 413
6.7. Hardness 414
6.8. Environmental Resistance 414
6.9. Miscellaneous Physical Properties 415
6.10. Oxygen Transfer Efficiency 415
xii Contents
Contents xiii
6.11. Dynamic Wet Pressure 416
6.12. Bubble Release Vacuum 419
6.13. Uniformmity 420
7. Performance in Clean Water 422

7.1. Steady-State DO Saturation Concentration (C ) 423
7.2. Oxygen Transfer 424
8. Performance in Process Water 432
8.1. Performance 432
8.2. Factors Affecting Performance 439
8.3. Operation and Maintenance 441
Nomenclature 442
References 443
9 Emerging Flotation Technologies
Lawrence K. Wang 449
1. Modern Flotation Technologies 450
2. Groundwater Decontamination Using DAF 452
3. Textile Mills Effluent Treatment Using DAF 459
4. Petroleum Refinery Wastewater Treatment Using DAF 459
5. Auto and Laundry Wasterwater Using DAF 460
6. Seafood Processing Wastewater Treatment Using DAF 462
7. Storm Runoff Treatment Usng DAF 464
8. Industrial Effluent Treatment by Biological Process Using DAF
for Secondary Flotation Clarification 465
9. Industrial Resource Recovery Using DAF for Primary Flotation Clarification 467
10. First American Flotation–Filtration Plant for Water Purification—Lenox
Water Treatment Plant, MA, USA 469
11. Once the World’s Largest Potable Flotation–Filtration Plant—Pittsfield
Water Treatment Plant, MA, USA 471
12. The Largest Potable Flotation–Filtration Plant in the Continent of North
America—Table Rock and North Saluda Water Treatment Plant, SC, USA 473
13. Emerging DAF Plants—AquaDAF™ 474
14. Emerging Full-Scale Anaerobic Biological Flotation—Kassel, Germany 476
15. Emerging Dissolved Gas Flotation and Sequencing Batch Reactor (DGF-SBR) 478
16. Application of Combined Primary Flotation Clarification and Secondary Flotation Clarification

for Treatment of Dairy Effluents—A UK Case History 479
17. Recent DAF Developments 480
References 481
10 Endocrine Disruptors: Properties, Effects, and Removal Processes
Nazih K. Shammas 485
1. Introduction 485
2. Endocrine System and Endocrine Disruptors 487
2.1. The Endocrine System 487
2.2. Endocrine Disruptors 487
3. Descriptions of Specific EDCs 488
3.1. Pesticide Residues 488
3.2. Highly Chlorinated Compounds 491
3.3. Alkylphenols and Alkylphenol Ethoxylates 494
3.4. Plastic Additives 495
4. Water Treatments for EDC Removal 496
4.1. Granular Activated Carbon 496
4.2. Powdered Activated Carbon 498
4.3. Coagulation/Filtration 498
4.4. Lime Softening 498
5. Point-of-Use/Point-of-Entry Treatments 499
6. Water Treatment Techniques for Specific EDC Removal 499
6.1. Methoxychlor 499
xiv Contents
6.2. Endosulfan 500
6.3. DDT 500
6.4. Diethyl Phthalate 500
6.5. Di-(2ethylhexyl) Phthalate 500
6.6. Polychlorinated Biphenyls 500
6.7. Dioxin 500
6.8. Alkylphenols and Alkylphenol Ethoxylates 501

Nomenclature 501
References 501
11 Filtration Systems for Small Communities
Yung-Tse Hung, Ruth Yu-Li Yeh, and Lawrence K. Wang 505
1. Introduction 505
2. Operating Characteristics 505
3. SDWA Implementation 506
4. Filtration Treatment Technology Overview 506
5. Common Types of Water Filtration Processes for Small Communities 507
5.1. Process Description 508
5.2. Operation and Maintenance Requirements 512
5.3. Technology Limitations 512
5.4. Financial Considerations 513
6. Other Filtration Processes 514
6.1. Direct Filtration 514
6.2. Membrane Processes 514
6.3. Bag and Cartridge Type Filtration 516
6.4. Summary of Compliance Technologies for the SWTR 519
7. Case Studies of Small Water Systems 519
7.1. Case Study of Westfir, OR 519
7.2. Mockingbird Hill, Arkansas, Case Study 524
8. Intermittent Sand Filters for Wastewater Treatment 527
8.1. Technology Applications 527
8.2. Process Descriptions 527
8.3. Operation and Maintenance (O&M) Requirements 529
8.4. Technology Limitations 529
8.5. Financial Considerations 529
8.6. Case Studies 530
References 539
12 Chemical Feeding System

Puangrat Kajitvichyanukul, Yung-Tse Hung,
and Jirapat Ananpattarachai 543
1. Introduction 543
2. Chemicals Used in Water Treatment 545
2.1. Aluminum Sulfate or Alum 546
2.2. Ammonia 546
2.3. Calcium Hydroxide and Calcium Oxide 546
2.4. Carbon Dioxide 546
2.5. Ferric Chloride 547
2.6. Ferric Sulfate 547
2.7. Ferrous Sulfate 547
2.8. Phosphate Compounds 547
2.9. Polymers 548
2.10. Potassium Permanganate 548
2.11. Sodium Carbonate 548
2.12. Sodium Chlorite 549
2.13. Sodium Hydroxide 549
2.14. Sodium Hypochlorite 550
Contents xv
2.15. Sulfuric Acid 550
3. Chemical Storage 550
3.1. Storage of Powder Chemicals 550
3.2. Storage of Liquid Chemicals 555
3.3. Storage of Gaseous Chemicals 555
3.4. Storage Facility Requirements 557
4. Chemical Preparation of Solutions and Suspensions 558
4.1. Preparation of Dilute Solutions from Concentrated Solutions 558
4.2. Preparation of Dilute Solutions from Solid Products 559
4.3. Preparation of Suspensions 560
5. Chemical Feeding System 560

5.1. Dry Feeders 561
5.2. Solution Feeders 566
5.3. Gas Feeders 567
6. Design Examples 567
References 572
13 Wet Air Oxidation for Waste Treatment
Linda Y. Zou, Yuncang Li, and Yung-Tse Hung 575
1. Introduction 575
1.1. Process Description 576
1.2. Mechanisms and Kinetics 578
1.3. Design 580
1.4. Issues and Considerations of Using Wet Air Oxidation 580
2. Catalytic WAO Processes 581
2.1. Process Description 581
2.2. Process Application and Limitation 582
2.3. Design Considerations 586
3. Emerging Technologies in Advanced Oxidation 587
3.1. Photocatalytic Oxidation (PCO) Process 587
3.2. Supercritical Water Oxidation 592
4. Application Examples 598
4.1. Case 1: WAO of Refinery Spent Caustic: A Refinery Case Study 598
4.2. Case 2: CWAO for the Treatment of H-Acid Manufacturing Process Wastewater 601
4.3. Case 3: Photocatlytic Decolorization of Lanasol Blue CE Dye Solution
in Flat-Plate Reactor 602
4.4. Case 4: Oxidation of Industrial Waste Waters in the Pipe Reactor (100) 604
References 605
14 Lime Calcination
Gupta Sudhir Kumar, Anushuya Ramakrishnan, and Yung-Tse Hung 611
1. Introduction 611
2. The Chemical Reactions 612

2.1. Calcium Carbonate 612
2.2. Magnesium Carbonate 612
2.3. Dolomite and Magnesian/Dolomitic Limestone 613
3. Kinetics of Calcination 613
3.1. Stages of Calcinations 613
3.2. Dissociation of High Calcium Limestone 614
3.3. Calorific Requirements for Dissociation of Calcium and Dolomitic Quick Lime 617
3.4. Dissociation of Magnesian/Dolomitic Limestones and Dolomite 618
3.5. Sintering of High Calcium Quickllime 618
3.6. Sintering of Calcined Dolomite 620
3.7. Steam Injection 621
3.8. Recarbonation 621
3.9. Calcination of Finely Divided Limestones 622
4. Properties of Limestones and Their Calcines 622
5. Factors Affecting Lime Calcination 623
xvi Contents
5.1. Effect of Stone Size 623
5.2. Effect of Crystal Ion Spacing 624
5.3. Effect of Salts 624
5.4. Influence of Stone Imurities 624
5.5. Effect of Steam 625
5.6. Effect of Storage and Production 625
5.7. Effect of Calcination Temperature 626
6. Calcination of Industrial Solid Wastes 627
7. Carbon Dioxide Emissions from Lime Calcination 628
8. Solar Lime Calcination 628
9. Conclusions 631
Nomenclature 631
References 632
Appendix: Conversion Factors for Environmental Engineers

Lawrence K. Wang 635
Index 699
Contributors
JIRAPAT ANANPATTARACHAI, PhD CANDIDATE • Research Assistant, Department of Envi-
ronmental Engineering, King Mongkut’s University of Technology Thonburi,
Bangkok, Thailand
G
UAHUA CHEN, PhD • Associate Professor, Department of Chemical Engineering, Hong
Kong University of Science & Technology, Hong Kong, China
J. P
AUL CHEN, PhD • Associate Professor, Division of Environmental Science and
Engineering, National University of Singapore, Singapore
E
DWARD S.K. CHAIN, PhD • Retired Professor, School of Civil and Environmental
Engineering, Georgia Institute of Technology, Atlanta, GA
Y
UNG-TSE HUNG, PhD, PE, DEE • Professor, Department of Civil and Environmental
Engineering, Cleveland State University, Cleveland, OH
P
UANGRAT KAJITVICHYANUKUL, PhD • Assistant Professor, Department of Environmental
Engineering, King Mongkut’s University of Technology, Thonburi, Bangkok, Thailand
G
UPTA SUDHIR KUMAR, PhD • Professor, Centre for Environmental Science and Engineering,
Indian Institute of Technology, Bombay, Powai, Mumbai, Maharashtra, India
Y
UNCANG LI, PhD • Research Fellow, School of Engineering and Technology, Faculty of
Science and Technology, Deakin University, Geelong, Victoria, Australia
S
OH-FONG LIM, MEng • Research Scholar, Department of Chemical and Environmental
Engineering, National University of Singapore, Singapore

M
ASAAKI OKUBO, PhD • Associate Professor, Department of Mechanical Engineering,
Osaka Prefecture University, Osaka, Japan
A
NUSHUYA RAMAKRISHNAN, MSc • Research Scholar, Centre for Environmental Science
and Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai,
Maharashtra, India
N
AZIH K. SHAMMAS, PhD • Professor and Environmental Engineering Consultant,
Ex-Dean and Director, Lenox Institute of Water Technology, Lenox, MA, Krofta
Engineering Corporation, Lenox, MA
P
ING-XIN SHENG, PhD • Research Fellow, Division of Environmental Science and
Engineering, National University of Singapore, Singapore
Y
EN-PENG TING, PhD • Associate Professor, Department of Chemical and Biomolecular
Engineering, National University of Singapore, Singapore
L
AWRENCE K. WANG, PhD, PE, DEE • Dean & Director (Retired), Lenox Institute of Water
Technology, Lenox, MA; Assistant to the President, Krofta Engineering Corporation,
Lenox, MA; Vice President, Zorex Corporation, Newtonville, NY
T
OSHIAKI YAMAMOTO, PhD • Professor, Department of Mechanical Engineering, Osaka
Prefecture University, Osaka, Japan
L
EI YANG, PhD • Research Fellow, Department of Chemical and Biomolecular Engineering,
National University of Singapore, Singapore
xvii
RUTH YU-LI YEH, PhD • Professor, Department of Chemical Engineering, Ming Hsin
University of Science and Technology, Hsin-Chu, Taiwan

R
OBERT C. ZIEGLER, PhD • Section Head (Retired),Environmental Systems Section,
Arvin-Calspan, Inc., Buffalo, NY
L
INDA ZOU, PhD • Associate Professor, Institute of Sustainability and Innovation,
Werribe Campus, Victoria University, Melbourne, Australia
xviii Contributors
1
Pressurized Ozonation
Lawrence K. Wang and Nazih K. Shammas
CONTENTS
INTRODUCTION
DESCRIPTION OF PROCESSES
FORMATION AND GENERATION OF OZONE
REQUIREMENTS FOR OZONATION EQUIPMENT
PROPERTIES OF OZONE
DISINFECTION BY OZONE
OXIDATION BY OZONE
OXYGENATION AND OZONATION SYSTEMS
NOMENCLATURE
ACKNOWLEDGMENTS
REFERENCES
1. INTRODUCTION
Increasing population and improving standards of living are placing increasing bur-
dens on water resources. The preservation of the limited natural water supplies and, in
the near future, the necessity for direct recycling of water in some parts of the world will
require improved technologies for the removal of contaminants from wastewater.
There are many contaminants in wastewater, which vary from time to time, and they
are not well characterized with respect to chemical species. Commonly, the level of
organic contamination is expressed by biochemical oxygen demand (BOD), chemical

oxygen demand (COD), or total organic carbon (TOC). Ozone and oxygen are power-
ful oxidants, which can oxidize many contaminants in wastewater and sludge biosolids.
Ozone is more powerful than oxygen, but it must be generated at the point of use
because it is an unstable material.
For many years in European countries, ozone has been used for disinfecting drinking
water. It has also been used for treating some special industrial wastes, notably for
removing cyanides and phenols. Since 1980, ozone has been used for wastewater, indus-
trial wastes, and sludge treatment on a large scale (1–6). Oxidative purification and
1
From: Handbook of Environmental Engineering, Volume 5: Advanced Physicochemical Treatment Technologies
Edited by: L. K. Wang, Y. -T. Hung, and N. K. Shammas © The Humana Press Inc., Totowa, NJ
disinfection with ozone as a tertiary wastewater treatment or sludge treatment has a
number of inherent advantages:
a. Reduction in BOD and COD.
b. Reduction of odor, color, turbidity, and surfactants.
c. Pathogenic organisms are destroyed.
d. The treatment products are beneficial.
e. The effluent water has a high dissolved oxygen (DO) concentration.
The relatively high cost of ozone generation requires a high ozone-utilization effi-
ciency if ozone treatment is to be economically competitive. A principal disadvantage
to the use of ozone in waste treatment is its cost. However, recent advances in ozone
generation have rendered the ozonation process more competitive.
This chapter deals with two newly developed oxygenation–ozonation (Oxyozosynthesis
®
)
systems for wastewater and sludge treatment. Each treatment scheme consists of a wet
well for flow equalization and pH adjustment, a hyperbaric reactor for oxygenation and
ozonation, a flotation clarifier for degasification and solid–water separation, and a filter
belt press for final sludge dewatering. Special emphasis is placed on theory, kinetics, and
disinfection effect of ozonation and oxygenation (7–12).

1.1. Oxyozosynthesis Sludge Management System
As shown in Figs. 1 and 2, the new sludge management system consists of the fol-
lowing unit operations and processes: sludge production from clarifiers, flow equaliza-
tion and pH adjustment in a wet well, oxygenation–ozonation in a hyperbaric reactor
vessel (Fig. 3), flotation, dewatering in a belt press, and resource recovery of final prod-
uct as fuel or for land application.
A full-scale Oxyozosynthesis sludge management system was installed at the West
New York Sewage Treatment Plant (WNYSTP), West New York, NJ. The plant treats
domestic wastewater flow of 10 MGD and produces 22,000 gpd of primary sludge.
Primary raw sludge is pumped from sumps located at the bottom of the primary sedi-
mentation clarifiers by means of two positive-displacement pumps to a sludge grinder,
then to the wet well. As the wet well is being filled with ground sludge, a chemical meter-
ing pump is used to add a 10% sulfuric acid solution to adjust the pH value to between
3.5 and 4.0. A mechanical mixer and a pH meter are mounted in the wet well for proper
mixing and pH monitoring, respectively. Following acidification, the sludge is pumped
by a progressive cavity pump to one of the two batch-operated hyperbaric reactor ves-
sels, each capable of treating 1500 gal of sludge in 90 min by oxygenation and ozona-
tion. To start each reactor vessel, the pressure in the reactor is increased to 40 psig with
liquid oxygen first and then up to 60 psig with ozone. There are two operational modes:
a. Continuous oxygenation–ozonation. After the startup with oxygen and ozone, ozone is
continuously fed into the reactor for a total of 90 min. The pressure is maintained at 60 psig
by bleeding off (or recycling) the excess gas.
b. Noncontinuous oxygenation–ozonation. After the startup with oxygen and ozone, ozone
is then shut off, to isolate the reactor and maintain the conditions for 90 min.
During the first 90 min contact time in the oxygenation–ozonation reactor,
pathogenic bacteria, viruses, total suspended solids, and volatile suspended solids in the
2 Lawrence K. Wang and Nazih K. Shammas
sludge are all significantly reduced. The reactor effluent is then released (at a flow rate
of about 1500 gal/90 min) into an open flotation unit where DO, ozone, and carbon
dioxide gases are released out of the solution to form tiny bubbles, which adhere to the

residual suspended solids causing them to float and thickened at the top of the unit. The
flotation unit is equipped with revolving paddles (or scoops) that transport these float-
ing solids onto a filter belt press for sludge dewatering. The subnatant liquor is recycled
Pressurized Ozonation 3
Fig. 1. General view of oxygenation–ozonation (Oxyozosynthesis
™
) system.
4
Fig. 2. Flow diagram of Oxyozosynthesis sludge management system.
to the head of the sewage treatment plant for further treatment with the incoming
wastewater flow.
The filter belt press produces a dry high-nutrient sludge cake with low metal content
and high BTU value. The sludge cake can be recycled by spreading on agricultural land,
reused as a fuel source, or disposed off in a landfill. The dry sludge can also be reused
as secondary fiber in paper manufacturing or as raw material for building blocks.
1.2. Oxyozosynthesis Wastewater Reclamation System
As shown in Fig. 4, the new wastewater reclamation system consists of the following
unit operations and processes: wastewater collection and preliminary treatment (bar
screens and grit chambers), flow equalization and pH adjustment in a wet well, oxy-
genation–ozonation in a hyperbaric reactor vessel, dissolved gas flotation (DGF), and
filtration.
A pilot-scale Oxyozosynthesis wastewater reclamation system was installed at the
Lenox Institute of Water Technology, Lenox, MA. The pilot plant treats a wastewater
flow of 6 gpm and produces small amount of sludge. Raw wastewater is pumped from
sumps located at the bottom of the grit chambers by means of positive-displacement
pumps to a wet well. As the wet well is being filled with the raw wastewater, a chemi-
cal metering pump is used to add a 10% sulfuric acid solution to adjust the pH value to
between 3.5 and 4.0 by a chemical metering pump. A mechanical mixer and a pH meter
are mounted in the wet well for proper mixing and pH monitoring, respectively.
From the wet well, a progressive cavity pump delivers the acidified wastewater to a

batch-operated hyperbaric reactor vessel capable of treating 100 gal of wastewater in
Pressurized Ozonation 5
Fig. 3. The hyperbaric reactor vessel.
6
Fig. 4. Flow diagram of Oxyozosynthesis wastewater reclamation system.
30–60 min depending on the characteristics of the wastewater. To start the reactor
vessel, the pressure in the reactor is increased to 40 psig with liquid oxygen first, and
then to 60 psig with ozone. There are two operational modes:
a. Continuous oxygenation–ozonation. After the startup with oxygen and ozone, ozone is
continuously fed into the reactor for a total of 30–60 min. The pressure is maintained at
60 psig by bleeding off (or recycling) the excess gas.
b.
Noncontinuous oxygenation–ozonation. After the startup with oxygen and ozone, ozone
is then shut off, to isolate the reactor and maintain the conditions for 30–60 min.
During the first 30–60 min contact time in the oxygenation–ozonation reactor,
pathogenic bacteria, viruses, total suspended and volatile suspended solids, phenols,
cyanides, manganese, and so on, in wastewater are all significantly reduced. The reac-
tor effluent is released into a DGF unit, where flocculant(s) can be added and the dis-
solved gases come out of aqueous phase forming tiny bubbles, which adhere to the flocs
and residual suspended solids causing them to float to the top of the unit. Heavy metals,
iron, phosphate, humic acids, hardness, toxic volatile organics, and so on, will all react
with the flocculant(s) to form insoluble flocs that are floated. The flotation unit is
equipped with revolving paddles (or scoops) that transport these floating solids onto a
subsequent filter belt press for final sludge dewatering. A dual-media filter further
polishes the subnatant clarified water.
The filter effluent quality is close to that of potable water, having extremely low
color, turbidity, suspended solids, hardness, iron, manganese, trihalomethane precursor
(humic acid), heavy metal, volatile organics, phenol, cyanide, and so on. The product
water is suitable for reuse for industrial and agricultural purposes. Further treatment of
the final filter effluent by adsorption on activated carbon is optional.

2. DESCRIPTION OF PROCESSES
2.1. Ozonation and Oxygenation Process
Ozone gas is sparingly soluble in water. The solubility of ozone in water increases
with its increasing partial pressure, decreasing water pH, and decreasing temperature.
However, oxidation rate increases with increasing temperature. For economic operation
of the hyperbaric oxygenation–ozonation reactor, it is operated at room temperature and
a pressure in the range of 40–60 psig, the influent liquid sludge pH is reduced with sul-
furic acid to a value in the 3.5–4.0 range.
The addition of oxygen at 40 psig and ozone at 60 psig ensure proper partial pres-
sures for solubilizing both oxygen and ozone gases in the sludge. Both DO and ozone
act to oxidize chemically the reducing pollutants found in the liquid sludge, thus
decreasing BOD and COD, which results in the formation of oxygenated organic inter-
mediates and end products. Ozonation–oxygenation treatment also reduces color and
odor in waste sludge.
Because there is a wide range of ozone reactivity with the diverse organic content of
wastewater, both the required ozone dose and reaction time are dependent on the quality
of the influent to the ozonation process. Generally, higher doses and longer contact times
are required for ozone oxidation reactions than are required for wastewater disinfection
using ozone. Ozone tertiary treatment may eliminate the need for a final disinfection
Pressurized Ozonation 7
step. Ozone breaks down to elemental oxygen in a relatively short period of time (its
half-life is about 20 min). Consequently, it must be generated on-site using either air or
oxygen as the feed gas. Ozone generation utilizes a silent electric arc or corona through
which air or oxygen passes, and yields ozone in the air/oxygen mixture, the percentage
of ozone being a function of voltage, frequency, gas flow rate, and moisture. Automatic
devices are commonly applied to control and adjust the ozone generation rate.
For sludge treatment or wastewater reclamation, it is a developing technology.
Recent developments and cost reduction in ozone generation and ozone dissolution
technology make the process very competitive. A full-scale application is currently in
the demonstration stage at the WNYSTP, West New York, NJ. If oxygen-activated

sludge is employed in the system, ozone treatment may be even more economically
attractive, because a source of pure oxygen is available facilitating ozone production.
For poor-quality wastewater or sludge with extremely high COD, BOD, and/or TOC
contents (>300 mg/L), ozone treatment can be economical only if there is adequate pre-
treatment. The process will not produce any halogenated hydrocarbons. Table 1 shows the
reduction of overall COD, BOD, and TOC, achieved in the US Environmental Protection
Agency (EPA) controlled tests after a 90 min contact time with ozone oxidation. Beyond
the 70% COD removal level, the oxidation rate is significantly slowed. In laboratory tests,
COD removal never reaches 100% even at a high ozone dose of 300 mg/L.
As a disinfectant with common dosages of 3–10 mg/L, ozone is an effective agent for
deactivating common forms of bacteria, bacterial spores, and vegetative microorgan-
isms found in wastewater, as well as eliminating harmful viruses. Additionally, ozone
acts to chemically oxidize materials found in the wastewater and sludge, forming oxy-
genated organic intermediates and end products. Furthermore, ozone treatment reduces
wastewater color and odor. Ozone disinfection is applicable in cases, where chlorine
(Cl
2
) disinfection might produce potentially harmful chlorinated organic compounds. If
oxygen-activated sludge is employed in the system, ozone disinfection is economically
attractive, because a source of pure oxygen is available for facilitating ozone produc-
tion. However, ozone disinfection does not form a residual that will persist and can be
easily measured to ensure adequate dosage. Ozonation may not be economically com-
petitive with chlorination under nonrestrictive local conditions.
8 Lawrence K. Wang and Nazih K. Shammas
Table 1
Effectiveness of Ozone as an Oxidant
Ozone dosage
COD (mg/L) BOD
5
(mg/L) TOC (mg/L)

(mg/L) Influent Effluent Influent Effluent Influent Effluent
50 318 262 142 110 93 80
100 318 245 142 100 93 77
200 318 200 142 95 93 80
325 318 159 142 60 93 50
50 45 27 13 7 20.5 15.5
100 45 11 13 3 20.5 9
200 45 5.5 13 1.5 20.5 5
Source: US EPA.