Ozone Reaction Kinetics for Water and Wastewater Systems

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ISBN: 9781566706292 | 1566706297
Cover: Hardcover
Copyright: 12/29/2003

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Interest in ozonation for drinking water and wastewater treatment has soared in recent years due to ozone's potency as a disinfectant, and the increasing need to control disinfection byproducts that arise from the chlorination of water and wastewater. Ozone Reaction Kinetics for Water and Wastewater Systems is a comprehensive reference that presents practical information to water treatment and wastewater treatment operators and researchers. It describes the application of kinetics to the effective evaluation, design, and implementation of ozone technology. This information will help plant operators determine whether or not ozone treatment is suitable for their facility, and help engineers and researchers design appropriate ozone treatment systems. By presenting complete coverage of ozone kinetics in water and wastewater, this book provides researchers and practitioners with fundamentals of ozone kinetics as well as practical "how to" information.

Introduction

(6)

Ozone in Nature

(1)

The Ozone Molecule

(4)

References

(2)

Reactions of Ozone in Water

(24)

Oxidation--Reduction Reactions

(2)

Cycloaddition Reactions

(2)

Electrophilic Substitution Reactions

(2)

Nucleophilic Reactions

(1)

Indirect Reactions of Ozone

(17)

The Ozone Decomposition Reaction

(7)

References

(5)

Kinetics of the Direct Ozone Reactions

(16)

Homogeneous Ozonation Kinetics

(10)

Batch Reactor Kinetics

(6)

Flow Reactor Kinetics

(1)

Influence of pH on Direct Ozone Rate Constants

(2)

Determination of the Stoichiometry

(1)

Heterogeneous Kinetics

(4)

Determination of the Stoichiometry

(1)

References

(3)

Fundamentals of Gas-Liquid Reaction Kinetics

(22)

Physical Absorption

(3)

The Film Theory

(2)

Surface Renewal Theories

(1)

Chemical Absorption

(19)

Film Theory

(1)

Irreversible First-Order or Pseudo First-Order Reactions

(3)

Irreversible Second-Order Reactions

(4)

Series-Parallel Reactions

(4)

Danckwerts Surface Renewal Theory

(1)

First-Order or Pseudo First-Order Reactions

(1)

Irreversible Second-Order Reactions

(3)

Series-Parallel Reactions

(1)

Influence of Gas Phase Resistance

(1)

Slow Kinetic Regime

(1)

Fast Kinetic Regime

(1)

Diffusion and Reaction Times

(1)

References

(1)

Kinetic Regimes in Direct Ozonation Reactions

(44)

Determination of Ozone Properties in Water

(11)

Diffusivity

(2)

Ozone Solubility: The Ozone-Water Equilibrium System

(9)

Kinetic Regimes of the Ozone Decomposition Reaction

(3)

Kinetic Regimes of Direct Ozonation Reactions

(24)

Checking Secondary Reactions

(1)

Some Common Features of the Kinetic Studies

(3)

The Ozone Solubility

(1)

The Individual Liquid Phase Mass-Transfer Coefficient, KL

(1)

Instantaneous Kinetic Regime

(3)

Fast Kinetic Regime

(9)

Moderate Kinetic Regime

101

(1)

Case of No Dissolved Ozone

102

(1)

Case of Pseudo First-Order Reaction with Moderate Kinetic Regime

102

(1)

Slow Kinetic Regime

102

(3)

The Slow Diffusional Kinetic Regime

105

(1)

Very Slow Kinetic Regime

105

(2)

Changes of the Kinetic Regimes during Direct Ozonation Reactions

107

(1)

Comparison between Absorption Theories in Ozonation Reactions

107

(6)

References

109

(4)

Kinetics of the Ozonation of Wastewaters

113

(38)

Reactivity of Ozone in Wastewater

118

(2)

Critical Concentration of Wastewater

120

(1)

Characterization of Wastewater

121

(4)

The Chemical Oxygen Demand

122

(1)

The Biological Oxygen Demand

123

(1)

Total Organic Carbon

123

(1)

Absorptivity at 254 nm (A254)

124

(1)

Mean Oxidation Number of Carbon

124

(1)

Importance of pH in Wastewater Ozonation

125

(4)

Chemical Biological Processes

129

(4)

Biodegradability

130

(2)

Sludge Settling

132

(1)

Sludge Production

132

(1)

Kinetic Study of the Ozonation of Wastewaters

133

(18)

Establishment of the Kinetic Regime of Ozone Absorption

134

(2)

Determination of Ozone Properties for the Ozonation Kinetics of Wastewater

136

(4)

Determination of Rate Coefficients for the Ozonation Kinetics of Wastewater

140

(1)

Fast Kinetic Regime (High COD)

141

(2)

Slow Kinetic Regime (Low COD)

143

(2)

References

145

(6)

Kinetics of Indirect Reactions of Ozone in Water

151

(24)

Relative Importance of the Direct Ozone-Compound B Reaction and the Ozone Decomposition Reaction

152

(2)

Application of Diffusion and Reaction Time Concepts

152

(2)

Relative Rates of the Oxidation of a Given Compound

154

(2)

Kinetic Parameters

156

(7)

The Ozone Decomposition Rate Constant

157

(2)

Influence of Alkalinity

159

(1)

Determination of the Rate Constant of the OH--Compound B Reaction

160

(1)

The Absolute Method

161

(1)

The Competitive Method

162

(1)

Characterization of Natural Waters Regarding Ozone Reactivity

163

(12)

Dissolved Organic Carbon, pH, and Alkalinity

163

(1)

The Oxidation--Competition Value

164

(6)

The RCT Concept

170

(2)

References

172

(3)

Kinetics of the Ozone/Hydrogen Peroxide System

175

(18)

The Kinetic Regime of the O3/H2O2 Process

176

(4)

Slow Kinetic Regime

177

(1)

Fast-Moderate Kinetic Regime

177

(1)

Critical Hydrogen Peroxide Concentration

178

(2)

Determination of Kinetic Parameters

180

(2)

The Absolute Method

180

(1)

The Competitive Method

181

(1)

The Effect of Natural Substances on the Inhibition of Free Radical Ozone Decomposition

181

(1)

The Ozone/Hydrogen Peroxide Oxidation of Volatile Compounds

182

(1)

The Competition of the Direct Reaction

183

(10)

Comparison between the Kinetic Regimes of the Ozone--Compound B and Ozone-Hydrogen Peroxide Reactions

183

(3)

Comparison between the Rates of the Ozone-Compound B and Hydroxyl Radical--Compound B Reactions

186

(4)

Relative Rates of the Oxidation of a Given Compound

190

(1)

References

191

(2)

Kinetics of the Ozone-UV Radiation System

193

(34)

Kinetics of the UV Radiation for the Removal of Contaminants from Water

193

(13)

The Molar Absorptivity

194

(1)

The Quantum Yield

194

(1)

Kinetic Equations for the Direct Photolysis Process

195

(4)

Determination of Photolytic Kinetic Parameters: The Quantum Yield

199

(1)

The Absolute Method

199

(2)

The Competitive Method

201

(1)

Quantum Yield for Ozone Photolysis

201

(3)

The Ozone Quantum Yield in the Gas Phase

204

(1)

The Ozone Quantum Yield in Water

205

(1)

Kinetics of the UV/H2O2 System

206

(5)

Determination of Kinetic Parameters

206

(1)

The Absolute Method

207

(1)

The Competitive Method

208

(1)

Contribution of Direct Photolysis and Free Radical Oxidation in the UV/H2O2 Oxidation System

209

(2)

Comparison between the Kinetic Regimes of the Ozone-Compound B and Ozone--UV Photolysis Reactions

211

(16)

Comparison between Ozone Direct Photolysis and the Ozone Direct Reaction with a Compound B through Reaction and Diffusion Times

211

(3)

Contributions of Direct Photolysis and Direct Ozone Reaction to the Ozone Absorption Rate

214

(1)

Strong UV Absorption Exclusively due to Dissolved Ozone

215

(1)

Strong UV Absorption due to Dissolved Ozone and a Compound B

216

(1)

Weak UV Absorption

216

(1)

Contributions of the Direct Ozone and Free Radical Reactions to the Oxidation of a Given Compound B

216

(1)

Strong UV Absorption Exclusively due to Dissolved Ozone

217

(1)

Strong UV Absorption due to Dissolved Ozone and a Compound B

218

(1)

Weak UV Absorption

218

(1)

Estimation of the Relative Importance of the Rates of the Direct Photolysis/Direct Ozonation and Free Radical Oxidation of a Compound B

218

(1)

Relative Importance of Free Radical Initiation Reactions in the UV/O3 Oxidation System

219

(2)

Relative Importance of the Direct Reactions and Free Radical Oxidation Rates of Compound B

221

(3)

References

224

(3)

Heterogeneous Catalytic Ozonation

227

(50)

Fundamentals of Gas--Liquid--Solid Catalytic Reaction Kinetics

241

(10)

Slow Kinetic Regime

242

(3)

Fast Kinetic Regime or External Diffusion Kinetic Regime

245

(1)

Internal Diffusion Kinetic Regime

246

(3)

General Kinetic Equation for Gas--Liquid--Solid Catalytic Reactions

249

(1)

Criteria for Kinetic Regimes

250

(1)

Kinetics of Heterogeneous Catalytic Ozone Decomposition in Water

251

(7)

Kinetics of Heterogeneous Catalytic Ozonation of Compounds in Water

258

(7)

The Slow Kinetic Regime

259

(2)

External Mass Transfer Kinetic Regime

261

(1)

Catalyst in Powder Form

262

(1)

Catalyst in Pellet Form

263

(1)

Internal Diffusion Kinetic Regime

263

(1)

Determination of the Effective Diffusivity and Tortuosity Factor of the Porous Catalyst

264

(1)

Determination of the Rate Constant of the Catalytic Reaction

264

(1)

Kinetics of Semiconductor Photocatalytic Processes

265

(12)

Mechanism of TiO2 Semiconductor Photocatalysis

267

(1)

Langmuir--Hinshelwood Kinetics of Semiconductor Photocatalysis

268

(1)

Mechanism and Kinetics of Photocatalytic Ozonation

269

(2)

References

271

(6)

Kinetic Modeling of Ozone Processes

277

(54)

Case of Slow Kinetic Regime of Ozone Absorption

279

(2)

Case of Fast Kinetic Regime of Ozone Absorption

281

(2)

Case of Intermediate or Moderate Kinetic Regime of Ozone Absorption

283

(2)

Time Regimes in Ozonation

285

(1)

Influence of the Type of Water and Gas Flows

286

(2)

Mathematical Models

288

(24)

Slow Kinetic Regime

289

(1)

Both Gas and Water Phases in Perfect Mixing Flow

289

(2)

Both Gas and Water Phases in Plug Flow

291

(8)

The Water Phase in Perfect Mixing Flow and the Gas Phase in Plug Flow

299

(1)

The Water Phase as N Perfectly Mixed Tanks in Series and the Gas Phase in Plug Flow

300

(1)

Both the Gas and Water Phases as N and N' Perfectly Mixed Tanks in Series

301

(2)

Both the Gas and Water Phases with Axial Dispersion Flow

303

(2)

Fast Kinetic Regime

305

(2)

Both the Water and Gas Phases in Perfect Mixing

307

(1)

The Gas Phase in Plug Flow and the Water Phase in Perfect Mixing Flow

307

(1)

Both the Gas and Water Phases in Plug Flow

308

(1)

The Moderate Kinetic Regime: A General Case

309

(3)

Examples of Kinetic Modeling for Model Compounds

312

(4)

Kinetic Modeling of Wastewater Ozonation

316

(15)

Case of Slow Kinetic Regime: Wastewater with Low COD

317

(1)

Kinetic Modeling of Wastewater Ozonation without Considering a Free Radical Mechanism

317

(1)

Kinetic Modeling of Wastewater Ozonation Considering a Free Radical Mechanism

318

(4)

Case of Fast Kinetic Regime: Wastewater with High COD

322

(2)

A General Case of Wastewater Ozonation Kinetic Model

324

(2)

References

326

(5)

Appendices

331

(20)

Appendix A1 Ideal Reactor Types: Design Equations

331

(3)

A1.1 Perfectly Mixed Reactor

331

(2)

A1.2 Plug Flow Reactor

333

(1)

Appendix A2 Useful Mathematical Functions

334

(1)

A2.1 Hyperbolic Functions

334

(1)

A2.2 The Error Function

335

(1)

Appendix A3 The Influence of the Type of Flow on Reactor Performance

335

(7)

A3.1 Nonideal Flow Study

335

(1)

A3.1.1 Fundamentals of RTD Function

336

(1)

A3.1.1.1 Determination of the E Function

336

(2)

A3.1.1.2 Moments of the RTD

338

(1)

A3.1.2 RTD Functions of Ideal Flows through the Reactors

338

(1)

A3.2 Some Fluid Flow Models

339

(1)

A3.2.1 The Perfectly Mixed Tanks in Series Model

340

(1)

A3.2.2 The Axial Dispersion Model

340

(2)

A3.3 Ozone Gas as a Tracer

342

(1)

Appendix A4 Actinometry

342

(3)

A4.1 Determination of Intensity of Incident Radiation

343

(1)

A.4.2 Determination of the Effective Path of Radiation

344

(1)

Appendix A5 Some Useful Numerical Procedures

345

(6)

A5.1 The Newton--Raphson Method for a Set of Nonlinear Algebraic Equations

345

(3)

A5.2 The Runge--Kutta Method for a Set of Nonlinear First-Order Differential Equations

348

(1)

References

349

(2)

Index

351

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Ozone Reaction Kinetics for Water and Wastewater Systems

Summary

Table of Contents

Supplemental Materials