Chemical Degradation Methods for Wastes and Pollutants: Environmental and Industrial Applications (Environmental Science & Pollution)

Chemical Degradation Methods for Wastes and Pollutants......Page 1
Preface......Page 5
Contributors......Page 9
Contents......Page 7
I. INTRODUCTION......Page 11
Contents......Page 0
II. BACKGROUND AND FUNDAMENTALS OF O3/ UV/H2O2 PROCESSES......Page 12
A. General Description......Page 13
1. Background and Fundamentals......Page 16
2. Kinetics of Ozonation......Page 20
3. Ozone Solubility, Rate Constants, and Mass Transfer Coefficients......Page 23
4. Kinetic Modeling......Page 24
C. Hydrogen Peroxide Oxidation......Page 25
1. Background and Fundamentals......Page 27
2. Kinetics of Photolysis......Page 30
1. Background and Fundamentals......Page 35
2. Chemical Kinetics......Page 39
3. Kinetic Modeling......Page 41
A. Ozone-Based Processes......Page 43
IV. DEGRADATION OF POLLUTANTS......Page 45
B. Examples of Laboratory Studies......Page 46
1. Phenols......Page 50
2. Atrazine......Page 52
3. Chlorinated Volatile Organic Compounds......Page 54
5. Natural Organic Matter and the Bromate Issue......Page 56
6. Wastewater Treatment......Page 59
V. SCALE-UP STUDIES AND ENVIRONMENTAL APPLICATIONS......Page 61
A. Experimental Design (Scale-Up Studies)......Page 62
1. Aromatic Hydrocarbons......Page 64
2. Atrazine and Other s-Triazine Compounds......Page 65
3. Volatile Organic Compounds......Page 66
VI. ECONOMIC ASPECTS......Page 67
VIII. NOMENCLATURE......Page 68
REFERENCES......Page 71
1. Role of Photonic Excitation, Electron Transfer, and Adsorption......Page 86
2. Photocatalytic Character of a Reaction......Page 90
3. Chemical Kinetics and Information on Reaction Mechanisms......Page 91
4. General Advantages and Disadvantages of Treatments by TiO2 Photocatalysis......Page 92
1. Roles of O2 and Effects of H2O2 and O3......Page 93
2. Properties Influencing the TiO2 Photocatalytic Activity......Page 95
3. Modifications of TiO2......Page 98
4. Fixing TiO2: Supporting Materials and Depositing Methods......Page 99
A. Laboratory-Scale Experimental Design......Page 100
1. Mechanisms......Page 101
2. Products......Page 106
3. Interferences......Page 109
A. Powder TiO2 vs. Supported TiO2......Page 111
B. Examples of Photocatalytic Reactors and Results......Page 112
1. Water Treatment......Page 113
2. Air Treatment......Page 114
V. CONCLUSIONS......Page 118
REFERENCES......Page 119
I. INTRODUCTION......Page 129
A. General Description......Page 131
1. Fluid Characteristics......Page 133
2. Phase Separations......Page 135
A. Laboratory-Scale Experimental Design......Page 140
1. Mechanisms......Page 143
2. Products from SCWO......Page 146
1. Reactor Selection......Page 150
2. System Operation Procedure......Page 153
B. Examples of Scale-Up, Environmental Application, and Industrial Application......Page 154
1. Efficiency......Page 155
2. Products......Page 157
3. Interferences......Page 159
V. CONCLUSIONS......Page 162
REFERENCES......Page 163
I. INTRODUCTION......Page 172
A. Fenton Reaction......Page 174
C. Haber–Weiss Reaction......Page 175
D. Iron Ligands and Coordination......Page 176
F. Ferryl Ion or Other High-Valent Iron Species......Page 178
A. General Mechanisms......Page 180
B. Mechanistic Examples......Page 181
C. Kinetics......Page 183
D. Other Important Factors......Page 184
A. Typical In Situ Applications......Page 185
B. Iron Minerals as Fenton Catalysts......Page 187
C. Iron Chelators......Page 190
D. Photo–Fenton......Page 192
E. Combined Fenton Biodegradation......Page 193
F. Examples of In Situ Applications......Page 194
A. Complexing Agents to Improve Fenton Selectivity and Efficiency......Page 197
B. Reductive Degradation......Page 199
REFERENCES......Page 201
I. INTRODUCTION......Page 208
A. Acoustical Cavitation and Bubble Dynamics......Page 209
B. Cavitation Chemistry as a Series of Processes......Page 213
1. Ultrasonic Frequency......Page 214
4. Temperature......Page 215
7. Sample Features......Page 216
A. Some Ultrasonic Basics: Near-Megahertz Sonochemistry......Page 217
B. Role of Higher Ultrasonic Frequencies in the Scale-Up’’ of Sonochemical Processes......Page 221
C. Incidental Destructive Effects of Cavitation......Page 222
D. Absorption of Ultrasound......Page 224
A. Chlorinated Organic Chemicals......Page 227
B. Aromatic Compounds......Page 229
C. Pesticides......Page 230
D. Methyl tert-Butyl Ether (MTBE)......Page 231
E. Surfactants......Page 232
F. Dyes......Page 233
1. Sonolysis/Ozonolysis......Page 234
2. Sonolysis/Fenton’s Reaction......Page 235
REFERENCES......Page 236
I. INTRODUCTION......Page 241
II. CATHODIC REDUCTION......Page 244
A. Aliphatic and Aromatic Compounds......Page 245
B. Chlorofluorocarbons......Page 248
A. Fundamentals......Page 253
B. Aromatics......Page 259
C. p-Benzoquinone......Page 263
D. Human Wastes......Page 264
IV. REDOX MEDIATORS......Page 266
A. Reduction Mediators......Page 269
B. Oxidation Mediators......Page 270
A. Electrogeneration Reactions for Ex Situ Applications......Page 276
B. In Situ Degradation of Organics with Electrogenerated Hypochlorite......Page 277
VI. CATHODIC GENERATION OF HYDROGEN PEROXIDE......Page 278
A. Oxidation of Organics by In Situ Electrogenerated H2O2......Page 280
B. Electrogenerated Fenton Reagent (EFR)......Page 281
C. Reticulated Vitreous Carbon (RVC)......Page 286
D. Oxygen Diffusion Cathode (ODC)......Page 287
E. Related Processes......Page 292
VII. METHODS OF PHASE SEPARATION......Page 293
B. Dyes......Page 296
VIII. CONCLUSIONS......Page 297
REFERENCES......Page 298
I. INTRODUCTION......Page 311
B. Process Efficiency......Page 312
C. Formation of Reactive Species......Page 313
D. Aqueous Electron (e-aq)......Page 314
E. Hydrogen Atom (H.)......Page 316
G. Hydrogen Peroxide ( H2O2)......Page 317
H. Determining Solute Removal Rates......Page 318
J. Rate Constants for Reaction with Solutes......Page 319
A. Chloroform and Related Compounds......Page 321
B. Trichloroethylene ( C2HCl3) and Perchloroethylene (C2Cl4)......Page 324
C. Benzene and Substituted Benzenes......Page 327
A. pH......Page 330
C. Oxygen......Page 331
E. Dissolved Organic Carbon......Page 332
V. KINETIC MODELING......Page 333
VI. OPERATIONAL EXPERIENCE......Page 334
A. Miami Electron Beam Research Facility......Page 335
B. Austrian Research Center, Seibersdorf Facility......Page 339
VII. CONCLUSIONS......Page 342
REFERENCES......Page 343
I. INTRODUCTION......Page 348
A. General Description......Page 349
B. Detailed Description of Method......Page 351
A. Laboratory-Scale and Commercial-Scale Setk Experiments......Page 354
1. Contaminated Soils and Sludges......Page 357
3. Oils......Page 360
4. PCBs/Hexachlorobenzene......Page 361
5. Pesticides......Page 362
6. Chlorofluorocarbons and Halons......Page 363
7. Polycyclic Aromatic Hydrocarbons......Page 364
8. Explosives......Page 365
10. Mixed Wastes......Page 366
12. Miscellaneous......Page 368
IV. COMPETING TECHNOLOGIES......Page 369
V. PRACTICAL ADVANTAGES OF SOLVATED ELECTRON REDUCTIONS......Page 370
ACKNOWLEDGMENTS......Page 371
REFERENCES......Page 372
A. Historical Context......Page 375
1. Permeable Reactive Barriers......Page 376
2. Reactive Media......Page 377
A. Removal by Sequestration......Page 379
B. Removal by Transformation......Page 381
2. Dechlorination......Page 382
3. Nitro and Azo Reduction......Page 385
4. Other Organic Transformations......Page 386
1. Corrosion Chemistry......Page 387
2. Common Types of Granular Iron......Page 389
IV. MICROSCALE PROCESSES......Page 390
1. Basic Kinetic Model......Page 391
2. Multiprocess Kinetic Models......Page 393
B. Mass Transport to the Surface......Page 396
V. MACROSCALE PROCESSES......Page 398
A. Geochemical Gradients and Zones......Page 399
2. Reactive Transport Modeling......Page 401
1. Coupling with Natural Attenuation (Microbiological Effects)......Page 404
2. Other Variations and Modifications......Page 405
VI. LIST OF SYMBOLS......Page 406
REFERENCES......Page 407
I. INTRODUCTION......Page 426
A. Introduction to Enzymes......Page 428
B. Advantages and Limitations of Enzyme Applications for Pollutant Transformation......Page 431
A. Enzymatic Treatment to Improve Waste Quality......Page 433
1. Aromatic Pollutants......Page 434
2. Pesticides......Page 441
3. Cyanide Wastes......Page 443
4. Solid Wastes......Page 444
1. Food Processing Wastes......Page 445
2. Solid Wastes......Page 448
IV. BARRIERS TO FULL-SCALE APPLICATION......Page 449
A. Enzyme Cost and Availability......Page 450
B. Enzyme Efficiency Under Waste-Treatment Conditions......Page 451
C. Fate and Disposal of Reaction Products......Page 452
V. CASE STUDY: TREATMENT OF AROMATIC POLLUTANTS USING PEROXIDASE ENZYMES......Page 453
A. Candidate Wastes and Enzymes......Page 454
B. Enzyme Activity and Stability......Page 456
C. Inactivation Mechanisms......Page 458
D. Kinetics and Reactor Design......Page 461
E. Assessment of Reaction Products......Page 464
F. Wastewater Treatment......Page 467
G. Commercial Availability of the Enzyme......Page 468
REFERENCES......Page 471