Preface ........................................................ ix
About the Authors .............................................. xi
1 Introduction ................................................. 1
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON, ALBERT RENKEN,
YURII SH. MATROS
1.1 Periodic Operation ...................................... 1
1.2 Origins of Periodic Operation ........................... 3
1.3 Variables in Periodic Operation ......................... 4
1.4 Cycle Structure in Periodic Operation ................... 6
1.5 Measuring Improvement ................................... 8
1.6 Inherently Periodic Processes ........................... 9
1.7 Objectives of Periodic Operation ....................... 10
1.8 Strategies in Periodic Operation ....................... 10
1.9 Equipment for Periodic Operation ....................... 13
1.10 Reaction Systems Examined .............................. 16
1.11 New Directions ......................................... 17
1.12 A Brief History of the Study of Periodic Operation ..... 19
2 Hydrogenation Processes ..................................... 23
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON
2.1 Ammonia Synthesis ...................................... 23
2.2 NOx Reduction .......................................... 33
2.3 Methanation ............................................ 34
2.4 Methanol Synthesis ..................................... 39
2.5 Ethylene Hydrogenation ................................. 43
2.6 Aromatics Hydrogenation ................................ 45
2.7 Oscillatory Behavior ................................... 47
3 Catalytic Oxidation and Reduction of Gases .................. 49
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON, ALBERT RENKEN
3.1 Introduction ........................................... 49
3.2 CO Oxidation ........................................... 50
3.3 Sulfur Dioxide Oxidation ............................... 66
3.4 Reduction of S03 by CO Over Platinum ................... 70
3.5 Reduction of Nitrogen Oxides ........................... 70
3.6 Traveling Waves in Packed Beds ......................... 76
4 Partial Oxidation and Dehydrogenation of Hydrocarbons ....... 79
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON, CHENG-YUE LI,
ADESOJI A. ADESINA
4.1 Introduction ........................................... 79
4.2 Partial Oxidation and Reforming of Methane to Syngas ... 80
4.3 Oxidative Coupling of Methane .......................... 88
4.4 Epoxidation ............................................ 92
4.5 Propene and Butene Partial Oxidation and Ammoxidation .. 95
4.6 Catalytic Dehydrogenation of Propane, Butane and
Higher Hydrocarbons ................................... 102
4.7 Maleic Anhydride from Butane .......................... 108
4.8 Anhydrides and Aldehydes from Aromatic Hydrocarbons ... 119
4.9 Aromatic Nitriles ..................................... 121
5 Combustion Systems ......................................... 123
PETER LEWIS SILVESTON, ROBERT ROSS HUDGINS
5.1 Non-Catalytic Combustion Reactions .................... 124
5.2 Catalytic Combustion .................................. 127
5.3 Looping Combustion .................................... 134
5.4 Simulated Loop Reactors ............................... 134
6 Automotive Exhaust Catalysis ............................... 141
PETER LEWIS SILVESTON, WILLIAM S. EPLING
6.1 Internal Combustion Engines ........................... 142
6.2 Modulation of Detoxification Reactions ................ 146
6.3 Modeling Studies ...................................... 155
6.4 Studies on Modulating Automotive Exhaust .............. 158
6.5 Effect of A/F Modulation on Poisoning and Sintering ... 160
6.6 Effects of Irregular A/F Variation .................... 161
6.7 Lean Burn Spark-Ignited Engines ....................... 162
6.8 Application of NSR to Diesel Exhausts ................. 168
6.9 Does A/F Modulation Improve Converter Performance? .... 169
7 Polymerization Under Modulation ............................ 171
GREGORIO R. MEIRA, PETER L. SILVESTON
7.1 Introduction .......................................... 171
7.2 Simulation of Polymerization Under Input Modulation ... 177
7.3 Experiments on Polymerization Under Input Modulation .. 188
7.4 Spontaneous Oscillations .............................. 194
7.5 Saturation of Polymers ................................ 200
7.6 Assessment ............................................ 201
8 Catalytic Gas-Solid Reactions .............................. 205
PETER LEWIS SILVESTON
8.1 Partial Oxidation and Oxidative Dehydrogenation of
Hydrocarbons .......................................... 206
8.2 Methane Cracking ...................................... 209
8.3 Non-Catalytic Gas-Solid Reactions ..................... 209
8.4 Catalytic Gasification Under Modulation ............... 216
8.5 Gasification Employing a Circulating Solid Oxygen
Carrier ............................................... 223
8.6 Combustion in Circulating Fluidized Beds .............. 228
8.7 Periodic Reaction Switching ........................... 233
9 Electrochemical Processes .................................. 235
MARK PRITZKER, PETER LEWIS SILVESTON
9.1 Introduction .......................................... 235
9.2 Electroplating ........................................ 246
9.3 Electroforming ........................................ 262
9.4 Anodization ........................................... 263
9.5 Electrochemical Machining and Polishing ............... 264
9.6 Electrowinning and Electrorefming ..................... 265
9.7 Galvanic Cells ........................................ 266
9.8 Electrolytic Production of Chemicals .................. 267
9.9 Applicability of Principles or Practices to Non-
Electrochemical Reactions ............................. 268
10 Modulation of Biological Processes ......................... 273
JENO M. SCHARER
10.1 Introduction .......................................... 273
10.2 Theoretical Considerations ............................ 275
10.3 Substrate and Flow Rate Modulation .................... 280
10.4 Dissolved Oxygen Modulation ........................... 283
10.5 Culture Medium Tuning ................................. 287
10.6 Survival in Mixed Cultures ............................ 289
10.7 Stabilization of Recombinant Cell Cultures ............ 292
10.8 Applications to Immobilized Cells or Enzymes .......... 298
10.9 Fed-Batch Operations .................................. 303
10.10 Overview ............................................. 312
11 Miscellaneous Reactions .................................... 317
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON, ALBERT RENKEN
11.1 Ethyl Acetate from Ethylene and Acetic Acid ........... 317
11.2 Claus Reaction ........................................ 324
11.3 Dehydrogenation of Methanol ........................... 325
11.4 Deamination and Alcohol Dehydration Reactions ......... 326
11.5 Photocatalytic Degradation of AZO Dyes ................ 332
11.6 The Minimal Bromate Reaction .......................... 332
11.7 Propanol Dehydrogenation .............................. 334
11.8 Glucose Oxidation ..................................... 336
11.9 Overview .............................................. 337
12 Modulation of Multiple Reactions ........................... 341
ROBERT ROSS HUDGINS, PETER LEWIS SILVESTON, ALBERT
RENKEN
12.1 Introduction .......................................... 341
12.2 Homogeneous Reactions ................................. 349
12.3 Solids Catalyzed Reactions ............................ 353
12.4 Competitive Reactions ................................. 359
12.5 Methane Homologation .................................. 361
12.6 Oligomerization of Ethene ............................. 365
12.7 Modulation of Multiple Inputs ......................... 366
13 Use of Modulation in Mechanistic Studies ................... 369
ALBERT REN KEN, ROBERT ROSS HUDGINS, PETER LEWIS
SILVESTON
13.1 Introduction .......................................... 369
13.2 Qualitative Applications .............................. 370
13.3 Quantitative Applications ............................. 371
13.4 Modulation of Light Intensity ......................... 374
13.5 Application of Modulation to the Testing of Rival
Models ................................................ 375
13.6 Overview .............................................. 385
14 Evaluation of Periodic Processes ........................... 387
MENKA PETKOVSKA, ANDREAS SEIDEL-MORGENSTERN
14.1 Introduction .......................................... 387
14.2 Nonlinear Frequency Response and Higher Order
Frequency Response Functions .......................... 389
14.3 Estimation of the Time Average Performance of
Periodic Processes Using Nonlinear Frequency
Response Analysis ..................................... 393
14.4 Application of Nonlinear Frequency Response
Analysis for the Estimation of the Periodic Steady
States of Cyclic Processes ............................ 405
14.5 Summary ............................................... 412
15 Pressure Modulation ........................................ 415
PETER LEWIS SILVESTON, ROBERT ROSS HUDGINS
15.1 Introduction .......................................... 415
15.2 Acceleration of Mass Transfer ......................... 416
15.3 Sonocatalysis ......................................... 427
15.4 Periodic Pressure Reduction ........................... 430
15.5 Combined Compression and Reaction ..................... 431
15.6 Application to Rate and Equilibrium Measurements ...... 432
15.7 Assessment and Research Opportunities ................. 433
16 Temperature Modulation ..................................... 435
JÜRGEN J. BRANDNER, PETER LEWIS SILVESTON, ROBERT ROSS
HUDGINS
16.1 Introduction .......................................... 435
16.2 Theoretical Studies ................................... 436
16.3 Simulation Studies .................................... 437
16.4 Experimental Studies with Conventional Laboratory
Equipment ............................................. 439
16.5 Temperature Modulation of Trickle Beds ................ 444
16.6 Experimental Studies with Microreactors ............... 444
16.7 Overview and Comments ................................. 462
17 Flow Interruption in Trickle Beds .......................... 463
PATRICIA HAURE, JIRI HANIKA, PETER LEWIS SILVESTON
17.1 Introduction .......................................... 463
17.2 Steady-State Operation of a Trickle Bed Reactor ....... 464
17.3 Periodic Operation of Trickle Bed Reactors ............ 474
17.4 Liquid Flow Modulation with Multiple Reactions ........ 481
17.5 Hydrodynamics Under Liquid Flow Modulation ............ 486
17.6 Modeling of the Periodic Operation of Trickle Bed
Reactors .............................................. 487
17.7 Summary ............................................... 493
18 Periodic Flow Reversal ..................................... 495
GRIGORII BUNIMOVICH, HRISTO SAPOUNDJIEV
18.1 The Heat-Trapping Concept ............................. 496
18.2 Theoretical Aspects ................................... 500
18.3 Oxidation of Volatile Organic Compounds ............... 511
18.4 Other Applications of Reverse Flow Reactors ........... 521
18.5 Thermal Reactors ...................................... 523
18.6 Endothermic Processes ................................. 528
18.7 Mass Trapping Reactors ................................ 534
18.8 Biofilters ............................................ 537
18.9 Miscellaneous Applications ............................ 537
18.10 Commercial Applications .............................. 538
19 Control of Periodically Operated Reactors .................. 543
HECTOR BUDMAN, PETER LEWIS SILVESTON
19.1 Formulation of an Optimal Control Problem for
a Periodically Operated Reactor ....................... 545
19.2 Chattering Controls ................................... 546
19.3 Controls for Stirred Slurry and Fluidized Bed
Reactors .............................................. 548
19.4 Controls for Packed Bed Reactors ...................... 553
19.5 Control of Packed Bed Reactors with Flow-Direction
Switching ............................................. 553
19.6 Control of Simulated Moving Bed Chromatographic
Reactors .............................................. 562
19.7 Other Control Schemes for Periodically Operated
Reactors .............................................. 564
19.8 Comments and Research Needs ........................... 565
20 Chromatographic Reactors ................................... 569
PETER LEWIS SILVESTON, KENJI HASHIMOTO, MOTOAKI KAWASE
20.1 Introduction .......................................... 569
20.2 Concept and Types ..................................... 570
20.3 General Models ........................................ 573
20.4 Cyclic Steady State ................................... 579
20.5 Pulse Chromatographic Reactor ......................... 580
20.6 Countercurrent Moving Bed Chromatographic Reactor ..... 587
20.7 Continuous Rotating Annular Chromatographic Reactor ... 590
20.8 Stepwise, Countercurrent Multi-Stage Fluidized Bed
Chromatographic Reactor ............................... 591
20.9 Fixed Bed Chromatographic Reactor With Flow Direction
Switching ............................................. 592
20.10 Extractive Reactor Systems ........................... 593
20.11 Centrifugal Partition Chromatographic Reactor ........ 593
21 Simulated Moving Bed Chromatographic Reactors .............. 597
KENJI HASHIMOTO, MOTOAKI KAWASE, PETER LEWIS SILVESTON
21.1 Operation and Application ............................. 598
21.2 Modeling and Simulation ............................... 599
21.3 Experimental Studies .................................. 620
21.4 Other Reactor Applications of Simulated Moving Beds ... 632
22 Pressure and Temperature Swing Reactors .................... 637
ALIRIO RODRIGUES, PETER LEWIS SILVESTON
22.1 Concepts and Types of Pressure Swing Reactors ......... 638
22.2 Models for Swing Reactors ............................. 640
22.3 Computational Considerations .......................... 642
22.4 Simulations of Pressure Swing Systems ................. 644
22.5 Experimental Studies .................................. 652
22.6 Temperature Swing Reactors ............................ 657
22.7 Simulation of Temperature Swing Systems ............... 660
22.8 Temperature Swing Reactor Networks .................... 663
22.9 Experimental .......................................... 663
22.10 Combined Pressure and Temperature Swing Reactors ..... 671
22.11 Overview and Assessment .............................. 674
23 New Directions—Research and Development Challenges ........ 679
KENJI HASHIMOTO, MOTOAKI KAWASE, MENKA PETSKOVSKA, JIRI
HANIKA, CHENC-YUE LI, ADESOJI ADESINA, HRISTO SAPOUNDJIEV,
JENO SCHARER, PETER LEWIS SILVESTON
23.1 Challenges ............................................ 680
23.2 New Directions ........................................ 686
References .................................................... 691
Index ......................................................... 749
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