Preface ........................................................ XV
About the Editors ............................................ XVII
List of Contributors .......................................... XIX
Part I Microreactor Design, Fabrication and Assembly ........... 1
1 Silicon and Class Microreaders ............................... 3
Roald M. Tiggelaar and J.С.E. (Han) Gardeniers
1.1 Introduction ............................................... 3
1.2 Design and Fabrication of Microreactors for Heterogeneous
Catalysis .................................................. 4
1.2.1 Low-temperature Microreactors ....................... 5
1.2.2 High-temperature Microreactors ...................... 7
1.3 Design and Fabrication of Microreactors for High-pressure
Applications .............................................. 14
1.4 Microreactors for Liquid-phase Organic Chemistry and
Biochemistry .............................................. 15
1.4.1 Integrated Microfluidic Networks for
High-throughput Experiments ........................ 15
1.4.2 Microreactors Employing Immobilized Molecular
Catalysts .......................................... 17
1.4.3 Enzymatic Microreactors ............................ 18
1.4.4 Synthesis of Bio-related Compounds: Peptides and
Sugars ............................................. 20
1.5 Conclusion ................................................ 21
References ..................................................... 21
2 Metallic, Steel, Ceramic and Plastic Microreactors .......... 25
Jürgen J. Brandner
2.1 Introduction .............................................. 25
2.2 Manufacturing Techniques for Metals ....................... 26
2.2.1 Etching ............................................ 26
2.2.2 Machining .......................................... 28
2.2.3 Generative Method: Selective Laser Melting ......... 30
2.2.4 Metal Forming Techniques ........................... 31
2.2.5 Assembling and Bonding of Metal Microstructures .... 32
2.3 Ceramic and Glass Devices ................................. 33
2.3.1 Ceramic Devices .................................... 33
2.3.1.1 Joining and Sealing ....................... 35
2.3.2 Glass Devices ...................................... 36
2.4 Polymer Microreactors ..................................... 37
2.4.1 Bonding of Polymer Materials ....................... 39
2.5 Conclusion ................................................ 39
References ..................................................... 40
Part II Bulk and Fine Chemistry ................................ 45
3 Liquid- and Liquid-Liquid-phase Reactions - Aliphatic
Substitution Reactions ...................................... 47
Paul Watts and Charlotte Wiles
3.1 Nucleophilic Substitution at Saturated Carbon ............. 47
3.2 Nucleophilic Substitution at Carbonyl Carbon .............. 49
3.2.1 Amide Synthesis .................................... 49
3.2.2 Ester Synthesis .................................... 54
3.3 Conclusion ................................................ 55
References ..................................................... 55
4 Liquid- and Liquid-Liquid-phase Reactions - Aromatic
Substitution Reactions ...................................... 57
Stefan Löbbecke
4.1 Electrophilic Aromatic Substitution ....................... 57
4.1.1 Friedel-Crafts Reactions ........................... 57
4.1.2 Nitrations ......................................... 60
4.1.3 Brominations and Iodinations ....................... 66
4.1.4 Other Electrophilic Aromatic Substitutions ......... 69
4.2 Nucleophilic Aromatic Substitution ........................ 73
4.3 Conclusion ................................................ 77
References ..................................................... 77
5 Liquid- and Liquid-Liquid-phase Reactions - Addition and
Elimination ................................................. 81
Jun-ichi Yoshida and Aiichiro Nagaki
5.1 Addition Reactions ........................................ 81
5.2 Elimination Reactions ..................................... 89
5.3 Addition-Elimination Reactions ............................ 90
5.4 Conclusion ................................................ 95
References ..................................................... 96
6 Liquid- and Liquid-Liquid-phase Reactions - Coupling
Reactions ................................................... 99
Ilhyong Ryu and Takahide Fukuyama
6.1 Metal-catalyzed Coupling .................................. 99
6.2 Reactions Using Organometallic Reagents .................. 102
6.3 Photochemical Coupling ................................... 104
6.4 Conclusion ............................................... 106
References .................................................... 106
7 Liquid- and Liquid-Liquid-phase Reactions - Oxidations
and Reduction .............................................. 109
Jun-ichi Yoshida and Aiichiro Nagaki
7.1 Oxidation ................................................ 109
7.1.1 Chemical Oxidation ................................ 109
7.1.2 Electrochemical Oxidation ......................... 112
7.1.3 Biochemical Oxidation ............................. 118
7.1.4 Miscellaneous Oxidations .......................... 122
7.2 Reduction ................................................ 123
7.3 Conclusion ............................................... 124
References .................................................... 125
8 Gas-Liquid-phase Reactions: Substitution ................... 131
Jun-ichi Yoshida and Aiichiro Nagaki
8.1 Fluorination ............................................. 131
8.2 Chlorination ............................................. 138
8.3 Nitration ................................................ 139
8.4 Conclusion ............................................... 139
References .................................................... 140
9 Gas-Liquid-phase Reactions: Addition ....................... 143
Claude de Bellefon
9.1 Types of Reactors ........................................ 143
9.2 Additions of H2, O2, O3 and CO/H2 Across C=C ............. 149
9.3 Other H2 Additions Across C=0, C≡N, C≡C, Aromatic,
Nitro and 0=0 Bonds ...................................... 154
9.4 Miscellaneous Additions .................................. 161
9.5 Conclusion ............................................... 162
References .................................................... 162
10 Cas-Liquid-phase Reactions: Reduction ...................... 167
Harshal Surangalikar, Shaun McCovern, and Ronald
S. Besser
10.1 Microreactor Configurations for Hydrogenation and
Dehydrogenation Reactions ................................ 168
10.1.1 Glass/Quartz Microreactors ........................ 168
10.1.2 Metal/Alloy Microreactors ......................... 168
10.1.3 Silicon-based Microreactors ....................... 169
10.1.4 Ceramic Microreactors ............................. 170
10.2 Catalysts ................................................ 170
10.3 Gas-phase Hydrogenation Reactions ........................ 170
10.4 Multiphase Hydrogenation Reactions ....................... 176
10.5 Conclusion ............................................... 182
References .................................................... 182
11 Cas-Liquid-phase Reactions: Miscellaneous Reactions ........ 187
Ilhyong Ryu and Md Taifur Rahman
11.1 Dehydration .............................................. 187
11.2 Phosgene Synthesis ....................................... 188
11.3 Fischer-Tropsch Synthesis ................................ 190
11.4 Carbonylation ............................................ 191
11.5 Conclusion ............................................... 195
References .................................................... 196
Part III Polymerization ....................................... 197
12 Free Radical Polymerization ................................ 199
Christophe Serra
12.1 Introduction ............................................. 199
12.1.1 Mechanism ......................................... 199
12.1.2 Main Features of FRP .............................. 201
12.1.3 Goodness of Mixing ................................ 202
12.2 Use of Microsystems in FRP ............................... 202
12.2.1 Advantages ........................................ 202
12.2.2 Experimental Investigations of the Use of
Microsystems in FRP ............................... 203
12.2.2.1 Micromixer-assisted Polymerization of
Acrylate Resins .......................... 203
12.2.2.2 FRP in Microreactors ..................... 204
12.2.2.3 Numerical Simulations of Styrene FRP in
Microsystems ............................. 209
12.3 Conclusion ............................................... 211
References .................................................... 212
13 Living Radical Polymerization .............................. 213
Thomas E. Enright
13.1 Living Polymerization .................................... 213
13.1.1 Free Radical Polymerization Mechanism ............. 215
13.2 Living Radical Polymerization General Mechanisms ......... 217
13.2.1 Dissociation-Combination .......................... 217
13.2.2 Atom Transfer ..................................... 217
13.2.3 Degenerative Chain Transfer ....................... 218
13.3 Nitroxide-mediated Polymerization ........................ 218
13.4 Atom Transfer Radical Polymerization ..................... 219
13.5 Reversible Addition-Fragmentation Chain Transfer ......... 220
13.6 NMP, ATRP and RAFT Summary ............................... 220
13.7 Living Radical Polymerization in Tubular Reactors ........ 221
13.8 Living Radical Polymerization in Microreactors ........... 221
13.9 Conclusion ............................................... 223
References .................................................... 223
14 Cationic Polymerization .................................... 229
Jun-ichi Yoshida and Aiichiro Nagaki
14.1 Introduction ............................................. 229
14.1.1 Basic Principles of Cationic Polymerization ....... 229
14.1.2 Controlled/Living Cationic Polymerization Based
on Cation Stabilization ........................... 230
14.2 Cationic Polymerization Involving Carbocationic
Intermediates Using Microflow Systems .................... 231
14.2.1 Controlled/Living Cationic Polymerization Based
on Cation Stabilization Using Microflow Systems ... 231
14.2.2 Controlled/Living Cationic Polymerization
Without Stabilization of Carbocationic
Intermediates Using Microflow Systems ............. 232
14.2.2.1 Concept of Microflow System-controlled
Polymerization Technology (MCPT) ......... 232
14.2.2.2 "Cation Рооl"-initiated Polymerization
Using a Microflow System ................. 233
14.2.2.3 Proton Acid-initiated Polymerization
Using Microflow Systems .................. 236
14.3 Ziegler-Natta Polymerization ............................. 241
14.4 Conclusion ............................................... 241
References .................................................... 242
15 Polycondensation ........................................... 245
Takeshi Honda and Hideaki Maeda
15.1 Introduction ............................................. 245
15.2 Synthesis of Fine Solid Material in a Microreactor ....... 246
15.2.1 Synthesis of Polymer Membranes .................... 246
15.2.2 Syntheses of Various Solid Materials by
Polycondensation .................................. 248
15.3 Solution-phase Polymerization Controlled in a
Microreactor ............................................. 249
15.3.1 Amino Acid Polymer Synthesis ...................... 249
15.3.2 Combinatorial and High-throughput Technologies
in Microfluidic Polymerization .................... 253
15.4 Conclusion ............................................... 254
References .................................................... 255
Part IV Functional Materials .................................. 257
16 Organic Particles and Pigments ............................. 259
Hieng Kim
16.1 Introduction ............................................. 259
16.1.1 Definition of Microfluidics ....................... 259
16.1.1.1 Further Definitions ..................... 260
16.1.2 Historical Development of Pigments/Colorants ...... 260
16.1.3 Conventional Production Methods/Conventional
Continuous Processes .............................. 261
16.2 Suitability of Microfluidic Devices for the Preparation
of Organic Particles and Pigments ........................ 264
16.2.1 Mixing and Nucleation ............................ 264
16.3 Laboratory-Scale Preparation ............................. 265
16.3.1 Pigments, Colorants ............................... 265
16.3.2 Monomeric Dyes .................................... 266
16.3.3 Polymer-analogue Dyes ............................. 267
16.4 Technical-scale Production of Organic Particles and
Pigments ................................................. 268
16.4.1 Pigments, Colorants .............................. 268
16.5 Conclusion and Outlook ................................... 269
References .................................................... 270
17 Inorganic Particles ........................................ 273
Michael Köhler
17.1 Introduction ............................................. 273
17.2 Dielectric Nanoparticles ................................. 274
17.3 Semiconductor Nanoparticles .............................. 275
17.4 Metal Nanoparticles ...................................... 276
17.5 Transport Conditions in Nanoparticle Formation ........... 284
17.6 Applications of Nanoparticles in Microreactors ........... 285
17.7 Conclusion ............................................... 286
References .................................................... 286
18 Polymer Particles .......................................... 289
Christophe Sena
18.1 Introduction ............................................. 289
18.2 Most Common Microsystems ................................. 290
18.2.1 Emulsification Technique .......................... 290
18.2.2 Projection Photolithography Technique ............. 291
18.3 Examples of Various Polymer Particles Produced with
Microsystems ............................................. 292
18.3.1 Terrace-like MicroChannel Devices ................. 292
18.3.2 T-junction MicroChannel Devices ................... 294
18.3.3 Flow Focusing Devices ............................. 298
18.3.4 Projection Photolithography Devices ............... 307
18.4 Conclusion ............................................... 310
References .................................................... 311
19 Microencapsulates, Proteins and Lipids/Vesicles ............ 313
John van der Schaaf
19.1 Introduction ............................................. 313
19.2 Production Methods ....................................... 314
19.3 Conclusion ............................................... 321
References .................................................... 321
20 Oil-in-Water and Water-in-Oil Emulsions .................... 325
Heike P. Schuchmann, Karsten Köhler, Freddy Aguilar, and
Andreas Hensel
20.1 Emulsion Basics .......................................... 325
20.1.1 Definitions, Major and Minor Ingredients .......... 325
20.1.2 Emulsion Properties and Their Design .............. 326
20.1.3 Principle of Emulsification ....................... 327
20.2 Emulsification Process Functions ......................... 327
20.2.1 Droplet Disruption Theory ......................... 327
20.2.2 Droplet Disruption in Turbulent and Laminar Flow .. 328
20.2.3 Droplet Formation and Detachment at Membrane
Surfaces .......................................... 330
20.3 Emulsification Processes ................................. 331
20.3.1 Conventional and Innovative Techniques ............ 331
20.3.2 Microengineered Devices ........................... 332
20.3.2.1 High-pressure Homogenization Nozzles ..... 332
20.3.2.2 Membranes, Microporous and MicroChannel
Systems .................................. 332
20.3.2.3 Microengineered Mixers (Micromixers) ..... 335
20.3.2.4 Simultaneous Mixing and Homogenization
(Microengineered SMH-Valve) .............. 337
20.3.3 Emulsification in Microengineered Devices ......... 339
20.4 Conclusion and Outlook ................................... 340
References .................................................... 341
21 Double, Triple and Complex Multilayered Emulsions .......... 345
Takasi Nisisako
21.1 Introduction ............................................. 345
21.2 Membrane Emulsification .................................. 347
21.3 MicroChannel (MC) Emulsification ......................... 348
21.4 Two-dimensional Microfluidic Systems ..................... 350
21.5 Three-dimensional (3D) Coaxial Microcapillary Systems .... 352
21.6 Applications to Novel Materials .......................... 355
21.7 Conclusion ............................................... 355
References .................................................... 355
22 Microreactor Applications in the Consumer Goods Industry ... 363
Patrick Löb, Volker Hessel, and Alberto Sinnoncelli
22.1 Introduction ............................................. 363
22.2 General Aspects of Microreactor Applications for
Emulsification Processes ................................. 364
22.3 Comparison of Micromixers with Regard to Performance in
Liquid-Liquid Dispersions ................................ 366
22.4 Dispersion and Mixing of High-viscosity Liquids .......... 368
22.5 Cream Formation in Micromixers Targeting a Reduction in
Emulsifiers and Preservatives ............................ 371
22.6 Customer-based Production of Emulsions and More .......... 372
22.7 Vesicle Formation in Microfluidic Structures ............. 376
22.8 Liquid Detergent Production by Surfactant Dispersion ..... 377
22.9 Screening of Cream Formulations .......................... 380
22.10 Microencapsulation Processes ............................ 381
22.11 Alginate Gelation in Microfluidic Channels .............. 383
22.12 Production of Base Chemicals Exemplified by SO3
and Detergent Production ................................ 384
22.12.1 Introduction ..................................... 385
22.12.2 Sulfonation of Toluene with Gaseous Sulfur
Trioxide in a Microreactor Setup ................. 385
22.12.3 One-pass Synthesis of Pure Sulfur Trioxide in
Microreactors .................................... 387
22.13 Homogenization of Dairy Products ........................ 389
22.14 Outline of Additional and Potential Aspects of
Microreactor Applications in the Consumer Goods
Industry ................................................. 390
22.14.1 Microfluidic Devices in Chemical Sensing of
Flavors and Fragrances ........................... 391
22.14.2 Accessibility of New Materials Exemplified by
the Controlled Synthesis of Polymer Particles .... 393
22.14.3 Controlled Formation of Monodisperse Double
Emulsions in a Microfluidic System ............... 394
22.15 Summary and Outlook ..................................... 395
References .................................................... 399
Part V Fuel Processing ........................................ 4O3
23 Application and Operation of Microreactors for Fuel
Conversion ................................................. 405
Peter Pfeifer, Katja Haas-Santo, and Oliver Görke
23.1 Applications of Fuel Conversion .......................... 405
23.1.1 Power Range ....................................... 405
23.1.2 Demands from Applications ......................... 406
23.1.3 Fuels ............................................. 407
23.2 Operation of Microreactors for Fuel Conversion ........... 407
23.2.1 Routes for Fuel Conversion ........................ 407
23.2.2 Gas Clean-up ...................................... 409
23.2.3 Heat Generation ................................... 410
23.2.4 Development Stages ................................ 411
23.2.5 Integrated Plant Concepts ......................... 411
23.2.6 Examples of Different Approaches and Integration
Levels ............................................ 412
23.2.7 Influences on Efficiency .......................... 417
23.3 Conclusion and Outlook ................................... 418
References .................................................... 419
24 Steam Reforming ............................................ 421
Gunther Kolb
24.1 Introduction ............................................. 421
24.2 Reaction System .......................................... 421
24.3 Catalyst Coatings for Steam Reforming in Microchannels ... 422
24.3.1 Catalyst Development and Characterization for
Alcohol Steam Reforming in Microchannels .......... 422
24.3.2 Development of Catalyst Coatings for Hydrocarbon
Steam Reforming in Microchannels .................. 425
24.4 System Design and Integrated Microstructured Reactors .... 426
24.4.1 Design Concepts of Microstructured Fuel
Processors for Fuel Cells ......................... 426
24.4.2 Reactors for Alcohol Steam Reforming .............. 427
24.4.2.1 Reactors for Methanol Steam Reforming
in the Low and Sub-watt Power Range ...... 428
24.4.2.2 Alcohol Steam Reforming in
Microstructured Plate Heat Exchangers .... 431
24.4.2.3 Hydrocarbon Steam Reforming in
Microstructured Plate Heat Exchangers .... 435
24.5 Conclusion ............................................... 439
References .................................................... 439
25 Partial Oxidation .......................................... 445
Peter Pfeifer
25.1 Distinction Between Catalytic and Industrial Processes ... 446
25.2 Catalysts ................................................ 446
25.2.1 Catalytically Active Species ...................... 447
25.2.2 Catalytic Supports and Promoters .................. 448
25.3 Reactor Design and Results ............................... 450
25.3.1 Packed Beds and Foams in Microstructures .......... 451
25.3.2 Catalytic Wall Reactors ........................... 453
25.3.2.1 Microstructured Catalytically Active
Materials ................................ 453
25.3.2.2 Deposition of Catalytically Active
Species on Microstructure Walls .......... 455
25.3.2.3 Deposition of Catalytically Active
Species on Additional Catalyst Supports .. 457
25.4 Reactor Comparison ....................................... 460
25.5 Conclusion ............................................... 462
References .................................................... 463
26 CO Clean-up: Water Gas Shift and Methanation Reactions ..... 465
Andre C. van Veen, Yves Schuurman, and Claude Mirodatos
26.1 Background of the Two Reactions .......................... 465
26.2 Commercial and R&D Catalysts ............................. 468
26.2.1 Temperature Range of Operation .................... 468
26.2.2 Operational Limits ................................ 469
26.2.3 Non-pyrophoric Catalysts .......................... 469
26.2.4 Methanation Catalysts ............................. 470
26.3 Motivation for Microstructured Reactors .................. 470
26.3.1 WGS Reaction ...................................... 470
26.3.2 Methanation Reaction .............................. 470
26.4 Examples of Microstructured Reactor Developments ......... 471
26.4.1 WGS Reaction ...................................... 471
26.4.2 Methanation Reaction .............................. 475
26.5 Conclusion ............................................... 476
References .................................................... 476
27 CO Clean-up: Preferential Oxidation ........................ 479
Xun Ouyang and Ronald S. Besser
27.1 Introduction ............................................. 479
27.2 PrOx Kinetics ............................................ 480
27.3 PrOx in Microreactors .................................... 482
27.3.1 Microreactors as Tools for Catalyst and Kinetic
Studies ........................................... 482
27.3.1.1 Catalyzed Microstructured Reactors for
PrOx Catalyst Screening .................. 482
27.3.1.2 Silicon Microfabricated PrOx Reactor
with Washcoated Microposts ............... 484
27.3.1.3 Improved PrOx Performance Versus
Monolith ................................. 484
27.3.1.4 PrOx Study with Grooved Stainless-steel
Foils and Au-based Catalysts ............. 485
27.3.2 PrOx in Integrated Fuel Processors ................ 486
27.3.2.1 A 2.4 We Micro Fuel Processor Based on
Microchannels ............................ 486
27.3.2.2 MicroChannel Reactors for a 100 We
Portable Fuel Processor .................. 488
27.3.2.3 A 100 We Gasoline Fuel Processor Based
on Foam Structure with Micropores ........ 489
27.3.2.4 A 2 kWe Multistage PrOx MicroChannel
Reactor .................................. 490
27.4 A Detailed Example: A Thin-film Catalytic Microreactor
as a Kinetic Tool ........................................ 491
27.4.1 Experimental ...................................... 492
27.4.2 Microkinetic Reaction Simulation .................. 493
27.4.3 Quasi-3D Non-isothermal Reactor Model ............. 495
27.5 Conclusion ............................................... 499
References .................................................... 499
Index ......................................................... 503
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