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W. Ehrfeld, V. Hessel, H.

Löwe
Microreactors

Microreactors: New Technology for Modern Chemistry. W. Ehrfeld, V. Hessel, H. Löwe
Copyright © 2000 WILEY-VCH Verlag GmbH, Weinheim
ISBN: 3-527-29590-9

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Holger Löwe Microreactors New Technology for Modern Chemistry Weinheim · New York · Chichester · Brisbane · Singapore · Toronto III . Volker Hessel.Wolfgang Ehrfeld.

even when not specifically marked as such are not to be considered unprotected by law. Registered names.: applied for British Library Cataloguing-in-Publication Data: A catalogue record for this book is available from the British Library Die Deutsche Bibliothek – CIP-Einheitsaufnahme A catalogue record for this book is available from Die Deutsche Bibliothek ISBN 3-527-29590-9 © WILEY-VCH Verlag GmbH. H.und Software-Service Manuela Treindl. Germany. 2000 Printed on acid-free and low chlorine paper All rights reserved (including those of translation into other languages). D-67433 Neustadt Printed in the Federal Republic of Germany IV . V. Löwe Institut für Mikrotechnik Mainz GmbH Carl-Zeiss-Straße 18–20 55129 Mainz Germany This book was carefully produced. Readers are advised to keep in mind that statements. illustrations. First Edition 2000 Cover Illustration: Interdigital micromixers realized by small series fabrication. Osswald & Co. D-93059 Regensburg Printing: Strauss Offsetdruck GmbH.W. Mainz. etc. Ehrfeld. trademarks. Hessel. procedural details or other items may inadvertently be inaccurate. D-69509 Mörlenbach Bookbinding: Wilh. Library of Congress Card No.. No part of this book may be reproduced in any form – by photoprinting. authors and publisher do not warrant the information contained therein to be free of errors. microfilm. D-69469 Weinheim (Federal Republic of Germany). or any other means – nor transmitted or translated into a machine language without written permission from the publishers. data. Nevertheless. used in this book. Courtesy of IMM Mainz GmbH. Composition: Text.

the series of “International Conferences on Microreaction Technology” being the focus of this exchange of scientific results. the authors strongly felt that it is high time to summarize and categorize the research work in recent years. as well as DuPont and UOP in the U. just to name a few. The numerous teams of researchers investigating microreaction technology belong to many disciplines. modeling. The Merck company presented their first example of implementing a new industrial process. But not only German companies are involved.A. and testing is provided and increasingly spread between different journals. Knowledge concerning microfabrication. thus stimulating a rapid accumulation of know-how in the field of micromixing. but is also designated to reveal its full beauty and breathless excitement. e. the corresponding habits of the researchers. It seems to be that something which was hidden for a long time is now bursting out. Innovative companies like DuPont and BASF promoted and supported these developments by own activities from the very beginning. to evidence the success of mutual interaction. a journal on microreaction technology. and mechanical engineers. e. the success of this emerging technology these days is beyond doubt. V . chemical engineers. Schering. Some of these devices even are available commercially and being tested by a growing community of researchers. the book. chemists.Preface Today’s microreaction technology is no longer in its infancy. Axiva seems to be interested to become a professional provider of modern process development utilizing microreactors. A number of companies followed these examples. Hence. sometimes even accompanied by skepticism and lack of understanding. maybe even more notable. holds for interdigital micromixers. as microreaction technology itself. and has the potential to a complete change of today’s chemical methodologies and. have become more and more active. physicists. and to high-light the benefits of such a strategy. e.g. a vivid communication has started. design concepts. for instance. Rhône-Poulenc/Rhodia in France. material scientists. Due to this growing number of publications and a so far missing common platform. In this context. this book presents the state of the art of this new discipline. Degussa-Hüls. Industrial contributions played an important role throughout the recent years’ developments.S.g.g. Meanwhile. and Bayer. Shell in the Netherlands and the United Kingdom. This. The technical and scientific development concerning micoreactors is tremendous. It tries to join the different disciplines. Whereas the first four years of development were characterized by basic feasibility work and the development of methods. It is neither intended to attract chemists or chemical engineers only nor being dedicated to “microtechnicians”. should be of interdisciplinary character in the true sense. Small microfabricated reactors have proven to provide excellent mass and heat transfer properties as well as uniform flow patterns and residence time distributions. at least assisted by means of microreaction technology. This book is written both for the newcomer and the expert as well as for researchers from industry and research institutions.

and Ch. concepts are introduced as well and the respective fields of applications are indicated. the authors would like to acknowlegde the aid of all members of the Microreaction Technology and Chemistry Departments at the Institut für Mikrotechnik Mainz. Finally. there is an ultimate need to expand this systematic analysis in a future version of this book. However. early recognizing the importance of microreaction technology and providing the possibility for this comprehensive volume. Presently. IMRET 4 in Atlanta is just around the corner. Standardization and system assembly as well as commercialization of microreactors may become relevant key topics.Preface The book contents are subdivided into two major parts. H. as all hard and genuine work. For instance. Hofmann for illustration. while in separate sections details are discussed therein. Additionally. These interesting topics certainly will contribute to the growing progress in microreaction technology. this refers to L. the authors are deeply indebted to the scientific community active in microreaction technology. The same holds for the VCH-Wiley publishers. Schiewe and Th. all funders and believers in this technology are acknowlegded. Hessel. seldom is elaborated by a single person or a small group on their own. V. The beginning of each chapter is aimed to present general aspects of a specific class of microdevices. We are really glad that we actively could take part in such a fascinating development. Nevertheless. Löwe VI Mainz. but rather in a framework of human co-operation. March 2000 . such a systematic analysis in most cases is limited since a number of activities regarding microreactors still remain in their starting phase. a number of researchers helped a lot by providing illustrations and proof-reading of sections. The technology development certainly will speed up. in particular from chemical industries as well as the DECHEMA and DARPA organizations. large parts of this book contain a multitude of single information compiled in a comprehensive volume. Consequently. In this context. In particular. Agueda for organization. Ehrfeld. Richter for discussion and proof-reading. A book. W. J. Production issues based on microreactors – a topic only mentioned in a whisper two years ago – attracts increasing interest.

.......... 16 Anisotropic Wet Etching of Silicon ...................Contents 1 1............ 1 Functional Classification of Microreactors ..... 30 Microlamination of Thin Metal Sheets ... 29 Interconnection Techniques ............2.. 20 Injection Molding ..................4 2.........................................2 1.............3 1........................ 17 Dry Etching of Silicon ........8......................................... 12 2 2.......................... 29 Laser Micromachining .......................2 2..... 35 VII ....... Turning and Drilling ........................................................................................ 33 Functional Coatings for Corrosion Prevention .....................................4 State of the Art of Microreaction Technology ..................................................... 8 Potential Benefits of Microreactors Regarding Applications .......................................2 2.......................4 1...........................................................................................................................1................................. 15 Evaluation of Suitability of a Technique ..............................1 2.............................10....... 4 Fundamental Advantages of Microreactors ..... 27 µ-EDM Drilling ........................................................................................................................1 2........... 6 Advantages of Microreactors Due to Increase of Number of Units ...................10 2........................1 1..............................3 1................. 5 Fundamental Advantages of Nano-Scale Reactors .....1...........4 1................2 2.............. 22 Advanced Mechanical Techniques ......................1 1.......... 4 Dividing Line Between Analysis and Reaction Systems ............................................................ 5 Advantages of Microreactors Due to Decrease of Physical Size ...................2.......... 24 Embossing ............................................................................................... 33 Functional Coatings for Fouling Prevention ....................... 25 Electro Discharge Machining (EDM) of Conductive Materials ........2 1.....................................................................8................13 2......6 2...................... 5 Fundamental Advantages of Miniaturized Analysis Systems .......... 1 Structural Hierarchy of Microreactors ..................................................5 2............................................................... 1 Definition ......................2 1....12 2..... 23 Surface Cutting with Diamond Tools .................................................................. 10 References .......................................................13....... 24 Isotropic Wet Chemical Etching of Metal Foils ..3 1................ 34 References ...1......................2..........................13......2 2.............................. 30 Functional Coatings .8......... 23 Milling......9 2.......3 2....................................................8............. 26 Wire-Cut Erosion and Die Sinking ................14 Modern Microfabrication Techniques for Microreactors .4 2.............. 23 Punching .11 2.................................1 2.......................................................................................................................................................... 21 Wet Chemical Etching of Glass .........10......... 19 LIGA Process ..7 2..... 1 Microsystems Termed Microreactor .................. 15 Microfabrication Techniques Suitable for Microreactor Realization ........3 2..............................1 2............1 1................................................................1.........................................................2......................................1 2...............12.........8 2..............

......................1 3.................................................................. 99 Heat Exchanger with Double-Sided Structured Channels .................3 4..........1 3.............................. 55 Multiple Flow Splitting and Recombination Using Fork-Like Elements .......3 3............................. 55 Multiple Flow Splitting and Recombination Combined with Channel Reshaping ........... 49 Mixing Tee-Type Configuration .............2 3.......................8.. e..............8 3..............7 3...1............................................................................7............................. 50 Collision of High-Energy Substreams for Spraying/Atomizing .....................g.. 80 Externally Forced Mass Transport.... 83 References .............. 53 Manifold Splitting and Recombination of a Stream Consisting of Two Fluid Lamellae of Both Components ...........10 VIII ....7...........g......................... 75 Multilamination Using a Stack of Platelets with Star-Shaped Openings .................. 62 Injection of Many Substreams of Both Components ....1.....4 3..........1.........6 3...... 49 Double Mixing Tee-Type Configuration .......10..........1 3....................................................2 3........... 83 4 4...........1 3....3 3.2 3................... 80 Decrease of Layer Thickness by Hydrodynamic Focusing ........................... Electrical and Thermal Energy .......................................................7.......11 Micromixers ..... 73 Multilamination Using a Stack of Platelets with Microchannels ...1 3. by Stirring...........4....6.2.. 53 Injection of Multiple Microjets ....1. 41 Mixing Principles and Classes of Miniaturized Mixers ..................... 83 Dynamic Micromixer Using Magnetic Beads ..................................................................... 100 3...8...1 3......................... 64 Vertical Multilamination of Fluid Layers Using a V-type Nozzle Array .........................................................2.2 3........... 60 Multiple Flow Splitting and Recombination Using a Ramp-Like Channel Architecture ..... e..........4 3...............8........7.....5................ 58 Multiple Flow Splitting and Recombination Using a Separation Plate .............4 4........ 52 Injection of Many Small Substreams of One Component into a Main Stream of Another Component .....................2 4...... 52 Collision of Three Substreams in a Microjet Reactor ....4 3.......... 41 Mixing Principles and Classes of Macroscopic Mixing Equipment .................................. in a Mixing Tee Configuration ............ 64 Multilamination of Fluid Layers in an Interdigital Channel Configuration .....................................................................1 3........... 89 Cross-Flow Heat Exchange in Stacked Plate Devices .........................4......... 89 Cross-Flow Heat Exchange Based on Cross-Mixing ..................... 99 Heat Exchanger with One-Sided Structured Channels .............8................5 3............1 4....................Contents 3 3............................9 3.... 87 Micro Heat Exchangers with Wide and Flat Channels .......2 Micro Heat Exchangers ........................................................................ 97 Micro Heat Exchangers with Narrow and Deep Channels ............................................................................................................. 92 Counter-Flow Heat Exchange in Stacked Plate Devices ... 94 Electrically Heated Stacked Plate Devices ...............1 4....................................... 79 Decrease of Diffusion Path Perpendicular to the Flow Direction by Increase of Flow Velocity . 43 Potential of Miniaturized Mixers ...........2 4................................ 46 Contacting of Two Substreams.....3 3...........................9.................................1 4.................1 3................ Ultrasonic Wave......

............. 143 Types of Liquid Phase Microreactors ............................................................ 115 Microextractors ...........................1 4.....................1 5........2 5..................6 6 6... 102 Axial Heat Conduction ......5 6....................... 126 MicromixerSettler Systems ......................................7 6......................................................................................................4 6......2 4.... 122 Contactor Microchannels Separated by Sieve-Like Walls ....................................................1................................................... 108 Performance Characterization of Micro Heat Exchangers ..............................2 6.............5 5............... 140 Microsystems for Liquid Phase Reactions ... 110 References .............................................................................................................. 115 Wedge-Shaped Flow Contactor .......... 136 Analytical Modules for In-Line IR Spectroscopy ............ 158 Dushman Reaction Using Hydrodynamic Focusing Micromixers and High-Aspect Ratio Heat Exchangers ..................4 5........... 133 Gas Separation Microdevices ..........................................................4 4...............................................................4............ 166 IX .........................................2............................... 154 Laboratory-Scale Organic Chemistry in Micromixer/Tube Reactors .....................3 5......................2 5.....6 6...... 109 Temperature Profiles of Micro Heat Exchangers Yielded by Thermograms of Infrared Cameras ...................................................... 107 Microtechnology-Based Chemical Heat Pumps .........1 5..1.............................. 104 Numerical Calculations of the Influence of Material Choice on Heat Transfer Efficiency .........Contents 4............................................1............ 144 Liquid/Liquid Synthesis of a Vitamin Precursor in a Combined Mixer and Heat Exchanger Device .... 105 Permanent Generation of Entrance Flow by Fins ..8 Micro Heat Exchangers with Breakthrough Channels ..................................................................................................................................... 131 Gas Purification Microsystems .............9 5 5.......................... 126 Microfilters ......................2.......... 112 Microseparation Systems and Specific Analytical Modules for Microreactors ...... 164 Electrochemical Microreactors .................... 134 Specific Analytical Modules for Microreactors .........................................6 4.........................................................3 4................................................... 136 References ..........5 4.. 144 Acrylate Polymerization in Micromixers ...................................8......................2 5............. 119 Contactor Microchannels Separated by a Micromachined Membrane .... 162 Synthesis of Microcrystallites in a Microtechnology-Based Continuous Segmented-Flow Tubular Reactor .................5.....1 5.....................1..........8 4.....................1 6........................ 131 Cross-Flow Microfilters ............................................................................5......................... 130 Isoporous-Sieve Microfilters ......1 5............... 115 Partially Overlapping Channels .......................4.............................3 5..........................................................7 4................................. 136 Analytical Module for Fast Gas Chromatography .................4 5.............................. 104 The Use of Thermal Blocking Structures .. 151 Ketone Reduction Using a Grignard Reagent in Micromixers ......... 106 Generation of a Periodic Flow Profile by Sine-Wave Microchannels .................2 5.........................................5 5........................1..1 4..3 6............................

.................5 7............2 8..............2.....9 7 7......8...................7 7.................... 178 Selective Partial Hydrogenation of a Cyclic Triene ...................................8..................... 177 Partial Oxidation of Propene to Acrolein ...............................3..................................... Catalyst Structures and Sensors ..................1 7..................................................6............................................................................................. 188 Microsystems with Integrated Catalyst Structures and Heat Exchanger ....3 7... 235 ..................................... 193 Oxidative Dehydrogenation of Alcohols .............................1 7........2 6................................................................. 186 Selective Oxidation of 1-Butene to Maleic Anhydride ..................................... 209 Oxidation of Ammonia ........... 187 Reactions Utilizing Periodic Operation ................................3....1 7....2...........................4 7...............................7........................ 229 Contacting of Two Gas and Liquid Substreams in a Mixing Tee Configuration ................7 7......................................................2 7... 197 H2/O2 Reaction in the Explosion Regime .........6 7...............8 8 8.4..........................1 8..1 8..........................4 7...... 180 H2/O2 Reaction .1 6....... 176 Microchannel Catalyst Structures .................6............................... 232 Injection of Many Gas and Liquid Substreams into One Common Channel ............... 209 H2/O2 Reaction ................2 7................................... 232 Injection of One Gas and Liquid Substream .................................. 224 Gas/Liquid Microreactors ..... 173 Catalyst Supply for Microreactors ......2 7.....................4.......................................... 171 Microsystems for Gas Phase Reactions .....................8 7.......................5.................................................................................. 233 Injection of Many Gas and Liquid Substreams into One Packed Channel ......................................4.................................... 217 HCN Synthesis via the Andrussov Process .........1 7.......................... 187 Selective Oxidation of Ethylene to Ethylene Oxide ................. 166 Scouting Potentiodynamic Operation of Closed Microcells ................................................................................................. 173 Types of Gas Phase Microreactors .......5 7........................... 229 Gas/Liquid Contacting Principles and Classes of Miniaturized Contacting Equipment .....................3................................1 7..................................... 203 Synthesis of Ethylene Oxide ................................3..............3 X Synthesis of 4-Methoxybenzaldehyde in a Plate-to-Plate Electrode Configuration ............................. 177 Flow Distribution in Microchannel Catalyst Reactors ................................................. Heat Exchanger and Sensors .....3............................ 214 Microsystems with Integrated Mixer..........................3 7.......2 8......... Heat Exchanger..........2.............3........................ 169 References .......................................................3.....................3 7..................................................................................... 217 References ................... 193 Synthesis of Methyl Isocyanate and Various Other Hazardous Gases .................................3.............................................1 7...............................................................2 7......................6 7......................Contents 6............ 203 Microsystems with Integrated Catalyst Structures..... 184 Selective Partial Hydrogenation of Benzene ................................ 200 Microsystems with Integrated Catalyst Structures and Mixer ...........................

..............2 10................................ 276 11......1 11...........................................................2.................................................................................. 274 References ...........................................................................................................3.......... 239 Generation of Thin Films in a Falling Film Microreactor ....................................... 285 XI ...... 278 The Disposable Batch Miniplant ..............3 9.......... 271 Parallel Screening of Heterogeneous Catalysts in Conventional Mini-Scale Reactors ............ 279 Paradigm Change in Large-Scale Reactor Design Towards Operability and Environmental Aspects Using Miniplants ............. 277 Miniplant Concept for HCN Manufacture ........... 260 Hydrogen Generation by Partial Oxidations ............2 9.................................... 257 Microdevices for Vaporization of Liquid Fuels ...........2 Injection of Many Gas Substreams into One Liquid Channel with Catalytic Walls .......... 277 The Miniplant Concept ......................................................................5 8..............................................................3 11 11...................................2.............4 9 9...........3 8....... 257 Microdevices for Conversion of Gaseous Fuels to Syngas by Means of Partial Oxidations . 255 Microsystems for Energy Generation .............3 Methodology for Distributed Production ........................................................ 265 Steam Reforming of Methanol in Microstructured Platelets ..............1...............................2.............. 271 Parallel Screening of Heterogeneous Catalysts in a Microchannel Reactor ............................. 237 Injection of Many Gas and Liquid Substreams into Multiple Channels .... 265 References ....... 244 References ................................................... 261 Partial Oxidation of Methane in a Microchannel Reactor ..........4 8..2...............................................................1 10........................................4 10 10..............................................................................................................2 11....... 260 Partial Oxidation of Methane in a Stacked Stainless Steel Sheet System ...................... 280 References ...........1 11......2....................................1 9......................................................3 9.................................................................... 283 Index ......................................................................................1 9..........Contents 8..................... 263 Microdevices for Conversion of Gaseous Fuels to Syngas by Means of Steam Reforming ...................................................1 9......1................................................... 268 Microsystems for Catalyst and Material Screening ...2 9..