Microreactors in Preparative Chemistry: Practical Aspects in Bioprocessing, Nanotechnology, Catalysis and more

This is the first book in the field to focus on these aspects, providing extremely valuable information unavailable elsewhere for anyone seeking the practical application of microreactor technology in preparative chemistry. The topics covered branch out in three different directions. To begin with, the knowledge necessary for the preparative chemistry concerning the influence of the so–called microeffects on the reaction procedure and on mass and heat transfer as well as the surface phenomena are provided in detail. Next, practical aspects of the synthesis of various basic chemicals and fine chemicals, polymers, bioproducts and nanoparticles are discussed, including important advice for both the researcher and industrial chemist. Finally, reaction examples in microreactors whose reaction guidance are best understood are given together with universally applicable correlations as well as modeling approaches and transfer potential on related reaction systems. With its specific instructions, tips and experimental procedures for product syntheses as well as the inclusion of both the technical and theoretical background this is a must–have for beginners and experts alike working in this emerging field.

Preface XI List of Contributors XIII 1 Principles of Microprocess Technology 1 Wladimir Reschetilowski 1.1 Introduction 1 1.2 History 2 1.3 Basic Characteristics 3 1.4 Industrial Applications 8 1.5 Concluding Remarks 9 References 10 2 Effects of Microfluidics on Preparative Chemistry Processes 13 Madhvanand Kashid, Albert Renken, and Lioubov Kiwi–Minsker 2.1 Introduction 13 2.2 Mixing 15 2.3 Heat Management 18 2.4 Mass Transfer and Chemical Reactions 26 2.5 Flow Separation 40 2.6 Numbering–Up Strategy 45 2.7 Practical Exercise: Experimental Characterization of Mixing in Microstructured Reactors 46 References 50 3 Modular Micro– and Millireactor Systems for Preparative Chemical Synthesis and Bioprocesses 55 Frank Schael, Marc–Oliver Piepenbrock, J€orn Emmerich, and Joachim Heck 3.1 Introduction 55 3.2 Modular Microreaction System 57 3.3 Examples for Microreactor Applications 60 3.4 Laboratory Exercise: Suzuki Reaction in a Modular Microreactor Setup 70 References 73 4 Potential of Lab–on–a–Chip: Synthesis, Separation, and Analysis of Biomolecules 77 Martin Bertau 4.1 Introduction 77 4.2 Learning from Nature: Analogies to Living Cells 77 4.3 Microenzyme Reactors 79 4.4 Microchip Electrophoresis 87 4.5 Microenzyme Membrane Reactor/Micromembrane Chromatography 89 4.6 Nucleic Acid Analysis in Microchannels 91 4.7 Saccharide Analyses in Microdevices 94 4.8 Practical Exercise: Lipase–Catalyzed Esterification Reaction 96 References 97 5 Bioprocessing in Microreactors 101 Fridolin Okkels and Dorota Kwasny 5.1 Introduction 101 5.2 Background 101 5.3 Practical Exercise: Functionalization of Silicon Surface 108 References 113 6 Synthesis of Fine Chemicals 115 Sandra H€ubner, Norbert Steinfeldt, and Klaus J€ahnisch 6.1 Introduction 115 6.2 Organic Synthesis in Liquid and Liquid–Liquid Phases 116 6.3 Gas–Liquid Biphasic Organic Synthesis 141 6.4 Practical Exercise: Photochemical Generation of Singlet Oxygen and Its [4þ2] Cycloaddition to Cyclopentadiene 159 References 161 7 Synthesis of Nanomaterials Using Continuous–Flow Microreactors 165 Chih–Hung Chang 7.1 Introduction 165 7.2 Microfluidic Devices 165 7.3 Synthesis of Nanomaterials Using Microreactors 166 7.4 Kinetic Studies 180 7.5 Process Optimization 183 7.6 Point–of–Use Synthesis and Deposition 185 7.7 Practical Exercises: Synthesis of Nanocrystals 187 References 192 8 Polymerization in Microfluidic Reactors 197 Jesse Greener and Eugenia Kumacheva 8.1 Introduction 197 8.2 Practical Considerations 198 8.3 Single–Phase Polymerization 205 8.4 Multiphase Polymerization 208 8.5 Beyond Synthesis: New Developments for Next–Generation MF Polymerization 220 8.6 Practical Exercise: MF Polymerization Reactor Kinetics Studies Using In Situ Characterization 224 References 227 9 Electrochemical Reactions in Microreactors 231 Jun–ichi Yoshida and Aiichiro Nagaki 9.1 Introduction 231 9.2 Electrode Configuration 232 9.3 Electrolysis without Supporting Electrolytes 234 9.4 Generation and Reactions with Unstable Intermediates 235 9.5 Practical Exercise: Electrochemical Reactions in Flow Microreactors 239 References 241 10 Heterogeneous Catalysis in Microreactors 243 Evgeny V. Rebrov 10.1 Introduction 243 10.2 Bulk Catalysts 244 10.3 Supported Catalysts 246 10.4 Mesoporous Supports 256 10.5 Microporous Supports 261 10.6 Practical Exercise: PdZn/TiO2–Catalyzed Selective Hydrogenation of Acetylene Alcohols in a Capillary Microreactor 263 References 265 11 Chemical Intensification in Flow Chemistry through Harsh Reaction Conditions and New Reaction Design 273 Timothy No€el and Volker Hessel 11.1 Introduction 273 11.2 High–Temperature Processing in Microflow 273 11.3 High–Pressure Processing in Microflow 278 11.4 Solvent Effects in Microflow 280 11.5 Ex–Regime Processing and Handling of Hazardous Compounds in Microflow 283 11.6 New Chemical Transformations in Microflow 284 11.7 Process Integration in Microflow 286 11.8 Practical Exercises 288 References 292 12 Modeling in Microreactors 297 Ekaterina S. Borovinskaya 12.1 Introduction 297 12.2 Processes in Microreactors and the Role of Mixing 298 12.3 Modeling of Processes in Microreactors Based on General Balance Equation 300 12.4 Computation of Reaction Flows in Microreactors 308 12.5 Practical Exercise: Alkylation of Phenylacetonitrile 320 References 323 Index 327

Wladimir Reschetilowski is Director of the Institute of Industrial Chemistry at the University of Technology Dresden, Germany. Having obtained his academic degrees from Technical University Leuna–Merseburg, he began his career working at the Leipzig University, continued it for DECHEMA (Society for Chemical Engineering and Biotechnology, Frankfurt/M.) as the Head of the Department of Technical Chemistry before taking up his present appointment as Full Professor at the University of Technology Dresden. Professor Reschetilowski has authored over 200 scientific publications in the field of acid and bifunctional catalytic conversion of hydrocarbons by microporous and mesoporous solids, asymmetric synthesis on chiral–modified catalyst systems, application of microstructured reactors in preparative chemistry and catalytic conversion of bio–based raw materials into organic base products and fuels. He is awarded with an honorary professorship by St.–Petersburg State University of Technology and is known as the principal author of the compendium ′Academic curriculum of teaching technical chemistry′ in German Universities as well as of the teaching book ′Technisch–chemisches Praktikum′. He is also appointed expert of the accreditation agency in engineering, computer sciences, natural sciences and mathematics (ASIIN).