Microreactors in Preparative Chemistry E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 569

Veröffentlichungsjahr: 2013

Beschreibung

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.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Principles of Microprocess Technology

1.1 Introduction

1.2 History

1.3 Basic Characteristics

1.4 Industrial Applications

1.5 Concluding Remarks

References

Chapter 2: Effects of Microfluidics on Preparative Chemistry Processes

2.1 Introduction

2.2 Mixing

2.3 Heat Management

2.4 Mass Transfer and Chemical Reactions

2.5 Flow Separation

2.6 Numbering-Up Strategy

2.7 Practical Exercise: Experimental Characterization of Mixing in Microstructured Reactors

References

Chapter 3: Modular Micro- and Millireactor Systems for Preparative Chemical Synthesis and Bioprocesses

3.1 Introduction

3.2 Modular Microreaction System

3.3 Examples for Microreactor Applications

3.4 Practical Exercise: Suzuki Reaction in a Modular Microreactor Setup

References

Chapter 4: Potential of Lab-on-a-Chip: Synthesis, Separation, and Analysis of Biomolecules

4.1 Introduction

4.2 Learning from Nature: Analogies to Living Cells

4.3 Microenzyme Reactors

4.4 Microchip Electrophoresis

4.5 Microenzyme Membrane Reactor/Micromembrane Chromatography

4.6 Nucleic Acid Analysis in Microchannels

4.7 Saccharide Analyses in Microdevices

4.8 Practical Exercise: Lipase-Catalyzed Esterification Reaction [62]

References

Chapter 5: Bioprocessing in Microreactors

5.1 Introduction

5.2 Background

5.3 Practical Exercise: Functionalization of Silicon Surface

References

Chapter 6: Synthesis of Fine Chemicals

6.1 Introduction

6.2 Organic Synthesis in Liquid and Liquid–Liquid Phases

6.3 Gas–Liquid Biphasic Organic Synthesis

6.4 Practical Exercise: Photochemical Generation of Singlet Oxygen and Its [4 + 2] Cycloaddition to Cyclopentadiene [41]

References

Chapter 7: Synthesis of Nanomaterials Using Continuous-Flow Microreactors

7.1 Introduction

7.2 Microfluidic Devices

7.3 Synthesis of Nanomaterials Using Microreactors

7.4 Kinetic Studies

7.5 Process Optimization

7.6 Point-of-Use Synthesis and Deposition

7.7 Practical Exercises: Synthesis of Nanocrystals

Acknowledgments

References

Chapter 8: Polymerization in Microfluidic Reactors

8.1 Introduction

8.2 Practical Considerations

8.3 Single-Phase Polymerization

8.4 Multiphase Polymerization

8.5 Beyond Synthesis: New Developments for Next-Generation MF Polymerization

8.6 Practical Exercise: MF Polymerization Reactor Kinetics Studies Using In Situ Characterization

References

Chapter 9: Electrochemical Reactions in Microreactors

9.1 Introduction

9.2 Electrode Configuration

9.3 Electrolysis without Supporting Electrolytes

9.4 Generation and Reactions with Unstable Intermediates

9.5 Practical Exercise: Electrochemical Reactions in Flow Microreactors [24]

References

Chapter 10: Heterogeneous Catalysis in Microreactors

10.1 Introduction

10.2 Bulk Catalysts

10.3 Supported Catalysts

10.4 Mesoporous Supports

10.5 Microporous Supports

10.6 Practical Exercise: PdZn/TiO2-Catalyzed Selective Hydrogenation of Acetylene Alcohols in a Capillary Microreactor [111]

References

Chapter 11: Chemical Intensification in Flow Chemistry through Harsh Reaction Conditions and New Reaction Design

11.1 Introduction

11.2 High-Temperature Processing in Microflow

11.3 High-Pressure Processing in Microflow

11.4 Solvent Effects in Microflow

11.5 Ex-Regime Processing and Handling of Hazardous Compounds in Microflow

11.6 New Chemical Transformations in Microflow

11.7 Process Integration in Microflow

11.8 Practical Exercises

References

Chapter 12: Modeling in Microreactors

12.1 Introduction

12.2 Processes in Microreactors and the Role of Mixing

12.3 Modeling of Processes in Microreactors Based on General Balance Equation

12.4 Computation of Reaction Flows in Microreactors

12.5 Practical Exercise: Alkylation of Phenylacetonitrile [3]

References

Index

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Print ISBN: 978-3-527-33282-3

ePDF ISBN: 978-3-527-65292-1

ePub ISBN: 978-3-527-65291-4

mobi ISBN: 978-3-527-65290-7

oBook ISBN: 978-3-527-65289-1

Cover Design Formgeber, Eppelheim

Typesetting Thomson Digital, Noida, India

Preface

At the beginning of the twenty-first century, the transfer of microreaction technology to the industrial sector remains in focus. Knowledge about the rate of chemical reactions as well as about heat and mass transfer processes is particularly essential. Since less time is required for the production of the desired product in the given reaction volume, a higher space–time yield – a measure of the reactor performance and consequently of the efficiency of the process guiding – can be obtained. Nevertheless, in spite of a large number of organic syntheses, which were successfully carried out in microstructured reactors, polymerization reactions, biocatalytic and electrocatalytic conversions as well as heterogeneously catalyzed reactions, or syntheses of inorganic nanoparticles still leave a lot to be desired. Moreover, the handling with this technology, especially in the area of the preparative chemistry, has not yet been described in sufficient detail up to now.

This book should help to clear out these existing deficits and give useful information for anyone to consider the application of microreaction technology regarding problem solving in preparative chemistry. Therefore, this book includes not only a number of reaction types that have already been described in the original literature and patents, but also a balance between the well-chosen research highlights and the general practical aspects resulting from it. Thus, careful consideration to the basic theoretical principles of the reaction in microreactors is given, so that the book appeals not only to specialists, but also to those who have just begun to deal with the application of the microreaction technology for preparative purposes. Moreover, specific instructions and test procedures for verified product syntheses are provided and therefore facilitate the collection of own practical experiences with the microreactor equipment. Hence, the topics discussed in the book assume a form that makes the practical discussion of research- and development-oriented problems comprehensible for both the specialist and the newcomer. Readers will obtain not only an understanding of the advantages of microstructured reactors, but also guidance as to the demands concerning used chemicals, production, pressure loss, and blockage danger. In addition, information is provided in matters of computer-supported measuring, regulation of temperature, pressure, flow rate, concentration, and quantitative proportions of the reactants even up to the special demands of miniaturized analysis systems such as the “lab-on-a-chip.” Ultimately integrated modular microsystems are described, which consist of microreactors, separation units, and analytic components presenting adaptable tools for the preparative chemist. Faster as well as economically and ecologically more favorable routes for the synthesis of new products and materials under optimum reaction terms are discussed.

After a short introductory chapter, the progress in the microreaction technology over the past 20 years is reviewed and emphasis put on the fact that implementation into microreactors often leads to better yield, higher safety, and less time and cost of materials involved. Single chapters are summarized according to greatest possible cohesion, that is, in groups by related reactions. Correspondingly, the main focus of the book is directed to the preparative side, for example, to the application of microreactors for organic syntheses, polymer reactions, biocatalytic and electrocatalytic as well as heterogeneously catalyzed conversions, and syntheses of nanoparticles. Besides, practice-oriented solutions are described in conjunction with economical and ecological aspects of the optimum reaction management. At the end of every chapter, the verified synthesis examples of the typical approach, the microreactor test equipment, and analysis techniques are provided in combination with straightforward calculation methods. Especially beginners should be able to obtain a first impression about the world of preparative chemistry in such microstructured apparatuses, preparing them optimally for the later process development.

I would like to thank all authors for their contribution to this book, and also on behalf of the authors I hope that we succeed in reaching a wide range of readers in academia and industry. I thank Wiley-VCH publishers for the invitation to edit this book and comprehensive support in the preparation of this book. Special thanks go to Dr.-Ing. Ekaterina Borovinskaya and Dr. Alexander Rüfer for carefully checking parts of the manuscript.

Wladimir Reschetilowski

Dresden December 2012

List of Contributors

Martin Bertau

Freiberg University of Mining and Technology

Institute of Industrial Chemistry

Leipziger Straße 29

09599 Freiberg

Germany

Ekaterina S. Borovinskaya

St. Petersburg State University of Technology

System Analysis Department

Moskovsky Avenue 26

190013 St. Petersburg

Russia

Chih-Hung Chang

Oregon State University

School of Chemical, Biological and Environmental Engineering

Corvallis, OR 97331

USA

Jörn Emmerich

SOPATec UG

Technische Universität Berlin

Department of Chemical Engineering Fraunhoferstraße 33-36

10587 Berlin

Germany

Jesse Greener

University of Toronto

Department of Chemistry

80 St. George Street

Toronto, Ontario M5S 3H6

Canada

Joachim Heck

Ehrfeld Mikrotechnik BTS GmbH Mikroforum Ring 1

55234 Wendelsheim

Germany

Volker Hessel

Eindhoven University of Technology

Micro Flow Chemistry and Process Technology

5600 MB Eindhoven

The Netherlands

Sandra Hübner

Leibniz Institute for Catalysis

Micro Reaction Engineering

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Klaus Jähnisch

Leibniz Institute for Catalysis

Micro Reaction Engineering

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Madhvanand Kashid

Ecole Polytechnique Fédérale de Lausanne (EPFL)

Group of Catalytic Reaction Engineering

Station 6

1015 Lausanne

Switzerland

Present address:

Syngenta Crop Protection Monthey SA Route de l'Ile-au-Bois1870 Monthey Switzerland

Lioubov Kiwi-Minsker

Ecole Polytechnique Fédérale de Lausanne (EPFL)

Group of Catalytic Reaction Engineering

Station 6

1015 Lausanne

Switzerland

Eugenia Kumacheva

University of Toronto

Department of Chemistry

80 St. George Street

Toronto, Ontario M5S 3H6

Canada

Dorota Kwasny

Technical University of Denmark

Department of Micro- and Nanotechnology

DTU Nanotech

Ørsteds Plads

Bygning 345Ø

2800 Kgs. Lyngby

Denmark

Aiichiro Nagaki

Kyoto University

Graduate School of Engineering

Department of Synthetic Chemistry and Biological Chemistry

Nishikyo-ku, Kyoto 615-8510

Japan

Timothy Noël

Eindhoven University of Technology

Micro Flow Chemistry and Process Technology

5600 MB Eindhoven

The Netherlands

Fridolin Okkels

Technical University of Denmark

Department of Micro- and Nanotechnology

DTU Nanotech

Ørsteds Plads

Bygning 345Ø

2800 Kgs. Lyngby

Denmark

Marc-Oliver Piepenbrock

Ehrfeld Mikrotechnik BTS GmbH

Mikroforum Ring 1

55234 Wendelsheim

Germany

Evgeny V. Rebrov

Queen's University Belfast

School of Chemistry and Chemical Engineering

Stranmillis Road Belfast BT9 5AG

UK

Albert Renken

Ecole Polytechnique Fédérale de Lausanne (EPFL)

Institute of Chemical Sciences and Engineering

Station 6

1015 Lausanne

Switzerland

Wladimir Reschetilowski

Dresden University of Technology

Institute of Industrial Chemistry

Zellescher Weg 19

01062 Dresden

Germany

Frank Schael

Ehrfeld Mikrotechnik BTS GmbH

Mikroforum Ring 1

55234 Wendelsheim

Germany

Norbert Steinfeldt

Leibniz Institute for Catalysis

Micro Reaction Engineering

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Jun-ichi Yoshida

Kyoto University

Graduate School of Engineering

Department of Synthetic Chemistry and Biological Chemistry

Nishikyo-ku, Kyoto 615-8510

Japan

1

Principles of Microprocess Technology

Wladimir Reschetilowski

1.1 Introduction

The microreactor technology is nowadays the key technology for process intensification. Manufacturers of microreactor systems bring their products to market with slogans like “A Chemical Factory in a Briefcase” or “Lab-on-a-chip.” Due to the small dimensions of microstructures, which do not exceed 1 mm, microreactors contribute to the minimization of material in terms of production as well as raw material and energy consumption during exploitation. Moreover, due to the intensification of heat and mass transfer, the productivity of plants with microreactors is in a number of cases significantly higher than that with classical batch reactors applied in industry.

Extensive research efforts have been made incessantly in this field during the past few years. Recent advances in the design and fabrication of microreactors, micromixers, microseparators, and so on show that they represent a cheap alternative for the production of special fine chemicals by a continuous process to observe simpler process optimization and rapid design implementation. It is possible to predict that in the near future chemical, pharmaceutical, and biological laboratories will change radically toward considerable improvement of process and synthesis efficiency at essential miniaturization of reactor devices.

One of the key moments in the microprocess technology is the effective way to increase the process productivity by the so-called reproduction (numbering-up) of continuous microreactor systems, that is, a series of continuous reactors works simultaneously. Hereby the dimensions of microreactors and their efficiency in heat exchange do not change, when transferring processes from laboratory to pilot and production scales. Due to the facility to change the process parameters (temperature, pressure, flow velocity, ratio of reagents, use of catalysts, etc.) rapidly and accurately, the microreactor systems can be predestined as an ideal tool for effective and fast optimization of investigated reactions. The full automation of such systems interfaced with integrated analytical devices in real time (online analytic) gives an opportunity to receive high-grade information about optimal parameters of multistage reactions within only a few hours.

Up to now different reactions of the preparative organic chemistry, such as Wittig reaction, Knoevenagel condensation, Michael addition, Diels–Alder reaction, or Suzuki coupling, have been successfully carried out in microreactors with predominantly improved conversion and selectivity. In addition, modern developments and benefits of microreactor technology are mentioned for heterogeneous reaction systems, which may differ by their nature and run in various types of microreactors: synthesis of organic polymers and inorganic nanoparticles, heterogeneous catalysis, and bio-, electro-, and photocatalysis. Therefore, it is very important to outline these aspects from the point of view of the preparative feasibility of chemical reactions to make it attractive for the chemical industry.

1.2 History

Since the times of alchemy, experiments in chemical laboratories were carried out in flasks and test tubes. Chemists begin research works in scales from a milliliter to several liters, spending a lot of time and energy to find the optimum reaction conditions. Furthermore, it is difficult to scale the processes for pilot and production plants.

Early studies with the detailed description of the so-called microstructured reactors (microreactors) are dated 1986; however, theoretical calculations of scientists of the former GDR were not put into practical application [1]. A patent of that time describes, very generally, a miniaturized chemical engineering apparatus and systems made by simple fabrication methods. A stack-like arrangement of platelets carrying microchannels and fluid connecting structures was also proposed.

The first microreactors that have confirmed huge potential of a new approach were designed and placed in operation in 1989 in Karlsruhe (Germany) at the Karlsruhe (Nuclear) Research Centre. Mechanical micromachining techniques were used to produce a spinoff from the manufacture of separation nozzles for uranium enrichment [2]. Wide development of this technology started in late 1995 after the workshop on microreaction technology in Mainz (Germany), organized by AIChE, DECHEMA, IMM, and PNNL. The 1st International Conference on Microreaction Technology (IMRET) at the DECHEMA, Frankfurt am Main, took place in early 1997 and was focused on studying and introducing microreactor technology. It is held regularly till date with the last one being IMRET 12.