Flow Chemistry: Volume 2 Flow Chemistry – Applications

Description

"Flow Chemistry fills the gap in graduate education by covering chemistry and reaction principles along with current practice, including examples of relevant commercial reaction, separation, automation, and analytical equipment. The Editors of Flow Chemistry are commended for having taken the initiative to bring together experts from the field to provide a comprehensive treatment of fundamental and practical considerations underlying flow chemistry. It promises to become a useful study text and as well as reference for the graduate students and practitioners of flow chemistry." Professor Klavs Jensen Massachusetts Institute of Technology, USA Broader theoretical insight in driving a chemical reaction automatically opens the window towards new technologies particularly to flow chemistry. This emerging concept promotes the transformation of present day's organic processes into a more rapid continuous set of synthesis operations, more compatible with the envisioned sustainable world. These two volumes Fundamentals and Applications provide both the theoretical foundation as well as the practical aspects. Starts from the principles of this new technology and develops promising applications in a clear and instructive manner Also available: Volume 1 FUNDAMENTALS, ISBN: 978-3-11-028915-2 Preface About the editors Contributing authors Abbreviations Part I Catalysis and activation Clemens Brechtelsbauer and King Kuok (Mimi) Hii 1. Catalysis in flow 1.1 Introduction 1.1.1 Flow versus batch chemistry 1.1.2 Development of catalytic reactions and flow for organic synthesis 1.2 Reactor types, catalytic reactions and productivity 1.2.1 Solid-liquid reactors 1.2.2 Solid-liquid-gas systems 1.3 Conclusion 2 Catalytic engineering aspects of flow chemistry 2.1 Introduction 2.2 Basis of (catalytic) reactor engineering 2.2.1 Flow motion in reactors 2.2.2 Relevant physics 2.2.3 Characteristic times 2.2.4 Characteristic lengths 2.2.5 Surface area 2.2.6 Mixing 2.2.7 Heat issues 2.3 Describing the chemistry 2.3.1 Kinetic rate laws 2.3.2 Rate measurement and reaction time 2.3.3 Catalyst deactivation 2.4 Methodology for Flow reactor dimensioning 2.4.1 Batch versus Flow reactor comparison 2.4.2 Checking for mass and heat transfer limitations 2.4.3 Basis for reactor scale-up 2.5 Conclusion 3 Continuous-flow photochemistry in microstructured environment 3.1 Environmental impact in view of Green Chemistry 3.2 Physical considerations – reasons why microstructured equipment is preferred for flow photochemistry 3.2.1 Absorption of light by molecules in solution 3.2.2 Role of solvent 3.2.3 Micrometer-sized structures as key elements of reactor equipment for flow photochemistry 3.3 Technological considerations for flow photochemistry 3.3.1 Light sources 3.3.2 Reactor concepts for flow photochemistry 3.4 Chemical considerations for flow photochemistry 3.4.1 Photochemical reactions without catalyst material 3.4.2 Heterogeneous flow photocatalysis 3.4.3 Flow photocatalysis with organic dyes or noble metal complexes 3.5 Summary and outlook 4 Electrochemistry in flow 4.1 Introduction 4.2 Electrochemistry in flow 4.3 Microreactor design 4.3.1 Thin gap cells 4.3.2 ELMI – microstructured high pressure single pass thin gap flow cell 4.3.3 Segmented thin gap flow cells 4.4 Electrochemistry in microreactors 4.4.1 Direct product synthesis 4.4.2 Electrolyte free synthesis 4.4.3 Activation of chemicals 4.5 Ionic liquids in electrochemistry Part II Cutting-edge applications in advanced and functional materials 5 Synthesis of materials in flow – principles and practice 5.1 Introduction 5.2 Unique properties of microreactors 5.2.1 Mixing 5.2.2 Thermal and pressure control 5.2.3 Fluid behavior 5.3 Synthesis of materials in flow 5.3.1 Linear polymers 5.3.2 Beads, disks, and other solid polymeric materials 5.3.3 Janus materials 5.3.4 Capsules 5.3.5 Membranes and fibers 5.3.6 Nanoparticles and inorganic nonpolymeric materials 5.4 Conclusions 6 Flow chemistry for nanotechnology 6.1 Introduction to nanotechnology and graphene technology 6.1.1 Introduction 6.1.2 Definition and concepts 6.1.3 Brief history of nanotechnology 6.1.4 Why nanotechnology? 6.1.5 Batch and flow-chemistry based nanonization technologies 6.1.6 Overview and principles of microfluidic reactors 6.2 Nanomaterials 6.2.1 Structure and properties: is the smaller better? 6.2.2 Organic nanoparticles: biologically active small molecules 6.2.3 Inorganic nanoparticles: metallic, bimetallic and semiconductor particles 6.2.4 Hybrid nanoparticles 6.3 Theoretical background of nanoparticle synthesis using flow-chemistry based approaches 6.3.1 Principles of nanoparticle stabilization 6.3.2 Classical nucleation theory 6.4 Application of flow technology in nanoparticle synthesis 6.4.1 Synthesis of metal nanoparticles 6.4.2 Synthesis of semiconductor nanoparticles 6.4.3 Synthesis of biologically active organic nanoparticles 6.5 Impact of nanotechnology: an outlook 7 Continuous-flow synthesis of carbon-11 radiotracers on a microfluidic chip 7.1 Introduction to continuous-flow microreactors and carbon-11 radiolabeling 7.2 Microfluidic synthesis of raclopride 7.2.1 Microfluidic nonradioactive synthesis of raclopride 7.2.2 Microchip radioactive synthesis of [11C]raclopride 7.3 Computational fluid dynamics (CFD) 7.3.1 Reaction engineering lab®(REL) module – “ideal” flow-reactor model 7.3.2 Microelectromechanical system (MEMS) module – “geometry-dependent” flow study 7.4 Conclusion Part III Additional features of the Flow Process: in-line analytics, safety and green principles 8 Lab environment: in-line separation, analytics, automation & self optimization 8.1 The role of analytics in flow applications 8.1.1 Applications of mass spectroscopy 8.1.2 ReactIR flow cell 8.1.3 Nuclear magnetic resonance (NMR) 8.2 Automation and self optimization 8.2.1 General description of the self-optimization methods 8.2.2 Automation and feedback control systems 8.2.3 Nelder–Mead Simplexmethod 8.2.4 Multidimensional optimization 8.2.5 Optimization and scale-up 8.2.6 Flow reactors with built-in optimization 8.3 In-line separation 8.3.1 Liquid-liquid separators 8.3.2 Scavenger and chromatography columns 8.3.3 Simulated moving Bed Chromatography 9 Safety aspects related to microreactor technology 9.1 Introduction 9.1.1 Chemical processes 9.1.2 Safety in chemical processes 9.2 Inherently safer processes using microreaction technology 9.2.1 Advantages of microreaction technology to safety 9.2.2 Recent examples of processes involving dangerous reagents/reactions under MRT conditions 9.2.3 MRT processes involving harsh conditions (elevated temperatures and pressures) 9.3 Conclusions 10 From green chemistry principles in flow chemistry towards green flow process design in the holistic viewpoint 10.1 Introduction of Green Chemistry principles 10.1.1 Green principles 10.1.2 Green flow chemistry 10.2 Flow process design and relation to green chemistry/engineering 10.2.1 Flow processing – major means in process intensification 10.2.2 Transport intensification – the flow-scale 10.2.3 Chemical intensification – the reactor scale 10.2.4 Process-design intensification – the full-process scale 10.2.5 Elemental green criteria with proven impact of flow process design 10.2.6 Elemental green criteria with suspected impact of flow process design 10.2.7 Elemental green criteria with uncertainty over impact of flow process design 10.3 Holistic methodology introduction for systematic green flow process design 10.4 Green flow process design for fine chemicals/pharmaceuticals 10.4.1 Technology comparison for green pharmaceutical process design 10.4.2 Flow process design of a green biphasic fine chemical synthesis 10.4.3 Exergetic LCA for improvement of an existing pharmaceutical production process 10.5 Green flow process design for bulk chemicals and benchmark to conventional process 10.5.1 Process simulation 10.5.2 LCA for continuous flow synthesis of ADA 10.5.3 LCA for two-step conventional synthesis of ADA 10.5.4 Complete LCA picture 10.5.5 Enlightment 10.6 Outlook for green flow process design Answers to the study questions Index