Title Details

About the Editors XIII

List of Contributors XV

Preface XIX

1 Chemical Engineering Science and Green Chemistry – The Challenge of Sustainability 1
Alexei A. Lapkin

1.1 Sustainability Challenge for the Chemical Industry 1

1.2 From Green to Sustainable Chemistry 5

1.3 Chemical Engineering Science for Sustainability 7

1.4 Trends in Chemical Engineering Science 9

1.5 Topics Covered in This Book 11

Acknowledgment 13

References 13

Part One: Molecular Engineering of Materials, Reactions, and Processes 17

2 Recent Advances in the Molecular Engineering of Solvents for Reactions 19
Eirini Siougkrou, Amparo Galindo, and Claire S. Adjiman

2.1 Introduction 19

2.2 Solvent Effects on Reactions 22

2.3 Design or Selection of Solvents for Chemical Reactions 26

2.3.1 Model-Based Screening Methods 27

2.3.2 Generate-and-Test Methods 28

2.3.3 Optimization-Based Methods 30

2.3.4 Discussion 34

2.4 A Case Study 35

2.5 Conclusions 38

Acknowledgments 38

References 39

3 Hierarchically Structured Pt and Non-Pt-Based Electrocatalysts for PEM Fuel Cells 47
Panagiotis Trogadas and Marc-Olivier Coppens

3.1 Introduction 47

3.2 Pure Hollow Pt Nanoparticles 49

3.3 Hollow Pt Metal Alloys 51

3.3.1 PtAu 52

3.3.2 PtAg 53

3.3.3 PtCo 56

3.3.4 PtNi 58

3.3.5 PtRu 59

3.3.6 PtPd 61

3.3.7 PtCu 62

3.4 Non-Pt Alloy Nanostructures 63

3.5 Conclusions and Outlook 64

Acknowledgment 65

References 65

4 New Frontiers in Biocatalysis 73
John M. Woodley and Nicholas J. Turner

4.1 Introduction 73

4.2 Recent Advances in Biocatalysis 74

4.3 Biocatalytic Retrosynthesis 75

4.4 Process-Driven Protein Engineering 80

4.5 Process Developments 83

4.5.1 Continuous Processes 83

4.5.2 Kinetic Analysis 84

4.6 Future Perspectives 84

References 85

Part Two: Innovations in Design, Unit Operations, and Manufacturing 87

5 Conceptual Process Design and Process Optimization 89
Alexander Mitsos, Ung Lee, Sebastian Recker, and Mirko Skiborowski

5.1 Introduction 89

5.2 Mathematical Background 89

5.2.1 System of Nonlinear Equations 90

5.2.2 Nonlinear Programming (NLP) 90

5.2.3 Mixed Integer Programming 92

5.3 Synthesis 93

5.3.1 Reactor Networks 93

5.3.2 Separation Systems 95

5.3.3 Overall Flowsheets 97

5.4 Superstructure-Based Techniques 101

5.4.1 Heat Exchange Networks 101

5.4.2 Process Flowsheet Optimization 103

5.5 Integrated Process Design, Operation, and Control 105

5.6 Water and Energy Processes 105

5.7 Conclusions and Outlook 107

References 107

6 Development of Novel Multiphase Microreactors: Recent Developments and Future Challenges 115
Evgeny Rebrov

6.1 Principles and Features 115

6.1.1 Continuous Phase Multiphase Microreactors 115

6.1.1.1 Falling Film Microreactor 115

6.1.1.2 Mesh Contactor 116

6.1.2 Dispersed Phase Multiphase Microreactors 116

6.1.2.1 Segmented Flow Microreactors 116

6.1.2.2 Microstructured Packed Beds 117

6.1.2.3 Prestructured Microreactors 118

6.1.2.4 Foam Microreactors 120

6.1.2.5 Microreactors with Fibrous Internal Structures 120

6.2 Experimental Practice 121

6.2.1 Flow Regimes 121

6.2.1.1 Capillary Microreactors 121

6.2.1.2 Structured Packed Beds 122

6.2.2 Dispersion and Holdup in Microstructured Packed Bed Reactors 123

6.2.2.1 Liquid Holdup 123

6.2.2.2 Hydrodynamic Dispersion 124

6.3 Modeling Features 125

6.3.1 Hydrodynamics 125

6.3.1.1 Falling Films Microreactors 125

6.3.2 Pressure Drop in Capillary Microreactors 127

6.3.2.1 Gas–Liquid Microreactors 127

6.3.2.2 Liquid–Liquid Microreactors 130

6.3.3 Mass Transfer 131

6.3.3.1 Capillary Microreactors 131

6.3.3.2 Falling Film Microreactors 133

6.3.4 Two-Phase Flow Distribution 133

6.4 Applications 136

6.4.1 Falling Film Microreactors 136

6.4.2 Capillary Microreactors 137

6.4.2.1 Wall Coated Catalytic Microreactors 137

6.4.2.2 Phase Transfer Catalysis in Microreactors 139

6.4.2.3 Microstructured Packed Bed Reactors 142

6.5 Conclusions and Outlook 144

References 144

7 Process Intensification through Continuous Manufacturing: Implications for Unit Operation and Process Design 153
Sebastian Falß, Nicolai Kloye, Manuel Holtkamp, Angelina Prokofyeva, Thomas Bieringer, and Norbert Kockmann

7.1 Continuous Processes as a Means of Process Intensification 153

7.2 Equipment for Continuous Processes 158

7.2.1 Upstream Equipment 159

7.2.1.1 Reactors without Active Mixing 159

7.2.1.2 Reactors with Dynamic Mixing 161

7.2.2 Downstream Equipment 163

7.2.3 Process Integration 165

7.2.4 Continuous Equipment as Enabling Technology 166

7.3 Process Development and Implementation for Continuous Processes 168

7.3.1 Process Development and Scale-Up 168

7.3.2 Flexible Implementation of Continuous Processes 172

7.4 Selected Case Studies 174

7.5 Conclusion and Outlook 180

References 182

8 How Technical Innovation in Manufacturing Is Fostered through Business Innovation 191
Nicolas Eghbali, Marianne Hoppenbrouwers, Steven Lemain, Gert De Bruyn, and Bart Vander Velpen

8.1 General Introduction 191

8.2 Concept of Chemical Leasing and Take Back Chemicals 192

8.2.1 The Concept of Take Back Chemicals 194

8.2.2 Advantages and Challenges of the Take Back Chemicals Model 195

8.2.2.1 What Are the Advantages of Implementing TaBaChem 196

8.2.2.2 What Are the Impediments in Implementing the New Business Models? 197

8.3 General Economic, Technical, and Management Aspects 198

8.3.1 Economic Aspects 198

8.3.1.1 Direct Gains, Indirect Gains, and Investments 198

8.3.1.2 Pricing 199

8.3.1.3 Conclusion on the Economic Aspects 200

8.3.2 Technical Aspects 201

8.3.2.1 Reuse of Chemicals 201

8.3.2.2 Process Optimization 201

8.3.2.3 Conclusion on the Technical Aspects 201

8.3.3 Organizational/Managerial Aspects 202

8.3.3.1 Sales 202

8.3.3.2 Quality Assurance 202

8.3.3.3 Tendering and Rewarding 202

8.3.3.4 Knowledge Sharing 202

8.3.3.5 Logistics 203

8.3.3.6 Conclusion on the Organizational/Managerial Aspects 203

8.4 Compatibility of the Service Model with the Actual Legislation: Some Important Aspects 203

8.4.1 Transition from Sales to Providing a Service to the Customer 204

8.4.1.1 The Supplier Retains Ownership of the Chemical 204

8.4.1.2 Result-Oriented Services Lead to Different Pricing of a Chemical 204

8.4.1.3 A Transparent and Elaborated Contract Is Necessary 205

8.4.2 Closing the Life Cycle and Preventing Waste 205

8.4.3 Business Confidentiality and the Protection of Competition 208

8.4.3.1 Intellectual Property Rights 208

8.4.3.2 Competition 208

8.5 General Conclusion 211

References 211

9 Applications of 3D Printing in Synthetic Process and Analytical Chemistry 215
Victor Sans, Vincenza Dragone, and Leroy Cronin

9.1 Introduction 215

9.1.1 Polymerization-Based Additive Manufacturing (AM) 216

9.1.1.1 Stereolithography (SLA) 217

9.1.1.2 Photopolymer Jetting (PJ) 217

9.1.1.3 Physical Binding 217

9.1.2 Melting-Based Techniques 218

9.1.2.1 Selective Laser Melting (SLM) 218

9.1.2.2 Electron Beam Melting (EBM) 218

9.1.2.3 Fused Deposition Modeling (FDM) 219

9.1.2.4 Laser Sintering (LS) 219

9.1.2.5 Material Jetting (MJ) 219

9.2 Chemical Reactors Manufacturing by Additive Manufacturing Techniques 220

9.2.1 3D Printing Technologies in Chemistry 220

9.3 3D Printing Applied to Flow Chemistry 226

9.3.1 Mesoscale Reactors 226

9.3.2 3D Printed Membranes 235

9.4 Applications of 3D Printed Flow Devices in Analytical Chemistry 239

9.4.1 3D Printing of Valves, Pumps and Actuators 239

9.4.2 Modular Devices Based on SL 242

9.5 Future Trends 248

9.5.1 Ultrafast Printing 249

9.5.2 Smart Materials through 4D Printing 250

9.6 Conclusions 251

References 252

Part Three: Enabling Technologies 257

10 Process Analytical Chemistry and Nondestructive Analytical Methods: The Green Chemistry Approach for Reaction Monitoring, Control, and Analysis 259
Miriam Fontalvo Gómez, Boris Johnson Restrepo, Torsten Stelzer, and Rodolfo J. Romañach

10.1 Green Chemistry and Chemical Analysis in Manufacturing 259

10.2 Process Analytical Chemistry: Concept and Objectives 260

10.3 Vibrational Spectroscopy 264

10.4 Challenges to Overcome 268

10.5 Applications of Process Analytical Chemistry and Nondestructive Analyses 270

10.5.1 Dairy Industry 270

10.5.2 Synthesis of Active Pharmaceutical Ingredients 271

10.5.3 Preparation of Polymeric Strip Film Unit Dosage Forms 273

10.5.4 Polymer Industry 274

10.5.5 Process Analytical Chemistry for Biodiesel Production 276

10.6 Future Trends in PAC 279

Acknowledgments 281

References 281

11 NMR Spectroscopy and Microscopy in Reaction Engineering and Catalysis 289
Carmine D’Agostino, Mick D. Mantle, and Andrew J. Sederman

11.1 Introduction 289

11.2 Basic Principles of NMR 290

11.2.1 Nuclear Spins and Bulk Magnetization 290

11.2.2 NMR Spectroscopy of Liquids 293

11.2.3 NMR Relaxation 295

11.2.3.1 Spin–Lattice Relaxation 295

11.2.3.2 Spin–Spin Relaxation 296

11.2.4 Pulsed Field Gradient NMR 297

11.3 The NMR Toolkit in Reaction Engineering and Catalysis 299

11.3.1 NMR Spectroscopy in Catalysis and Reaction Engineering 300

11.3.2 Diffusion of Fluids Confined in Porous Catalysts 306

11.3.2.1 Catalyst Deactivation Studies Using PFG NMR 311

11.3.3 NMR Relaxation Time Analysis in Porous Catalytic Materials 314

11.3.4 Combining NMR Spectroscopy withMagnetic Resonance Imaging 319

11.4 Summary 324

References 324

12 An Introduction to Closed-Loop Process Optimization and Online Analysis 329
Christopher S. Horbaczewskyj, Charlotte E. Willans, Alexei A. Lapkin, and Richard A. Bourne

12.1 Introduction 329

12.2 Principles of Self-Optimization and Requirements for Experimental Systems 330

12.3 Analytical Techniques for Closed-Loop Optimization 332

12.4 Decision Algorithms in Closed-Loop Optimization 334

12.4.1 Algorithms for Discovery 335

12.4.2 Algorithms for Developing Process Understanding 337

12.4.3 Algorithms for Automated Process Optimization 338

12.5 Application Examples of Closed-Loop Discovery and Optimization 341

12.5.1 Discovery in Closed-Loop Self-Optimization 341

12.5.2 High-Throughput Screening 342

12.5.3 Examples of One-Variable-at-a-Time Reaction Optimization 344

12.5.4 Examples of Application of Design of Experiments 346

12.5.5 Rate-Based/Physical Organic Approaches 350

12.5.6 Examples of Algorithm-Based Self-Optimization 364

12.6 Conclusions and Future Directions 368

Acknowledgments 369

References 369

Index 375