<p>About the Editors XIII</p> <p>List of Contributors XV</p> <p>Preface XIX</p> <p><b>1 Chemical Engineering Science and Green Chemistry – The Challenge of Sustainability 1<br /></b><i>Alexei A. Lapkin</i></p> <p>1.1 Sustainability Challenge for the Chemical Industry 1</p> <p>1.2 From Green to Sustainable Chemistry 5</p> <p>1.3 Chemical Engineering Science for Sustainability 7</p> <p>1.4 Trends in Chemical Engineering Science 9</p> <p>1.5 Topics Covered in This Book 11</p> <p>Acknowledgment 13</p> <p>References 13</p> <p><b>Part One: Molecular Engineering of Materials, Reactions, and Processes 17</b></p> <p><b>2 Recent Advances in the Molecular Engineering of Solvents for Reactions 19</b><i><br />Eirini Siougkrou, Amparo Galindo, and Claire S. Adjiman</i></p> <p>2.1 Introduction 19</p> <p>2.2 Solvent Effects on Reactions 22</p> <p>2.3 Design or Selection of Solvents for Chemical Reactions 26</p> <p>2.3.1 Model-Based Screening Methods 27</p> <p>2.3.2 Generate-and-Test Methods 28</p> <p>2.3.3 Optimization-Based Methods 30</p> <p>2.3.4 Discussion 34</p> <p>2.4 A Case Study 35</p> <p>2.5 Conclusions 38</p> <p>Acknowledgments 38</p> <p>References 39</p> <p><b>3 Hierarchically Structured Pt and Non-Pt-Based Electrocatalysts for PEM Fuel Cells 47<br /></b><i>Panagiotis Trogadas and Marc-Olivier Coppens</i></p> <p>3.1 Introduction 47</p> <p>3.2 Pure Hollow Pt Nanoparticles 49</p> <p>3.3 Hollow Pt Metal Alloys 51</p> <p>3.3.1 PtAu 52</p> <p>3.3.2 PtAg 53</p> <p>3.3.3 PtCo 56</p> <p>3.3.4 PtNi 58</p> <p>3.3.5 PtRu 59</p> <p>3.3.6 PtPd 61</p> <p>3.3.7 PtCu 62</p> <p>3.4 Non-Pt Alloy Nanostructures 63</p> <p>3.5 Conclusions and Outlook 64</p> <p>Acknowledgment 65</p> <p>References 65</p> <p><b>4 New Frontiers in Biocatalysis 73<br /></b><i>John M. Woodley and Nicholas J. Turner</i></p> <p>4.1 Introduction 73</p> <p>4.2 Recent Advances in Biocatalysis 74</p> <p>4.3 Biocatalytic Retrosynthesis 75</p> <p>4.4 Process-Driven Protein Engineering 80</p> <p>4.5 Process Developments 83</p> <p>4.5.1 Continuous Processes 83</p> <p>4.5.2 Kinetic Analysis 84</p> <p>4.6 Future Perspectives 84</p> <p>References 85</p> <p><b>Part Two: Innovations in Design, Unit Operations, and Manufacturing 87</b></p> <p><b>5 Conceptual Process Design and Process Optimization 89<br /></b><i>Alexander Mitsos, Ung Lee, Sebastian Recker, and Mirko Skiborowski</i></p> <p>5.1 Introduction 89</p> <p>5.2 Mathematical Background 89</p> <p>5.2.1 System of Nonlinear Equations 90</p> <p>5.2.2 Nonlinear Programming (NLP) 90</p> <p>5.2.3 Mixed Integer Programming 92</p> <p>5.3 Synthesis 93</p> <p>5.3.1 Reactor Networks 93</p> <p>5.3.2 Separation Systems 95</p> <p>5.3.3 Overall Flowsheets 97</p> <p>5.4 Superstructure-Based Techniques 101</p> <p>5.4.1 Heat Exchange Networks 101</p> <p>5.4.2 Process Flowsheet Optimization 103</p> <p>5.5 Integrated Process Design, Operation, and Control 105</p> <p>5.6 Water and Energy Processes 105</p> <p>5.7 Conclusions and Outlook 107</p> <p>References 107</p> <p><b>6 Development of Novel Multiphase Microreactors: Recent Developments and Future Challenges 115<br /></b><i>Evgeny Rebrov</i></p> <p>6.1 Principles and Features 115</p> <p>6.1.1 Continuous Phase Multiphase Microreactors 115</p> <p>6.1.1.1 Falling Film Microreactor 115</p> <p>6.1.1.2 Mesh Contactor 116</p> <p>6.1.2 Dispersed Phase Multiphase Microreactors 116</p> <p>6.1.2.1 Segmented Flow Microreactors 116</p> <p>6.1.2.2 Microstructured Packed Beds 117</p> <p>6.1.2.3 Prestructured Microreactors 118</p> <p>6.1.2.4 Foam Microreactors 120</p> <p>6.1.2.5 Microreactors with Fibrous Internal Structures 120</p> <p>6.2 Experimental Practice 121</p> <p>6.2.1 Flow Regimes 121</p> <p>6.2.1.1 Capillary Microreactors 121</p> <p>6.2.1.2 Structured Packed Beds 122</p> <p>6.2.2 Dispersion and Holdup in Microstructured Packed Bed Reactors 123</p> <p>6.2.2.1 Liquid Holdup 123</p> <p>6.2.2.2 Hydrodynamic Dispersion 124</p> <p>6.3 Modeling Features 125</p> <p>6.3.1 Hydrodynamics 125</p> <p>6.3.1.1 Falling Films Microreactors 125</p> <p>6.3.2 Pressure Drop in Capillary Microreactors 127</p> <p>6.3.2.1 Gas–Liquid Microreactors 127</p> <p>6.3.2.2 Liquid–Liquid Microreactors 130</p> <p>6.3.3 Mass Transfer 131</p> <p>6.3.3.1 Capillary Microreactors 131</p> <p>6.3.3.2 Falling Film Microreactors 133</p> <p>6.3.4 Two-Phase Flow Distribution 133</p> <p>6.4 Applications 136</p> <p>6.4.1 Falling Film Microreactors 136</p> <p>6.4.2 Capillary Microreactors 137</p> <p>6.4.2.1 Wall Coated Catalytic Microreactors 137</p> <p>6.4.2.2 Phase Transfer Catalysis in Microreactors 139</p> <p>6.4.2.3 Microstructured Packed Bed Reactors 142</p> <p>6.5 Conclusions and Outlook 144</p> <p>References 144</p> <p><b>7 Process Intensification through Continuous Manufacturing: Implications for Unit Operation and Process Design 153<br /></b><i>Sebastian Falß, Nicolai Kloye, Manuel Holtkamp, Angelina Prokofyeva, Thomas Bieringer, and Norbert Kockmann</i></p> <p>7.1 Continuous Processes as a Means of Process Intensification 153</p> <p>7.2 Equipment for Continuous Processes 158</p> <p>7.2.1 Upstream Equipment 159</p> <p>7.2.1.1 Reactors without Active Mixing 159</p> <p>7.2.1.2 Reactors with Dynamic Mixing 161</p> <p>7.2.2 Downstream Equipment 163</p> <p>7.2.3 Process Integration 165</p> <p>7.2.4 Continuous Equipment as Enabling Technology 166</p> <p>7.3 Process Development and Implementation for Continuous Processes 168</p> <p>7.3.1 Process Development and Scale-Up 168</p> <p>7.3.2 Flexible Implementation of Continuous Processes 172</p> <p>7.4 Selected Case Studies 174</p> <p>7.5 Conclusion and Outlook 180</p> <p>References 182</p> <p><b>8 How Technical Innovation in Manufacturing Is Fostered through Business Innovation 191<br /></b><i>Nicolas Eghbali, Marianne Hoppenbrouwers, Steven Lemain, Gert De Bruyn, and Bart Vander Velpen</i></p> <p>8.1 General Introduction 191</p> <p>8.2 Concept of Chemical Leasing and Take Back Chemicals 192</p> <p>8.2.1 The Concept of Take Back Chemicals 194</p> <p>8.2.2 Advantages and Challenges of the Take Back Chemicals Model 195</p> <p>8.2.2.1 What Are the Advantages of Implementing TaBaChem 196</p> <p>8.2.2.2 What Are the Impediments in Implementing the New Business Models? 197</p> <p>8.3 General Economic, Technical, and Management Aspects 198</p> <p>8.3.1 Economic Aspects 198</p> <p>8.3.1.1 Direct Gains, Indirect Gains, and Investments 198</p> <p>8.3.1.2 Pricing 199</p> <p>8.3.1.3 Conclusion on the Economic Aspects 200</p> <p>8.3.2 Technical Aspects 201</p> <p>8.3.2.1 Reuse of Chemicals 201</p> <p>8.3.2.2 Process Optimization 201</p> <p>8.3.2.3 Conclusion on the Technical Aspects 201</p> <p>8.3.3 Organizational/Managerial Aspects 202</p> <p>8.3.3.1 Sales 202</p> <p>8.3.3.2 Quality Assurance 202</p> <p>8.3.3.3 Tendering and Rewarding 202</p> <p>8.3.3.4 Knowledge Sharing 202</p> <p>8.3.3.5 Logistics 203</p> <p>8.3.3.6 Conclusion on the Organizational/Managerial Aspects 203</p> <p>8.4 Compatibility of the Service Model with the Actual Legislation: Some Important Aspects 203</p> <p>8.4.1 Transition from Sales to Providing a Service to the Customer 204</p> <p>8.4.1.1 The Supplier Retains Ownership of the Chemical 204</p> <p>8.4.1.2 Result-Oriented Services Lead to Different Pricing of a Chemical 204</p> <p>8.4.1.3 A Transparent and Elaborated Contract Is Necessary 205</p> <p>8.4.2 Closing the Life Cycle and Preventing Waste 205</p> <p>8.4.3 Business Confidentiality and the Protection of Competition 208</p> <p>8.4.3.1 Intellectual Property Rights 208</p> <p>8.4.3.2 Competition 208</p> <p>8.5 General Conclusion 211</p> <p>References 211</p> <p><b>9 Applications of 3D Printing in Synthetic Process and Analytical Chemistry 215<br /></b><i>Victor Sans, Vincenza Dragone, and Leroy Cronin</i></p> <p>9.1 Introduction 215</p> <p>9.1.1 Polymerization-Based Additive Manufacturing (AM) 216</p> <p>9.1.1.1 Stereolithography (SLA) 217</p> <p>9.1.1.2 Photopolymer Jetting (PJ) 217</p> <p>9.1.1.3 Physical Binding 217</p> <p>9.1.2 Melting-Based Techniques 218</p> <p>9.1.2.1 Selective Laser Melting (SLM) 218</p> <p>9.1.2.2 Electron Beam Melting (EBM) 218</p> <p>9.1.2.3 Fused Deposition Modeling (FDM) 219</p> <p>9.1.2.4 Laser Sintering (LS) 219</p> <p>9.1.2.5 Material Jetting (MJ) 219</p> <p>9.2 Chemical Reactors Manufacturing by Additive Manufacturing Techniques 220</p> <p>9.2.1 3D Printing Technologies in Chemistry 220</p> <p>9.3 3D Printing Applied to Flow Chemistry 226</p> <p>9.3.1 Mesoscale Reactors 226</p> <p>9.3.2 3D Printed Membranes 235</p> <p>9.4 Applications of 3D Printed Flow Devices in Analytical Chemistry 239</p> <p>9.4.1 3D Printing of Valves, Pumps and Actuators 239</p> <p>9.4.2 Modular Devices Based on SL 242</p> <p>9.5 Future Trends 248</p> <p>9.5.1 Ultrafast Printing 249</p> <p>9.5.2 Smart Materials through 4D Printing 250</p> <p>9.6 Conclusions 251</p> <p>References 252</p> <p><b>Part Three: Enabling Technologies 257</b></p> <p><b>10 Process Analytical Chemistry and Nondestructive Analytical Methods: The Green Chemistry Approach for Reaction Monitoring, Control, and Analysis 259<br /></b><i>Miriam Fontalvo Gómez, Boris Johnson Restrepo, Torsten Stelzer, and Rodolfo J. Romañach</i></p> <p>10.1 Green Chemistry and Chemical Analysis in Manufacturing 259</p> <p>10.2 Process Analytical Chemistry: Concept and Objectives 260</p> <p>10.3 Vibrational Spectroscopy 264</p> <p>10.4 Challenges to Overcome 268</p> <p>10.5 Applications of Process Analytical Chemistry and Nondestructive Analyses 270</p> <p>10.5.1 Dairy Industry 270</p> <p>10.5.2 Synthesis of Active Pharmaceutical Ingredients 271</p> <p>10.5.3 Preparation of Polymeric Strip Film Unit Dosage Forms 273</p> <p>10.5.4 Polymer Industry 274</p> <p>10.5.5 Process Analytical Chemistry for Biodiesel Production 276</p> <p>10.6 Future Trends in PAC 279</p> <p>Acknowledgments 281</p> <p>References 281</p> <p><b>11 NMR Spectroscopy and Microscopy in Reaction Engineering and Catalysis 289<br /></b><i>Carmine D’Agostino, Mick D. Mantle, and Andrew J. Sederman</i></p> <p>11.1 Introduction 289</p> <p>11.2 Basic Principles of NMR 290</p> <p>11.2.1 Nuclear Spins and Bulk Magnetization 290</p> <p>11.2.2 NMR Spectroscopy of Liquids 293</p> <p>11.2.3 NMR Relaxation 295</p> <p>11.2.3.1 Spin–Lattice Relaxation 295</p> <p>11.2.3.2 Spin–Spin Relaxation 296</p> <p>11.2.4 Pulsed Field Gradient NMR 297</p> <p>11.3 The NMR Toolkit in Reaction Engineering and Catalysis 299</p> <p>11.3.1 NMR Spectroscopy in Catalysis and Reaction Engineering 300</p> <p>11.3.2 Diffusion of Fluids Confined in Porous Catalysts 306</p> <p>11.3.2.1 Catalyst Deactivation Studies Using PFG NMR 311</p> <p>11.3.3 NMR Relaxation Time Analysis in Porous Catalytic Materials 314</p> <p>11.3.4 Combining NMR Spectroscopy withMagnetic Resonance Imaging 319</p> <p>11.4 Summary 324</p> <p>References 324</p> <p><b>12 An Introduction to Closed-Loop Process Optimization and Online Analysis 329<br /></b><i>Christopher S. Horbaczewskyj, Charlotte E. Willans, Alexei A. Lapkin, and Richard A. Bourne</i></p> <p>12.1 Introduction 329</p> <p>12.2 Principles of Self-Optimization and Requirements for Experimental Systems 330</p> <p>12.3 Analytical Techniques for Closed-Loop Optimization 332</p> <p>12.4 Decision Algorithms in Closed-Loop Optimization 334</p> <p>12.4.1 Algorithms for Discovery 335</p> <p>12.4.2 Algorithms for Developing Process Understanding 337</p> <p>12.4.3 Algorithms for Automated Process Optimization 338</p> <p>12.5 Application Examples of Closed-Loop Discovery and Optimization 341</p> <p>12.5.1 Discovery in Closed-Loop Self-Optimization 341</p> <p>12.5.2 High-Throughput Screening 342</p> <p>12.5.3 Examples of One-Variable-at-a-Time Reaction Optimization 344</p> <p>12.5.4 Examples of Application of Design of Experiments 346</p> <p>12.5.5 Rate-Based/Physical Organic Approaches 350</p> <p>12.5.6 Examples of Algorithm-Based Self-Optimization 364</p> <p>12.6 Conclusions and Future Directions 368</p> <p>Acknowledgments 369</p> <p>References 369</p> <p>Index 375</p>