Process Intensification Technologies for Green Chemistry

Dr Kamelia Boodhoo, Newcastle University, UK.Dr Boodhoo's research in the area of Process Intensification focuses on the development of centrifugal field reactors with particular emphasis on Spinning Disc Reactors. She also has a keen interest in intensification applications involving green chemistry and engineering and renewable resources such as the use of biomass for biopolymers. Dr Boodhoo has been involved in designing and delivering a specialist module on Process Intensification targeted at final year MEng students and MSc students at Newcastle University. For the last two years, she has also been a guest lecturer on the MSc in Green Chemistry and Sustainable Industrial Technology programme at the University of York, teaching "Improved Reactor Designs through Process intensification". Dr Adam Harvey, Newcastle University, UK.Dr Harvey is an active member of the Process Intensification Group at Newcastle. He is a member of the steering committee of the international research network "Process Intensification Network" and co-author of "Process Intensification", published in 2008. He currently lectures on Oscillatory Flow Reactors as part of the Process Intensification module delivered to final year MEng and MSc students.

• List of Contributors xiii Preface xv1 Process Intensification: An Overview of Principles and Practice 1Kamelia Boodhoo and Adam Harvey1.1 Introduction 11.2 Process Intensification: Definition and Concept 21.3 Fundamentals of Chemical Engineering Operations 31.3.1 Reaction Engineering 31.3.2 Mixing Principles 51.3.3 Transport Processes 81.4 Intensification Techniques 111.4.1 Enhanced Transport Processes 111.4.2 Integrating Process Steps 191.4.3 Moving from Batch to Continuous Processing 201.5 Merits of PI Technologies 211.5.1 Business 221.5.2 Process 221.5.3 Environment 231.6 Challenges to Implementation of PI 241.7 Conclusion 25Nomenclature 26Greek Letters 26References 272 Green Chemistry Principles 33James Clark, Duncan Macquarrie, Mark Gronnow and Vitaly Budarin2.1 Introduction 332.1.1 Sustainable Development and Green Chemistry 352.2 The Twelve Principles of Green Chemistry 352.2.1 Ideals of Green Chemistry 362.3 Metrics for Chemistry 372.3.1 Effective Mass Yield 382.3.2 Carbon Efficiency 382.3.3 Atom Economy 382.3.4 Reaction Mass Efficiency 392.3.5 Environmental (E) Factor 392.3.6 Comparison of Metrics 402.4 Catalysis and Green Chemistry 412.4.1 Case Study: Silica as a Catalyst for Amide Formation 432.4.2 Case Study: Mesoporous Carbonaceous Material as a Catalyst Support 452.5 Renewable Feedstocks and Biocatalysis 462.5.1 Case Study: Wheat Straw Biorefinery 482.6 An Overview of Green Chemical Processing Technologies 502.6.1 Alternative Reaction Solvents for Green Processing 502.6.2 Alternative Energy Reactors for Green Chemistry 522.7 Conclusion 55References 553 Spinning Disc Reactor: Continuous Thin-film Flow Processing for Green Chemistry Applications 59Kamelia Boodhoo3.1 Introduction 593.2 Design and Operating Features of SDRs 603.2.1 Hydrodynamics 633.2.2 SDR Scale-up Strategies 643.3 Characteristics of SDRs 663.3.1 Thin-film Flow and Surface Waves 663.3.2 Heat and Mass Transfer 683.3.3 Mixing Characteristics 713.3.4 Residence Time and Residence Time Distribution 723.3.5 SDR Applications 753.4 Case Studies: SDR Application for Green Chemical Processing and Synthesis 763.4.1 Cationic Polymerization using Heterogeneous Lewis Acid Catalysts 763.4.2 Solvent-free Photopolymerization Processing 783.4.3 Heterogeneous Catalytic Organic Reaction in the SDR: An Example of Application to the Pharmaceutical/Fine Chemicals Industry 803.4.4 Green Synthesis of Nanoparticles 833.5 Hurdles to Industry Implementation 843.5.1 Control, Monitoring and Modelling of SDR Processes 843.5.2 Limited Process Throughputs 863.5.3 Cost and Availability of Equipment 863.5.4 Lack of Awareness of SDR Technology 863.6 Conclusion 86Nomenclature 87Greek Letters 87Subscripts 87References 874 Micro Process Technology and Novel Process Windows – Three Intensification Fields 91Svetlana Borukhova and Volker Hessel4.1 Introduction 914.2 Transport Intensification 934.2.1 Fundamentals 934.2.2 Mixing Principles 944.2.3 Micromixers 964.2.4 Micro Heat Exchangers 1024.2.5 Exothermic Reactions as Major Application Examples 1064.3 Chemical Intensification 1084.3.1 Fundamentals 1084.3.2 New Chemical Transformations 1084.3.3 High Temperature 1184.3.4 High Pressure 1224.3.5 Alternative Reaction Media 1244.4 Process Design Intensification 1284.4.1 Fundamentals 1284.4.2 Large-scale Manufacture of Adipic Acid – A Full Process Design Vision in Flow 1304.4.3 Process Integration – From Single Operation towards Full Process Design 1314.4.4 Process Simplification 1354.5 Industrial Microreactor Process Development 1374.5.1 Industrial Demonstration of Specialty/Pharma Chemistry Flow Processing 1384.5.2 Industrial Demonstration of Fine Chemistry Flow Processing 1384.5.3 Industrial Demonstration of Bulk Chemistry Flow Processing 1394.6 Conclusion 140Acknowledgement 141References 1415 Green Chemistry in Oscillatory Baffled Reactors 157Adam Harvey5.1 Introduction 1575.1.1 Continuous versus Batch Operation 1575.1.2 The Oscillatory Baffled Reactor’s ‘Niche’ 1575.2 Case Studies: OBR Green Chemistry 1645.2.1 A Saponification Reaction 1645.2.2 A Three-phase Reaction with Photoactivation for Oxidation of Waste Water Contaminants 1665.2.3 ‘Mesoscale’ OBRs 1685.3 Conclusion 170References 1726 Monolith Reactors for Intensified Processing in Green Chemistry 175Joseph Wood6.1 Introduction 1756.2 Design of Monolith Reactors 1766.2.1 Monolith and Washcoat Design 1766.2.2 Reactor and Distributor Design 1786.3 Hydrodynamics of Monolith Reactors 1796.3.1 Flow Regimes 1796.3.2 Mixing and Mass Transfer 1806.4 Advantages of Monolith Reactors 1826.4.1 Scale-out, Not Scale-up? 1826.4.2 PI for Green Chemistry 1836.5 Applications in Green Chemistry 1856.5.1 Chemical and Fine Chemical Industry 1856.5.2 Cleaner Production of Fuels 1876.5.3 Removal of Toxic Emissions 1886.6 Conclusion 192Acknowledgement 193Nomenclature 193Greek Letters 193Subscripts and Superscripts 193References 1937 Process Intensification and Green Processing Using Cavitational Reactors 199Vijayanand Moholkar, Parag Gogate and Aniruddha Pandit7.1 Introduction 1997.2 Mechanism of Cavitation-based PI of Chemical Processing 2007.3 Reactor Configurations 2017.3.1 Sonochemical Reactors 2017.3.2 Hydrodynamic Cavitation Reactors 2057.4 Mathematical Modelling 2077.5 Optimization of Operating Parameters in Cavitational Reactors 2097.5.1 Sonochemical Reactors 2097.5.2 Hydrodynamic Cavitation Reactors 2107.6 Intensification of Cavitational Activity 2117.6.1 Use of PI Parameters 2127.6.2 Use of a Combination of Cavitation and Other Processes 2137.7 Case Studies: Intensification of Chemical Synthesis using Cavitation 2147.7.1 Transesterification of Vegetable Oils Using Alcohol 2147.7.2 Selective Synthesis of Sulfoxides from Sulfides Using Sonochemical Reactors 2177.8 Overview of Intensification and Green Processing Using Cavitational Reactors 2187.9 The Future 2217.10 Conclusion 222References 2228 Membrane Bioreactors for Green Processing in a Sustainable Production System 227Rosalinda Mazzei, Emma Piacentini, Enrico Drioli and Lidietta Giorno8.1 Introduction 2278.2 Membrane Bioreactors 2288.2.1 Membrane Bioreactors with Biocatalyst Recycled in the Retentate Stream 2288.2.2 Membrane Bioreactors with Biocatalyst Segregated in the Membrane Module Space 2308.3 Biocatalytic Membrane Reactors 2308.3.1 Entrapment 2308.3.2 Gelification 2318.3.3 Chemical Attachment 2318.4 Case Studies: Membrane Bioreactors 2328.4.1 Biofuel Production Using Enzymatic Transesterification 2338.4.2 Waste Water Treatment and Reuse 2378.4.3 Waste Valorization to Produce High-added-value Compounds 2398.5 Green Processing Impact of Membrane Bioreactors 2458.6 Conclusion 247References 2479 Reactive Distillation 251Anton Kiss9.1 Introduction 2519.2 Principles of RD 2529.3 Design, Control and Applications 2539.4 Modelling RD 2569.5 Economical and Technical Evaluation 2579.5.1 Economical Evaluation 2579.5.2 Technical Evaluation 2609.6 Case Studies: RD 2619.6.1 Biodiesel Production by Heat-Integrated RD 2619.6.2 Fatty Ester Synthesis by Dual RD 2679.7 Green Processing Impact of RD 2709.8 Conclusion 271References 27110 Reactive Extraction Technology 275Keat T. Lee and Steven Lim10.1 Introduction 27510.1.1 Definition and Description 27510.1.2 Literature Review 27610.2 Case Studies: Reactive Extraction Technology 27710.2.1 Reactive Extraction for the Synthesis of FAME from Jatropha curcas L. Seeds 27710.2.2 Supercritical Reactive Extraction for FAME Synthesis from Jatropha curcas L. Seeds 28110.3 Impact on Green Processing and Process Intensification 28410.4 Conclusion 286References 28611 Reactive Absorption 289Anton A. Kiss11.1 Introduction 28911.2 Theory and Models 29011.2.1 Equilibrium Stage Model 29011.2.2 HTU/NTU Concepts and Enhancement Factors 29111.2.3 Rate-based Stage Model 29111.3 Equipment, Operation and Control 29111.4 Applications in Gas Purification 29311.4.1 Carbon Dioxide Capture 29311.4.2 Sour Gas Treatment 29611.4.3 Removal of Nitrogen Oxides 29611.4.4 Desulfurization 29711.4.5 Sulfuric Acid Production 29911.4.6 Nitric Acid Production 29911.4.7 Biodiesel and Fatty Esters Synthesis 30211.5 Green Processing Impact of RA 30711.6 Challenges and Future Prospects 307References 30712 Membrane Separations for Green Chemistry 311Rosalinda Mazzei, Emma Piacentini, Enrico Drioli and Lidietta Giorno12.1 Introduction 31112.2 Membranes and Membrane Processes 31212.3 Case Studies: Membrane Operations in Green Processes 31812.3.1 Membrane Technology in Metal Ion Removal from Waste Water 31812.3.2 Membrane Operations in Acid Separation from Waste Water 33012.3.3 Membrane Operation for Hydrocarbon Separation from Waste Water 33312.3.4 Membrane Operations for the Production of Optically Pure Enantiomers 33612.4 Integrated Membrane Processes 34212.4.1 Integrated Membrane Processes for Water Desalination 34212.4.2 Integrated Membrane Processes for the Fruit Juice Industry 34312.5 Green Processing Impact of Membrane Processes 34412.6 Conclusion 347References 34713 Process Intensification in a Business Context: General Considerations 355Dag Eimer and Nils Eldrup13.1 Introduction 35513.2 The Industrial Setting 35613.3 Process Case Study 35813.3.1 Essential Lessons 36413.4 Business Risk and Ideas 36613.5 Conclusion 367References 36714 Process Economics and Environmental Impacts of Process Intensification in the Petrochemicals, Fine Chemicals and Pharmaceuticals Industries 369Jan Harmsen14.1 Introduction 36914.2 Petrochemicals Industry 37014.2.1 Drivers for Innovation 37014.2.2 Conventional Technologies Used 37214.2.3 Commercially Applied PI Technologies 37214.3 Fine Chemicals and Pharmaceuticals Industries 37614.3.1 Drivers for Innovation 37614.3.2 Conventional Technologies Used 37714.3.3 Commercially Applied PI Technologies 377References 37715 Opportunities for Energy Saving from Intensified Process Technologies in the Chemical and Processing Industries 379Dena Ghiasy and Kamelia Boodhoo15.1 Introduction 37915.2 Energy-Intensive Processes in UK Chemical and Processing Industries 38015.2.1 What Can PI Offer? 38015.3 Case Study: Assessment of the Energy Saving Potential of SDR Technology 38315.3.1 Basis for Comparison 38415.3.2 Batch Process Energy Usage 38415.3.3 Batch/SDR Combined Energy Usage 38615.3.4 Energy Savings 38915.4 Conclusion 389Nomenclature 390Greek Letters 390Subscripts 390Appendix: Physical Properties of Styrene, Toluene and Cooling/Heating Fluids 391References 39116 Implementation of Process Intensification in Industry 393Jan Harmsen16.1 Introduction 39316.2 Practical Considerations for Commercial Implementation 39316.2.1 Reactive Distillation 39416.2.2 Dividing Wall Column Distillation 39616.2.3 Reverse Flow Reactors 39616.2.4 Microreactors 39716.2.5 Rotating Packed Bed Reactors 39716.3 Scope for Implementation in Various Process Industries 39716.3.1 Oil Refining and Bulk Chemicals 39716.3.2 Fine Chemicals and Pharmaceuticals Industries 39816.3.3 Biomass Conversion 39916.4 Future Prospects 399References 399Index 401