Process intensification for green chemistry engineering solutions for sustainable chemical processing

Process Intensification for Green Chemistry Process Intensification for Green Chemistry Engineering Solutions for Sustainable Chemical Processing Edited by KAMELIA BOODHOO and ADAM HARVEY School of Chemical Engineering & Advanced Materials Newcastle University, UK This edition first published 2013 # 2013 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd., The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988 All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or 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with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose This work is sold with the understanding that the publisher is not engaged in rendering professional services The advice and strategies contained herein may not be suitable for every situation In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read No warranty may be created or extended by any promotional statements for this work Neither the publisher nor the author shall be liable for any damages arising herefrom Library of Congress Cataloging-in-Publication Data applied for A catalogue record for this book is available from the British Library ISBN: 9780470972670 Set in 10/12 pt Times by Thomson Digital, Noida, India Contents List of Contributors Preface Process Intensification: An Overview of Principles and Practice Kamelia Boodhoo and Adam Harvey 1.1 1.2 1.3 Introduction Process Intensification: Definition and Concept Fundamentals of Chemical Engineering Operations 1.3.1 Reaction Engineering 1.3.2 Mixing Principles 1.3.3 Transport Processes 1.4 Intensification Techniques 1.4.1 Enhanced Transport Processes 1.4.2 Integrating Process Steps 1.4.3 Moving from Batch to Continuous Processing 1.5 Merits of PI Technologies 1.5.1 Business 1.5.2 Process 1.5.3 Environment 1.6 Challenges to Implementation of PI 1.7 Conclusion Nomenclature Greek Letters References Green Chemistry Principles James Clark, Duncan Macquarrie, Mark Gronnow and Vitaly Budarin 2.1 2.2 2.3 Introduction 2.1.1 Sustainable Development and Green Chemistry The Twelve Principles of Green Chemistry 2.2.1 Ideals of Green Chemistry Metrics for Chemistry 2.3.1 Effective Mass Yield 2.3.2 Carbon Efficiency 2.3.3 Atom Economy 2.3.4 Reaction Mass Efficiency 2.3.5 Environmental (E) Factor xiii xv 1 3 11 11 19 20 22 22 23 23 24 25 26 27 27 33 33 35 35 36 37 38 38 38 39 39 vi Contents 2.3.6 Comparison of Metrics Catalysis and Green Chemistry 2.4.1 Case Study: Silica as a Catalyst for Amide Formation 2.4.2 Case Study: Mesoporous Carbonaceous Material as a Catalyst Support 2.5 Renewable Feedstocks and Biocatalysis 2.5.1 Case Study: Wheat Straw Biorefinery 2.6 An Overview of Green Chemical Processing Technologies 2.6.1 Alternative Reaction Solvents for Green Processing 2.6.2 Alternative Energy Reactors for Green Chemistry 2.7 Conclusion References 2.4 Spinning Disc Reactor for Green Processing and Synthesis Kamelia Boodhoo 3.1 3.2 Introduction Design and Operating Features of SDRs 3.2.1 Hydrodynamics 3.2.2 SDR Scale-up Strategies 3.3 Characteristics of SDRs 3.3.1 Thin-film Flow and Surface Waves 3.3.2 Heat and Mass Transfer 3.3.3 Mixing Characteristics 3.3.4 Residence Time and Residence Time Distribution 3.3.5 SDR Applications 3.4 Case Studies: SDR Application for Green Chemical Processing and Synthesis 3.4.1 Cationic Polymerization using Heterogeneous Lewis Acid Catalysts 3.4.2 Solvent-free Photopolymerization Processing 3.4.3 Heterogeneous Catalytic Organic Reaction in the SDR: An Example of Application to the Pharmaceutical/Fine Chemicals Industry 3.4.4 Green Synthesis of Nanoparticles 3.5 Hurdles to Industry Implementation 3.5.1 Control, Monitoring and Modelling of SDR Processes 3.5.2 Limited Process Throughputs 3.5.3 Cost and Availability of Equipment 3.5.4 Lack of Awareness of SDR Technology 3.6 Conclusion Nomenclature Greek Letters Subscripts References 40 41 43 45 46 48 50 50 52 55 55 59 59 60 63 64 66 66 68 71 72 75 76 76 78 80 83 84 84 86 86 86 86 87 87 87 87 Contents Micro Process Technology and Novel Process Windows – Three Intensification Fields Svetlana Borukhova and Volker Hessel 4.1 4.2 Introduction Transport Intensification 4.2.1 Fundamentals 4.2.2 Mixing Principles 4.2.3 Micromixers 4.2.4 Micro Heat Exchangers 4.2.5 Exothermic Reactions as Major Application Examples 4.3 Chemical Intensification 4.3.1 Fundamentals 4.3.2 New Chemical Transformations 4.3.3 High Temperature 4.3.4 High Pressure 4.3.5 Alternative Reaction Media 4.4 Process Design Intensification 4.4.1 Fundamentals 4.4.2 Large-scale Manufacture of Adipic Acid – A Full Process Design Vision in Flow 4.4.3 Process Integration – From Single Operation towards Full Process Design 4.4.4 Process Simplification 4.5 Industrial Microreactor Process Development 4.5.1 Industrial Demonstration of Specialty/Pharma Chemistry Flow Processing 4.5.2 Industrial Demonstration of Fine Chemistry Flow Processing 4.5.3 Industrial Demonstration of Bulk Chemistry Flow Processing 4.6 Conclusion Acknowledgement References Green Chemistry in Oscillatory Baffled Reactors Adam Harvey 5.1 Introduction 5.1.1 Continuous versus Batch Operation 5.1.2 The Oscillatory Baffled Reactor’s ‘Niche’ 5.2 Case Studies: OBR Green Chemistry 5.2.1 A Saponification Reaction 5.2.2 A Three-phase Reaction with Photoactivation for Oxidation of Waste Water Contaminants 5.2.3 ‘Mesoscale’ OBRs 5.3 Conclusion References vii 91 91 93 93 94 96 101 106 108 108 108 118 122 124 128 128 130 133 136 138 138 139 139 140 141 141 157 157 157 157 164 164 166 168 170 172 viii Contents Monolith Reactors for Intensified Processing in Green Chemistry Joseph Wood 6.1 6.2 Introduction Design of Monolith Reactors 6.2.1 Monolith and Washcoat Design 6.2.2 Reactor and Distributor Design 6.3 Hydrodynamics of Monolith Reactors 6.3.1 Flow Regimes 6.3.2 Mixing and Mass Transfer 6.4 Advantages of Monolith Reactors 6.4.1 Scale-out, Not Scale-up? 6.4.2 PI for Green Chemistry 6.5 Applications in Green Chemistry 6.5.1 Chemical and Fine Chemical Industry 6.5.2 Cleaner Production of Fuels 6.5.3 Removal of Toxic Emissions 6.6 Conclusion Acknowledgement Nomenclature Greek Letters Subscripts and Superscripts References Process Intensification and Green Processing Using Cavitational Reactors Vijayanand Moholkar, Parag Gogate and Aniruddha Pandit 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 Introduction Mechanism of Cavitation-based PI of Chemical Processing Reactor Configurations 7.3.1 Sonochemical Reactors 7.3.2 Hydrodynamic Cavitation Reactors Mathematical Modelling Optimization of Operating Parameters in Cavitational Reactors 7.5.1 Sonochemical Reactors 7.5.2 Hydrodynamic Cavitation Reactors Intensification of Cavitational Activity 7.6.1 Use of PI Parameters 7.6.2 Use of a Combination of Cavitation and Other Processes Case Studies: Intensification of Chemical Synthesis using Cavitation 7.7.1 Transesterification of Vegetable Oils Using Alcohol 7.7.2 Selective Synthesis of Sulfoxides from Sulfides Using Sonochemical Reactors Overview of Intensification and Green Processing Using Cavitational Reactors The Future 175 175 176 176 178 179 179 180 182 182 183 185 185 187 188 192 193 193 193 193 193 199 199 200 201 201 205 207 209 209 210 211 212 213 214 214 217 218 221 Contents 7.10 Conclusion References Membrane Bioreactors for Green Processing in a Sustainable Production System Rosalinda Mazzei, Emma Piacentini, Enrico Drioli and Lidietta Giorno 8.1 8.2 Introduction Membrane Bioreactors 8.2.1 Membrane Bioreactors with Biocatalyst Recycled in the Retentate Stream 8.2.2 Membrane Bioreactors with Biocatalyst Segregated in the Membrane Module Space 8.3 Biocatalytic Membrane Reactors 8.3.1 Entrapment 8.3.2 Gelification 8.3.3 Chemical Attachment 8.4 Case Studies: Membrane Bioreactors 8.4.1 Biofuel Production Using Enzymatic Transesterification 8.4.2 Waste Water Treatment and Reuse 8.4.3 Waste Valorization to Produce High-added-value Compounds 8.5 Green Processing Impact of Membrane Bioreactors 8.6 Conclusion References Reactive Distillation Technology Anton A Kiss 9.1 9.2 9.3 9.4 9.5 Introduction Principles of RD Design, Control and Applications Modelling RD Feasibility and Technical Evaluation 9.5.1 Feasibility Evaluation 9.5.2 Technical Evaluation 9.6 Case Studies: RD 9.6.1 Biodiesel Production by Heat-Integrated RD 9.6.2 Fatty Esters Synthesis by Dual RD 9.7 Green Processing Impact of RD 9.8 Conclusion References 10 Reactive Extraction Technology Keat T Lee and Steven Lim 10.1 Introduction 10.1.1 Definition and Description 10.1.2 Literature Review ix 222 222 227 227 228 228 230 230 230 231 231 232 233 237 239 245 247 247 251 251 252 253 256 257 257 260 261 261 267 270 271 271 275 275 275 276 x Contents 10.2 Case Studies: Reactive Extraction Technology 10.2.1 Reactive Extraction for the Synthesis of FAME from Jatropha curcas L Seeds 10.2.2 Supercritical Reactive Extraction for FAME Synthesis from Jatropha curcas L Seeds 10.3 Impact on Green Processing and Process Intensification 10.4 Conclusion Acknowledgement References 11 Reactive Absorption Technology Anton A Kiss 11.1 Introduction 11.2 Theory and Models 11.2.1 Equilibrium Stage Model 11.2.2 HTU/NTU Concepts and Enhancement Factors 11.2.3 Rate-based Stage Model 11.3 Equipment, Operation and Control 11.4 Applications in Gas Purification 11.4.1 Carbon Dioxide Capture 11.4.2 Sour Gas Treatment 11.4.3 Removal of Nitrogen Oxides 11.4.4 Desulfurization 11.5 Applications to the Production of Chemicals 11.5.1 Sulfuric Acid Production 11.5.2 Nitric Acid Production 11.5.3 Biodiesel and Fatty Esters Synthesis 11.6 Green Processing Impact of RA 11.7 Challenges and Future Prospects References 12 Membrane Separations for Green Chemistry Rosalinda Mazzei, Emma Piacentini, Enrico Drioli and Lidietta Giorno 12.1 Introduction 12.2 Membranes and Membrane Processes 12.3 Case Studies: Membrane Operations in Green Processes 12.3.1 Membrane Technology in Metal Ion Removal from Waste Water 12.3.2 Membrane Operations in Acid Separation from Waste Water 12.3.3 Membrane Operation for Hydrocarbon Separation from Waste Water 12.3.4 Membrane Operations for the Production of Optically Pure Enantiomers 12.4 Integrated Membrane Processes 12.4.1 Integrated Membrane Processes for Water Desalination 277 277 281 284 286 286 286 289 289 290 290 291 291 291 293 293 296 296 297 299 299 299 302 307 307 307 311 311 312 318 318 330 333 336 342 342 Contents 12.4.2 Integrated Membrane Processes for the Fruit Juice Industry 12.5 Green Processing Impact of Membrane Processes 12.6 Conclusion References 13 Process Intensification in a Business Context: General Considerations Dag Eimer and Nils Eldrup 13.1 Introduction 13.2 The Industrial Setting 13.3 Process Case Study 13.3.1 Essential Lessons 13.4 Business Risk and Ideas 13.5 Conclusion References xi 343 344 347 347 355 355 356 358 364 366 367 367 14 Process Economics and Environmental Impacts of Process Intensification in the Petrochemicals, Fine Chemicals and Pharmaceuticals Industries 369 Jan Harmsen 14.1 Introduction 14.2 Petrochemicals Industry 14.2.1 Drivers for Innovation 14.2.2 Conventional Technologies Used 14.2.3 Commercially Applied PI Technologies 14.3 Fine Chemicals and Pharmaceuticals Industries 14.3.1 Drivers for Innovation 14.3.2 Conventional Technologies Used 14.3.3 Commercially Applied PI Technologies References 15 Opportunities for Energy Saving from Intensified Process Technologies in the Chemical and Processing Industries Dena Ghiasy and Kamelia Boodhoo 15.1 Introduction 15.2 Energy-Intensive Processes in UK Chemical and Processing Industries 15.2.1 What Can PI Offer? 15.3 Case Study: Assessment of the Energy Saving Potential of SDR Technology 15.3.1 Basis for Comparison 15.3.2 Batch Process Energy Usage 15.3.3 Batch/SDR Combined Energy Usage 15.3.4 Energy Savings 15.4 Conclusion Nomenclature Greek Letters Subscripts 369 370 370 372 372 376 376 377 377 377 379 379 380 380 383 384 384 386 389 389 390 390 390 Implementation of Process Intensification in Industry 399 16.3.3 Biomass Conversion Biomass conversions to fuels and chemicals are generally more expensive than fossil oil conversions to the same products This is due to the fact that biomass is produced on land and has to be transported by truck to the conversion plants Moreover, a large part of the crude biomass is water, which does not end up in the product, further increasing the transport cost per ton of final product Therefore, biomass conversions are carried out on a relatively small scale near the biomass growth areas This small scale generally means higher capital cost per ton of product, however, due to the low economy of scale power (see Chapter 14) The business drivers for biomass conversions are therefore: low transport cost, low-cost separation of water from biomass and low capital cost per ton of biomass at small pants (low plant production capacities) [15] These drivers then provide ample opportunities for PI technologies in biomass conversion processing Biomass processing to fuel and chemical products involves reactions and separations In most cases the latter means separating oxygenates like alcohols, esters or ethers from water In this field, multifunctional PIs, such as RD, extractive RD, hybrids of membranes and distillation have a large scope of application Microsystems such as microreactors are already applied in the small-scale Fischer–Tropsch synthesis of diesel fuel using syngas from biomass gasification at Guessing biorefinery The microreactor, with 900 microchannels, catalytically converts the syngas to alkanes [16] N.B An overview of biomass conversions to chemicals, using process intensification technologies, has appeared in ref [17] 16.4 Future Prospects In future, PI technologies will see increasing implementation due to the good fit with business drivers mentioned in Section 16.3 In the oil refining and bulk chemical industries, future applications will be in all kinds of innovative multifunctional processes, such as reactive extractive distillation, reactive dividing wall column distillation and hybrid systems of distillation with membranes All these applications will reduce the energy requirements, the capital cost, the operational cost, the maintenance cost and environmental diffuse emissions, and they will often also reduce the need for precautionary safety measures, since runaway behaviour will be prevented by the low reactive hold-up In the fine chemicals and pharmaceuticals industries, microsystems will be increasing applied to the reducing the feedstock cost per mass of product and to improving commercial-scale production, as scale-up effects are avoided by these reactors The number of commercial PI applications will be further increased by the introduction of courses on PI in BSc and MSc Chemical Engineering programmes References (1) J Harmsen, Reactive distillation: the frontrunner of Industrial Process Intensification: a full review of commercial applications, research, scale-up, design and operation Chemical Engineering & Processing: Process Intensification, 46(9), 774–780 (2007) 400 Process Intensification for Green Chemistry (2) K Sundmacher and A Kienle, Reactive Distillation Status and Future Directions, WileyVCH: Weinheim (2003) (3) M F Doherty and M F Malone, Chapter 10 in Conceptual Design of Distillation Systems, McGraw-Hill: Boston (2001) (4) T Adrian, H Schoenmakers and M Boll, Model predictive control of integrated unit operations: control of a divided wall column Chem Eng And Processing 43, 347–355 (2004) (5) P Marın, S Ordo~nez and F V Diez, Simplified design methods of reverse flow catalytic combustors for the treatment of lean hydrocarbon–air mixtures Chemical Engineering and Processing: Process Intensification, 48(1), 229–238 (2009) (6) J Harmsen, Process intensification: its drivers and hurdles for commercial implementation Chemical Engineering and Processing, 49, 70–73 (2010) (7) J F Chen, Characterisation of micromixing efficiency in rotating packed bed reactors Chemical Eng J., 121, 147–152 (2006) (8) J.-F Chen and L Shao, Progress of high gravity technology – from fundamentals to nanomaterials, chemicals and pharmaceutical industrial applications, lecture and abstract, WCCE 8th Congress, Montreal, 23–27 August 2009 (9) Y Fei, Z Haikui, C Guangwen, S Lei and C Jianfeng, Modelling and experimental studies on absorption of CO2 by Benfield solution in rotating packed bed, Chemical Eng J., 145, 377–384 (2009) (10) A L Tonkovich et al., Micro channel technology scale-up to commercial capacity, 7th World Congress of Chemical Engineering, Glasgow, Congress Manuscripts, IChemE, 10–14 July 2005 (11) D L Trent, Chemical processing in high gravity fields, in Re-engineering the Chemical Processing Plant, A Stankiewicz and J A Moulijn (Eds.), Marcel Dekker (2004) (12) N Zuidhof, The Beckmann rearrangement of cyclohexanone oxime to e-caprolactam in micromixers and micro channels, PhD thesis, TU Eindhoven (2011) (13) M C de Jong, Reactive distillation for cosmetic ingredients: an alternative for the production of isopropyl myristate? PhD thesis, TU Eindhoven (2010) (14) B Schuur, Enantioselective liquid-liquid extraction in centrifugal contactor separators, PhD thesis, University Groningen (2008) (15) J Harmsen and J B Powell, Sustainable Development in the Process Industries: Cases and Impact, John Wiley & Sons: New York (2010) (16) Velocys, www.velocys.com, last accessed 14 September 2012 (17) J P M Sanders, et al (a.o Jan Harmsen), Process intensification in the future production of base chemicals from biomass, Special Issue of the journal “Chemical Engineering & Processing: Process Intensification”, 51, 117–136 (2012) Index Note: Figures are indicated by italic page numbers and Tables by emboldened numbers; abbreviations: OBR ¼ oscillatory baffled reactor; PI ¼ process intensification; SDR ¼ spinning disc reactor absorption definition, 290 see also reactive absorption acoustic cavitational reactor, 12, 200, 201 acoustic/ultrasonic streaming, 199, 202 active micromixers, 96 adipic acid manufacture, two-step vs direct routes, 130–1, 132, 133 aerobic granular sludge membrane bioreactor, 239 aerobic submerged membrane bioreactor, 237 affinity membranes, industrial applications, 323 agrowastes, high-added-value compounds produced from, 48–9, 240–2 air oxidation by [in waste water treatment], 166 purification of, 189 alternative reaction media/solvents, 50–2, 124–7 American Petroleum Institute (API) standard(s), pumps, 356, 358 amide formation, silica as catalyst for, 43–4 amines, acid gases removed by, 290, 292, 293, 295, 296, 358 ammonia scrubbing process [for removal of sulfur-containing gases], 296, 297, 298 anaerobic–aerobic [integrated] bioreactors, 238 anaerobic membrane bioreactors, 237–8 Arrhenius equation, 118 atom economy, 35, 38–9, 40 in OBRs/PFRs, 171 batch processing advantages, 21–2 compared with continuous processing, 20–1, 157, 357 styrene polymerization, 384–5, 386 pre-polymerization stage in combined batch/SDR process, 386 batch reactor, compared with OBR, 165 Batchelor length scale, 6, Benfield process, 295, 296 Bhopal accident, 23, 37 bifurcation-type lamination-based micromixers, 97 biocatalytic membrane reactors, 230 adsorption [immobilization] technique, 229, 231–2 application(s), 242, 243 chemical attachment techniques, 229, 231–2 in enantiomer production and separation, 340 entrapment [immobilization] technique, 229, 230–1 gelatification [immobilization] technique, 229, 231 integrated with membrane emulsification process, 242, 243 site-specific immobilization techniques, 232 types, 229, 230–2 biodiesel production cavitational reactors used, 214–17 comparison of different reactive separation methods, 285, 302, 303, 306 conventional process, 214, 215, 285 energy requirements, 303 Process Intensification for Green Chemistry: Engineering Solutions for Sustainable Chemical Processing, First Edition Edited by Kamelia Boodhoo and Adam Harvey Ó 2013 John Wiley & Sons, Ltd Published 2013 by John Wiley & Sons, Ltd 402 Index biodiesel production (Continued ) by enzymatic transesterification, 216, 233–7 enzymes used, 233, 235, 236 feedstocks used, 233, 235 solvents used, 236–7 heat-integrated reactive absorption used, 302–6 heat-integrated reactive distillation used, 261, 263–6, 271 by liquid–liquid reactive extraction [of oil], 276, 285 OBRs used, 166, 170, 171 by solid–liquid reactive extraction [of biomass], 276, 277–84, 285 see also fatty acid methyl esters (FAME) production biofilm membrane bioreactors, 238 biofiltration, 190 biomass conversion into chemicals, 48, 399 as renewable feedstock, 46, 47 bioreactors, monolith reactors as, 189–90 biorefinery concept, 47–8 case study [wheat straw], 48–9 biphasic biocatalytic membrane reactors, with immobilized lipase, 235, 236, 243, 244, 340 biphasic systems, 51 bubble dynamics, in cavitational reactors, 207–9 bulk chemicals manufacture, PI technologies used, 139–40, 372–6, 398 business benefits of PI, 22–3 business risks, 366–7 n-butyl acrylate, photopolymerization of, 79–80 campholenic anhydride, 80–1 preparation of, 81–2 capital costs CO2 capture process, 360–1, 363 petrochemicals plant, 371 carbon cycle, 46 carbon dioxide capture by reactive absorption, 293–5, 358–66 phase diagram, 51 as reagent in microflow processing, 110, 123 sources, 293, 294 see also CO2; supercritical carbon dioxide carbon efficiency [metric], 38 carboxylation reactions, 110, 112 catalysis, 41–3 case studies, 43–6 effect of solvent, 42–3 factors affecting reaction rate, 42 in oscillatory baffled reactors, 166, 167, 168, 171 turnover number, 42 catalyst replacement in reactions, 136–7 catalyst supports, 44, 45 cationic polymerization case studies cationic polymerization, 76–8 free-radical polymerization, 76, 383–9 pharmaceutical/fine chemicals, 80–3 photopolymerization, 78–80 polymerization, 76–80, 383–9 SDR, 76–8 CAV-OX process, 213 cavitation, 12, 13, 199 combination with other processes, 213–14 microwave irradiation, 214 photocatalytic oxidation, 213 cavitational activity factors affecting, 210–11 intensification of, 211–14 cavitational collapse effects, 12, 13, 202 in heterogeneous systems, 12, 200–1, 220 in homogeneous reactions, 12, 200, 220 cavitational reactors, 199–222 bubble dynamics in, 207–9 case studies sulfoxide synthesis, 217–18, 219 transesterification of vegetable oils, 214–17 configurations, 201–7 future developments, 221–2 mathematical modelling, 207–9 optimization of operating parameters, 209–11 PI and, 201, 218, 220–1 pressure field distributions, 208, 209 see also hydrodynamic cavitational reactors; sonochemical reactors cavity dynamics, 200 centrifugal field-based processing equipment, 11–12 see also rotating packed beds; spinning disc reactors chaotic advection-based micromixers, 100–1 Index chaotic mixing, 101 chemical absorption, 290 see also reactive absorption chemical engineering operations consequences of PI, 2–3 fundamentals, 3–10 mixing processes, 5–8 reactor engineering, 3–5 transport processes, 8–10 chemical equilibrium constant, in reactive distillation evaluation, 259, 260–1 chemical intensification, 93, 108–28 alternative reaction media, 124–8 fundamentals, 108 high-pressure reactions, 122–4 high-temperature reactions, 118–22 new chemical transformations, 108–18 chemical plants maintenance requirements, 356 operational philosophy, 356–7 chirality of compounds, 336–7 chirally imprinted membranes, 340, 341, 342 chitosan, 44, 45, 341 Claisen rearrangement reactions, 106, 120, 122, 127 clays, as catalysts, 44 close-clearance impellers, power requirements, 385 CO2 capture, 293–5, 358 PI case study, 358–66 ‘absorber’ section, 360–1, 362 ‘amine stripping’ section, 360, 361, 363 ‘CO2 compression section, 363, 364 effect of HiGee process, 365 lessons to be learnt, 364–6 CO2 emissions sources, 25, 293, 294 see also carbon dioxide cocurrent downflow contactor reactor (CDCR), 178, 185, 186, 191 coke oven gas purification, 296 compact heat-exchanger reactors, 184 compact heat exchangers, 9, 363, 381, 382 contact process [sulfuric acid production], 299, 300 continuous membrane fermentors, 230 continuous microflow, multistep syntheses using, 112, 113–15, 137, 138 continuous processing advantages, 21 403 compared with batch processing, 20–1, 157, 357 continuously stirred tank reactors (CSTRs), 4, 158 limitations, 4–5, 158 and OBRs, 158 convective transport, 95 Coriolis effect/forces, 64, 71 cost savings, 357 Cottrell precipitator, 13 counterflow heat exchangers, 103 critical Dean number, 96 crossflow heat exchangers, 102–3 cryogenic conditions, not required in microflow processing, 116, 118, 121, 136 b-cyclodextrin, in sulfoxide synthesis, 218 Damkohler number, 260 Darcy’s law, 313 Dean number, 95 critical, 96 debottlenecking [of chemical plant], 357, 383 desalination processes, 11, 314, 318, 319, 321, 342–3, 347 desulfurization processes, 297, 298 diazonium chemistry, in microreactors, 116 dielectric constant effects, in high-pressure reactions, 123 Diels–Alder cycloaddition reactions, 120, 121, 122, 220 diesel see biodiesel diffusion dialysis, industrial applications 330, 332 diffusion mixing, 95 Dimroth rearrangement reaction, 121 Dittus–Boelter equations, 10 dividing wall column distillation, 254, 374, 396 drying operations, 380 equipment used, 381 PI approach, 382 dual-pressure plant [for nitric acid production], 300–1 dual reactive distillation, fatty esters synthesis using, 267–70 Eastman methyl acetate process, 20, 252 economic drivers for process innovation, petrochemicals industry, 370–2 404 Index economic evaluation CO2 capture process, 360–5 reactive distillation, 257–60 education and training requirements, 86, 399 effective mass yield, 38 electric fields, applications, 13–14 electrochemistry, 117–18 electrodialysis, 318 industrial applications, 320, 322–5, 329, 330, 332, 333, 346 electromagnetic spectrum, 14, 53 electronics industry applications, membrane operations used, 322 electrostatic separations, 14 emulsion enzyme membrane reactor, 339 enantiomers, 336 separation of, 242–5, 336–42 enantioselective membranes, 339, 340–1 energy dissipation rates [of mixers/reactor], energy efficiency green chemistry, 35, 171, 345 PI, 23–4, 25 energy-intensive processes, 380 conventional equipment used, 381 energy requirements petrochemicals plant, 370 reactive separation methods, 265, 267, 302, 303, 306 energy saving [from PI technologies], 379–91 case study [SDR technology], 383–9 potential savings for UK chemical sector, 380, 381 enhancement factors, in reactive absorption, 291 entrapped catalysts, 189, 229, 230–1, 235 environmental benefits of PI, 23–4 environmental (E) factor, 39–40, 41 typical values, 40 enzymatic transesterification in biodiesel production, 216, 233–7 enzymes used, 233, 235, 236 feedstocks used, 233, 235 solvents used, 236–7 European Commission, membrane technology research projects, 246, 343 exothermic reactions, 106–7, 109 explosions, factors affecting, 107, 110 extractive membrane bioreactors, 230 fatty acid methyl esters (FAME) production by reactive distillation, 252, 255, 264, 265, 265, 266 by reactive extraction, 277–84 see also biodiesel production fatty acids (FAs) odour-cut material, biodiesel production from, 215–16 fatty esters synthesis by dual reactive distillation, 267–70 by heat-integrated reactive absorption, 302–6 uses, 267, 302 feed–effluent heat exchangers, 264, 303 fertilizer industry, PI example, 358 Fick’s law [of diffusion], 95, 313 filtration, heterogeneous catalysts separated by, 41, 76, 191 fin-type heat exchangers, 103–4 fine/specialty chemicals industry conventional technologies used, 377 economic drivers for innovation, 376 environmental drivers, 376–7 PI technologies used microreactors, 134, 138–9, 377, 398 monolith reactors, 185–7 SDRs, 80–3 Fischer–Tropsch process, 139–40, 175, 399 ‘flash chemistry’, 109, 118 flash flow pyrolysis, 121 flow intensification, 93–4 flue gas desulfurization processes, 297 fluorination, by elemental fluorine, 109–10 fluorous biphasic solvents, 50, 51 food processing membrane operations used, 324–5, 343–4 microwave drying used, 383 SDRs used, 76 supercritical solvents used, 50 force fields, enhanced, in intensification techniques, 11–16 fossil fuel combustion, CO2 emissions from, 25, 293, 294 Fourier’s law, 313 free-radical generation, cavitation-based, 199, 200 Friedel–Crafts alkylation reactions, 44, 117–18, 220 Index fruit juice concentration, integrated membrane processes used, 343–4 fuel cells, 187, 188 fuel processing microreactors in, 129, 133–4 monolith reactors in, 187–8 gas–liquid conversion, micro process technology used, 139–40, 399 gas-separation membranes, 315, 316, 346 glycerol, oxidation of, 187 green chemistry definitions, 33 ideals, 36 meaning of term, 33–4 and membrane processes, 345–6 metrics for, 37–41 and oscillatory baffled reactors, 166, 168, 169–70, 170–2 ‘Twelve Principles’, 35–6, 170–2, 345–6 green processing and synthesis in SDRs, 76–84 Hatta number, 256–7, 261 hazardous and toxic substances, minimization of use in cavitational reactors, 220–1 in microreactors, 92, 107 in monolith reactors, 184 in oscillatory baffled reactors, 172 heat exchangers, 102–6 in reactive separation technologies, 264, 303 see also micro heat exchangers heat-integrated reactive absorption biodiesel production using, 302–6 compared with other reactive separation methods, 302, 303, 306 heat-integrated reactive distillation advantages, 265, 383 biodiesel production using, 264–5 compared with other reactive separation methods, 302, 303, 306 future developments, 271 heat transfer, 8–9 in spinning disc reactors, 68–71 heat-transfer intensification, 94, 382 in microchannel systems, 102–6 in oscillatory baffled reactors, 161–2 heavy metals 405 effects on human health, 327 removal from waste water by membrane processes, 318, 328–30 by traditional techniques, 318, 327–8 Heck aminocarbonylation reaction, 119 heterogeneous catalysis, reactive distillation equipment selection for, 254 heterogeneous catalysts, 41–2 compared with homogeneous catalysts, 41, 42, 256 in microchannels/microreactors, 116–17 SDR case studies, 76–8, 80–3 heterogeneous systems, cavitational collapse effects, 12, 200–1, 220 HiGee[rotating packed bed] technology, 357,383 effect on CO2 case study, 365 high-concentration processing, 127 high-pressure homogenizer, 206 high-pressure reactions, 122–4 density and viscosity effects, 123 dielectric constant effects, 123 reaction volume effects, 122 solubility effects, 123–4 high-pressure,temperature reactions, 118, 119, 120, 121, 137 high-temperature reactions, 118–22 application examples, 119–22 fundamentals, 118 homogeneous catalysis, reactive distillation equipment selection for, 254 homogeneous catalysts, compared with heterogeneous catalysts, 41, 42, 256 homogeneous reactions, cavitational collapse effects, 12, 200, 220 hybrid technologies, 238, 239, 383, 399 hydrocarbons environmental effects, 334–5 separation from waste water, 333–6 hydrodesulfurization, 373 hydrodynamic barrier [on catalyst surface], 42 solvent effects, 42–3 hydrodynamic cavitation, 200, 205 in rotating equipment, 206 hydrodynamic cavitation reactors, 205–7 biodiesel production using, 214, 215, 216 combination with photochemical/ photocatalytic reactors, 213–14 mathematical modelling, 208 optimization of operating parameters, 210–11 with flow loop, 206–7, 210, 214 406 Index hydrodynamics fluid flow, 94 monolith reactors, 179–82 spinning disc reactors, 63–4 hydrofocusing, in lamination-based micromixers, 98–9 hydrogen, production of, 187–8, 375, 398 hydrogen peroxide as oxidizing agent, 119, 130, 213, 217, 218 production of, 175, 183 hydrogen sulfide, removal by reactive separation, 294, 296, 373 idea development process, 356 imine synthesis, meso-OBRs used, 169–70 implementation of PI, challenges to, 24–5 imprinted polymers, 340, 341–2, 341 in situ transesterification, 276 inductive heaters, 105–6 inherently safer chemistry for accident prevention, 36 in membrane processes, 346 in oscillatory baffled reactors, 166, 172 ‘inherently safer design’ (ISD) concept, 37 inorganic acids separation from waste waters, 330–1, 331–2 uses, 330, 331 ‘installation factor’ (Lang factor), 360 integrated membrane processes, 342–4 industrial applications fruit juice concentration, 324, 343–4 waste water treatment, 319, 320, 325, 326 water treatment, 319, 342–3 integration of process control and sensing, 134–5 integration of process steps, 19–20, 131, 133–5 intensification techniques, 11–22 continuous vs batch processing, 20–2 enhanced transport processes, 11–19 integrating process steps, 19–20 ion-exchange membrane bioreactors, 230 ion-exchange membranes, industrial applications, 322, 329, 336 ionic liquids, 51–2, 120, 126–7 jatropha oil, biofuel production from, 233, 235 jatropha seeds determination of moisture and oil content, 277, 279 FAME synthesis from effect of seed sizes, 279–80, 281, 283–4 by reactive extraction, 277–81 by supercritical reactive extraction, 281–4 oil extraction efficiency, 279 jet-impingement reactors, energy-dissipation rates, kinetic explosions, 107 Knoevenagel condensation reactions, 43, 134 Knudsen diffusion, 315 Kolbe–Schmitt reaction, 119 Kolgomorov length scale, 6, 7, lactic acid, 240, 332 production from biomass, 240–1 separation from waste waters, 332–3 laminar flow, 94 lamination-based micromixers, 96–9 light-activated polymerization, 15, 78 limestone gypsum process, 297 limitations of PI, 24–5, 26 lipase enzymes, 233 use in biocatalytic membrane reactors, 235, 236, 243 liquid membranes, industrial applications, 322, 323, 329 macromixing, 6–7, marginal costs, petrochemicals plant, 370 mass transfer, 9–10 in monolith reactors, 180, 181–2 in spinning disc reactors, 68–9 mass-transfer intensification, 17, 94 MEDINA project, 343 membrane-based solvent extraction, 317, 318 membrane bioreactors, 227–47 advantages, 228 case studies biofuel production, 233–7 valorization of waste materials, 239–45 waste water treatment, 237–9 in enantiomer production and separation, 339, 340 examples of use, 228, 232–45 fouling control strategies, 238, 239 global market, 246 green processing impact, 245–6 industrial applications, 232–45, 319, 321, 323, 324, 326 patents, 245, 246 types, 228–30 Index in waste water treatment, 343 with biocatalyst recycled in retentate stream, 228–30 with biocatalyst segregated in membrane module space, 229, 230 membrane contactors, 315 industrial applications, 319, 322, 324, 343, 346 types, 315, 317, 318 membrane crystallizers, 317, 318 membrane distillation process, 315, 317 industrial applications, 319, 324, 344 membrane emulsification process, 242, 243, 244, 339 membrane filtration, in waste water treatment, 238, 239 membrane operations, 311 industrial applications, 318–42 electronics industry, 322 enantiomers separation, 242–5, 336–42 food industry, 324–5, 343–4 metal plating industry, 322 paper industry, 321 pharmaceuticals industry, 322–3, 336–42 tannery industry, 322 textile industry, 321 waste water treatment, 318, 319, 320, 328–36 water industry, 319–21, 342–3 membrane processes, 312–18 green processing impact, 344–7 pressure-driven, 313–15 see also integrated membrane processes membrane reactors, 19 biocatalytic, 229, 230–2, 340 industrial applications, 319, 324 phase-transfer membrane reactors, 317, 318 submerged membrane reactors, 228, 229, 237, 239, 245, 347 see also membrane bioreactors membrane strippers/scrubbers, 317, 318 membranes classification of, 313 definition, 312 driving forces, 312–13 mass transport through, 312 mesomixing, 6, mesoporous carbons, as catalyst support, 45–6 mesoscale channel reactors, 17 407 mesoscale oscillatory baffled reactors, 166, 168–70 meso-structured slurry bubble column (MSSBC), 187 metal plating industry applications, membrane operations used, 322 methane, hydrogen produced from, 139, 375, 398 methyl acetate production, Eastman process, 20, 252 methyl tertiary butyl ether (MTBE), production using reactive distillation, 252, 259 metrics [for ‘green’ improvements], 37–41 comparison of, 40–1 micellar-enhanced ultrafiltration (MEUF), 328 industrial applications, 329, 341 Michael addition reaction, 126, 127 micro fuel processing systems, 129, 133–4 micro heat exchangers, 102–6, 382 counterflow, 103 crossflow, 102–3 fin-type, 103–4 fundamentals, 102 micro process technology, 91–2 advantages compared with larger-scale equipment, 93–4 microalgae oil, 233 microburner/thermoelectric device, integration of, 134 microchannel electrical heaters and evaporators, 104 microchannel reactors, 16–17, 52, 91–2 microchannels, chaotic advection-based segmented multiphase flow in, 101–2 microfibrous entrapped catalysts (MFECs), 189 microfiltration, 233, 241, 313, 314, 315 industrial applications, 319–26, 329, 343, 344, 346 microflow process design, 128 microflow systems, 92 micromixers, 96–102 active, 96 chaotic advection-based, 100–1 characteristic parameters, 95 lamination-based, 96–9 passive, 96 split-and-recombine, 99–100 T- and Y-shaped, 96–7 408 Index micromixing, 6, 7–8 in spinning disc reactors, 72 microreactors, 16–17 characteristics, 92, 109, 382 concept design, 397 industrial process development, 137–40 integration with sensors and control components, 134–5 in petrochemicals industry, 375 microstructured steam reformer and catalytic converter, integration of, 133, 134 microwave-assisted processing, 14–15, 52–4 case study, 54 with sonochemical reactors, 214 microwave drying, 382–3 microwave heating, 14–15, 53, 105, 120 mixing principles, 94–6 mixing processes, 5–8 effect on reactions, energy dissipation rates, equipment used, 18–19, 381, 382 macromixing, 6–7, mesomixing, 6, micromixing, 6, 7–8 molecular imprinting, 341 molecular reactors, 16 momentum transfer, 10 monoethanolamine (MEA), acid gases removed by, 290, 292, 293, 295, 358 monolith reactors, 17, 175–92 advantages, 182–4 applications in green chemistry chemicals/fine chemicals manufacture, 185–7 fuel production, 187–8 removal of toxic emissions, 188–91 as bioreactors, 189–90 compared with other reactors, 184, 186 design, 176–8 flow regimes in, 179–80 green chemistry advantages, 183–4 hydrodynamics, 179–81 mass-transfer processes, 180, 181–2 mixing mechanisms in, 180–1 monolith support structure, 176–7 reactor and distributor design, 178 scale-up strategies, 182–3 washcoat used, 177 Muharashi coupling, 116 multistep synthesis in continuous microflow, 112, 113–15, 137, 138 vs one-pot synthesis, 112 vs one-step synthesis, 109–12 municipal waste water treatment, 245, 246 nanofiltration, 241, 313, 314, 315 industrial applications, 319–26, 328, 329, 330, 332, 336, 343, 344, 346 nanoparticles, 83–4 preparation of, 76, 84 naproxcinod manufacture, microreactors used, 138 naproxen esters, enantioselective production of, 243–4 Navier–Stokes equations, 63 new chemical transformations, 108–18 nitric acid, 299 disadvantages as oxidant, 130, 131 production of, 299–302 nitrogen oxides (NOx) catalytic reduction of, 175, 188–9 removal by reactive absorption, 296–7 ‘novel process windows’, 23, 92–3, 108, 141 Nusselt number, 102 Ohm’s law, 313 oil industry, gas/oil/water phase separator, 358 oil refining, PI technologies used, 296, 297, 372–6, 397–8 oleuropein, 241–2 oleuropein aglycon, 242 olive mill waste water, phenolic compounds in, 240, 241–2 optically pure enantiomers, production of, 242–5, 336–42 organic acids separation from waste waters, 331, 332–3 uses, 330, 331 orifice flow, cavitational activity affected by, 210, 211 oscillatory baffled reactors (OBRs), 22, 157–73 case studies saponification reactions, 164–6 waste water treatment, 166–8 compared with batch reactors, 165 design procedure, 162–4 green chemistry elements, 166, 168, 169–70, 170–2 heat-transfer enhancement in, 161–2 Index mesoscale OBRs, 166, 168–70 mixing in, 159–60 plug flow in, 160 typical configuration, 158, 159 use with solids suspensions, 160–1 osmotic distillation (OD) technique, 317, 318 industrial applications, 324, 325, 344 osmotic membrane bioreactor, 239 Ostwald process [nitric acid production], 299–302 oxidation by air [in waste water treatment], 166 by molecular oxygen, 107, 110, 187 by ozonolysis, 110, 111 ozonolysis, 110, 111 paper industry applications, membrane operations used, 321 parallel interdigital lamination-based micromixers, 97–8 passive micromixers, 96 Peclet number, 95 pervaporation, 315, 316 industrial applications, 322, 323, 324, 333, 344, 346 petrochemicals industry conventional technologies used, 372 economic drivers for innovation, 370–2 environmental drivers, 372 PI implementation, 397–8 PI technologies used divided wall column distillation, 374, 398 microreactors, 375, 398 reactive absorption, 296, 297 reactive distillation, 373–4, 398 reverse flow reactors, 374–5, 398 rotating packed bed reactors, 376, 398 pharmaceuticals industry conventional technologies used, 377 economic drivers for innovation, 376 environmental drivers, 376–7 PI technologies used membrane processes, 322–3, 336–42 microreactors, 377, 398 multistep synthesis in continuous microflow, 113–15, 137, 138 SDRs, 80–3 sulfoxides in, 217 phase-transfer catalysts (PTCs), 51, 171 409 phase-transfer membrane reactors, 317, 318 phenol, nitration of, 122 phenylboronic acid production, 136 photocatalytic oxidation, 166, 167, 191 combined with cavitation, 213 photochemical/photocatalytic reactors, combined with hydrodynamic cavitation reactors, 213–14 photochemistry, 15–16 in microflow reactors, 117 photopolymerization, SDR case study, 78–80 phytotherapic(s), production from olive mill waste water, 241–2 a-pinene oxide, rearrangement reactions, 76, 80–3 platform molecules [bio-derived molecules], 48 plug flow reactors (PFRs), 3–4, 158 advantages, 4–5, 171 green chemistry elements, 170–2 limitations, 158 and OBRs, 158 Podbielniak liquid–liquid contactors, 10 pollutants removal from gas streams, 188–90 treatment in liquid-phase streams, 191, 192 polyacrylonitrile hollow-fibre membranes, 339 polydimethylsiloxane (PDMS) membranes, 333 polymer-enhanced ultrafiltration (PEUF), 328 industrial applications, 321, 328, 329 polyphenols in fruit juice waste, 326 in olive mill waste water, 240, 241–2 polysulphone membranes, 242, 243, 341 portable plants, 139–40, 184 potable water production, 246, 318 pressure-driven membrane processes, 313–15 pressure field distributions, in cavitational reactors, 208, 209 process benefits of PI, 23, 52 process design intensification, 93, 108, 128–37, 141 adipic acid manufacture example, 130–1, 132, 133 fundamentals, 128–9 process integration, 129, 131, 133–5 process simplification, 129, 135–7 process heating conventional equipment for, 381 PI technologies, 9, 102–6, 363, 381, 382 process innovation stages, 393–4 410 Index process integration, 129, 131, 133–5 of process control and sensing, 134–5 thermal integration, 135 of unit operations, 133–4 of units on racks etc., 135 process intensification (PI) in business context, 355–67 cavitational reactors, 201, 218, 220–1 chemical industry background, 356–8 classification of equipment and methods, 2, CO2 capture case study, 358–66 commercial implementation, 393–7 consequences for chemical-engineering operations, 2–3 definition, European Roadmap, 346 goals, 93, 176, 355, 365 monolith reactors, 176, 183–4 reactive extraction, 284 process simplification, 129, 135–7 catalyst omission, 136–7 fast processing, 135–6 separation simplification, 136 Raman spectroscopy, SDR process monitored using, 85 rapeseed oil, biofuel production from, 233, 235, 236 Rayleigh–Plesset [bubble dynamics] equation, 208 reaction mass efficiency, 39, 40–1 reactive absorption (RA), 289–307 challenges, 307 chemicals production using, 299–306 control methods, 292–3 enhancement factors, 291 equipment, 291–2 future developments, 307 gas-purification applications, 293–8 green processing impact, 307 HTU/NTU concepts, 291 industrial applications biodiesel and fatty esters synthesis, 302–6 carbon dioxide capture, 293–5 desulfurization processes, 297, 298 hydrogen sulfide removal, 294, 296 nitric acid production, 299–302 nitrogen oxides removal, 296–7 sour gas treatment, 294, 296 sulfuric acid production, 299, 300 models equilibrium stage model, 290–1 rate-based stage model, 291 two-film model, 291, 292 operation, 292 theory, 290 reactive distillation (RD), 20, 251–71 case studies biodiesel production by heat-integrated RD, 261, 263–6 fatty acid synthesis by dual RD, 267–70 concept design, 394–6 configuration alternatives, 254 controllability, 256 design, 253–4, 394–6 economic evaluation, 257–60 future developments, 271 green processing impact, 270–1 heuristic rules, 394, 395 industrial applications, 252, 254, 255 match between reaction and separation temperatures, 258–9 modelling, 256–7 in petrochemicals industry, 373–4 principles, 252–3 production rate criterion, 259–60 reaction types used in, 252, 253 residue curve maps (RCMs), 253, 260, 271 technical evaluation, 260–1, 262 see also dual reactive distillation; heat-integrated reactive distillation reactive extraction technology, 20, 275–86 definition, 275 green processing impact, 284, 286 liquid–liquid reactive extraction, 275–6 solid–liquid reactive extraction, 276, 277–8, 285 types, 275–6 reactor engineering, 3–5 continuously stirred tank reactors, plug flow reactors, 3–4 renewable feedstocks, 35, 46–9 use in membrane processes, 346 use in OBRs, 170, 171 residence time distributions (RTDs), continuously stirred tank reactors, oscillatory baffled reactors, 160, 161 plug flow reactors, 3–4 Index spinning disc reactors, 73–4 residence times, micromixers, 116 microreactors, 109, 119, 120, 398 monolith reactors, 190 OBRs, 166, 169, 170 SDRs, 63, 65, 66, 72–3 residue curve maps (RCMs) [in reactive distillation], 253, 260, 271 retrofitting techniques, 139, 357, 383 return on investment (ROI) calculations, 371–2 reverse flow reactors, 374–5, 396–7 reverse osmosis, 241, 313, 314, 315 industrial applications, 319–26, 328, 329, 330, 332, 333, 343, 344, 346 Reynolds number, 94–5 risk aversion, 24, 356, 366 risk management, 366 rotating liquid–liquid extractors, 10 rotating packed bed (RPB) reactors, 12, 397 concept design, 397 in petrochemicals industry, 376, 398 thin-film processing in, 11 see also HiGee technology rotor–stator mixers, energy-dissipation rates, running costs reduction, 25 safety aspects of green chemistry, 35, 36 and OBRs, 165–6, 172 safety benefits of PI, 23, 25, 107 scale-up strategies ‘brute-force’ scale-up, 394, 395, 396 microchannel reactors, 52, 92 monolith reactors, 182–3 reactive distillation, 394, 395, 396 reverse flow reactors, 396 rotating packed bed reactors, 397 SDRs, 64–5 Schmidt number, sea water washing (SWW) process, 297, 298 selective catalytic reduction (SCR), 188–9 separation processes, PI approaches, 383 separation simplification, 136 sequencing aerobic sludge blanket reactor, 239 sequencing batch reactors, 238 silica-supported BF3 Lewis acid catalyst, 77 silica with organic functionalities, in heterogeneous catalysts, 42 silicon micromonolith reactors, 188 silver nanoparticles, preparation of, 84 411 solids suspensions, in OBRs, 160–1 solubility effects, in high-pressure reactions, 123–4 solution–diffusion mechanism [in gas separation], 315, 316 solvent-free processing, 127–8 solvents, alternative, 50–2 sonochemical reactors, 201–5 bath systems, 203–4 biodiesel production using, 214, 215, 216 combination with microwave irradiation, 214 flow systems, 204–5 low-output transducers used, 205 mathematical modelling, 208, 209 optimization of operating parameters, 209–10 selective synthesis of sulfoxides using, 217–18, 219 ultrasonic horn based, 202–3 sonolysis, 12–13 sour gas treatment, 296 soybean oil, biofuel production from, 215, 233, 235 spinning disc reactors (SDRs), 12, 55 applications, 75, 76, 382 barriers to industrial implementation, 84–6 catalyst immobilisation, 81–3 characteristics, 66–75 compared with stirred tank reactors, 77, 78, 82, 83, 383–9 control and monitoring of SDR processes, 84–6 cost and availability of equipment, 86 design, 60–5 energy-dissipation rates, energy-saving potential, 386–9 energy usage, 387–9 green processing and synthesis in SDRs, 76–84 heat transfer rates, 68–71, 382 hydrodynamics, 63–4 industrial awareness of SDR technology, 86 industry implementation, 84–6 mass transfer rates, 68, 69, 382 mixing characteristics, 71–2 online monitoring of SDR processes, 85–6 operating parameters, 59–60, 61 plug flow behaviour, 73–5 412 Index spinning disc reactors (SDRs) (Continued ) residence times, 72–3 scale-up strategies, 64–5 solvent-free processing, 78–80 surface wave formation, 60, 66–8 thermograms, 69–71 thin-film flow, 11, 66 throughput limitations, 61, 86 split-and-recombine (SAR) micromixers, 99–100 Starbon(R) catalyst support, 45–6 static mixers, 18–19 advantages, 18 applications, 19, 381, 382 energy-dissipation rates, limitations, 18–19 steam methane reforming (SMR) process, 139, 375 stirred tank reactors (STRs) combined with sonochemical reactors, 202 comparison monolith reactors, 184, 186 OBRs, 160, 382 SDRs, 77, 78, 82, 83, 382 energy dissipation rates, limitations, 4–5, 158, 382 see also continuously stirred tank reactors (CSTRs) Strouhal number, 95 styrene cationic polymerization of, 76, 77, 78 free-radical polymerization of, 76, 383–9 batch process energy usage, 384–5 combined batch/SDR energy usage, 386–9 energy savings, 389 subcritical water, 126 submerged membrane reactors, 228, 229, 237, 239, 245, 347 sulfoxides, 217 selective synthesis, 217–18, 219 sulfur oxides (SOx), removal by reactive absorption, 297, 298 sulfuric acid production, 299, 300 supercritical alcohols, 126 supercritical carbon dioxide (scCO2), 20, 43, 50, 125–6, 237 supercritical reactive extraction biodiesel production using, 281–4 reactor system used, 282 supercritical solvents, 43, 50–1, 124–6, 281 in enzymatic reactions, 237 supercritical water (scH2O), 50, 119, 126 dielectric constant, 123 SuperFocus interdigital micromixer, 97, 99 superheated processing, 118 superparamagnetic magnetite nanoparticles inductive heating of, 106 preparation of, 84 surface configurations, enhanced, in intensification techniques, 16–19 sustainable chemistry see green chemistry sustainable development, 34, 35 Swern–Moffat oxidation, 116 syngas (synthesis gas) diesel fuel produced from, 399 production of, 176 tannery industry applications, membrane operations used, 322 Taylor [bubble train] flow, 176, 179 mass-transfer processes, 180, 181 Telsonic [ultrasonic] horn, 202–3 textile industry applications, membrane operations used, 321 thermal desalination, 342 thermal explosions, 107 thermal integration, 135 thiophene, bromination of, 122, 127 three-phase reactors monolith reactors, 175, 176 OBRs, 166–8 titanium dioxide catalyst, photoactivation by UV irradiation, 166, 167, 191 toxic emissions, catalytic removal of, 188–91 transesterification, in biofuel production, 166, 214–17, 233–7, 276–84 transport intensification, 11–19, 93–107 transport processes, 8–10 enhanced [intensification techniques], 11–19 heat transfer, 8–9 mass transfer, 9–10 momentum transfer, 10 trickle bed reactors, compared with other reactors, 184, 186 2,4,6-trimethylbenzoic acid, synthesis, 112 turbulence promoters, turbulent flow, 94 turbulent mixing, 5–8 Index in SDRs, 75 turnover number [of catalyst], 42 two-separate-phase membrane reactor, 243–4 two-step synthesis, with unstable intermediate, 112, 116 ultrafiltration, 241, 313, 314, 315 industrial applications, 319–26, 329, 343, 344, 346 in membrane bioreactors, 229, 233 ultrasonic baths, 203–4, 214, 217 see also sonochemical reactors ultrasonic processing, benefits, 13, 220–1 ultrasound, 12 chemical effects due to, 12–13, 218, 220–1 valorization of waste materials [to produce highadded-value compounds], 239–45 vapour permeation, industrial applications, 324, 333 vegetable oils, transesterification of, 166, 214–17, 233–7 venturi, cavitational activity, 210, 211 waste cooking/frying oils, biodiesel production from, 216, 233, 235, 261 waste materials, valorization to produce highadded-value compounds, 239–45 waste water treatment cavitational reactors used, 213–14 membrane bioreactors used, 237–9, 245, 246 membrane processes used, 318, 319, 320, 321, 322, 325, 328–36 413 for acids separation, 330–3 for heavy metals removal, 318, 328–30 for hydrocarbons removal, 333–6 for inorganic acids separation, 331–2 for organic acids separation, 332–3 oscillatory baffled reactors used, 166–8 traditional techniques, 327–8 water treatment biocides removal, 320 denitrification, 320 desalination, 11, 314, 318, 319, 321, 342–3, 347 fluoride removal, 320 membrane technology used, 319–21, 342–3, 347 monolith reactors used, 191 organic pollutants removal, 320 phosphorus removal, 320 softening, 320 sulfate removal, 320 Wellman–Lord process, 297 ‘wet sieving’, 161 wheat straw, as biorefinery feedstock, 48–9 yield metric, 40 see also effective mass yield Zenon Environmental Inc., membrane reactor systems, 245–6 zwitterion mechanism, reaction of amines with CO2, 293, 295 .. .Process Intensification for Green Chemistry Engineering Solutions for Sustainable Chemical Processing Edited by KAMELIA BOODHOO and ADAM HARVEY School of Chemical Engineering &... Biorefinery 2.6 An Overview of Green Chemical Processing Technologies 2.6.1 Alternative Reaction Solvents for Green Processing 2.6.2 Alternative Energy Reactors for Green Chemistry 2.7 Conclusion References... important for commercial success Process intensification (PI) can provide such sought-after innovation of equipment design and processing to enhance process efficiency Process Intensification for Green