Intensification of Biobased Processes Green Chemistry Series Editor-in-chief: James H. Clark, Department of Chemistry, University of York, UK Series editors: George A. Kraus, Iowa State University, USA Andrzej Stankiewicz, Delft University of Technology, The Netherlands Peter Siedl, Federal University of Rio de Janeiro, Brazil Titles in the series: 1: The Future of Glycerol: New Uses of a Versatile Raw Material 2: Alternative Solvents for Green Chemistry 3: Eco-Friendly Synthesis of Fine Chemicals 4: Sustainable Solutions for Modern Economies 5: Chemical Reactions and Processes under Flow Conditions 6: Radical Reactions in Aqueous Media 7: Aqueous Microwave Chemistry 8: The Future of Glycerol: 2nd Edition 9: Transportation Biofuels: Novel Pathways for the Production of Ethanol, Biogas and Biodiesel 10: Alternatives to Conventional Food Processing 11: Green Trends in Insect Control 12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications 13: Challenges in Green Analytical Chemistry 14: Advanced Oil Crop Biorefineries 15: Enantioselective Homogeneous Supported Catalysis 16: Natural Polymers Volume 1: Composites 17: Natural Polymers Volume 2: Nanocomposites 18: Integrated Forest Biorefineries 19: Sustainable Preparation of Metal Nanoparticles: Methods and Applications 20: Alternative Solvents for Green Chemistry: 2nd Edition 21: Natural Product Extraction: Principles and Applications 22: Element Recovery and Sustainability 23: Green Materials for Sustainable Water Remediation and Treatment 24: The Economic Utilisation of Food Co-Products 25: Biomass for Sustainable Applications: Pollution Remediation and Energy 26: From C–H to C–C Bonds: Cross-Dehydrogenative-Coupling 27: Renewable Resources for Biorefineries 28: Transition Metal Catalysis in Aerobic Alcohol Oxidation 29: Green Materials from Plant Oils 30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites and Nanocomposites 31: Ball Milling Towards Green Synthesis: Applications, Projects, Challenges 32: Porous Carbon Materials from Sustainable Precursors 33: Heterogeneous Catalysis for Today's Challenges: Synthesis, Characterization and Applications 34: Chemical Biotechnology and Bioengineering 35: Microwave-Assisted Polymerization 36: Ionic Liquids in the Biorefinery Concept: Challenges and Perspectives 37: Starch-based Blends, Composites and Nanocomposites 38: Sustainable Catalysis: With Non-endangered Metals, Part 1 39: Sustainable Catalysis: With Non-endangered Metals, Part 2 40: Sustainable Catalysis: Without Metals or Other Endangered Elements, Part 1 41: Sustainable Catalysis: Without Metals or Other Endangered Elements, Part 2 42: Green Photo-active Nanomaterials 43: Commercializing Biobased Products: Opportunities, Challenges, Benefits, and Risks 44: Biomass Sugars for Non-Fuel Applications 45: White Biotechnology for Sustainable Chemistry 46: Green and Sustainable Medicinal Chemistry: Methods, Tools and Strategies for the 21st Century Pharmaceutical Industry 47: Alternative Energy Sources for Green Chemistry 48: High Pressure Technologies in Biomass Conversion 49: Sustainable Solvents: Perspectives from Research, Business and International Policy 50: Fast Pyrolysis of Biomass: Advances in Science and Technology 51: Catalyst-free Organic Synthesis 52: Hazardous Reagent Substitution: A Pharmaceutical Perspective 53: Alternatives to Conventional Food Processing: 2nd Edition 54: Sustainable Synthesis of Pharmaceuticals: Using Transition Metal Complexes as Catalysts 55: Intensification of Biobased Processes How to obtain future titles on publication: A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication. For further information please contact: Book Sales Department, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247 Email: [email protected] Visit our website at www.rsc.org/books Intensification of Biobased Processes Edited by Andrzej Górak TU Dortmund University, Germany and Lodz University of Technology, Poland Email: [email protected] and Andrzej Stankiewicz Delft University of Technology, The Netherlands Email: [email protected] Green Chemistry Series No. 55 Print ISBN: 978-1-78262-855-2 PDF ISBN: 978-1-78801-032-0 EPUB ISBN: 978-1-78801-457-1 ISSN: 1757-7039 A catalogue record for this book is available from the British Library © The Royal Society of Chemistry 2018 All rights reserved Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry or the copyright owner, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. 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The Royal Society of Chemistry is a charity, registered in England and Wales, Number 207890, and a company incorporated in England by Royal Charter (Registered No. RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK, Telephone: +44 (0) 207 4378 6556. For further information see our web site at www.rsc.org Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK Preface Process intensification is commonly mentioned as one of the most promi sing development paths for the chemical processing industry and one of the most important progress areas for chemical engineering research. While remaining a hot topic, bioprocessing still poses various important tech noeconomic and environmental challenges, such as product yields, exces sive energy consumption for separations in highly watery systems, batch operation or the downstream processing bottlenecks in the production of biopharmaceutical products. Many of those challenges can be addressed by application of the different process intensification technologies discussed in the present book. The book addresses process intensification in white, green and red biotechnology, both in upstream and downstream processing. Appli cation of an intensified process is demonstrated for the whole spectrum of manufacturing processes. Consequently, the book addresses four clusters of bioproducts: biofuels and commodity, fine chemicals, cosmetics and pharmaceuticals, food products and advanced materials. Chapter 1 by Noorman, van Winden, Heijnen and van der Lans shows how the four principles of intensification of chemical processes, published by van Gerven and Stankiewicz,1 can improve fermentation processes. The four intensification examples provided demonstrate that debottlenecking of the oxygen transfer capacity is the most important principle, followed by liquid mixing. The next chapter by Boodhoo reviews the progress made in developing and applying rotating reactors for bioprocessing. It focuses on the whole cell fermentation and biotransformations in the rotating fluidi zed bed, the rotating bed bioreactor, the rotating biofilm contactor and the rotating membrane reactor. Chapter 3 by Kiss and Bîldea presents intensi fied downstream processing options in the production of the major biofuels, Green Chemistry Series No. 55 Intensification of Biobased Processes Edited by Andrzej Górak and Andrzej Stankiewicz © The Royal Society of Chemistry 2018 Published by the Royal Society of Chemistry, www.rsc.org vii viii Preface such as biodiesel, bioethanol, biobutanol and dimethyl ether. It reviews sev eral intensified separation technologies: reactive distillation, dividingwall column, reactive dividingwall column, catalytic cyclic distillation and heat pumpassisted extractive distillation. In situ product removal is discussed in Chapter 4. Cuellar and Straathof show here how to enhance yield and pro ductivity through the removal of biotransformation products from the reac tion mixture. In Chapter 5, de Haan and Birajdar analyze the application of new materials (ionic liquids, deep eutectic solvents, polymers, modifiers and supramolecular structures) and new techniques (ultrasound, micro wave, centrifugal and electric field) as a means to increase the extraction efficiency and selectivity in solvent extraction processes. Organic solvent nanofiltration presents another separation method applicable to renew able feedstocks or products. Chapter 6 by Werth and Skiborowski discusses the potential of this membrane technique for important application areas in the oleochemical industry. Integrating separation and reaction in a single device, the Simulated Moving Bed Reactor is a paradigmatic representative of multifunctional reactors, one of the most relevant process intensification strategies. In Chapter 7, Rodrigues, Faria and Graça discuss the application of this multifunctional reactor for production of biodiesel, additives and blending agents. Chapter 8 by Adewuyi addresses intensification of the enzy matic hydrolysis of cellulose using a high multifrequency ultrasonic reactor and the effects of ultrasound on enzyme stability. The technique has appli cation potential in biofuel production and biorefinery processes. Chapter 9 by Sinha and Rai deals with the hydroprocessing of vegetable oils in micro channel reactors with catalyst coatings. Innovative concepts for reactive sep aration processes, such as reactive absorption and reactive distillation, that make use of enzymes are discussed in Chapter 10 by Wierschem, Leimbrink, Skiborowski, Heils, Smirnova and Górak. These techniques offer energy and investment savings or improved selectivity by high enantioselectivity and high reaction rates at mild process conditions. Enantioselective reactions are also discussed in Chapter 11 by Shivaprasad and Emanuelsson, which focuses on the integration of upstream and downstream through new equip ment concepts like membrane reactors, microreactors, monolithic reactors and rotating disc reactors for enzyme catalyzed reactions. In Chapter 12, Weatherley, Gangu, Scurto and Petera present a short review of the field of enzymatic biotransformations and their application to chemical reactions and products of industrial relevance. Extractive wholecell biotransforma tion involving the benzylic chiral hydroxylation of naphthalene and lipolytic hydrolysis of a triglyceride ester using a microbial lipase are discussed in detail. Recent developments in microalgae cultivation and downstream pro cessing with a focus on microalgae biorefinery are presented by Lam, Ver- muë, Janssen, Barbosa, Wiffels, Eppink and van den Berg in Chapter 13. Here, the current stateofdevelopment and future directions towards large scale bulkchemical production from microalgae are discussed. Chapter 14 by Pal discusses process intensification and business sustainability in production of a very important bioproduct i.e. glutamic acid. Integration of appropriate Preface ix membrane modules with a traditional fermenter leads to an economically viable green process. The next two chapters deal with intensified production methods of recombinant proteins. Baur and Morbidelli describe, in Chapter 15, novel techniques involving continuous or semicontinuous steadystate upstream and downstream processing. They show that continuous perfu sion bioreactors enable large reductions in reactor volumes. In Chapter 16, aqueous twophase extraction is discussed by Brandenbusch, Zeiner and Merz as an alternative to chromatography in purification of biopharmaceuticals. The contribution emphasizes the role of phase thermodynamics in process design. Chapter 17 by Vaghari, Jafarizadeh-Malmiri, Harcourt, Sarabadani, Anarjan and Berenjian deals with functional foods, like essential oils and carotenoids, that are hydrophobic components having low water solubility and consequently low bioavailability. They present an overview on process intensification technologies used in functional foods for increasing the ecoefficiency of the process with the benefit of lower capital costs, substan tial energy saving and decreased utilization of solvents. Chapter 18, written by Turk, Perino, Petitcolas and Chemat, presents a panorama of current knowl edge on microwaveassisted extractions of antioxidants, flavors, fragrances, natural colors, fats and oils. Industrial scale applications in some pioneer ing companies are shown. An overview of membrane processes in the food processing industry is presented by Cassano, Conidi and Drioli in Chapter 19. The combination of membrane unit operations leads to high quality products, recovery of high addedvalue compounds and savings on pro duction and energy costs. The two most important bottlenecks in brewing processes are time consuming enzymatic reactions and the fact that many processes are running simultaneously. In addition, large volumes need to be transported along the production chain. Chapter 20 by Muster-Slawitsch and Brunner highlights several approaches to process intensification and shows that a holistic optimization is important in brewing, as changes in one pro cess may have implications in another. In Chapter 21, Dekkers and van der Goot present novel routes and processing concepts to make meat analogs in order to reduce meat consumption. The chapter ends by reviewing pos sible raw materials to be used in those applications and the importance of understanding the effect on functional properties when preparing the ingre dients. The last two chapters of the book deal with the intensified manu facturing of advanced biomaterials. Direct Digital Manufacturing emerged as a technological innovation that reduces the capital required to achieve the required economy of scale. Chapter 22 by Morouço highlights its use in the pharmaceutical domain, for surgical planning and training and for tissue engineering. These areas of research can overlap the drawbacks of con ventional methods, exploring advances in the design and printing processes as a process intensification method. Finally, the last chapter by Stankiewicz shows how alternative energy forms like electric, magnetic, electromagnetic and acoustic fields can be used in manufacturing of advanced biomaterials with a broad range of medical applications, from body parts replacements and tissue repairs to targeted drug delivery and advanced diagnostics.