Sustainable Developmentin Chemical Engineering

Sustainable Developmentin Chemical EngineeringInnovative Technologies

Editors

VINCENZO PIEMONTE

University Campus Bio-Medico of Rome, Italy

MARCELLO DE FALCO

University Campus Bio-Medico of Rome, Italy

ANGELO BASILE

ITM-CNR, Rende (CS) Italy

This edition first published 20132013 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 toreuse 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 formor by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright,Designs and Patents Act 1988, without the prior permission of the publisher.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available inelectronic books.

Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and productnames used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. Thepublisher is not associated with any product or vendor mentioned in this book. Limit of Liability/Disclaimer of Warranty:While the publisher and author have used their best efforts in preparing this book, they make no representations or warrantieswith respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties ofmerchantability or fitness for a particular purpose. It is sold on the understanding that the publisher is not engaged inrendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom. Ifprofessional advice or other expert assistance is required, the services of a competent professional should be sought.

The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipmentmodifications, changes in governmental regulations, and the constant flow of information relating to the use of experimentalreagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insertor instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in theinstructions or indication of usage and for added warnings and precautions. The fact that an organization or Website isreferred to in this work as a citation and/or a potential source of further information does not mean that the author or thepublisher 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 workwas 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: 978-1-119-95352-4

Set in 10/12pt Times by Laserwords Private Limited, Chennai, India

Contents

List of Contributors xiiiPreface xv

1. Sustainable Development Strategies: An Overview 1Vincenzo Piemonte, Marcello De Falco, and Angelo Basile

1.1 Renewable Energies: State of the Art and Diffusion 11.2 Process Intensification 4

1.2.1 Process Intensifying Equipment 51.2.2 Process Intensifying Methods 6

1.3 Concept and Potentialities of Bio-based Platforms for BiomoleculeProduction 81.3.1 Biogas Platform 91.3.2 Sugar Platform 101.3.3 Vegetable Oil Platform 101.3.4 Algae Oil Platform 111.3.5 Lignin Platform 111.3.6 Opportunities and Growth Predictions 12

1.4 Soil and Water Remediation 131.4.1 Soil Remediation 181.4.2 Water Remediation 18Acknowledgement 18References 18

2. Innovative Solar Technology: CSP Plants for Combined Production ofHydrogen and Electricity 25Marcello De Falco

2.1 Principles 252.2 Plant Configurations 28

2.2.1 Solar Membrane Reactor Steam Reforming 292.2.2 Solar Enriched Methane Production 31

2.3 Mathematical Models 332.3.1 Solar Enriched Methane Reactor Modelling 342.3.2 Membrane Reactor Modelling 362.3.3 WGS, Separation Units and the Electricity Production Model 38

2.4 Plant Simulations 39

vi Contents

2.4.1 EM Reactor 392.4.2 Membrane Reactor 412.4.3 Global Plant Simulations and Comparison 45

2.5 Conclusions 46Nomenclature 47References 48

3. Strategies for Increasing Electrical Energy Production fromIntermittent Renewables 51Alessandro Franco

3.1 Introduction 513.2 Penetration of Renewable Energies into the Electricity Market and

Issues Related to Their Development: Some Interesting Cases 553.3 An Approach to Expansion of RES and Efficiency Policy in an

Integrated Energy System 573.3.1 Optimization Problems 593.3.2 Operational Limits and Constraints 613.3.3 Software Tools for Analysis 62

3.4 Analysis of Possible Interesting Scenarios for Increasing Penetrationof RES 623.4.1 Renewable Energy Expansion in a Reference Scenario 633.4.2 Increasing Thermoelectric Generation Flexibility 633.4.3 Effects of Introducing the Peak/Off-Peak Charge Tariff 643.4.4 Introducing Electric Traction in the Transport Sector:

Connection between Electricity and Transport Systems 643.4.5 Increasing Industrial CHP Electricity Production 653.4.6 Developing the Concept of ‘Virtual Power Plants’ 66

3.5 Analysis of a Meaningful Case Study: The Italian Scenario 663.5.1 Renewable Energy Expansion in a Reference Scenario 683.5.2 Increasing Thermoelectric Generation Flexibility 693.5.3 Effects of Introducing a Peak/Off-Peak Charge Tariff 693.5.4 Introduction of a Connection between Electricity and

Transport Systems: The Increase in Electric Cars 703.5.5 Increasing Industrial CHP Electricity Production 71

3.6 Analysis and Discussion 743.7 Conclusions 75

Nomenclature and Abbreviations 76References 77

4. The Smart Grid as a Response to Spread the Concept of DistributedGeneration 81Yi Ding, Jacob Østergaard, Salvador Pineda Morente, and Qiuwei Wu

4.1 Introduction 814.2 Present Electric Power Generation Systems 82

Contents vii

4.3 A Future Electrical Power Generation System with a High Penetrationof Distributed Generation and Renewable Energy Resources 83

4.4 Integration of DGs into Smart Grids for Balancing Power 864.5 The Bornholm System – A “Fast Track” for Smart Grids 914.6 Conclusions 92

References 93

5. Process Intensification in the Chemical Industry: A Review 95Stefano Curcio

5.1 Introduction 955.2 Different Approaches to Process Intensification 965.3 Process Intensification as a Valuable Tool for the Chemical Industry 975.4 PI Exploitation in the Chemical Industry 100

5.4.1 Structured Packing for Mass Transfer 1005.4.2 Static Mixers 1005.4.3 Catalytic Foam Reactors 1005.4.4 Monolithic Reactors 1005.4.5 Microchannel Reactors 1015.4.6 Non-Selective Membrane Reactors 1015.4.7 Adsorptive Distillation 1025.4.8 Heat-Integrated Distillation 1025.4.9 Membrane Absorption/Stripping 1025.4.10 Membrane Distillation 1035.4.11 Membrane Crystallization 1045.4.12 Distillation-Pervaporation 1045.4.13 Membrane Reactors 1045.4.14 Heat Exchanger Reactors 1045.4.15 Simulated Moving Bed Reactors 1055.4.16 Gas-Solid-Solid Trickle Flow Reactor 1055.4.17 Reactive Extraction 1065.4.18 Reactive Absorption 1065.4.19 Reactive Distillation 1065.4.20 Membrane-Assisted Reactive Distillation 1065.4.21 Hydrodynamic Cavitation Reactors 1065.4.22 Pulsed Compression Reactor 1075.4.23 Sonochemical Reactors 1075.4.24 Ultrasound-Enhanced Crystallization 1085.4.25 Electric Field-Enhanced Extraction 1085.4.26 Induction and Ohmic Heating 1085.4.27 Microwave Drying 1095.4.28 Microwave-Enhanced Separation and Microwave Reactors 1095.4.29 Photochemical Reactors 1105.4.30 Oscillatory Baffled Reactor Technologies 1115.4.31 Reverse Flow Reactor Operation 111

viii Contents

5.4.32 Pulse Combustion Drying 1115.4.33 Supercritical Separation 112

5.5 Conclusions 113References 113

6. Process Intensification in the Chemical and Petrochemical Industry 119Angelo Basile, Adolfo Iulianelli, and Simona Liguori

6.1 Introduction 1196.2 Process Intensification 120

6.2.1 Definition and Principles 1206.2.2 Components 121

6.3 The Membrane Role 1226.4 Membrane Reactor 124

6.4.1 Membrane Reactor and Process Intensification 1266.4.2 Membrane Reactor Benefits 127

6.5 Applications of Membrane Reactors in the Petrochemical Industry 1286.5.1 Dehydrogenation Reactions 1296.5.2 Oxidative Coupling of Methane 1346.5.3 Methane Steam Reforming 1356.5.4 Water Gas Shift 137

6.6 Process Intensification in Chemical Industry 1396.6.1 Reactive Distillation 1396.6.2 Reactive Extraction 1406.6.3 Reactive Adsorption 1406.6.4 Hybrid Separation 141

6.7 Future Trends 1416.8 Conclusion 142

Nomenclature 143References 143

7. Production of Bio-Based Fuels: Bioethanol and Biodiesel 153Sudip Chakraborty, Ranjana Das Mondal, Debolina Mukherjee, andChiranjib Bhattacharjee

7.1 Introduction 1537.1.1 Importance of Biofuel as a Renewable Energy Source 153

7.2 Production of Bioethanol 1557.2.1 Bioethanol from Biomass: Production, Processes, and

Limitations 1567.2.2 Substrate 1577.2.3 Future Prospects for Bioethanol 164

7.3 Biodiesel and Renewable Diesels from Biomass 1667.3.1 Potential of Vegetable Oil as a Diesel Fuel Substitute 1687.3.2 Vegetable Oil Ester Based Biodiesel 1697.3.3 Several Approaches to Biodiesel Synthesis 170

Contents ix

7.3.4 Sustainability of Biofuel Use 1717.3.5 Future Prospects 171

7.4 Perspective 172List of Acronyms 172References 173

8. Inside the Bioplastics World: An Alternative to Petroleum-based Plastics 181Vincenzo Piemonte

8.1 Bioplastic Concept 1818.2 Bioplastic Production Processes 183

8.2.1 PLA Production Process 1838.2.2 Starch-based Bioplastic Production Process 185

8.3 Bioplastic Environmental Impact: Strengths and Weaknesses 1868.3.1 Life Cycle Assessment Methodology 1868.3.2 The Ecoindicator 99 Methodology: An End-Point Approach 1878.3.3 Case Study 1: PLA versus PET Bottles 1898.3.4 Case Study 2: Mater-Bi versus PE Shoppers 1918.3.5 Land Use Change (LUC) Emissions and Bioplastics 193

8.4 Conclusions 195Acknowledgements 196References 196

9. Biosurfactants 199Maria Giovanna Martinotti, Gianna Allegrone, Massimo Cavallo, andLetizia Fracchia

9.1 Introduction 1999.2 State of the Art 200

9.2.1 Glycolipids 2019.2.2 Lipopeptides 2019.2.3 Fatty Acids, Neutral Lipids, and Phospholipids 2049.2.4 Polymeric Biosurfactants 2049.2.5 Particulate Biosurfactants 205

9.3 Production Technologies 2059.3.1 Use of Renewable Substrates 2059.3.2 Medium Optimization 2099.3.3 Immobilization 211

9.4 Recovery of Biosurfactants 2129.5 Application Fields 213

9.5.1 Environmental Applications 2139.5.2 Biomedical Applications 2179.5.3 Agricultural Applications 2209.5.4 Biotechnological and Nanotechnological Applications 221

9.6 Future Prospects 225References 225

x Contents

10. Bioremediation of Water: A Sustainable Approach 241Sudip Chakraborty, Jaya Sikder, Debolina Mukherjee, Mrinal Kanti Mandal,and D. Lawrence Arockiasamy

10.1 Introduction 24110.2 State-of-the-Art: Recent Development 24210.3 Water Management 24710.4 Overview of Bioremediation in Wastewater Treatment and Ground

Water Contamination 25010.5 Membrane Separation in Bioremediation 25210.6 Case Studies 256

10.6.1 Bioremediation of Heavy Metals 25610.6.2 Bioremediation of Nitrate Pollution 25810.6.3 Bioremediation in the Petroleum Industry 259

10.7 Conclusions 260List of Acronyms 261References 262

11. Effective Remediation of Contaminated Soils by Eco-CompatiblePhysical, Biological, and Chemical Practices 267Filomena Sannino and Alessandro Piccolo

11.1 Introduction 26711.2 Biological Methods (Microorganisms, Plants, Compost, and Biochar) 269

11.2.1 Microorganisms 26911.2.2 Plants 27311.2.3 Plant-Microorganism Associations: Mycorrhizal Fungi 27511.2.4 Compost and Biochar 276

11.3 Physicochemical Methods 27711.3.1 Humic Substances as Natural Surfactants 278

11.4 Chemical Methods 28011.4.1 Metal-Porphyrins 28211.4.2 Nanocatalysts 284

11.5 Conclusions 286List of Symbols and Acronyms 288Acknowledgments 289References 289

12. Nanoparticles as a Smart Technology for Remediation 297Giuseppe Chidichimo, Daniela Cupelli, Giovanni De Filpo,Patrizia Formoso, and Fiore Pasquale Nicoletta

12.1 Introduction 29712.2 Silica Nanoparticles for Wastewater Treatment 298

12.2.1 Silica Nanoparticles: An Overview 29812.2.2 Preparation of Nanosilica 29912.2.3 Removal of Dyes by Silica Nanoparticles 29912.2.4 Removal of Metallic Pollutants by Silica Nanoparticles 303

Contents xi

12.3 Magnetic Nanoparticles: Synthesis, Characterization and Applications 30512.3.1 Magnetic Nanoparticles: An Overview 30512.3.2 Synthesis of Magnetic Nanoparticles 30612.3.3 Characterization of Magnetic Nanoparticles 31512.3.4 Applications of Magnetic Nanoparticles 316

12.4 Titania Nanoparticles in Environmental Photo-Catalysis 31712.4.1 Advanced Oxidation Processes 31712.4.2 TiO2 Assisted Photo-Catalysis 32012.4.3 Developments in TiO2 Assisted Photo-Catalysis 324

12.5 Future Prospects: Is Nano Really Good for the Environment? 32612.6 Conclusions 328

List of Abbreviations 328References 329

Index 349

List of Contributors

Gianna Allegrone, Department of Chemical, Food, Pharmaceutical and PharmacologicalSciences (DiSCAFF), Universita del Piemonte Orientale “Amedeo Avogadro”, Italy

D. Lawrence Arockiasamy, King Abdullah Institute for Nanotechnology, King SaudUniversity, Saudi Arabia

Angelo Basile, Institute of Membrane Technology, Italian National Research Council(ITM-CNR), c/o University of Calabria, Italy

Chiranjib Bhattacharjee, Department of Chemical Engineering, Jadavpur University,India

Massimo Cavallo, Department of Chemical, Food, Pharmaceutical and PharmacologicalSciences (DiSCAFF), Universita del Piemonte Orientale “Amedeo Avogadro”, Italy

Sudip Chakraborty, Department of Chemical Engineering, Jadavpur University, WestBengal, India and Department of Chemical Engineering and Materials, CNR-ITM,University of Calabria, Italy

Giuseppe Chidichimo, Department of Chemistry, University of Calabria, Italy

Daniela Cupelli, Department of Pharmaceutical Sciences, University of Calabria, Italy

Stefano Curcio, Department of Engineering Modeling, University of Calabria, Italy

Ranjana Das Mondal, Department of Chemical Engineering, Jadavpur University, India

Professor Yi Ding, Centre for Electric Technology, Department of Electrical Engineer-ing, Technical University of Denmark, Denmark

Marcello de Falco, Faculty of Engineering, University Campus Bio-Medico of Rome,Italy

Giovanni De Filpo, Department of Chemistry, University of Calabria, Italy

Patrizia Formoso, Department of Pharmaceutical Sciences, University of Calabria, Italy

xiv List of Contributors

Letizia Fracchia, Department of Chemical, Food, Pharmaceutical and PharmacologicalSciences (DiSCAFF), Universita del Piemonte Orientale “Amedeo Avogadro”, Italy

Alessandro Franco, Department of Energy and System Engineering (DESE), Universitadi Pisa, Italy

Adolfo Iulianelli, Institute of Membrane Technology, Italian National Research Council(ITM-CNR), c/o University of Calabria, Italy

Simona Liguori, Institute of Membrane Technology, Italian National Research Council(ITM-CNR), c/o University of Calabria, Italy

Mrinal Kanti Mandal, Chemical Engineering Department, National Institute ofTechnology Durgapur, India

Maria Giovanna Martinotti, Department of Chemical, Food, Pharmaceutical andPharmacological Sciences (DiSCAFF), Universita del Piemonte Orientale “AmedeoAvogadro”, Italy

Salvador Pineda Morente, Centre for Electric Technology, Department of ElectricalEngineering, Technical University of Denmark, Denmark

Debolina Mukherjee, Department of Geological Sciences, University of Calabria, Italy

Fiore Pasquale Nicoletta, Department of Pharmaceutical Sciences, University ofCalabria, Italy

Jacob Østergaard, Centre for Electric Technology, Department of Electrical Engineer-ing, Technical University of Denmark, Denmark

Alessandro Piccolo, Dipartimento di Science del Suolo, della Pianta dell’Ambientee delle Produzioni Animali, Universita di Napoli Federico II, Italy

Vincenzo Piemonte, Faculty of Engineering, University Campus Bio-Medico of Rome,Italy

Filomena Sannino, Dipartimento di Science del Suolo, della Pianta dell’Ambiente e delleProduzioni Animali, Universita di Napoli Federico II, Italy

Jaya Sikder, Chemical Engineering Department, National Institute of TechnologyDurgapur, India

Qiuwei Wu, Centre for Electric Technology, Department of Electrical Engineering,Technical University of Denmark, Denmark

Preface

This book aims to examine the newest technologies for sustainable development, througha careful analysis not only of the technical aspects but also on the possible fields ofindustrial development. In other words, the book aims to shed light, giving a broad butvery detailed view on the latest technologies aimed at sustainable development, througha point of view typical of an industrial engineer.

The book is divided in four sections (Energy, Process Intensification, Bio-Based Plat-form for Biomolecule Production and Soil and Water Remediaton) in order to provide apowerful and organic tool to the readers.

The first chapter (by Piemonte, Basile, De Falco) is devoted to an overview of themain arguments in the book and to provide a useful key lecture to the reader for a moreeasy understanding of the topics analysed in further chapters.

In the second chapter (De Falco), Concentrated Solar Power (CSP) technology ispresented and a particular application, that is, the cogenerative production of electricityand pure hydrogen by means of a steam reforming reactor is studied in depth and assessedin order to make clear the huge potentialities of CSP plants in the industrial sector.

The third chapter (Franco) analyses some aspects in connection with the problem ofnew renewable energy penetration. The case of Italian energy production is consideredas a meaningful reference due to its characteristic size and the complexity. The variousenergy scenarios are evaluated with the aid of multipurpose software, taking into accountthe interconnections between different energy uses.

The last chapter (Ding, Østergaard, Morente, and Wu) in the Energy section discussesthe smart grid as response for integrating Distributed Generation to provide a balancingcapacity for mitigating the high volatility of renewable energy resources in the future.

The second section opens with a chapter on Process Intensification (PI) in the chemicalindustry. In this chapter (Curcio) a description of some process units designed on thebasis of PI concepts has been presented, pointing out their major features, the advantagesdetermined by the exploitation of these PI units and, in some cases, on the existingbarriers that are currently limiting their spread on an industrial scale.

The sixth chapter (Basile, Iulianelli, Liguori) is devoted to summarizing the impor-tance of PI in the chemical and petrochemical industries focusing on the membranereactor (MR) role as a new technology. In particular, it illustrates how integration ofMRs in the industrial field could constitutes a good solution to the reduction of the

xvi Preface

reaction/separation/purification steps, thus allowing a reduction in plant size and improv-ing overall process performance.

The first chapter (Chakraborty, Das Mondal, Mukherjee, Bhattacharjee) in the sectionon the bio-based platform for biomolecule production deals with a wide and detailedreview of the science and technology for sustainable biofuel production. In particular,the production processes of bioethanol and biodiesel are analysed deeply, paying attentionalso to the sustainability of biofuel use issue.

The eighth chapter (Piemonte) depicts the complex world of bioplastics through theanalysis of the bioplastics concept and the description of the most important productionprocesses of bioplastics. Particular attention has been paid to the bioplastic footprint onthe environment by analysing the environmental impact of two of the most importantbioplastics in the world (PLA and Mater-Bi) in comparison with some petroleum-basedplastics (PET and PE) in order to answer, if possible, the most important reader’s ques-tion: how green are bioplastics?

The ninth chapter (Martinotti, Allegrone, Cavallo, and Fracchia) focuses on themost recent results obtained in the field of production, optimization, recovery, andapplications of biosurfactants. The chapter spans environmental to biomedical applica-tions of biosurfactants, covering agricultural, biotechnological and nanotechnologicalapplications.

The first chapter (Chakraborty, Sikder, Mukherjee, Mandal, and Arockiasamy) of thesoil and water remediaton section presents a state-of-the-art report on the past and existingknowledge of water remediation technologies for the environmentalist who evaluates thequality of environment, implements and evaluates the remediation alternatives at a givencontaminated site. The chapter provides a basic understanding of the bioremediationtechnologies for water recycling to the reader.

The fourth section continues with a chapter (Sannino and Piccolo) on soil remedia-tion, which reviews innovative sustainable strategies that can be applied to remediatesoil contaminated by organic pollutants and based on biological, physical and advancedchemical processes. These approaches are illustrated together with the related technical,environmental and economic aspects which should be considered when selecting themost useful remediation method for given soil conditions.

The book concludes with the last chapter (Chidichimo, Cupelli, De Filpo, Formoso,and Fiore) in the soil and water remediaton section, which reports on recent progress inremediation by nanomaterials, describing synthesis and properties of different classes ofnanoparticles. The main physico-chemical principles and advantages of using nanopar-ticles in remediation of wastewaters contaminated by dyes, heavy metals and organicpollutants are discussed. Special attention is given to the modification of nanoparticlesurface properties in order to increase efficiency and selectivity. Advances in some par-ticular nanosystems, and perspectives on environment and health impacts by massiveuse of nanodevices are also reported.

Finally, let us conclude this preface by thanking all the authors who have contributedto the realization of this book, without whom this project would never have been born.We wish to thank them for their participation and patience during the preparation of this

Preface xvii

book. We are also grateful that they have entrusted us with editing their contributions asper the requirements of each chapter. We hope that readers will find this book useful.

Powerpoint slides of figures in this book for teaching purposes can be downloadedfrom http://booksupport.wiley.com by entering the book title, author or ISBN.

Vincenzo PiemonteMarcello De FalcoAngelo Basile

ItalyDecember 2012

1Sustainable Development Strategies:

An Overview

Vincenzo Piemonte1 ,∗ , Marcello De Falco1 , and Angelo Basile2

1Faculty of Engineering, University Campus Bio-Medico of Rome, 00128 Rome, Italy2CNR-ITM, c/o University of Calabria87030 Rende (CS), Italy

1.1 Renewable Energies: State of the Art and Diffusion

Energy is a crucial challenge that scientific and technological communities face with moreto come in the future. The environmental impact of fossil fuels, their cost fluctuationsdue both to economical/political reasons and their reducing availability boost researchtoward the development of new processes and technologies, which are more sustainableand renewable, such as solar energy, wind, biomass and geothermal.

Governments have facilitated renewable energy production diffusion by means ofincentive schemes as the feed-in tariff (FIT) and Green Certificates (GCs), achievingunforeseeable success. In fact, the change in the world energy politics is substantiallymodifying the energy production network. The European Union target to increase theshare of renewable energy sources (RES) in its gross final consumption of energyto 20% by 2020 from the 9.2% in 2006, which seemed unlikely up until recently, isnow almost there thanks mainly to the strong increase of wind power, photovoltaicsand plant biomass installations, together with the implementation of more efficientenergy-consuming technologies in domestic, industrial and transport sectors, able toreduce global energy consumption.

The following charts in Figures 1.1–1.3 report wind power, photovoltaic and biomass-fired power station (by wood, municipal solid wastes and bio-gas) electrical energyproduction trends in recent years in EU-27 (Ruska and Kiviluoma, 2011): it is a worthy

Sustainable Development in Chemical Engineering – Innovative Technologies, First Edition.Edited by Vincenzo Piemonte, Marcello De Falco and Angelo Basile.c© 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.

2 Sustainable Development in Chemical Engineering

01999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

20

40

60

80

100

120

Year

Ene

rgy

prod

uctio

n (T

Wh)

Figure 1.1 Wind energy production in EU-27 (2000–2008)

2004 2005 2006 2007 2008 2009 2010

Year

0

2

4

6

8

10

12

14

16

Ene

rgy

prod

uctio

n (T

Wh)

Figure 1.2 PV energy production in EU-27 (2000–2008)

Sustainable Development Strategies: An Overview 3

0

20

40

60

80

100

120

20001999 2001 2002 2003 2004 2005 2006 2007 2008 2009

Year

Ene

rgy

prod

uctio

n (T

Wh)

Figure 1.3 Biomass plant energy production in EU-27 (2000–2008)

assessment that the diffusion of such technologies follows an exponential profile. Thetotal renewable installed capacity (hydropower, wind, biomass-fired power stations,geothermal plants, photovoltaics) was 200 GW in 2008 and it is continuously increasing.

The International Energy Outlook (Bloomberg, 2009) estimates that more than 42%of the new electrical power capacity to be installed up to 2020 will be based on renew-able energies, with an average annual growth rates of 4.1%. By 2020 it is foreseenthat US$150 bn will be invested worldwide on renewable energies. In Europe, ¤35 bnhas been devoted to clean energy investment in 2008 (http://www.newenergyfinance.com,2019–2013), and capital expenditure needed to achieve the EU objectives will be approx-imately ¤70 bn per year until 2020 in order to reach the 20% target.

From all these data, it is clear how the renewable energy market is becomingmainstream both from technical and financial points of view. Surely, public incentivesmust be one of the main reasons for renewable penetration in the energy sector, sincethey have allowed convenient investment when the technologies were not competitive.The increase of investors’ interest on this market has pushed industrial production,with the effect of a strong reduction in prices. Taking the PV sector as an example,polycrystalline modules had a cost of about 3000 ¤/kW in 2009, while now the averageprice is 700–800 ¤/kW in 2011 thanks to the development of numerous modularmanufacturing industries in Europe and China.

But, concerning the perspectives of renewable energies market in the next years, twocrucial aspects have to be considered:

• The economic crisis is stimulating a debate about renewable energy public incentives,which have an increasing effect on the energy bills. The next target is the ‘grid parity’,

4 Sustainable Development in Chemical Engineering

that is, the point at which generating electricity from alternative energy produces powerat a levelled cost equal to or less than the price of purchasing power from the grid.

• The penetration of renewable energy and the increase in its contribution to total elec-tricity input in the grid lead to the problem of electricity network overload due toclean energy production fluctuations. PV and wind energy production depends onenvironmental conditions: during sunny and windy days renewable production couldinvoke serious problems for the grid. This problem stimulates the development ofsmart grid technologies, able to control and manage grid overloading and electricitystorage systems.

Solving both these problems, which have the potential stop renewable energy use, isthe main scientific and technological challenge for the future. In this context, proposing,developing and implementing new technologies able to reduce installation costsreaching grid parity and managing energy production is absolutely necessary in orderto assure a clean energy future and further enhance its share in energy total production.

The EU assists innovative technology research and development process by allocatingmany resources to renewable energy projects funding. Figure 1.4 summarizes theorganization of the RES financing programmes within the EU (ECOFYS project, 2011)for a total funding amount devoted to energy projects equal to about ¤4 bn for the nexttwo years.

Thanks to EU support and to the expertise and creativity of worldwide scientific com-munity, the next issues of renewable energy sector can be suitably overcome, allowingthe implementation of a 100% clean energy system and achieving the objective of totaldecarbonation of economies and industries.

1.2 Process Intensification

Following Gorak and Stankiewicz (2011), process intensification (PI) is commonlyconsidered to be one of the most promising development paths for the chemical processindustry and one of the most important progress areas for chemical engineering researchnowadays.

European commission IEB

FP7 SMEG GIF ELENA ALTENER Structural Funds RE funds SEI TCFPLoans

CIP Regional Policy

EIP IEE

EBRD

FP7

Figure 1.4 Financial organization of renewable energy in Europe

Sustainable Development Strategies: An Overview 5

When introduced in the 1970s as a general approach, PI suggested a design strategywhich aspired to the reduction in processing size of existing technology without anyreduction in process output and quality. From that time, PI meaning has been changedseveral times and many definitions have been proposed, which, despite to their commonpoint of view on innovation, were often different in substance. In 2009, Gerven andStankiewicz (2009) defined the fundamentals of PI, suggesting that PI should follow afunction oriented approach distinguishing four main principles:

• maximize the effectiveness of intra and intermolecular events;• give each molecule the same processing experience;• optimize the driving forces at every scale and maximize the specific surface area to

which these forces apply;• maximize the synergistic effects from partial processes.

In particular, the PI principles refer to all scales existing in chemical processes, frommolecular to meso- and macro-scales and represent the targets that an intensified processaims to reach.

By applying these principles the PI offers, to an industrial company, many opportuni-ties which can be summarized using only four words: smaller, cheaper, safer and slicker.Indeed, PI leads to the reduction of both investment (reduced equipment or integratedprocessing units) and operating costs (raw materials and utilities) and less waste. More-over, by reducing the size of process equipment and the amount of raw material it ispossible to ensure a safety benefit, especially in the nuclear/oil industry.

Generally, the PI can be divided in two domains: (1) process intensifying equipment,which considers equipment for both carrying out chemical reactions and not involvingchemical reactions; and (2) process intensifying methods, which takes into accountunit operations and is classified furthermore into four different areas (Stankiewicz andMoulijn, 2000).

1.2.1 Process Intensifying Equipment

As mentioned previously, this domain includes both equipment for carrying out thereaction such as the spinning disk reactor, spinning mixer reactor, static mixer catalyst,microreactors and heat exchange reactors, and equipment for non-reactive operationssuch as the static mixer, compact heat exchangers, rotor/stator mixers and so on.

As a classic example of process intensifying equipment already used in industrial pro-cesses, the static mixer reactors must be mentioned, due to their capability in combiningmixing and intensive heat removal/supply (Thakur et al., 2003). Moreover, they requireless space, low equipment cost and good mixing at low shear rates. On the contrary,one of the most important drawbacks is their sensitivity to clogging by solids. It mustalso be said that this problem can be partially avoided by developing an open-crossflow-structure catalyst, a structured packing with good static-mixing properties and at thesame time, used as catalytic support. The best known of this family is the so-calledKatapak, commercialized by Sulzer, and characterized by both good mixing and radialheat-transfer (Stringaro et al., 1998; Irandoust et al., 1998). Usually, Katapak can beapplied in catalytic distillation as well as in some gas-phase exothermic oxidation.

6 Sustainable Development in Chemical Engineering

Heterogeneous catalytic processes can be intensified by using monolithic catalysts(Kapteijn et al., 1999). Among their many features, it is possible to distinguish somevery important benefits such as low pressure drop, high mass transfer area, a lowspace requirement, low cost and better safety. Another interesting example of processintensifying equipment is the microreactor, used for highly exothermic reactions orfor toxic or explosive reactants/products. This device is a small reactor characterizedby a structure that has a considerable number of layers with micro-channels. Thelayers perform various functions such as: mixing, catalytic reaction, heat exchange, orseparation (Charpentier, 2007).

1.2.2 Process Intensifying Methods

Process intensifying methods can be divided into four areas: multifunctional reactors,hybrid separation, alternative energy sources and other methods. In the first twocategories, the PI is expressed by the novelty of the processing methods in whichtwo or more operations are combined, such as reaction/separation or separation/heatexchange and so on.

A well-known example of a multifunctional reactor is the membrane reactor, in whichseparation and reaction take place in the same tool. This alternative device represents areal model of intensification showing a higher efficiency compared to both conventionalseparation and reaction operations. An extensive discussion on these membrane reactorswill be given in Chapter 6.

Another example of multifunctional reactors widely studied is the reverse-flow reactor,in which the reaction is combined with the heat transfer in only one unit operation(Matros and Bunimovich, 1996). The idea is to couple indirectly the energy necessary forendothermic reactions and energy released by exothermic reactions, without mixing bothendothermic and exothermic reactants in closed-loop reverse flow operation. Usually, thisreactor is used for SO2 oxidation, total oxidation of hydrocarbons and NOx reduction(Matros and Bunimovich, 1995).

Reactive distillation is another one of the best known examples of reaction andseparation combination used commercially (De Garmo et al., 1992). In this case, the reac-tor consists of a distillation column filled with catalyst. The aim of the distillation columnis to separate the reaction products by fractionation or to remove impurities or undesiredspecies. The main benefits of reactive distillation are reduced energy requirements andlower capital investment. Moreover, the continuous removal of reaction products allowsus to obtain higher yields compared to conventional systems (Stadig, 1987). Nowadays,this device has been used on a commercial scale even if the potential of this techniquehas not yet completely exploited.

Reactive extraction is the combination of processes such as reaction and solventextraction. The main benefit of this integration results in fewer process steps overall,thereby reducing capital cost. Moreover, this combination allows the enhancement ofboth selectivity and yields of desired products consequently reducing recycle flows andwaste formation (Krishna, 2002).

Multifunctional reactors can also combine reaction and phase transition, and thereactive extrusion represents an example of such combination. Currently, this reactoris used in polymer industries, which enables the processing of highly viscous materials

Sustainable Development Strategies: An Overview 7

without requiring large amounts of solvents (Minotti et al., 1998; Samant and Ng, 1999).Also hybrid separations are characterized by coupling of two or more different unitoperations, which lead to a sustainable increase in the process performances owing tothe synergy effects among the operations. The most important category in this area isrepresented by the combination of membranes with another separation unit operation.

Membrane distillation is probably the best known of hybrid separation (Lawson et al.,1997; Godino et al., 1996). It consists of the permeation of a volatile component con-tained in a liquid stream through a porous membrane as a vapour and condensing onthe other side into a permeate liquid. In this process, the driving force is representedby the temperature difference. This technique is widely considered as an alternative toreverse osmosis and evaporation. In comparison with other separation operations, mem-brane distillation shows very important benefits, such as a complete rejection of colloids,macro-molecules and non-volatile species, lower operating temperature and pressure, andtherefore lower risk and low equipment cost, and less membrane fouling due to largerpore size (Tomaszewska, 2000).

Other examples of hybrid separation are membrane absorption and stripping, in whichthe membrane serves as a permeable barrier between the gas and liquid phases (Jansenet al., 1995; Poddar et al., 1996).

Adsorptive distillation represents a hybrid separation process not involving membranes(Yu et al., 1996). In this technique, a selective adsorbent is added to a distillation mixturewhich allows us to increase separation ability. Adsorptive distillation can be used for theremoval of trace impurities in the manufacturing of fine chemicals or it can present anattractive option in separation of azeotropes or close boiling components. Also alternativeenergy sources can be considered as an example of PI. Indeed, for instance, alternativeforms of energy, such as microwaves, can accelerate chemical processes by hundreds oftimes compared to the conventional unit operation.

However, other techniques not belonging to the three aforementioned areas can also beconsidered as intensified processes, such as supercritical fluids and cryogenic techniques.In particular, supercritical fluids are currently applied in mass transfer operations, suchas extraction (McHugh and Krukonis, 1994) and for chemical reactions (Savage et al.,1995; Hyde et al., 2001) owing to their high diffusion coefficient; instead, the cryogenictechnique, combining distillation with adsorption, is used for industrial gas productionbut it can present a future option for separation operations in fine chemical industries(Jain and Tseng, 1997; Stankiewicz, 2003).

Anyhow, despite the benefits arising by application of PI principles and by consideringthat some PI technologies have already been implemented, PI industrial applicationson a large scale are faced with several barriers. These obstacles are represented byan insufficient PI knowledge and know-how among process technologists, no pilotplant or possibility to use an existing pilot line, both technical and financial risk inthe development of first industrial prototype and the implementation of PI modules inexisting production plants and low awareness of potential benefits of PI technologies atthe management level.

Only a broad action plan including not only technical factors (technological R&D, up-scaling and industrial implementation), but also social and economic factors, can ensurethe fast and successful implementation of PI.

8 Sustainable Development in Chemical Engineering

1.3 Concept and Potentialities of Bio-based Platforms for BiomoleculeProduction

Around the world significant steps are being taken to move from today’s fossil basedeconomy to a more sustainable economy based on biomass. The transition to a bio-basedeconomy has multiple drivers:

• the need to develop an environmentally, economically and socially sustainable globaleconomy;

• the anticipation that oil, gas, coal and phosphorus will reach peak production in thenot-too-distant future and that prices will climb;

• the desire of many countries to reduce an over dependency on fossil fuel imports, sothe need for countries to diversify their energy sources;

• the global issue of climate change and the need to reduce atmospheric greenhousegases (GHG) emissions.

The production of bio-based chemicals is not new, nor is it an historic artefact. Currentglobal bio-based chemical and polymer production (excluding biofuels) is estimated tobe around 50 000 000 tonnes (Higson, 2011). Notably, examples of bio-based chemicalsinclude non-food starch, cellulose fibres and cellulose derivatives, tall oils, fatty acids andfermentation products such as ethanol and citric acid. However, the majority of organicchemicals and polymers are still derived from fossil based feedstocks, predominantly oiland gas.

Historically, bio-based chemical producers have targeted high value fine or specialitychemical markets, often where specific functionality played an important role. The lowprice of crude oil acted as barrier to bio-based commodity chemical production and pro-ducers focussed on the specific attributes of bio-based chemicals, such as their complexstructure, to justify production costs.

The recent climb in oil prices, the consumer demand for environmentally friendlyproducts, population growth and limited supplies of non-renewable resources have nowopened new windows of opportunity for bio-based chemicals and polymers. Bio-basedproducts (chemicals, materials) can be produced in single product processes; however,the production in integrated biorefinery processes producing both bio-based products andsecondary energy carriers (fuels, power, heat), in analogy with oil refineries, probablyis a more efficient approach for the sustainable valorization of biomass resources in afuture bio-based economy (Kamm, 2006; World Economic Forum, 2010).

However, the main driver for the development and implementation of biorefineryprocesses today is the transportation sector. Significant amounts of renewable fuels arenecessary in the short and midterm to meet policy regulations both in- and outsideEurope. A very promising approach to reduce biofuel production costs is to use socalled biofuel-driven biorefineries for the co-production of both value-added products(chemicals, materials, food, feed) and biofuels from biomass resources in a very efficientintegrated approach.

From an overall point of view, a key factor in the realization of a successful biobasedeconomy will be the development of biorefinery systems that are well integrated intothe existing infrastructure. Through biorefinery development, highly efficient and costeffective processing of biological raw materials into a range of bio-based products

Sustainable Development Strategies: An Overview 9

Biomass Precursors Platforms BuildingBlocks

SecondaryChemicals Intermediates Products/

Uses

Industrial

Fuel additivesEtherMethanol

SynGasC1

Aro-matics

directPolymers

Lactic acid

Propionicacid

Levulinicacid

Furfural

Lysine

Gallic acid

Ethanol

Glycerol

....

Olefins

Diacids, Esters

Dilactid

Acrylate

1,3-PDO

Furane

THF

Caprolactam

Carnitine

phenolics

Solvents

Green solvents

Chemicalintermediates

Emulsifiers

PLA

Polyacrylate

......

......

Nylons

Polyurethanes

Polysaccharides

Resins

Transportation

Textiles

Safe Food

Environment

Communication

Housing

Recreation

Health a.

C2

Carbohydrates

Starch

Hemicellulose

Cellulose

Lignin

Lipids, Oil

Protein

C3

C4

C5

C6

SynGas

Lignin

Lipids/Oil

Protein

- Xylose

Sugar

- Fructose- Glucose

Figure 1.5 Biorefinery system scheme (Kamm et al., 2006). Copyright Wiley-VCH VerlagGmbH & Co. KGaA. Reproduced with permission.

can be achieved. On a global scale, the production of bio-based chemicals couldgenerate US$10–15 bn of revenue for the global chemical industry (World EconomicForum, 2010).

Biorefineries can be classified on the basis of a number of their key characteristics(see Figure 1.5). Major feedstocks include perennial grasses, starch crops (e.g. wheat andmaize), sugar crops (e.g. beet and cane), lignocellulosic crops (e.g. managed forest, shortrotation coppice, switchgrass), lignocellulosic residues (e.g. stover and straw), oil crops(e.g. palm and oilseed rape), aquatic biomass (e.g. algae and seaweeds), and organicresidues (e.g. industrial, commercial and post-consumer waste). These feedstocks canbe processed to a range of biorefinery streams termed platforms. The platforms includesingle carbon molecules such as biogas and syngas, five- and six-carbon carbohydratesfrom starch, sucrose or cellulose; a mixed five- and six-carbon carbohydrate streamderived from hemicelluloses, lignin, oils (plant-based or algal), organic solutions fromgrasses, pyrolytic liquids. These primary platforms can be converted to wide range ofmarketable products using combinations of thermal, biological and chemical processes.

1.3.1 Biogas Platform

Currently, biogas production is mainly based on the anaerobic digestion of ‘highmoisture content biomass’ such as manure, waste streams from food processing plantsor biosolids from municipal effluent treatment systems. Biogas production from energycrops will also increase and will have to be based on a wide range of crops thatare grown in versatile, sustainable crop rotations. Biogas production can be part ofsustainable biochemical and biofuel-based biorefinery concepts as it can derive valuefrom wet streams. Value can be increased by optimizing methane yield and economicefficiency of biogas production (Bauer et al., 2007), and deriving nutrient value fromthe digestate streams (De Jong et al., 2011).

10 Sustainable Development in Chemical Engineering

1.3.2 Sugar Platform

Six-carbon sugar platforms can be accessed from sucrose or through the hydrolysisof starch or cellulose to give glucose. Glucose serves as feedstock for (biological) fer-mentation processes providing access to a variety of important chemical building blocks.Glucose can also be converted by chemical processing to useful chemical building blocks.Mixed six- and five-carbon platforms are produced from the hydrolysis of hemicelluloses.The fermentation of these carbohydrate streams can in theory produce the same productsas six-carbon sugar streams; however, technical, biological and economic barriers needto be overcome before these opportunities can be exploited. Chemical manipulation ofthese streams can provide a range of useful molecules (see Figure 1.6).

Six- and five-carbon carbohydrates can undergo selective dehydration, hydrogenationand oxidation reactions to give useful products, such as: sorbitol, furfural, glucaric acid,hydroxymethylfurfural (HMF), and levulinic acid. Over 1 000 000 tonnes of sorbitol isproduced per year as a food ingredient, a personal care ingredient (e.g. toothpaste), andfor industrial use (Vlachos et al., 2010, ERRMA, 2011).

1.3.3 Vegetable Oil Platform

Global oleochemical production in 2009 amounted to 7.7 million tonnes of fatty acidsand 2.0 million tonnes of fatty alcohols (ICIS Chemical Business, 2010). The majority offatty acid derivatives are used as surface active agents in soaps, detergents and personalcare products (Taylor et al., 2011).

C6

C1CO2/CH2

C2

C3

C4

C5

C4+

C6C6+

C8C8+

(C5)

Sugar

Ethylene Ethanol

Ethyl lactate

Methanol

Malic acid

1,3-Propandiol

Aerobic Fermentation Anaerobic Fermentation

Acetic acid

Acetone

Aconitic acid

2- Ethyl hexanol

Isoascorbic acidParasorbic acid

sorbic acid

Acetaldehyde

Acetic acid anhyoxide

Diethyl ether

Dilactide

Prophylene

Pentandione

Butadiene

Butyraldohyde

n-Butanol

Vinyl acetate

ltaconic acid

Citric acid

Poly(vinyl acetate)

Crotone'dehyde

2,3-Butandiol

Poly(lactic acid)

Kojic acid

Maltol

Prophylene oxide

Lactic acid

Acrylic acid

Figure 1.6 Sugar platform scheme (Kamm et al., 2006). Copyright Wiley-VCH Verlag GmbH& Co. KGaA. Reproduced with permission.