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Biofuels Biofuels. Edited by Wim Soetaert, Erick J. Vandamme. © 2009 John Wiley & Sons Ltd. ISBN: 978-0-470-02674-8

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Biofuels

i

Biofuels. Edited by Wim Soetaert, Erick J. Vandamme.© 2009 John Wiley & Sons Ltd. ISBN: 978-0-470-02674-8

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Wiley Seriesin

Renewable Resources

Series Editor

Christian V. Stevens, Department of Organic Chemistry, Ghent University, Belgium

Titles in the Series

Wood Modification: Chemical, Thermal and Other ProcessesCallum A.S. Hill

Renewables-Based Technology: Sustainability AssessmentJo Dewulf & Herman Van Langenhove

Introduction to Chemicals from BiomassJames H. Clark & Fabien E.I. Deswarte

BiofuelsWim Soetaert & Erick J. Vandamme

Forthcoming Titles

Handbook of Natural ColorantsThomas Bechtold & Rita Mussak

Starch Biology, Structure & FunctionalityAnton Huber & Werner Praznik

Industrial Applications of Natural Fibres: Structure, Propertiesand Technical ApplicationsJorg Mussig

Surfactants from Renewable ResourcesMikael Kjellin & Ingegard Johansson

Thermochemical Processing of BiomassRobert C. Brown

Bio-based PolymersMartin Peter & Telma Franco

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Biofuels

Edited by

WIM SOETAERT

Ghent University, Ghent, Belgium

ERICK J. VANDAMME

Ghent University, Ghent, Belgium

A John Wiley and Sons, Ltd., Publication

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This edition first published 2009C© 2009 John Wiley & Sons, Ltd

Registered officeJohn 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 reusethe 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, Designsand 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 byany means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designsand 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. This publication is designed to provide accurateand authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is notengaged in rendering professional services. If professional advice or other expert assistance is required, the services of acompetent professional should be sought.

The publisher and the author make no representations or warranties with respect to the accuracy or completeness of thecontents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness fora particular purpose. This work is sold with the understanding that the publisher is not engaged in rendering professionalservices. 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 ofexperimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in thepackage insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes inthe instructions 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, readersshould be aware that Internet Websites listed in this work may have changed or disappeared between when this work waswritten and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither thepublisher nor the author shall be liable for any damages arising herefrom.

Library of Congress Cataloging-in-Publication Data

Soetaert, Wim.Biofuels / Wim Soetaert, Erick J. Vandamme.

p. cm. – (Wiley series in renewable resource)Includes bibliographical references and index.ISBN 978-0-470-02674-8 (cloth)1. Biomass energy–Technological innovations. 2. Biomass energy–Economic aspects.

3. Renewable natural resources. I. Vandamme, Erick J., 1943– II. Title.TP339.S64 2008333.95′39–dc22 2008027967

A catalogue record for this book is available from the British Library.

ISBN 978-0-470-02674-8

Set in 10/12pt Times by Aptara Inc., New Delhi, IndiaPrinted and bound in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire

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Contents

Series Preface ix

Preface xi

List of Contributors xiii

1 Biofuels in Perspective 1Wim Soetaert and Erick J. Vandamme1.1 Fossil versus Renewable Energy Resources 11.2 Economic Impact 21.3 Comparison of Bio-energy Sources 41.4 Conclusion 7

References 7

2 Sustainable Production of Cellulosic Feedstock for Biorefineriesin the USA 9Matthew T. Carr and James R. Hettenhaus2.1 Introduction 92.2 Availability of Cellulosic Feedstocks 112.3 Feedstock Options 132.4 Sustainable Removal 162.5 Erosion Control 182.6 Tilling Practice 192.7 Transitioning to No-till 212.8 Realizing Removal 222.9 Removal Economics 252.10 Climate Change Mitigation 272.11 Pretreatment 292.12 Farmer in Value Chain 322.13 The Start: Preprocessing Pentose Sugars and Lignin 322.14 Continuing Downstream: Fungible Fermentation Sugars 322.15 Looking Upstream 33

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vi Contents

2.16 Logistics 332.17 Conclusions 332.18 Policy Recommendations 34

References 35

3 Bio-Ethanol Development in the USA 39Brent Erickson and Matthew T. Carr3.1 Introduction 393.2 Federal Policy 403.3 The US Ethanol Market 413.4 Corn Ethanol Technology 463.5 Cellulosic Ethanol 493.6 The Future 52

References 53

4 Bio-Ethanol Development(s) in Brazil 55Arnaldo Walter4.1 Overview 554.2 Introduction 564.3 The Brazilian Experience with Ethanol 564.4 Policy and Regulatory Instruments Applied to Deploy Large-Scale

Ethanol Production 594.5 Cost Reductions 614.6 Technological Development 624.7 Is the Ethanol Production in Brazil Sustainable? 654.8 Is the Brazilian Experience Replicable? 724.9 Conclusions 73

References 74

5 Process Technologies for Biodiesel Production 77Martin Mittelbach5.1 Introduction 775.2 Biodiesel Production Worldwide 775.3 Feedstocks for Biodiesel Production 795.4 Chemical Principles of Biodiesel Production 805.5 Catalysts for Transesterification and Esterification Reactions 815.6 Transesterification in Supercritical Alcohols 865.7 Alternative Approaches 875.8 Overview of Process Technologies 87

References 91

6 Bio-based Fischer–Tropsch Diesel Production Technologies 95Robin Zwart and Rene van Ree6.1 Introduction 956.2 Theoretical Background Catalytic FT-Diesel Synthesis Process 96

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Contents vii

6.3 Biomass Gasification-Based FT-Diesel Production Concepts 1006.4 Economics of Biomass-Based FT-Diesel Production Concepts 1106.5 Conclusions 113

References 114

7 Plant Oil Biofuel: Rationale, Production and Application 117Barnim Jeschke7.1 Introduction 1177.2 Plant Oil Biofuels: the Underlying Idea 1187.3 Perspectives of the Plant Oil Fuel Market 1197.4 System Requirements 1227.5 Plant Oil Conversion Technology 1247.6 The User Perspective 125

References 127

8 Enzymatic Production of Biodiesel 129Hideki Fukuda8.1 Introduction 1298.2 Enzymatic Transesterification by Lipase 1308.3 Use of Extracellular Lipases 1318.4 Use of Intracellular Lipase as Whole-Cell Biocatalyst 1368.5 Use of Cell-Surface Displaying Cells as Whole-Cell Biocatalyst 1438.6 Conclusions and Future Prospects 147

References 147

9 Production of Biodiesel from Waste Lipids 153Roland Verhe and Christian V. Stevens9.1 Introduction 1539.2 Alternative Resources for Biodiesel Production 1559.3 Conversion of Waste Frying and Cooking Oils into Biodiesel 1559.4 Conclusion 168

References 169

10 Biomass Digestion to Methane in Agriculture: A Successful Pathwayfor the Energy Production and Waste Treatment Worldwide 171Peter Weiland, Willy Verstraete and Adrianus Van Haandel10.1 Overview 17110.2 Introduction 17210.3 Biogas Production Potential 17410.4 Biogas Production Configurations 18310.5 Outlook 19110.6 Conclusions 193

References 194

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viii Contents

11 Biological Hydrogen Production by Anaerobic Microorganisms 197Serve W.M. Kengen, Heleen P. Goorissen, Marcel Verhaart,Alfons J.M. Stams, Ed W.J. van Niel and Pieternel A.M. Claassen

Abbreviations 19711.1 Introduction 19811.2 Hydrogen Formation in Natural Ecosystems 19811.3 Thermodynamics of Hydrogen Formation 19911.4 Enzymology 20411.5 Enterobacteria 20611.6 The Genus Clostridium 20711.7 The Genus Caldicellulosiruptor 20811.8 The Genus Thermoanaerobacter 21011.9 The Genus Thermotoga 21111.10 The Genus Pyrococcus/Thermococcus 21211.11 Approaches for Improving Hydrogen Production 21311.12 Concluding Remarks 214

References 215

12 Improving Sustainability of the Corn–Ethanol Industry 223Paul W. Gallagher and Hosein Shapouri12.1 Introduction 22312.2 Energy Balance 22412.3 Crop Production and Greenhouse Gas Emissions 22612.4 CO2 Adjustment in a Changing Ethanol Industry 22812.5 Conclusions 232

References 233

Index 235

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Series Preface

Renewable resources, their use and modification are involved in a multitude of importantprocesses with a major influence on our everyday lives. Applications can be found in theenergy sector, chemistry, pharmacy, the textile industry, paints and coatings, to name buta few.

The area interconnects several scientific disciplines (agriculture, biochemistry, chem-istry, technology, environmental sciences, forestry, ...), which makes it very difficult tohave an expert view on the complicated interaction. Therefore, the idea to create a seriesof scientific books, focussing on specific topics concerning renewable resources, has beenvery opportune and can help to clarify some of the underlying connections in this area.

In a very fast changing world, trends are not only characteristic for fashion and politicalstandpoints, also science is not free from hypes and buzzwords. The use of renewableresources is again more important nowadays; however, it is not part of a hype or a fashion.As the lively discussions among scientists continue about how many years we will still beable to use fossil fuels, with opinions ranging from 50 years to 500 years, they do agreethat the reserve is limited and that it is essential not only to search for new energy carriersbut also for new material sources.

In this respect, renewable resources are a crucial area in the search for alternatives forfossil-based raw materials and energy. In the field of energy supply, biomass and renewable-based resources will be part of the solution alongside other alternatives such as solar energy,wind energy, hydraulic power, hydrogen technology and nuclear energy.

In the field of material sciences, the impact of renewable resources will probably be evenbigger. Integral utilization of crops and the use of waste streams in certain industries willgrow in importance, leading to a more sustainable way of producing materials.

Although our society was much more (almost exclusively) based on renewable resourcescenturies ago, this disappeared in the Western world in the nineteenth century. Now it istime to focus again on this field of research. However, it should not mean a retour a lanature, but it should be a multidisciplinary effort on a highly technological level to performresearch towards new opportunities, to develop new crops and products from renewableresources. This will be essential to guarantee a level of comfort for a growing number ofpeople living on our planet. It is ‘the’ challenge for the coming generations of scientists todevelop more sustainable ways to create prosperity and to fight poverty and hunger in theworld. A global approach is certainly favoured.

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x Series Preface

This challenge can only be dealt with if scientists are attracted to this area and arerecognized for their efforts in this interdisciplinary field. It is therefore also essential thatconsumers recognize the fate of renewable resources in a number of products.

Furthermore, scientists do need to communicate and discuss the relevance of their work.The use and modification of renewable resources may not follow the path of the geneticengineering concept in view of consumer acceptance in Europe. Related to this aspect, theseries will certainly help to increase the visibility of the importance of renewable resources.

Being convinced of the value of the renewables approach for the industrial world, aswell as for developing countries, I was myself delighted to collaborate on this series ofbooks focussing on different aspects of renewable resources. I hope that readers becomeaware of the complexity, the interaction and interconnections, and the challenges of thisfield and that they will help to communicate on the importance of renewable resources.

I certainly want to thank the people of Wiley from the Chichester office, especially DavidHughes, Jenny Cossham and Lyn Roberts, in seeing the need for such a series of books onrenewable resources, for initiating and supporting it and for helping to carry the project tothe end.

Last, but not least I want to thank my family, especially my wife Hilde and childrenPaulien and Pieter-Jan for their patience and for giving me the time to work on the serieswhen other activities seemed to be more inviting.

Christian V. StevensFaculty of Bioscience Engineering

Ghent University, BelgiumSeries Editor ‘Renewable Resources’

June 2005

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Preface

This volume on Biofuels fits within the series Renewable Resources. It covers the use andconversion technologies of biomass as a renewable resource to produce bio-energy in asustainable way, mainly in the form of liquid and gaseous biofuels.

These biofuels are a convenient renewable energy carrier for specific purposes, withtransportation as an important application sector. Renewable biomass is produced annually,based on photosynthesis, and is available in different forms, depending on climatic condi-tions and economic situations around the world. Chemical and thermochemical methods,as well as fermentation and biocatalysis technologies, are essential to efficiently convertbiomass directly or indirectly into biofuels, with bio-ethanol, biodiesel and biogas as to-day’s main practical players. In this context, green biotechnology, green chemistry andwhite biotechnology are to join forces to arrive at sustainable processes and fuels. Theuse of biofuels is quickly gaining momentum all over the world, and can be expected tohave an ever-increasing impact on the energy and agricultural sector in particular. Newand efficient ‘bio-cracking’ technologies for biomass are under development, while ex-isting (thermo)chemical, fermentation and enzyme technologies are further optimized.These developments cover basic and applied research, pilot scale experimentation anddemonstration plants for second generation biofuels.

All foregoing scientific and technological aspects are treated in this volume by renownedexperts in their field. In addition, the economical and ecological aspects of biofuels devel-opment and application are receiving due attention: market developments are commentedas well as the sustainability of biofuels production and use. Particularly, the links betweenthe technical, economical and ecological aspects are clearly expressed in this volume andare actually covered here for the first time in a single comprehensive volume. The editorsare indebted to the John Wiley & Sons staff (Jenny Cossham, Zoe Mills, Richard Davies)for their invaluable supportive help along the editorial process, and to the secretarial inputof Dominique Delmeire (Ghent University) who kept us abreast of the ‘labour’ efforts ofall the contributors. Without all of them, this volume would not have been born and growninto an active youngster, a real player in and on the biofuels-field.

Wim SoetaertErick J. Vandamme

Ghent, January 2008

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xii Preface

Note on conversion factors

The following conversion factors can be used:

1 acre = 0.4047 hectare1 US bushel of corn = 35.2 litres = 25.4 kg1 US gallon = 3.78541 litre.

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List of Contributors

Editors

Wim Soetaert Laboratory of Industrial Microbiology and Biocatalysis, Faculty ofBioscience Engineering, Ghent University, Ghent, Belgium

Erick J. Vandamme Laboratory of Industrial Microbiology and Biocatalysis, Faculty ofBioscience Engineering, Ghent University, Ghent, Belgium

Contributors

Matthew T. Carr Policy Director, Industrial and Environmental Section, BiotechnologyIndustry Organization, Washington, USA.

Pieternel A.M. Claassen Agrotechnology and Food Sciences group, Wageningen Uni-versity and Research Center, Wageningen, The Netherlands.

Brent Erickson Executive Vice President, Industrial & Environmental Section, Biotech-nology Industry Organization, Washington, USA.

Hideki Fukuda Division of Molecular Science, Graduate School of Science and Tech-nology, Kobe University, Japan.

Paul Gallagher Department of Economics, Iowa State University, Iowa, USA.

Heleen P. Goorissen Laboratory of Microbiology, Wageningen University and ResearchCenter, Wageningen, The Netherlands.

Adrianus Van Haandel, Federal University of Paraıba, Department of Civil Engineering,Campina Grande, Brazil.

James R. Hettenhaus President and CEO, Chief Executive Assistance, Inc. Charlotte.NC, USA.

Barnim Jeschke Co-founder and former Non-Executive Director, ELSBETT Technolo-gies GmbH, Munich, Germany.

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xiv List of Contributors

Serve W.M. Kengen Laboratory of Microbiology, Wageningen University and ResearchCenter, Wageningen, The Netherlands.

Martin Mittelbach Department of Renewable Resources, Institute of Chemistry, Karl-Franzens-University, Graz, Austria.

Ed W.J. van Niel Laboratory of Applied Microbiology, University of Lund, Sweden.

Rene van Ree Wageningen University and Research Centre, Wageningen, The Nether-lands.

Hosein Shapouri USDA, OCE, OE, Washington, DC, USA.

Alfons J.M. Stams Wageningen University and Research Centre, Wageningen, TheNetherlands.

Christian V. Stevens Faculty of Bioscience-engineering, Department of Organic Chem-istry, Ghent University, Ghent, Belgium.

Marcel Verhaart Laboratory of Microbiology, Wageningen University and ResearchCenter, Wageningen, The Netherlands.

Roland Verhe Faculty of Bioscience-engineering, Department of Organic Chemistry,Ghent University, Ghent, Belgium.

Willy Verstraete Faculty of Bioscience-engineering, Laboratory of Microbial Ecologyand Technology, Ghent University, Ghent, Belgium

Arnaldo Walter Department of Energy and NIPE, State University of Campinas (Uni-camp), Brazil.

Peter Weiland Bundesforschungsanstalt fur Landwirtschaft, Institut fur Technologieund Biosystemtechnik, Braunschweig, Germany.

Robin Zwart Energy Research Centre of the Netherlands Biomass, Coal and Environ-mental Research Petten, The Netherlands.