Table Of ContentHemicelluloses and Lignin
in Biorefineries
GREEN CHEMISTRY AND CHEMICAL ENGINEERING
Series Editor: Sunggyu Lee
Ohio University, Athens, Ohio, USA
Proton Exchange Membrane Fuel Cells: Contamination and Mitigation Strategies
Hui Li, Shanna Knights, Zheng Shi, John W. Van Zee, and Jiujun Zhang
Proton Exchange Membrane Fuel Cells: Materials Properties and Performance
David P. Wilkinson, Jiujun Zhang, Rob Hui, Jeffrey Fergus, and Xianguo Li
Solid Oxide Fuel Cells: Materials Properties and Performance
Jeffrey Fergus, Rob Hui, Xianguo Li, David P. Wilkinson, and Jiujun Zhang
Efficiency and Sustainability in the Energy and Chemical Industries:
Scientific Principles and Case Studies, Second Edition
Krishnan Sankaranarayanan, Jakob de Swaan Arons, and Hedzer van der Kooi
Nuclear Hydrogen Production Handbook
Xing L. Yan and Ryutaro Hino
Magneto Luminous Chemical Vapor Deposition
Hirotsugu Yasuda
Carbon-Neutral Fuels and Energy Carriers
Nazim Z. Muradov and T. Nejat Vezirogˇlu
Oxide Semiconductors for Solar Energy Conversion: Titanium Dioxide
Janusz Nowotny
Lithium-Ion Batteries: Advanced Materials and Technologies
Xianxia Yuan, Hansan Liu, and Jiujun Zhang
Process Integration for Resource Conservation
Dominic C. Y. Foo
Chemicals from Biomass: Integrating Bioprocesses into Chemical Production Complexes
for Sustainable Development
Debalina Sengupta and Ralph W. Pike
Hydrogen Safety
Fotis Rigas and Paul Amyotte
Biofuels and Bioenergy: Processes and Technologies
Sunggyu Lee and Y. T. Shah
Hydrogen Energy and Vehicle Systems
Scott E. Grasman
Integrated Biorefineries: Design, Analysis, and Optimization
Paul R. Stuart and Mahmoud M. El-Halwagi
Water for Energy and Fuel Production
Yatish T. Shah
Handbook of Alternative Fuel Technologies, Second Edition
Sunggyu Lee, James G. Speight, and Sudarshan K. Loyalka
GREEN CHEMISTRY AND CHEMICAL ENGINEERING Environmental Transport Phenomena
A. Eduardo Sáez and James C. Baygents
Series Editor: Sunggyu Lee Resource Recovery to Approach Zero Municipal Waste
Ohio University, Athens, Ohio, USA Mohammad J. Taherzadeh and Tobias Richards
Energy and Fuel Systems Integration
Proton Exchange Membrane Fuel Cells: Contamination and Mitigation Strategies Yatish T. Shah
Hui Li, Shanna Knights, Zheng Shi, John W. Van Zee, and Jiujun Zhang Sustainable Water Management and Technologies, Two-Volume Set
Proton Exchange Membrane Fuel Cells: Materials Properties and Performance Daniel H. Chen
David P. Wilkinson, Jiujun Zhang, Rob Hui, Jeffrey Fergus, and Xianguo Li Sustainable Water Management
Daniel H. Chen
Solid Oxide Fuel Cells: Materials Properties and Performance
Jeffrey Fergus, Rob Hui, Xianguo Li, David P. Wilkinson, and Jiujun Zhang Sustainable Water Technologies
Daniel H. Chen
Efficiency and Sustainability in the Energy and Chemical Industries:
Scientific Principles and Case Studies, Second Edition The Water-Food-Energy Nexus: Processes, Technologies, and Challenges
Krishnan Sankaranarayanan, Jakob de Swaan Arons, and Hedzer van der Kooi Iqbal M. Mujtaba, Rajagopalan Srinivasan, and Nimir Elbashir
Nuclear Hydrogen Production Handbook Managing Biogas Plants: A Practical Guide
Xing L. Yan and Ryutaro Hino Mario Alejandro Rosato
Magneto Luminous Chemical Vapor Deposition Hemicelluloses and Lignin in Biorefineries
Hirotsugu Yasuda Jean-Luc Wertz, Magali Deleu, Séverine Coppée, and Aurore Richel
Carbon-Neutral Fuels and Energy Carriers
Nazim Z. Muradov and T. Nejat Vezirogˇlu
Oxide Semiconductors for Solar Energy Conversion: Titanium Dioxide
Janusz Nowotny
Lithium-Ion Batteries: Advanced Materials and Technologies
Xianxia Yuan, Hansan Liu, and Jiujun Zhang
Process Integration for Resource Conservation
Dominic C. Y. Foo
Chemicals from Biomass: Integrating Bioprocesses into Chemical Production Complexes
for Sustainable Development
Debalina Sengupta and Ralph W. Pike
Hydrogen Safety
Fotis Rigas and Paul Amyotte
Biofuels and Bioenergy: Processes and Technologies
Sunggyu Lee and Y. T. Shah
Hydrogen Energy and Vehicle Systems
Scott E. Grasman
Integrated Biorefineries: Design, Analysis, and Optimization
Paul R. Stuart and Mahmoud M. El-Halwagi
Water for Energy and Fuel Production
Yatish T. Shah
Handbook of Alternative Fuel Technologies, Second Edition
Sunggyu Lee, James G. Speight, and Sudarshan K. Loyalka
Hemicelluloses and Lignin
in Biorefineries
by
Jean-Luc Wertz
Magali Deleu
Séverine Coppée
Aurore Richel
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2018 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
International Standard Book Number-13: 978-1-1387-2098-5 (Hardback)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts
have been made to publish reliable data and information, but the author and publisher cannot assume
responsibility for the validity of all materials or the consequences of their use. The authors and publishers
have attempted to trace the copyright holders of all material reproduced in this publication and apologize to
copyright holders if permission to publish in this form has not been obtained. If any copyright material has
not been acknowledged please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmit-
ted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented,
including photocopying, microfilming, and recording, or in any information storage or retrieval system,
without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.
com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood
Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and
registration for a variety of users. For organizations that have been granted a photocopy license by the CCC,
a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used
only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Contents
Foreword ..................................................................................................................xv
Preface....................................................................................................................xvii
Acknowledgments ...................................................................................................xix
About the Authors ...................................................................................................xxi
Chapter 1 Introduction ..........................................................................................1
1.1 Bioeconomy and Circular Bioeconomy .....................................1
1.2 Bioeconomy ...............................................................................4
1.2.1 Definition and Stakes ...................................................4
1.2.2 Societal Challenges ......................................................5
1.3 Biobased Economy ....................................................................6
1.4 Life-Cycle Assessment ..............................................................6
CRC Press 1.5 Lignocellulosic Biomass ............................................................7
Taylor & Francis Group 1.5.1 Cellulose .......................................................................9
6000 Broken Sound Parkway NW, Suite 300
1.5.2 Hemicelluloses .............................................................9
Boca Raton, FL 33487-2742
1.5.3 Lignin .........................................................................10
© 2018 by Taylor & Francis Group, LLC
1.6 Plant Cell Wall .........................................................................10
CRC Press is an imprint of Taylor & Francis Group, an Informa business
1.6.1 Structure of Cell Walls ...............................................10
No claim to original U.S. Government works 1.6.2 Diversity .....................................................................10
Printed on acid-free paper 1.7 Lignocellulosic Biorefineries ...................................................15
1.7.1 Biorefinery Concept ...................................................15
International Standard Book Number-13: 978-1-1387-2098-5 (Hardback)
1.7.2 Feedstock ....................................................................16
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts 1.7.2.1 Biomass Residues and Wastes ....................16
have been made to publish reliable data and information, but the author and publisher cannot assume 1.7.2.2 Dedicated Crops .........................................16
responsibility for the validity of all materials or the consequences of their use. The authors and publishers
1.7.3 Conversion Processes .................................................17
have attempted to trace the copyright holders of all material reproduced in this publication and apologize to
copyright holders if permission to publish in this form has not been obtained. If any copyright material has 1.7.3.1 Biochemical Processes ...............................17
not been acknowledged please write and let us know so we may rectify in any future reprint. 1.7.4 Valorization of Hemicelluloses and Lignin
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmit- Derived from Biomass ................................................18
ted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, 1.8 Structure of the Book ..............................................................19
including photocopying, microfilming, and recording, or in any information storage or retrieval system,
References ..........................................................................................20
without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.
Chapter 2 Carbohydrate-Active Enzymes...........................................................25
com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood
Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and
2.1 Introduction .............................................................................25
registration for a variety of users. For organizations that have been granted a photocopy license by the CCC,
a separate system of payment has been arranged. 2.2 Glycosyltransferases ................................................................26
2.2.1 Glycosyltransferase Activities ....................................26
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used
only for identification and explanation without intent to infringe. 2.2.2 Glycosyltransferase Folds ...........................................27
2.2.3 Glycosyltransferase Classification ..............................28
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com 2.2.4 Mechanism of Inverting Glycosyltransferases ...........29
2.2.5 Mechanism of Retaining Glycosyltransferases ..........31
and the CRC Press Web site at
http://www.crcpress.com
vii
viii Contents
2.3 Glycoside Hydrolases ..............................................................32
2.3.1 Glycoside Hydrolase Activities ..................................32
2.3.2 Endo- and Exo-Action ................................................32
2.3.3 Active-Site Topologies ...............................................32
2.3.4 Catalytic Mechanism ..................................................34
2.3.5 Catalytic Modules ......................................................37
2.3.5.1 Classification of Various Glycoside
Hydrolase Families .....................................37
2.3.5.2 Folds of the Catalytic Module ....................39
2.3.6 Carbohydrate-Binding Module ..................................40
2.3.7 Nomenclature .............................................................41
2.4 Esterases ..................................................................................43
2.4.1 Overview ....................................................................43
2.4.2 Carboxylesterases .......................................................44
2.4.3 Carbohydrate Esterases ..............................................45
References ..........................................................................................47
Chapter 3 Cellulose, the Main Component of Biomass ......................................51
3.1 Structure ..................................................................................52
3.1.1 Molecular Structure....................................................52
3.1.2 Supramolecular Structure ...........................................52
3.1.2.1 Cellulose I ...................................................53
3.1.2.2 Cellulose II..................................................54
3.1.3 Morphological Structure ............................................54
3.1.3.1 Microfibrils .................................................54
3.1.3.2 Plant Cell Walls ..........................................56
3.1.3.3 Primary Cell Walls .....................................56
3.1.3.4 Primary and Secondary Walls ....................57
3.2 Biosynthesis .............................................................................58
3.2.1 Cellulose-Synthesizing Terminal Complexes ............58
3.2.2 Glucose Polymerization by Cellulose Synthases .......59
3.2.2.1 Cellulose Synthase Substrate ......................59
3.2.2.2 Cellulose Synthases and Other Plant
Glycosyltransferases ...................................59
3.2.2.3 Models of Glucose Polymerization .............61
3.2.2.4 Genes Encoding Cellulose Synthases .........62
3.2.3 Chain Assembly into Microfibrils ..............................65
3.2.3.1 Chain Assembly in Plants ...........................65
3.2.3.2 Chain Assembly in Bacteria .......................66
3.3 Enzymatic Hydrolysis ..............................................................66
3.3.1 Cellulases ...................................................................67
3.3.2 Non-Complexed Cellulase Systems ...........................67
3.3.2.1 Trichoderma reesei (Hypocrea jecorina) ...67
3.3.2.2 Humicola insolens ......................................69
3.3.2.3 Synergism ...................................................70
Contents ix
3.3.3 Multienzyme Complexes ............................................70
3.3.3.1 Clostridium cellulolyticum .........................71
3.3.3.2 Clostridium thermocellum ..........................72
3.3.3.3 Designer Cellulosomes ...............................73
References ..........................................................................................73
Chapter 4 Structure and Biosynthesis of Hemicelluloses ...................................77
4.1 Introduction .............................................................................77
4.2 General Structure of Hemicelluloses ......................................78
4.3 Detailed Structure and Occurrence of Hemicelluloses ...........81
4.3.1 Xyloglucans ................................................................81
4.3.2 Xylans .........................................................................83
4.3.3 Mannans .....................................................................85
4.3.4 Mixed-Linkage Glucans .............................................89
4.3.5 Related Molecules: Pectins.........................................90
4.4 Biosynthesis .............................................................................90
4.4.1 General .......................................................................90
4.4.2 Xyloglucans ................................................................90
4.4.2.1 Glycosyltransferases Involved in
Xyloglucan Synthesis ..................................90
4.4.2.2 Hydrolases Involved in Xyloglucan
Synthesis .....................................................91
4.4.2.3 Acetylation ..................................................92
4.4.3 Xylans .........................................................................92
4.4.3.1 Backbone ....................................................93
4.4.3.2 Reducing End Oligosaccharide...................94
4.4.3.3 Side Chains .................................................95
4.4.4 Mannans .....................................................................95
4.4.5 Mixed-Linkage Glucans .............................................96
4.4.6 Role of CESA-CSL Superfamily................................96
4.5 Function in Plant Cell Walls ....................................................96
4.5.1 Xyloglucans ................................................................96
4.5.1.1 Xyloglucan Endo-Transglycosylase/
Hydrolases ..................................................96
4.5.1.2 Action of XTHs ..........................................99
4.5.2 Xylans, Mannans, and Mixed-Linkage Glucans ........99
4.6 Summary ...............................................................................102
References ........................................................................................102
Chapter 5 Biodegradation of Hemicelluloses ...................................................107
5.1 Introduction ...........................................................................107
5.2 Hemicellulases: Overview .....................................................108
5.3 Biodegradation of Xyloglucans..............................................108
5.3.1 Overview ..................................................................108
