Biorefinery : from biomass to chemicals and fuels

465 Pages·2012·7.508 MB·English

by  Aresta, Michele, Dibenedetto, Angela, Dumeignil, Franck

Biorefi nery: From Biomass to Chemicals and Fuels
Edited by Aresta, Dibenedetto and Dumeignil

Biorefi nery
From Biomass to Chemicals
and Fuels
Edited by Michele Aresta,
Angela Dibenedetto and Franck Dumeignil
DE GRUYTER
Editors
Prof. Michele Aresta Prof. Franck Dumeignil
CIRCC and Department of Chemistry Univ. Lille Nord de France
University of Bari CNRS UMR8181
Via E. Orabona 4, Campus Universitario 1bis rue Georges Lefèvre
70126 Bari 59000 Lille
Italy France
[email protected] [email protected]
Prof. Angela Dibenedetto
CIRCC and Department of Chemistry
University of Bari
Via E. Orabona 4, Campus Universitario
70126 Bari
Italy
[email protected]
ISBN 978-3-11-026023-6
e-ISBN 978-3-11-026028-1
Library of Congress Cataloging-in-Publication Data
A CIP catalog record for this book has been applied for at the Library of Congress.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e;
detailed bibliographic data are available in the internet at http://dnb.d-nb.de.
© 2012 by Walter de Gruyter GmbH & Co. KG, Berlin/Boston.
The publisher, together with the authors and editors, has taken great pains to ensure that all
information presented in this work (programs, applications, amounts, dosages, etc.) refl ects
the standard of knowledge at the time of publication. Despite careful manuscript preparation
and proof correction, errors can nevertheless occur. Authors, editors and publisher disclaim all
responsibility and for any errors or omissions or liability for the results obtained from use of the
information, or parts thereof, contained in this work.
Typesetting: Apex CoVantage
Printing and binding: Hubert & Co. GmbH & Co. KG, Göttingen
Printed on acid-free paper.
Printed in Germany
www.degruyter.com
Contents
Preface ................................................................................................................. xiii
List of Contributing Authors ..................................................................................... xv
1 A new concept of biorefi nery comes into
operation: the EuroBioRef concept ..................................................................... 1
Franck Dumeignil
1.1 General context ............................................................................................ 1
1.1.1 Toward a bio-based economy ............................................................. 1
1.1.2 Biorefi neries and the level of integration ............................................. 2
1.2 The EuroBioRef biorefi nery concept, objectives, and methodology ............... 3
1.2.1 Flexibility, adaptability, and multidimensional integration
of the EuroBioRef project .................................................................... 3
1.2.2 The concept principles of EuroBioRef ................................................. 5
1.2.3 The objectives of the EuroBioRef project ............................................. 7
1.2.4 The EuroBioRef approach to reach the objectives ................................ 9
1.2.5 EuroBioRef innovation and expected results (Fig. 1.7) ........................ 11
1.2.6 S/T methodology and associated subprojects ..................................... 12
1.3 Main achievements of the fi rst year of the project ........................................ 14
Acknowledgements ............................................................................................ 17
References ......................................................................................................... 17
2 Refi nery of the future: feedstock, processes, products ...................................... 19
Jean-Luc Dubois
2.1 Introduction ................................................................................................ 19
2.2 Competition ................................................................................................ 19
2.3 Impact of legislation .................................................................................... 22
2.4 Regional impacts ......................................................................................... 23
2.5 Biorefi neries – defi nitions and examples ...................................................... 23
2.5.1 Arkema’s castor oil-based biorefi nery................................................. 25
2.5.2 Elevance Renewable Sciences oil-based biorefi nery .......................... 26
2.5.3 Vandeputte oil-based biorefi nery ....................................................... 28
2.5.4 The “Les Sohettes” biorefi nery ........................................................... 29
2.5.5 The starch-based Cargill biorefi nery ................................................... 29
2.5.6 Other biorefi neries ............................................................................ 29
2.6 Processing units ........................................................................................... 31
2.7 Capital cost ................................................................................................. 39
2.8 Conclusions ................................................................................................ 47
Acknowledgements ............................................................................................ 47
References ......................................................................................................... 47
vi (cid:2) Contents
3 The terrestrial biomass: formation and properties
(crops and residual biomass) ............................................................................. 49
Myrsini Christou and Efthimia Alexopoulou
3.1 Residual biomass ......................................................................................... 49
3.1.1 Straw ................................................................................................. 49
3.1.2 Wood ................................................................................................ 51
3.2 The oil crops ................................................................................................ 53
3.2.1 Castor seed (Ricinus communis L, Euphorbiaceae) ............................. 53
3.2.2 Crambe (Crambe abysinica Hochst ex R.E. Fries,
Brassicaceae/Crucifera) ...................................................................... 55
3.2.3 Cuphea (Cuphea sp., Lythraceae) ....................................................... 59
3.2.4 Lesquerella (Lesquerella fendlheri L, Communis L,
Cruciferae/Brassicaceae) .................................................................... 61
3.2.5 Lunaria (Lunaria annua L, Brassicaciae/Crusiferae) ............................. 62
3.2.6 Saffl ower (Carthamus tinctorius L, Compositae) ................................. 64
3.3 The lignocellulosic crops ............................................................................. 66
3.3.1 Cardoon (Cynara cardunculus L, Compositae) ................................... 66
3.3.2 Giant reed ......................................................................................... 68
3.3.3 Miscanthus (Miscanthus x giganteus, Poaceae)................................... 72
3.3.4 Switchgrass (Panicum virgatum L, Poaceae) ....................................... 74
References ......................................................................................................... 76
4 Production of aquatic biomass and extraction of bio-oil ................................... 81
Angela Dibenedetto
4.1 Introduction ................................................................................................ 81
4.2 Characterization of aquatic biomass and its cultivation ............................... 82
4.2.1 Macro-algae ...................................................................................... 82
4.2.2 Micro-algae ....................................................................................... 84
4.3 Harvesting of aquatic biomass ..................................................................... 87
4.3.1 Macro-algae ...................................................................................... 87
4.3.2 Micro-algae ....................................................................................... 88
4.4 Composition of aquatic biomass .................................................................. 89
4.5 Bio-oil content of aquatic biomass .............................................................. 91
4.6 The quality of bio-oil ................................................................................... 92
4.7 Technologies for algal oil and chemicals extraction ..................................... 94
4.7.1 Conventional solvent extraction ......................................................... 95
4.7.2 Supercritical fl uid extraction (SFE)...................................................... 95
4.7.3 Mechanical extraction ....................................................................... 96
4.7.4 Biological extraction .......................................................................... 96
4.8 Conclusions ................................................................................................ 96
References ......................................................................................................... 97
5 Biomass pretreatment: separation of cellulose, hemicellulose,
and lignin – existing technologies and perspectives .......................................... 101
Anna Maria Raspolli Galletti and Claudia Antonetti
5.1 Introduction ............................................................................................... 101
5.2 Biomass composition ................................................................................. 101
Contents (cid:2) vii
5.3 Physical and physicochemical pretreatments of biomass ............................ 102
5.3.1 Mechanical pretreatments................................................................. 102
5.3.2 Irradiation ......................................................................................... 103
5.3.3 Pyrolysis ........................................................................................... 104
5.3.4 Torrefaction ...................................................................................... 105
5.3.5 Steam explosion and liquid hot water ............................................... 105
5.3.6 Ammonia fi ber explosion .................................................................. 107
5.3.7 CO explosion .................................................................................. 108
2
5.4 Chemical pretreatments .............................................................................. 109
5.4.1 Alkaline hydrolysis ........................................................................... 109
5.4.2 Acid hydrolysis ................................................................................. 111
5.4.3 Ozonolysis ....................................................................................... 112
5.4.4 Organosolv processes ....................................................................... 113
5.4.5 Ionic liquid pretreatments ................................................................. 114
5.5 Conclusions and perspectives ..................................................................... 114
References ........................................................................................................ 117
6 Conversion of cellulose and hemicellulose into
platform molecules: chemical routes ................................................................ 123
David Serrano, Juan M. Coronado, and Juan A. Melero
6.1 Introduction ............................................................................................... 123
6.2 Selective transformation of sugars to platform molecules ............................ 124
6.2.1 Dehydration of hexoses into furan
compounds: 5-HMF and derivates .................................................... 124
6.2.2 Dehydration of pentoses into furans: synthesis
of furfural and derivatives ................................................................. 130
6.3 Catalytic routes for the aqueous-phase conversion of sugars
and derivatives into liquid hydrocarbons for transportation fuels ................ 132
6.3.1 Conversion of HMF and furfural platform chemicals into
hydrocarbon fuels ............................................................................. 132
6.3.2 Aqueous phase reforming of sugars ................................................... 134
6.3.3 Conversion of levulinic acid platform into hydrocarbon fuels ........... 136
6.4 Future outlook ............................................................................................ 136
References ........................................................................................................ 138
7 Conversion of cellulose, hemicellulose, and lignin into
platform molecules: biotechnological approach ............................................... 141
Gudbrand Rødsrud, Anders Frölander, Anders Sjöde, and Martin Lersch
7.1 History of bioethanol from wood ................................................................ 141
7.2 Case history: 40 years experience from running a biorefi nery ..................... 143
7.2.1 From commodity pulp to a range of specialty chemicals ................... 143
7.2.2 Profi tability from a range of co-products ........................................... 145
7.2.3 Composition of feedstock is given – demand is never in balance ...... 147
7.2.4 Continuous need for product development ....................................... 147
7.2.5 High-value biomass for products – low-value
organic waste for energy ................................................................... 147
7.2.6 Long-term commitment to sustainability has given results ................. 148
viii (cid:2) Contents
7.3 The sugar platform – biotechnological approach ......................................... 150
7.3.1 Less-expensive feedstocks for low-value
products – high-value coproducts from costly feedstocks .................. 152
7.3.2 The sugar platform process train and the major challenges ................ 153
7.3.3 The challenge of making chemicals and materials from lignin ........... 157
7.3.4 Fermentation, distilling, and dewatering ........................................... 158
7.4 The BALI pretreatment and separation process ............................................ 160
7.4.1 The BALI process – technical description .......................................... 160
7.4.2 The BALI process – benefi cial enzymatic hydrolysis .......................... 160
7.4.3 The BALI process – high-value products from all three main
components of the lignocellulosic feedstock ..................................... 162
7.5 Pilot plant for the BALI process ................................................................... 165
Acknowledgements ........................................................................................... 165
References ........................................................................................................ 165
8 Conversion of lignin: chemical technologies and
biotechnologies – oxidative strategies in lignin upgrade ................................... 167
Silvia Decina and Claudia Crestini
8.1 Introduction ............................................................................................... 167
8.2 Lignin structure, pretreatment, and use in the biorefi nery ........................... 169
8.2.1 Lignin structure ................................................................................. 169
8.2.2 Lignin pretreatment .......................................................................... 171
8.2.3 Potential sources of biorefi nery lignin ............................................... 174
8.2.4 The use of lignin in current and future biorefi nery schemes ............... 178
8.3 O xidative strategies in lignin chemistry: a new
environmentally friendly approach for the valorization of lignin ................. 181
8.3.1 Oxidation of lignin by biocatalysis processes .................................... 182
8.3.2 Catalysis ........................................................................................... 190
8.4 Concluding remarks ................................................................................... 200
References ........................................................................................................ 202
9 Process development and metabolic engineering for
bioethanol production from lignocellulosic biomass ........................................ 207
Gennaro Agrimi, Isabella Pisano, and Luigi Palmieri
9.1 Introduction ............................................................................................... 207
9.2 Pretreatment ............................................................................................... 208
9.3 Enzymatic hydrolysis and detoxifi cation ..................................................... 208
9.3.1 Enzymatic hydrolysis ........................................................................ 209
9.3.2 Fermentation inhibitors ..................................................................... 210
9.3.3 Detoxifi cation ................................................................................... 211
9.4 Fermentation .............................................................................................. 212
9.4.1 Separate hydrolysis and fermentation (SHF) ...................................... 212
9.4.2 Simultaneous saccharifi cation and fermentation (SSF) ....................... 213
9.4.3 Simultaneous saccharifi cation and co-fermentation (SSCF) ............... 214
9.4.4 Consolidated bioprocessing (CBP) .................................................... 214
Contents (cid:2) ix
9.5 Microbial biocatalysts ................................................................................ 215
9.5.1 Escherichia coli ................................................................................. 216
9.5.2 Z. mobilis .......................................................................................... 217
9.5.3 Other bacteria .................................................................................. 218
9.5.4 S. cerevisiae ...................................................................................... 218
9.5.5 Other yeasts ..................................................................................... 224
References ........................................................................................................ 225
10 Catalytic conversion of biosourced raw materials:
homogeneous catalysis ................................................................................... 231
Cédric Fischmeister, Christian Bruneau, Karine De Oliveira Vigier, and
François Jérôme
10.1 Lignocellulosic biomass ......................................................................... 232
10.1.1 Acid-catalyzed fractionation of lignocellulosic biomass .............. 233
10.1.2 Homogeneously catalyzed conversion of
cellulose and related polysaccharides......................................... 234
10.1.3 Synergistic effect between homogeneous
and heterogeneous catalysis ....................................................... 239
10.2 Vegetable oils ......................................................................................... 243
10.2.1 Catalytic conversion of renewable alkenes ................................. 244
10.2.2 Catalytic conversion of glycerol.................................................. 252
10.3 Conclusion............................................................................................. 255
References ...................................................................................................... 257
11 Catalytic conversion of oils extracted from seeds: from polyunsaturated long
chains to functional molecules ....................................................................... 263
Eva Garrier and Dirk Packet
11.1 Introduction ........................................................................................... 263
11.2 Reactions occurring on the carboxyl group of fatty
acids/esters............................................................................................. 263
11.2.1 Hydrolysis .................................................................................. 263
11.2.2 Transesterifi cation ....................................................................... 265
11.2.3 Esterifi cation ............................................................................... 266
11.2.4 Amidation .................................................................................. 267
11.2.5 Reduction of the carboxyl function ............................................. 268
11.2.6 Polycondensation ....................................................................... 269
11.3 Reactions occurring on the double bond(s)
(unsaturation) of fatty acids/esters ........................................................... 270
11.3.1 Hydrogenation ........................................................................... 270
11.3.2 Dimerization .............................................................................. 271
11.3.3 Epoxidation ................................................................................ 272
11.3.4 Metathesis .................................................................................. 274
11.3.5 Isomerization ............................................................................. 276
11.4 Conclusion............................................................................................. 276
References ...................................................................................................... 277