Thermochemical Conversion of Biomass for the Production of Energy and Chemicals

190 Pages·2016·11.96 MB·English

by  Anthony Dufour

Thermochemical Conversion of Biomass for
the Production of Energy and Chemicals

FOCUS SERIES
Series Editor Alain Dollet
Thermochemical Conversion of
Biomass for the Production of
Energy and Chemicals

Anthony Dufour
First published 2016 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.
Apart from any fair dealing for the purposes of research or private study, or criticism or review, as
permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced,
stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers,
or in the case of reprographic reproduction in accordance with the terms and licenses issued by the
CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the
undermentioned address:
ISTE Ltd John Wiley & Sons, Inc.
27-37 St George’s Road 111 River Street
London SW19 4EU Hoboken, NJ 07030
UK USA
www.iste.co.uk www.wiley.com

© ISTE Ltd 2016
The rights of Anthony Dufour to be identified as the author of this work have been asserted by him in
accordance with the Copyright, Designs and Patents Act 1988.
Library of Congress Control Number: 2015957826

British Library Cataloguing-in-Publication Data
A CIP record for this book is available from the British Library
ISSN 2051-2481 (Print)
ISSN 2051-249X (Online)
ISBN 978-1-84821-823-9
Contents
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Chapter 1. Bioenergy Chain and Process Scales . . . . . . . . . . . . . . . 1
1.1. Biomass production and ecological issues . . . . . . . . . . . . . . . . . . . . 1
1.2. Modeling of bioenergy chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1. Global model of the whole bioenergy chain . . . . . . . . . . . . . . . . 3
1.2.2. Model of a gasification plant . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.3. Models of biorefinery sections . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3. Technical–economical analysis of bioenergy chains . . . . . . . . . . . . . 15
1.3.1. Technical–economical analysis of power production . . . . . . . . . . 15
1.3.2. Technical–economical analysis of heat production . . . . . . . . . . . 18
1.4. Life-cycle and multicriteria assessment of bioenergy chains. . . . . . . . 20
1.4.1. Methodology of life-cycle assessment
applied to bioenergy routes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.4.2. Life-cycle assessment of heat production from biomass . . . . . . . . 21
1.4.3. Various aspects of the bioenergy chain . . . . . . . . . . . . . . . . . . . . 24
1.4.4. An example of a multicriteria discussion on a bioenergy
route: the sequestration of biochar to mitigate climate change . . . . . . . . 25
Chapter 2. Reactor Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1. Introduction about the reactions occurring
in biomass thermochemical reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2. Reactors for biomass combustion . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2.1. Basics of biomass composition, drying and combustion . . . . . . . . 32
2.2.2. Technologies of biomass combustion . . . . . . . . . . . . . . . . . . . . . 35
vi Thermochemical Conversion of Biomass for the Production of Energy and Chemicals
2.3. Reactors for biomass gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.1. Main applications for syngas produced
from biomass gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.2. Different type of reactors for biomass gasification . . . . . . . . . . . . . 39
2.3.3. Purification and valorization of syngas . . . . . . . . . . . . . . . . . . . . . 44
2.3.4. Detailed modeling of a dual fluidized-bed gasifier . . . . . . . . . . . . . 47
2.3.5. Methodology for modeling tar formation
and conversion in a fluidized-bed reactor . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4. Reactors for biomass pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.4.1. Wood torrefaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.4.2. Char uses and production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.4.3. Pyrolysis bio-oils uses and production . . . . . . . . . . . . . . . . . . . . . 56
2.5. Reactors for biomass liquefaction . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Chapter 3. Particle Scale and Mesoscale ...................... 67
3.1. Introduction on the main mechanisms
occurring during wood pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.2. Physical–chemical mechanism of pyrolysis at the particle scale . . . . . . 68
3.2.1. Main characteristic times of phenomena
occurring during pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2.2. Modeling intraparticle mechanisms of biomass pyrolysis . . . . . . . . 71
3.2.3. Heat of biomass pyrolysis studied by calorimetry . . . . . . . . . . . . . 74
3.3. Evolution of polymer network in biomass at the mesoscale . . . . . . . . . 78
3.3.1. In situ analysis by 1H NMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.3.2. In situ analysis by rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.3.3. Relations between 1H NMR and rheology analysis . . . . . . . . . . . . 87
3.4. Structure of a char particle and mechanisms of its oxidation . . . . . . . . 89
Chapter 4. Molecular Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.1. Introduction on the variability of biomass composition and
the decoupling of reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2. Chemical structure of lignocellulosic biomass . . . . . . . . . . . . . . . . . . 94
4.3. Chemical mechanisms of primary pyrolysis . . . . . . . . . . . . . . . . . . . . 96
4.3.1. Chemical mechanism of cellulose pyrolysis . . . . . . . . . . . . . . . . . 96
4.3.2. Chemical mechanism of hemicellulose pyrolysis . . . . . . . . . . . . . . 98
4.3.3. Chemical mechanism of lignin pyrolysis . . . . . . . . . . . . . . . . . . . 98
4.3.4. Analysis of biomass primary tar by
online soft photoionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Contents vii
4.3.5. Analysis of bio-oils by high-resolution mass
spectrometry and GC*GC/MS-FID . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.3.6. Analysis of biomass and biochar by solid-state nuclear magnetic
resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.4. Molecular mechanisms of gas-phase reactions . . . . . . . . . . . . . . . . . . 109
4.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.4.2. Gas-phase conversion of model compounds . . . . . . . . . . . . . . . . . 110
4.4.3. Gas-phase conversion of real primary tar . . . . . . . . . . . . . . . . . . . 112
4.4.4. Gas-phase conversion of methane in a syngas . . . . . . . . . . . . . . . . 116
4.5. Molecular mechanisms of catalytic reactions . . . . . . . . . . . . . . . . . . . 117
4.5.1. Catalytic fast pyrolysis of biomass . . . . . . . . . . . . . . . . . . . . . . . . 117
4.5.2. Catalytic reforming of tar to produce a syngas . . . . . . . . . . . . . . . 119
4.5.3. Catalytic hydrodeoxygenation of bio-oils . . . . . . . . . . . . . . . . . . . 122
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157