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Literature Review of Physical and Chemical Pretreatment Processes for Lignocellulosic Biomass

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Literature Review of Physical and Chemical Pretreatment Processes for Lignocellulosic Biomass Literature review of physical and chemical pretreatment processes for lignocellulosic biomass Paulien Harmsen1, Wouter Huijgen2, Laura Bermudez3, Robert Bakker1 1) Wageningen UR Food & Biobased Research (WUR-FBR, NL) 2) Energy Research Centre of the Netherlands (ECN, NL) 3) Abengoa Bioenergía Nuevas Tecnologías (ABNT, ES) September 2010, Report 1184 Colophon Title Literature review of physical and chemical pretreatment processes for lignocellulosic biomass Author(s) Paulien Harmsen, Wouter Huijgen (ECN), Laura Bermudez (ABNT), Robert Bakker Number 1184 ISBN-number 978-90-8585-757-0 Date of publication September 2010 Confidentiality No OPD code - Approved by Rene van Ree Wageningen UR Food & Biobased Research P.O. Box 17 NL-6700 AA Wageningen Tel: +31 (0)317 480 084 E-mail: [email protected] Internet: www.wur.nl © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek All rights reserved. No part of this publication may be reproduced, stored in a retrieval system of any nature, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the publisher. The publisher does not accept any liability for inaccuracies in this report. 2 © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek Preface This literature review was performed within the BioSynergy project (2007-2010). BioSynergy is a European Integrated Project supported through the Sixth Framework Programme for Research and Technological Development (038994-SES6). BioSynergy stands for “BIOmass for the market competitive and environmentally friendly SYNthesis of bio-products together with the production of secondary enERGY carriers through the biorefinery approach”. Within the BioSynergy project the overall goal of the pretreatment routes being developed is to convert raw lignocellulosic biomass into its composing sugars and lignin in a market competitive and environmentally sustainable way. This report reviews lignocellulose pretreatment in general as well as specific pretreatment technologies that are developed within the BioSynergy project including steam explosion (ABNT), mechanical/alkaline fractionation (WUR) and organosolv fractionation (ECN). In addition to these pretreatment technologies, other pretreatment technologies are studied within the BioSynergy project such as acetic/formic acid pretreatment and mild- and strong acid pretreatment. © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek 3 Content Preface 3 1 Introduction 6 2 Physical and chemical characteristics of lignocellulosic biomass 7 2.1 Composition 7 2.2 Internal structure - physical properties 8 2.2.1 Cellulose 8 2.2.2 Hemicellulose 10 2.2.3 Lignin 11 2.2.4 Lignocellulose 12 2.3 Chemical interaction between components 13 2.3.1 Intrapolymer linkages 13 2.3.2 Interpolymer linkages 14 2.3.3 Functional groups and chemical properties of lignocellulose components 14 2.4 Formation of fermentation inhibitors 18 2.4.1 Sugar degradation products 19 2.4.2 Lignin degradation products 19 2.4.3 Acetic acid 19 2.4.4 2.4.4 Inhibitory extractives 20 2.4.5 Heavy metal ions 20 2.4.6 Summary 20 3 Overview pretreatment routes 21 3.1 Introduction 21 3.2 Mechanical pretreatment 22 3.2.1 Milling 22 3.2.2 Ultrasonic pretreatment 22 3.3 Chemical pretreatment 22 3.3.1 Liquid hot water 22 3.3.2 Weak acid hydrolysis 23 3.3.3 Strong acid hydrolysis 23 3.3.4 Alkaline hydrolysis 23 3.3.5 Organosolv 25 3.3.6 Oxidative delignification 25 3.3.7 Room Temperature Ionic Liquids (RTIL) 26 3.4 Combined chemical and mechanical pretreatment 27 3.4.1 Steam explosion 27 3.4.2 Ammonia fibre explosion (AFEX) 27 3.4.3 CO2 explosion 27 3.4.4 Mechanical/alkaline pretreatment 28 4 © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek 3.5 Biological pretreatment 29 3.6 Economic analysis of pretreatment routes 29 3.7 Conclusions 30 4 Concluding remarks and future perspectives 32 References 34 Summary 42 Acknowledgements 44 Annex A: Overview literature studies pretreatment technologies 45 Annex B: Organosolv 49 Annex C: Mechanical/alkaline pretreatment 53 © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek 5 1 Introduction Lignocellulose is the most abundant renewable biomass with a worldwide annual production of 1x1010 MT (Sánchez and Cardona, 2008). Lignocellulosic biomass is composed of cellulose, hemicellulose and lignin, as well as other minor components. Both the cellulose and hemicellulose fractions are polymers of sugars, and thereby a potential source of fermentable sugars, or other processes that convert sugars into products. Hemicellulose can be readily hydrolysed under mild acid or alkaline conditions. The cellulose fraction is more resistant and therefore requires more rigorous treatment. After initial biomass processing by milling, the production of fermentable sugars is usually approached in two steps: 1. A pretreatment process in which the cellulose polymers are made accessible for further conversion. In this step hydrolysis of hemicellulose may occur (depending on the process conditions) as well as separation of the lignin fraction (for production of chemicals, combined heat and power production or other purposes); 2. Enzymatic cellulose hydrolysis, using cellulase enzyme cocktails produced on location or acquired from enzyme manufacturers. Obstacles in the existing pretreatment processes include insufficient separation of cellulose and lignin (which reduces the effectiveness of subsequent enzymatic cellulose hydrolysis), formation of by-products that inhibit ethanol fermentation (e.g. acetic acid from hemicellulose, furans from sugars and phenolic compounds from the lignin fraction), high use of chemicals and/or energy, and considerable waste production. Research is focussed on converting biomass into its constituents in a market competitive and environmentally sustainable way. This literature review provides an overview of available pretreatment technologies. The literature review is divided into three major chapters. In Chapter 2, physical and chemical properties of lignocellulose that are relevant to pretreatment are reviewed. Subsequently, Chapter 3 presents a general overview of different pretreatment pathways for lignocellulose. Finally, Chapter 4 describes in more detail two pretreatment processes that were evaluated during the BioSynergy project. Furthermore, a final chapter with concluding remarks and recommendations is included. 6 © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek 2 Physical and chemical characteristics of lignocellulosic biomass 2.1 Composition The term "lignocellulosic biomass" is used when referring to higher plants, softwood or hardwood. The main components of the lignocellulosic materials are cellulose, hemicellulose and lignin. Cellulose is a major structural component of cell walls, and it provides mechanical strength and chemical stability to plants. Solar energy is absorbed through the process of photosynthesis and stored in the form of cellulose. (Raven et al.,1992) Hemicellulose is a copolymer of different C5 and C6 sugars that also exist in the plant cell wall. Lignin is polymer of aromatic compounds produced through a biosynthetic process and forms a protective layer for the plant walls. In nature, the above substances grow and decay during the year. It has been estimated that around 7.5x1010 tonnes of cellulose are consumed and regenerated every year (Kirk-Otmer, 2001). It is thereby the most abundant organic compound in the world. Apart from the three basic chemical compounds that lignocellulose consists of, water is also present in the complex. Furthermore, minor amounts of proteins, minerals and other components can be found in the lignocellulose composition as well. The composition of lignocellulose highly depends on its source. There is a significant variation of the lignin and (hemi)cellulose content of lignocellulose depending on whether it is derived from hardwood, softwood, or grasses. Table 1 summarizes the composition of lignocellulose encountered in the most common sources of biomass. Table 1 Composition of lignocellulose in several sources on dry basis (Sun and Cheng, 2002) Lignocellulosic materials Cellulose (%) Hemicellulose (%) Lignin (%) Hardwoods stems 40–55 24–40 18–25 Softwood stems 45–50 25–35 25–35 Nut shells 25–30 25–30 30–40 Corn cobs 45 35 15 Grasses 25–40 35–50 10–30 Paper 85–99 0 0–15 Wheat straw 30 50 15 Sorted refuse 60 20 20 Leaves 15–20 80–85 0 Cotton seed hairs 80–95 5–20 0 Newspaper 40–55 25–40 18–30 Waste papers from chemical pulps 60–70 10–20 5–10 Primary wastewater solids 8–15 NA 24–29 Swine waste 6.0 28 NA Solid cattle manure 1.6–4.7 1.4–3.3 2.7–5.7 Coastal Bermuda grass 25 35.7 6.4 Switchgrass 45 31.4 12.0 © Wageningen UR Food & Biobased Research, institute within the legal entity Stichting Dienst Landbouwkundig Onderzoek 7 2.2 Internal structure - physical properties Lignocellulosic biomass has a complex internal structure. It is comprised of a number of major components that have, in their turn, also complex structures. To obtain a clear picture of the material, an analysis of the structure of each main component is made in this section, concluding with the description of the structure of lignocellulose
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