Lignin as a renewable aromatic resource for the chemical industry

196 Pages·2011·5.19 MB·English

Lignin as a renewable aromatic
resource for the chemical industry

Richard Johannes Antonius Gosselink

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Chapter

Thesis committee

Thesis supervisor
Prof. dr. J.P.M. Sanders
Professor of Valorisation of Plant Production Chains
Wageningen University

Thesis co-supervisors
Prof. dr. G. Gellerstedt
Professor of Wood Chemistry, Department of Fibre and Polymer Technology
Royal Institute of Technology (KTH), Stockholm, Sweden

Dr. J.E.G. van Dam
Senior scientist, Department of Biomass pretreatment and fibre technology
Wageningen UR Food & Biobased Research

Other members
Prof. dr. J.T. Zuilhof, Wageningen University
Prof. dr. S.R.A. Kersten, University of Twente, Enschede
Dr. P. Berben, BASF Nederland B.V., De Meern
Dr. P. Axegård, Innventia, Stockholm, Sweden

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This research was conducted under the auspices of the Graduate School VLAG

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Lignin as a renewable aromatic
resource for the chemical industry

Richard Johannes Antonius Gosselink

Thesis

Submitted in fulfilment of the requirements for the degree of doctor
at Wageningen University
by the authority of the Rector Magnificus
Prof. dr. M.J. Kropff,
in the presence of the
Thesis Committee appointed by the Academic Board
to be defended in public
on Wednesday 7 December 2011 3
at 1.30 p.m. in the Aula.

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Chapter

Richard Johannes Antonius Gosselink
Lignin as a renewable aromatic resource for the chemical industry
195 pages

PhD Thesis, Wageningen University, Wageningen, NL (2011)
With propositions, and summaries in English and Dutch

ISBN: 978-94-6173-100-5
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Table of contents

Chapter 1 Introduction: Lignin valorization for wood adhesives
and aromatic chemicals 7

Chapter 2 Development of a universal method for the molar mass
determination of lignin 53

Chapter 3 Fractionation, analysis, and PCA modeling of properties
of four technical lignins for prediction of their application
potential in binders 91

Chapter 4 Effect of periodate on lignin for wood adhesive application 109

Chapter 5 Lignin depolymerization in supercritical carbon dioxide/
acetone/water fluid for the production of aromatic chemicals 125

Chapter 6 Discussion and perspectives 145

Summary 167

Samenvatting 171

Acknowledgements / Dankwoord 175

Curriculum vitae 179

List of publications 181

Overview of completed training activities 185

Glossary 187
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Chapter

Voor Ellis, Kay, Ryan, mijn ouders en mijn schoonouders

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Chapter 1
Introduction: Lignin valorization for wood
adhesives and aromatic chemicals

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Chapter 1
This chapter describes the background, context and topics of this thesis. Options for
lignin valorization makes sense especially when this issue is positioned within the wider
context of biorefinery and the biobased economy. These terms and definitions will be
subsequently described followed by an introduction of lignin as a biopolymer and its
versatile and intriguing properties will be discussed. This leads to the choices made in
this thesis research, which is outlined at the end of this introduction.

1.1 General introduction

Today, we use and rely on many commodity consumer products like energy, materials,
plastics, chemicals and transportation fuels. These consumer products largely originate
from fossil resources which will be depleted sooner or later and contribute to CO
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emissions and climate change. Therefore, alternatives are sought with low carbon
emissions and these are inexhaustible resources like wind, solar energy and plant
derived biomass. While energy can be produced by wind, solar systems and biomass,
the other mentioned consumer products can only be made from biomass. Also to secure
the energy supply, which is now unreliable due to unstable fossil oil supply chains in
politically unstable countries and the expected increased demand for oil from emerging
economies, plant biomass can be a suitable alternative source.
This sustainable resource is to be used within the biobased economy which is
expected in the years to come to gradually take a larger share compared to the fossil-
based economy. The biobased economy is not just the implementation of innovative
technologies using renewable resources, but it will be a real transition with a broad and
high impact on society at different levels (Langeveld and Sanders 2010). To promote
the implementation of the biobased economy the governments of many countries have
set ambitious goals for replacing fossil derived fuel and chemical commodities by
biomass (Table 1.1).

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Introduction
Table 1.1 Indicative goals (%) for fossil replacement by biomass.
Region Transportation fuels Chemical commodities Reference
2020 2030 2040 2020 2030 2040
NL 10 30 30 30 20-45 Dutch ministry of Economic Affairs
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and Platform Biobased Raw Materials
(Ree van & Annevelink, 2007)
EU 10 25 EC (2009); ERTRAC (2010)
US 10 20 18 25 Perlack et al. (2005)

Lignocellulosic biomass offers many possibilities as feedstock for the energy sector but
also for the chemical industry due to its chemical composition, abundant availability
and relative low costs when the conversion to products can be carried out in an
economic and sustainable manner. This abundant availability is supported by the large
numbers of world-wide annual lignocellulosic biomass production of about 200 billion
tons (Zhang 2008) compared to the 0.3 billion tons of organic chemicals yearly
produced by the chemical industry (Haveren et al. 2008). Other advantages of biomass
as a feedstock are the lowered demand for crude oil supplies and less dependence on
politically unstable oil exporting countries. Furthermore, sustainability criteria and
fixation of atmospheric CO are important drivers in using biomass resources.
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Disadvantages (or challenges) in using biomass are the need for fertile arable land and
more complicated collection and logistic systems to mobilize this relatively low density
organic material compared to crude oil. As biomass is commonly heterogeneous and has
a different composition to fossil resources different processing conditions are needed.
New opportunities in the production of functionalized chemicals and materials can be
found due to the carbohydrate, protein and phenolic building blocks contained in
biomass. In contrast to petrochemical resources that need to be cracked, decomposed
and functionalized, biomass often needs to be partially defunctionalized.
The key to the most efficient use of biomass is to design a suitable and
sustainable integral biorefinery to separate biomass in its major compounds in order to
generate the highest value added for all fractions. According to the International Energy
Agency (IEA) Bioenergy Task 42 Biorefinery: “A biorefinery is the sustainable
processing of biomass into a spectrum of marketable products ranging from energy,
food, feed, chemicals and materials applications” (Figure 1.1).
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Chapter 1

Figure 1.1 Biorefinery and its role in the transformation of biomass (IEA Task 42 Biorefineries 2010).

Schematically, a fully integrated agro-biofuel-biomaterial-biopower biorefinery using
sustainable technologies is given in Figure 1.2. Ragauskas et al. (2006) stated that for a
widely applicable lignocellulosic biorefinery not only the carbohydrates are of interest
but the value added application of the lignin component should also be addressed.

Figure 1.2 The fully integrated agro-biofuel-biomaterial-biopower cycle for sustainable technologies
(Ragauskas et al. 2006).

An example of such an industrial biorefinery is the well established sustainable
biorefinery operated by Borregaard in Norway as depicted in Figure 1.3. This
biorefinery separates woody biomass into cellulose specialty fibres (dissolving
cellulose) and lignosulfonates. Additionally, part of the dissolved lignin is converted via
catalytic oxidation to vanillin and dissolved carbohydrates are fermented into the second
generation (2G) biofuel bioethanol. In this way more than 90% of the wood input is
used as marketable products.

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