Biomass Valorization Sustainable Methods For The Production of Chemicals Davide Ravelli Full Chapter PDF

Biomass Valorization: Sustainable
Methods for the Production of

Chemicals Davide Ravelli
Visit to download the full and correct content document:
https://ebookmass.com/product/biomass-valorization-sustainable-methods-for-the-pro
duction-of-chemicals-davide-ravelli/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Biomass, Biofuels, Biochemicals – Biochemicals and

Materials Production From Sustainable Biomass Resources
Hu Li
https://ebookmass.com/product/biomass-biofuels-biochemicals-
biochemicals-and-materials-production-from-sustainable-biomass-
resources-hu-li/
Valorization of Microalgal Biomass and Wastewater

Treatment Suhaib A. Bandh
https://ebookmass.com/product/valorization-of-microalgal-biomass-
and-wastewater-treatment-suhaib-a-bandh/
Strategic Planning for the Sustainable Production of

Biofuels Jose Ezequiel Santibanez-Aguilar
https://ebookmass.com/product/strategic-planning-for-the-
sustainable-production-of-biofuels-jose-ezequiel-santibanez-
aguilar/
Genetic and Metabolic Engineering for Improved Biofuel

Production from Lignocellulosic Biomass Arindam Kuila
https://ebookmass.com/product/genetic-and-metabolic-engineering-
for-improved-biofuel-production-from-lignocellulosic-biomass-
arindam-kuila/
Biomass-Derived Carbon Materials: Production and
Applications Alagarsamy Pandikumar
https://ebookmass.com/product/biomass-derived-carbon-materials-
production-and-applications-alagarsamy-pandikumar/
Hydrocarbon Biorefinery: Sustainable Processing of

Biomass for Hydrocarbon Biofuels 1st Edition Sunil
Kumar Maity (Editor)
https://ebookmass.com/product/hydrocarbon-biorefinery-
sustainable-processing-of-biomass-for-hydrocarbon-biofuels-1st-
edition-sunil-kumar-maity-editor/
Agri-Waste and Microbes for Production of Sustainable

Nanomaterials Kamel A. Abd-Elsalam
https://ebookmass.com/product/agri-waste-and-microbes-for-
production-of-sustainable-nanomaterials-kamel-a-abd-elsalam/
Sustainable Production System: Eco-development versus

Sustainable Development Clément Morlat
https://ebookmass.com/product/sustainable-production-system-eco-
development-versus-sustainable-development-clement-morlat/
Heating, Cooling, Lighting: Sustainable Design Methods

for Architects 4th
https://ebookmass.com/product/heating-cooling-lighting-
sustainable-design-methods-for-architects-4th/
Biomass Valorization
Biomass Valorization
Sustainable Methods for the Production of Chemicals
Edited by
Davide Ravelli
Chiara Samorì
Editors All books published by WILEY-VCH
are carefully produced. Nevertheless,
Prof. Davide Ravelli authors, editors, and publisher do not
University of Pavia warrant the information contained in
Department of Chemistry these books, including this book, to
viale Taramelli 12 be free of errors. Readers are advised
27100 Pavia to keep in mind that statements, data,
Italy illustrations, procedural details or other
items may inadvertently be inaccurate.
Prof. Chiara Samorì
University of Bologna Library of Congress Card No.:
Department of Chemistry applied for
“Giacomo Ciamician”
via S. Alberto 163 British Library Cataloguing-in-Publication
48123 Ravenna Data
Italy A catalogue record for this book is
available from the British Library.
Cover © TB studio/Shutterstock
Bibliographic information published by
the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed
bibliographic data are available on the
Internet at <http://dnb.d-nb.de>.
© 2021 WILEY-VCH GmbH, Boschstr.

12, 69469 Weinheim, Germany
All rights reserved (including those of

translation into other languages). No
part of this book may be reproduced in
any form – by photoprinting,
microfilm, or any other means – nor
transmitted or translated into a
machine language without written
permission from the publishers.
Registered names, trademarks, etc.
used in this book, even when not
specifically marked as such, are not to
be considered unprotected by law.
Print ISBN: 978-3-527-34717-9

ePDF ISBN: 978-3-527-82501-1
ePub ISBN: 978-3-527-82503-5
oBook ISBN: 978-3-527-82502-8
Typesetting SPi Global, Chennai, India
Printed on acid-free paper
10 9 8 7 6 5 4 3 2 1
v
Contents
Foreword xi
Preface xiii
1 Role of Biomass in the Production of Chemicals 1

Layla Filiciotto, Evan Pfab and Rafael Luque
1.1 Introduction 1
1.2 Biomass Valorization 3
1.3 Lignocellulosic Biomass 5
1.4 Key Biomolecules 6
1.5 Solvents 10
1.6 Pretreatment of Lignocelluloses 12
1.7 Conclusions and Perspectives 15
References 15
Section I Catalytic Strategies 23
2 Biomass Processing via Acid Catalysis 25

Iurii Bodachivskyi, Unnikrishnan Kuzhiumparambil and D. Bradley G.
Williams
2.1 Introduction 25
2.1.1 Is an Acid the Best Catalyst? 26
2.2 Acid-Catalyzed Processing of Cellulosic Polysaccharides 29
2.3 Acid-Catalyzed Processing of Lignin 44
References 47
3 Biomass Processing via Base Catalysis 57

Lichen Liu, Maria J. Climent and Sara Iborra
3.1 Introduction 57
3.2 Aldol Condensation 60
3.2.1 Aldol Condensation of Furanic Aldehydes 60
3.2.2 Self-Aldol Condensation of Acetone 63
vi Contents
3.2.3 Aldol Condensation Between Alcohols: Guerbet Coupling Reaction 64

3.3 Ketonization Reaction of Carboxylic Acids 65
3.4 Transesterification Reaction 68
3.4.1 Biodiesel Production 68
3.4.2 High Value-Added Chemicals from Transesterification Reactions 70
References 74
4 Biomass Processing via Metal Catalysis 81

Sofia Capelli and Alberto Villa
4.1 Introduction 81
4.2 Synthetic Strategies for Supported Metal Nanoparticles 83
4.2.1 Impregnation 83
4.2.2 Precipitation 84
4.2.3 Sol Immobilization 85
4.3 Furfural 86
4.3.1 Furfural Hydrogenation 87
4.3.1.1 Furfural to Furfuryl Alcohol 87
4.3.1.2 Furfural to Tetrahydrofurfuryl Alcohol 88
4.3.1.3 Furfural to Pentanediols 89
4.3.1.4 Furfural to 2-Methylfuran 90
4.3.2 Furfural Oxidation 92
4.3.2.1 Furfural to Furoates 92
4.4 5-Hydroxymethylfurfural (HMF) 92
4.4.1 HMF Hydrogenation 93
4.4.1.1 HMF to 2,5-Dimethylfuran (DMF) 94
4.4.1.2 HMF to 2,5-Dihydroxymethyltetrahydrofuran (DHMTHF) 95
4.4.2 HMF Oxidation 96
4.4.2.1 HMF to 2,5-Furandicarboxylic Acid (FDCA) Using Monometallic
Systems 96
4.4.2.2 HMF Oxidation over Bimetallic Catalysts 100
References 103
5 Biomass Processing with Biocatalysis 113

Roger A. Sheldon
5.1 Introduction 113
5.2 Generations of Renewable Biomass: Advantages and Limitations 113
5.3 Advantages and Limitations of Biocatalysis 116
5.4 Enzyme Discovery and Optimization of Enzyme Performance 117
5.5 Enzyme Immobilization 118
5.5.1 Enzyme Immobilization by Cross-linking Enzyme Molecules 119
5.5.2 Advantages and Limitations of Cross-Linked Enzyme Aggregates
(CLEAs) 120
5.5.3 Magnetically Separable Immobilized Enzymes 120
Contents vii
5.6 Enzymatic Hydrolysis of Starch to Glucose 121

5.7 Enzymatic Depolymerization of Lignocellulose 122
5.8 Enzymatic Hydrolysis of Cellulose and Hemicellulose 123
5.8.1 Magnetizable Immobilized Enzymes in Lignocellulose Conversion 124
5.9 Enzymatic Hydrolysis of 3rd Generation (3G) Polysaccharides 124
5.10 Commodity Chemicals from Carbohydrates (Monosaccharides) 126
5.10.1 Fermentative Production of Commodity Chemicals 126
5.10.2 Deoxygenation via Dehydration of Carbohydrates to Furan
Derivatives 129
5.10.3 Polyethylene Furandicarboxylate (PEF) as a Renewable Alternative to
PET 129
5.10.4 Enzymatic Synthesis of Bio-based Polyesters 131
5.11 Enzymatic Conversions of Triglycerides: Production of Biodiesel and
Bulk Chemicals 132
References 133
Section II Thermal Strategies 147
6 Biomass Processing via Pyrolysis 149

Daniele Fabbri, Yunchao Li and Shurong Wang
6.1 Brief Introduction 149
6.2 Chemicals from Cellulose Pyrolysis 151
6.2.1 General Aspects 151
6.2.2 Levoglucosan 154
6.2.3 Levoglucosenone 156
6.2.4 LAC,
(1R,5S)-1-Hydroxy-3,6-Dioxabicydioxabicyclo-[3.2.1]octan-2-one 157
6.3 Chemicals from Lignin Pyrolysis 160
6.4 Pyrolysis of Biomass 161
6.4.1 Levoglucosan 161
6.4.1.1 Effects of Metal Oxides 162
6.4.1.2 Effects of Alkali and Alkaline Earth Metals 162
6.4.1.3 Effects of Acid Impregnation 162
6.4.1.4 Effects of Other Components 163
6.4.2 Levoglucosenone 163
6.4.2.1 Effects of Metal Chlorides 163
6.4.2.2 Effects of Acid Catalysts 163
6.4.2.3 Others 164
6.4.3 Furfural 164
6.4.4 Aromatic Hydrocarbons 167
6.4.5 Phenolic Compounds 169
References 171
viii Contents
7 Biomass Processing via Thermochemical–Biological Hybrid

Processes 181
Cristian Torri, Alessandro Girolamo Rombolà, Alisar Kiwan and Daniele
Fabbri
7.1.1 Hybrid Thermochemical/Biological Processing with Single-Strain
Microorganisms 183
7.1.2 Hybrid Thermochemical/Biological Processing with Microbial Mixed
Consortia (MMC) 183
7.2 Pyrolysis Products (PyP) from the Microorganism’s Standpoint 185
7.2.1 What Pyrolysis Can Do for Microorganisms: Yields and Bioavailability of
PyP 186
7.2.2 Viable Pathways According to Thermodynamics Laws 188
7.2.3 Rate of MMC Biological Conversions in Relationship with PyP
Treatment 191
7.2.4 Toxicity of PyP Toward MMC 193
7.3 Conversion of PyP with MMC: Survey of Experimental Evidence 198
7.3.1 Syngas Conversion to Methane 203
7.3.2 Syngas Conversion to H2 , Volatile Fatty Acids (VFA), and Alcohols 203
7.3.3 Conversion of Condensable PyP to Methane 205
7.3.4 Conversion of Condensable PyP to VFA and Other Intermediates 206
7.4 Feasible Pathways for Producing Chemicals from PyP with MMC 207
7.4.1 Hybrid Pyrolysis Fermentation and Extraction of Mixed
VFA/Alcohols 207
7.4.2 Alkaline Fermentation of Pyrolysis Products to VFA Salts, Ketonization,
and Hydrogenation to C3–C6 Mixed Alcohols 209
7.4.3 Alkaline Fermentation of Pyrolysis Products to VFA Salts and
Polyhydroxyalkanoates (PHA) Production via Aerobic MMC 211
7.4.4 Direct Alcohol Production by Means of Fermentation of PyP under High
Hydrogen Pressure 213
References 216
Section III Advanced/Unconventional Strategies 225
8 Biomass Processing via Electrochemical Means 227

Roman Latsuzbaia, Roel Johannes Martinus Bisselink, Marc Crockatt, Jan
Cornelis van der Waal and Earl Lawrence Vincent Goetheer
8.2 Electrochemical Conversion of Bio-Based Molecules 228
8.3 Conversion of Sugars 230
8.4 Conversion of Furanics 234
8.4.1 5-(Hydroxymethyl)furfural (5-HMF) 234
8.4.1.1 5-HMF Oxidation 235
Contents ix
8.4.1.2 5-HMF Reduction 238

8.4.2 Furfural 240
8.5 Conversion of Levulinic Acid 244
8.6 Conversion of Glycerol 246
8.7 Lignin Depolymerization 248
8.8 Scale-up of Electrosynthesis of Biomass-Derived Chemicals 248
References 254
9 Biomass Processing via Photochemical Means 265

Andrey Shatskiy and Markus D. Kärkäs
9.2 Fundamental Aspects of Photoredox Catalysis 266
9.3 Photochemical Valorization of Lignin 267
9.3.1 Strategies for Cα —Cβ Bond Cleavage 268
9.3.2 Strategies for Lignin Oxidation and Cβ —O Bond Cleavage 272
9.3.3 Strategies for Ar—O Bond Cleavage 278
References 282
10 Biomass Processing via Microwave Treatment 289

Roberto Rosa, Giancarlo Cravotto and Cristina Leonelli
10.2 Microwave–Matter Interaction: Advantages and Limitations in the
Processing of Biomass 291
10.3 Microwave Pyrolysis 296
10.4 Microwave-assisted Hydrolysis 299
10.5 Microwave-assisted Extraction of Phytochemical Compounds 303
References 307
11 Biomass Processing Assisted by Ultrasound 315

Cezar A. Bizzi, Daniel Santos, Gabrielle D. Iop and Erico M. M. Flores
11.2 Ultrasound Background 316
11.3 Ultrasound-Assisted Biomass Pretreatments 319
11.4 Ultrasound-Assisted Biomass Conversion 322
11.4.1 Thermochemical Conversion Assisted by Ultrasound 323
11.4.2 Biochemical Conversion Assisted by Ultrasound 324
11.4.3 Chemical Conversion (Synthesis) Assisted by Ultrasound 325
11.5 Ultrasound-Assisted Extraction of Value-Added Compounds 326
11.5.1 Ultrasound Contribution to Biomass Extraction Processes 326
11.5.2 Uses of Alternative Approaches for Biomass Extractions Assisted by
Ultrasound 328
11.6 Alternative Solvents 331
x Contents

References 333
12 Biomass Processing via Mechanochemical Means 343

George Margoutidis and Francesca M. Kerton
12.1 Overview and Introduction 343
12.1.1 Background to the Method 343
12.1.2 Properties of a Typical Laboratory Mixer/Mill 346
12.2 Crystallinity Reduction in Biopolymers via Mechanochemistry 348
12.3 Mechanochemical Transformations of Polysaccharides 352
12.3.1 Cellulose Depolymerization 352
12.3.2 Cellulose Modification Toward Composite Materials 355
12.3.3 Transformations of Chitin 355
12.4 Mechanochemical Transformations of Amino Acids, Nucleotides, and
Related Materials 357
12.5 Mechanochemical Treatment of Lignin 359
12.6 Biominerals from Mechanochemical Processing of Biomass 360
References 361
Section IV Closing Remarks 367
13 Industrial Perspectives of Biomass Processing 369

Tommaso Tabanelli and Fabrizio Cavani
13.1 Replacing Existing Petrochemicals with Alternatives from Biomass: An
Introduction 369
13.2 Oleochemical Biorefinery: A Consolidated and Multifaceted Example of
Biomass Processing 371
13.2.1 Biofuels and Coproduced Chemicals from Oils and Fats 371
13.2.2 Skeletal Isomerization of Unsaturated Fatty Acids for Isostearic Acid
Production 379
13.2.3 Bio-based Synthesis of Azelaic and Pelargonic Acids: A Renewable Route
Toward Bio-based Polyesters and Cosmetics 382
13.3 From Sugar to Bio-monomers: The Case of 2,5-Furandicarboxylic Acid
(FDCA) 385
13.4 From Bioethanol to Rubber: The Synthesis of Bio-butadiene 388
References 391
Index 411
xi
Foreword
Why bother with biomass conversion? It seems so difficult compared to converting

hydrocarbons into products. People used to think that we were about to run out of
fossil fuels, but that was a red herring – there is enough left in the ground to serve
us for hundreds of years. So, if running out of hydrocarbons is not the problem, then
why are we trying to convert biomass? The problem is in the consequences of hydro-
carbon usage, not in the depletion of hydrocarbons. Those consequences are severe.
Fossil fuel resources are heavily contaminated with sulfur, mercury, and other pollu-
tants. Many products from such feedstocks are persistent, leading to problems such
as plastics in the oceans. However, most importantly, burning fossil-based fuels or
incinerating fossil-based products generates carbon dioxide while the production of
the feedstocks consumes no CO2 .
Now, imagine a sustainable future – a future in which all of our needs are met with
products made from renewable resources, and those same products are themselves
recycled into new products. The feedstocks are nontoxic, the products are biodegrad-
able, and greenhouse gas emissions are completely offset by CO2 consumption.
Everyone would agree with that as a desirable goal, but we are a long way from that
future. There is so much work to do before we get there. We as a society are married
to our petrochemical past in so many ways, from the products we choose to make,
the ways in which we make those products, and even what we teach our future
chemists and chemical engineers at the universities. We need to divorce ourselves
from our petrochemical past in order to bring about that sustainable future.
Make no mistake about it. That divorce is going to be messy, but it is still worth
doing. At first, we thought that it would be easy. Just make existing products from
biomass instead of fossil fuels. It sounds so simple, but study after study has shown
that the environmental impact of transforming biomass into traditional chemical
products is usually more harmful than making the same products from fossil fuels.
So, what are we going to do? We have to be smarter about it. Those traditional
chemical products were chosen in the past because they were easy to make from
hydrocarbons. Why cannot we choose new chemical products? Let us choose
chemical products that are easy to make from biomass!
xii Foreword
Choosing new products is not the only task on our To Do list. There is a long list
of tasks ahead of us. We have to
● increase our knowledge of biomass conversions.
● evaluate new conversion processes and products in terms of potential environ-
mental impact, not just as an afterthought but during the design stage,
● use only renewable energy in the biomass conversion processes,
● develop less energetically costly ways of removing organic products from water,
given that water is often the solvent for fermentations and other standard tech-
niques for biomass transformations,
● build up supply chains from producers of raw biomass, through transportation and
conversion to platform chemicals, all the way to manufacture finished products,

● seek new sustainable feedstocks and new platform chemicals, keeping in mind
their potential availability at industrial scale and the environmental impact of

using such feedstocks at scale,
● design our new products so that they can be recycled efficiently, can biodegrade if
discarded, and do not themselves lead to environmental crises,

● change how organic chemistry is taught at the universities so that biomass feed-
stocks become the norm.

That sounds like a lot of work, but do not despair. There are so many talented peo-
ple working on biomass conversion, such as the authors and editors of this volume,
that each of these items on our “To Do” list can be achieved. The sheer variety of
approaches described in the following chapters assures me that there is great hope
for the future of biomass conversion. Many of you, the readers, are also develop-
ing new technologies for sustainable chemical manufacturing. We will attain that
sustainable future, and this book demonstrates that we are making progress toward
that goal.
My commendations to Chiara Samorì and Davide Ravelli for putting this work
together, to the authors for their many contributions to the book and the field, and
indeed to everyone in the green and sustainable chemistry research community for
their efforts in developing the chemistry that will make sustainable living a reality.
August 2020 Philip Jessop

Queen’s University
xiii
Preface
It is nowadays apparent that the chemistry of the future will involve the exploita-
tion of biomass-based renewable materials, the currently available stock of fossil
resources being doomed to exhaustion. This transition may indeed bring about sev-
eral benefits because having recourse to renewable resources should limit the impact
human activities are having on climate change.
Currently, the use of biomass by mankind is limited to addressing a few specific
needs, notably fulfilling the feed demand and supplementing energy production in
addition to the fossil fuel portfolio. The impact of these activities on the net primary
production (NPP) of terrestrial and marine biomass can be accounted for by con-
sidering the human appropriation of net primary production (HANPP) parameter,
which corresponds to all the human alterations of photosynthetic production in the
ecosystems. This constant HANPP represents a significant fraction of the NPP and
has a huge impact on ecosystems because it reduces the amount of energy available
to other species, influences biodiversity, and alters water, energy, and carbon flows
within food webs, also modifying the distribution of resources. In the prospected
future scenario of a massive use in industry, biomass will at some point become
a scarce resource, and its utilization should be considered wisely, accordingly. In
particular, the entire substitution of fossil fuels with biomass for energy produc-
tion purposes is unrealistic because of the huge amount of biomass that should be
devoted at this end. Furthermore, one may argue if this kind of application is the
best use possible of biomass, fully exploiting its characteristics in terms of chemical
composition.
Through history, a variety of biomass constituents have been employed in the
preparation of valuable drugs, flavors, and fragrances, or to provide, especially in
the second half of the nineteenth century, commodity materials such as cellulose
esters (nitrate and acetate) and oxidized linseed oil (linoleum). Indeed, there exist
different options of using biomass to produce chemicals. Nowadays, let apart the
use of wood in the paper industry, bio-based surfactants, lubricants, coatings/dyes,
additives for plastics and solvents (mostly based on vegetable oils/animal fats,
sugar, or starch) are the most important applications of biomass in chemistry. As
for future applications, the question is still open; however, it can be anticipated
that the use of biomass for chemicals production is a much more sustainable
option than having recourse to it for energetic purposes. Furthermore, in addition
xiv Preface
to merely duplicating existing products deriving from fossil resources, the chemistry
of biomass opens the opportunity to develop a new portfolio of products, having
no equivalence among those presently manufactured by classical synthetic routes
from hydrocarbons. A subsidiary advantage is that the development of bioproducts
requires fewer legislative constraints.
Accordingly, there is an increasing interest in developing suitable techniques to
tackle the valorization of biomass to produce chemicals and this area is expected to
further expand in the future. Along the same line, bio-based waste materials, to be
included in a circular economy perspective, can likewise contribute significantly.
Independently from the actual biomass employed, this is a challenging area because
inhomogeneous materials with variable composition must be processed with
tailored technologies. The book “Biomass Valorization: Sustainable Methods for
the Production of Chemicals” is intended to present the state of the art of the
different strategies available nowadays to convert biomass into useful building
blocks/commodity chemicals.
Each chapter features an introductory section, detailing the core details of the
described technology and showcasing the typical chemical pathways that can be
activated by having recourse to it. Next, peculiar advantages and limitations of
the described strategy in the processing of biomass are described. Finally, relevant
examples from the recent literature are reported, with attention to the organic
chemistry perspective, also indicating how the different approaches can modify and
valorize the native functionalities present in the starting biomass.
After an introductory section (Chapter 1), intended to set the stage and describe
how biomass can contribute to the production of chemicals, the rest of the book has
been organized according to the diverse approaches that can be exploited, also high-
lighting the potential, challenges, and innovative solutions associated with them.
Biomass valorization processes have been explored using catalytic routes, including
acid catalysis (Chapter 2), base catalysis (Chapter 3), metal catalysis (Chapter 4), and
biocatalysis (Chapter 5). Various thermal strategies that can be applied for the val-
orization of biomass involve pyrolysis (Chapter 6) and thermochemical–biological
hybrid processes (Chapter 7). Different advanced/unconventional strategies have
also shown great promise, such as those involving electrochemical (Chapter
8) and photochemical (Chapter 9) means, microwave treatment (Chapter 10),
ultrasound-assisted approaches (Chapter 11), and mechanochemical approaches
(Chapter 12). As a final contribution, biomass processing from an industrial
perspective is assessed (Chapter 13).
There is no doubt that in the future, the production of chemicals will be based
on the exploitation of biomass and the time has come to find the best methods to
address this challenge and put it into practice.
November 2020 Chiara Samorì, University of Bologna, Italy

Davide Ravelli, University of Pavia, Italy
1
Role of Biomass in the Production of Chemicals

Layla Filiciotto, Evan Pfab, and Rafael Luque
Universidad de Córdoba, Campus de Rabanales, Departamento de Quimica Organica, Edificio Marie Curie
(C-3), Ctra Nnal IV-A, Km 396, Córdoba, Spain
1.1 Introduction
Chemistry is a fundamental part of everything around us. Nature is largely responsi-

ble for all of the chemistry that occurs and has been so from the dawn of time. How-
ever, societal advances and technological developments in recent years have allowed
us to contribute far more chemistry than in the past. Quality-of-life improvements
for major parts of the world with better food distribution, clothing, technological
devices, and medical treatments have required the chemistry to progress further with
detrimental unknown effects on the environment. Policies and scientists worldwide
are now striving toward the development of a truly sustainable society, culminat-
ing into the implementation of the UN’s 17 Sustainable Development Goals that
tackle various issues including infrastructures, education, equality, peace, and envi-
ronmental protection [1]. In the active search for solutions, biomass valorization has
emerged as the most viable option for a more sustainable chemical industry.
The impact that sustainability could have on the chemical industry is best reflected
in the magnitude of the chemical industry itself. Today, the chemical industry gen-
erates approximately $4 trillion in global sales with the production of more than 95%
of all commodities [2]. One of the biggest turning points in the chemical industry,
and what arguably led it to such heights, was the advent of catalytic cracking in the
nineteenth century for the refining of fossil resources. Catalytic cracking allowed for
most of the products we use daily to be easily sourced from petroleum [3]. Biomass
valorization processes were also being explored around the same time. However, the
complex nature of biomass and the wide availability of fossil resources gained all
of society’s attention on the use of the latter [4]. As such, petroleum processes have
been the major focus of scientists and engineers for the past two centuries. Although
significant developments have been achieved considering this with higher resource
efficiency and cleaner technologies, the resulting environmental concerns driven by
the emissions and spills have led much attention back to renewable processes such
as biomass valorization.
Biomass Valorization: Sustainable Methods for the Production of Chemicals, First Edition.
Edited by Davide Ravelli and Chiara Samorì.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Role of Biomass in the Production of Chemicals
Biomass valorization and more sustainable practices are important steps for over-
turning the “disposable society” mindset where resources are viewed as infinite,
cheap, and harmless. One of the most straightforward examples of this can be seen
with plastic. Advances in chemistry not only created plastics but also helped notice
the alarming consequences.
Plastics were developed in conjunction with the advent of petroleum processes.
Plastic products possess desirable characteristics (lightweight, durable, etc.) that
allow for endless applications at a low manufacturing cost. Plastics found their
way into daily use with things such as clothing and packaging. However, we
were unequipped to properly handle this new technology. The characteristics that
make plastic so appealing for a wide variety of applications (i.e. durable and heat
resistant) are the same that make plastic so difficult to deal with. Its inherent
non-degradability, along with extremely careless handling and littering, created a
plastic waste crisis with the now widespread problem of microplastics in our oceans
[5, 6]. Biomass is a more attractive feedstock that can create bio-based and/or
biodegradable plastics to help overturn the drastic impact from petroleum-based
products. Much initial research has focused on using biomass for drop-in solutions,
i.e. plastics with the same composition and properties as the traditional ones (e.g.
polyethylene [PE] and polyethylene terephthalate [PET]). However, the process
chemistry limits the efficiency to sugars. On the other hand, other bio-based
plastics with new properties have been developed, e.g. polyethylene furanoate
(PEF) or poly-lactate (PLA). The former is a durable plastic based on furan and the
latter a compostable plastic. Developing bio-based plastics that are also biodegrad-
able – a fundamental challenge in biomass valorization – can ensure a higher
sustainability at the waste management stage, as their waste is less dangerous
to animals and humans (microplastics, trapped in fishing nets). However, differ-
entiation in the lifetimes of plastics will also require the development of durable
bioplastics.
Accumulating plastic waste is just one of the many concerns that is helping to
drive sustainable practices forward. Other concerns from the fossil-driven industrial
revolution include the following:
● Irreversible depletion of fossil fuels (i.e. oil and gas) and their detrimental envi-
ronmental issues [7, 8].
● Higher average temperatures and aggravation of weather conditions worldwide
(e.g. heavier rains) from an increase of greenhouse gases and record levels of CO2
in the atmosphere [9].
● Global population growth (>9 billion projected by 2050) leading to higher energy,
food, and chemical demands [10].
These concerns require a sustainable chemical industry that embraces the con-
cepts of green chemistry [11], circular [12] and low-carbon economies [13], and high
resource efficiency [14]. As such, biomass valorization and conversion of renewable
feedstocks through green processes are advancing to fully shift toward a safer and
sustainable chemical industry.
1.2 Biomass Valorization 3
1.2 Biomass Valorization
The sustainable production of chemicals and products can be achieved from

conversion of biomass, an inherently renewable source. Biomass covers a wide
range of bio-based resources from plants or animals. These resources include
plant-based materials, biowastes, and aquatic organisms. Valorizing renewable
biomass feedstocks can offer environmental benefits that include reduced emis-
sions, safer feedstocks, better geographic distribution of resources, and achievement
of a circular economy [12, 15–18].
In a circular economy, resources – such as carbon, nitrogen, and phosphorous
compounds – are used with a circular “take–make–reuse/recycle” approach, as
opposed to a linear “take–make–dispose” approach [12]. A closed cycle can be
achieved with biomass valorization processes by recycling the generated CO2
through natural photosynthetic processes [19, 20]. This process happens par-
ticularly with biodegradable plastics. Further, the existence of nonedible and
rapidly growing plants parallel to the development of high-throughput agricultural
technologies can lead to a carbon-neutral cycle in short periods of time, readjusting
the increased levels of CO2 emission given by the fossil industries [21].
In the context of biofuels, biomass has been subdivided in three categories given
as follows along with the major evidenced drawbacks:
(1) First-generation biomass: This includes all edible biomasses (e.g. sugarcane,
corn, whey, barley, and sugar beet) that are composed of sucrose or starchy
carbohydrates, hence relatively simple macromolecules with low recalcitrance.
Biological fermentation of said sugar polymers yields bioethanol, one of
the most studied drop-in biofuels with current industrial production [22].
Food-derived vegetable oils are also considered as first-generation biomass and
they yield biodiesel through transesterification [23]. The main issue of this
type of biomass is the clear competition with food resources (which will be
continuously more precious, given the increase of world population) as well as
the intensive use of water and land for the growth of said crops [24].
(2) Second-generation biomass: Nonfood raw materials, including by-products
and waste materials. Generally, second-generation biofuels are produced from
lignocelluloses (e.g. grasses, soft or hard wood, and forestry residues) or various
wastes/by-products (e.g. agricultural: stover, wheat straw, corn cob, rice husk,
and sugarcane bagasse; industrial: glycerol, grains from distilleries, and paper
sludge; or urban: household and municipal solid wastes). Given the structural
composition of these feedstocks (mixtures of cellulose, hemicellulose, and
lignin), pretreatment is usually required for fermentation to biofuels and
biochemicals, and the process economics are hindered by the use of multiple
steps, leading to lower overall conversions [25–30]. The main technological
challenge of these feedstocks is, in fact, the structural complexity that hinders
the efficient use of the lignocelluloses as a whole, calling for pretreatments that
in turn possess drawbacks depending on the method (vide infra).
(3) Third-generation biomass: This includes nonedible feedstocks that do not

require agricultural lands for their cultivation, namely, aquatic biomass, such
as algae and other microorganisms (e.g. cyanobacteria). Depending on the
strain, these feedstocks may contain mono/polyunsaturated hydrocarbons to
produce gasoline-like fuels via cracking or higher lipid content for biodiesel
applications via transesterification. When considering algae, the main issue is
correlated with the high water content that hinders transportation or requires
significant energy inputs or long times to dry them, whereas microorganisms
require specific operating conditions. Furthermore, the economic challenges
of these feedstocks limit their industrial application, given the low cultivation
volumes and resource efficiency in processing [31–33].
A fourth generation of biomass is also contemplated and exemplified as modi-
fied microorganisms considered in the third generation, finally used to harvest solar
energy through photosynthetic processes [34, 35]. However, these microbial species
require improvements of genomics-based breeding and carry the usual concerns of
modified organisms, such as unexpected microbial resistance.
The available volumes of these types of biomass will play a major role in iden-
tifying the biggest driver for chemical sustainability. According to a 2018 report
from the European Union (EU), the annual production of agricultural biomass
(i.e. first generation) was estimated at 956 million tonnes (Mt) of dry matter of
which 54% directly used for food consumption and 46% of residues (e.g. leaves
and stems) partially used for animal bedding or bioenergy production. In fact,
80% of the agricultural biomass is used as food and feed, showing the limited
potential of using first-generation biomass for chemicals and energy production.
As it concerns third-generation biomass, in particular algae (including macro and
micro), only 0.23 Mt of wet matter was estimated, corresponding to a mere 0.027 Mt
of dry mass. On the other hand, the total woody biomass (above ground, second
generation) was estimated at 18 600 Mt of dry weight [36]. Looking at the quantities
of the different biomasses, the high availability of lignocelluloses in Europe makes
them the most attractive. The >18 000 Mt of woody resources can make Europe
competitive worldwide and support sustainable processes. Particularly, the efficient
use of lignocelluloses and residues would improve the long-term sustainability of
the chemical industry, given the volumes and little impact on the food resources,
although these feedstocks still rely on forest management constraints. Other waste
materials (e.g. food and municipal) are increasing in volumes, given the concomi-
tant increase of world population and improvement of their living conditions. For
example, 61 Mt of food waste are produced yearly in the EU alone [37]. However,
the major challenges of these products are the variable seasonal composition as
well as the implementation of a proper supply chain of these anthropological side
streams to biorefineries [38].
Conversion strategies of biomass, however, generally come with low resource
efficiency, causing higher production costs and limited competitiveness with the
well-established petroleum market. Thus, for economic advantage, high volumes,
ease of production, and limited competition with other markets (e.g. food) are
required. In this sense, the use of lignocellulosic biomass may again offer a
1.3 Lignocellulosic Biomass 5
promising alternative to the fossil-based industry. From an energetic perspective,

lignocelluloses and other waste materials possess lower energy densities compared
to nonrenewable resources such as coal, oil, and natural gas. However, biopower
possesses negative emissions thanks to the photosynthetic process, whereas fossil
fuels cause significant life cycle greenhouse gas emissions [39]. Also, conversion of
biomass to key molecules (e.g. ethanol, 2-methylfuran, and hydrogenated ethers
and fatty acids) can offer biofuel diversification with various energy contents for
different transport applications, including aviation; these processes rely on the
separation of the different biomass components [21, 40]. From a chemical point
of view, the use of lignocelluloses can offer a wide variety of platform chemicals
for the synthesis of not only traditional but also new products to satisfy different
areas in the chemical industry (pharmaceuticals, textiles, and materials), which
are discussed in the following paragraph. A separation of bio-components will be
required and explained therein.
1.3 Lignocellulosic Biomass

Of all types of biomass, lignocelluloses are the most available on the planet,
ranging from wood and forestry waste to straw and agricultural waste. Lignocel-
lulosic biomass is composed of cellulose (40–50%), hemicellulose (15–20%), lignin
(25–35%), and other elements (Figure 1.1). Both cellulose and hemicellulose are
carbohydrate-based polymers, while lignin is an aromatic polymer. Cellulose is
a linear, glucose-based polymer, making it a good source of this C6-sugar. Cellu-
lose cross-links with hemicellulose, a branched polymer composed of different
C5-carbohydrates, uronic acids, and C6-sugars. Lignin, perhaps the most irregular
component of lignocellulose, is a polyaromatic macromolecule composed of phenyl-
propane derivatives. Lignin is mostly responsible for structural rigidity within the
OH
R O OH
O HO R Cellulose
HO O O
O
OH n
OH
R OH
O O HO R Hemicellulose
O O
HO O
OH n
OCH3 OH
O OCH3
HOCH2
O OCH3
OH O
Grasses HOCH2 O
HOH2C
O
O
O
Lignin
OCH3
O
H3CO OCH3
O
O
H3CO OH OH
OH
Softwood Hardwood
CH2OH
Other elements
(e.g. chlorophyll,
inorganic metals)
Figure 1.1 Schematic representation of the components of lignocelluloses.

lignocellulose. Further, lignocellulosic bio-feedstocks include variable quantities of

pigments; terpenes; inorganic elements such as Mn, K, P, Cl, Ca, Mg, and Na, as
well as Al, C, Fe, N, S, Si, and Ti to a smaller extent; and various extractives, e.g.
carbohydrates, proteins, lipids, waxes, chlorophyll, terpenes, tannins, and uronic
acids.
An extensive and systematic review on the composition of various types of biomass
shows the significant changes in the composition of these elements depending on
the type of biomass [41].
Overall, lignocelluloses are made of highly oxygenated C5- and C6-derivatives.
The oxygen functionalities make lignocelluloses a much different feedstock to
petroleum sources that are mainly hydrocarbons. The oxygen functionalities in lig-
nocelluloses are in some cases advantageous because they can minimize oxidation
reactions, which usually have a negative environmental impact, and favor reduction
reactions, which are typically milder processes and have less environmental impact.
Further, the propensity to produce coke/humins and ash obliges the use of mild
temperatures for these by-products’ minimization, as opposed to the traditional
catalytic cracking/reforming of fossils. In fact, the presence of plenty of oxygen
functionalities and low volatility tend to lead to the molecules’ decomposition at
high temperatures, generating carbonaceous residues.
Lignocelluloses have variable composition in their singular components depend-
ing on the plant origin. Water and inorganic residue contents also vary significantly
from grass to wood. Although composition does vary significantly, biomass can
source several useful compounds, including carbohydrates, aromatics, terpene, and
fatty esters. These different components can be isolated and converted for use in
many applications including pharmaceutical, cosmetics/perfumes, plastics, textiles,
and specialty chemicals. For this, several different biomass valorization routes can
be envisioned with a wide range of obtainable products.
1.4 Key Biomolecules

During the first attempts of biomass valorization, drop-in energy solutions have
been investigated as they could directly substitute the use of fossil resources for
transportation vehicles. The most common examples are the use of bioethanol and
biodiesel as additives to common automotive fuels. Bioethanol is mostly produced
in industry using yeast fermentation of C6-sugars. With an increase of 25 billion
gallons (roughly 75 Mt) worldwide, bioethanol is one of the most mass-produced
bio-based molecules. However, starchy feedstocks (i.e. first generation) are mostly
used in the production of bioethanol, causing direct competition with the food
market, widespread deforestation, and concerns on the presence of enough food
sources for both humans and animals [42]. Also, bioethanol has limited competi-
tiveness with petroleum options because of low product value and relatively high
price, especially when considering food sustainability. To add perspective, the price
of oil would have to be above $70–80 per barrel for bioethanol to be competitive
from a cost standpoint, while today, oil is at <$40 per barrel [43].
Alternatively, another approach is to obtain different platform molecules from

biomass that can be used for production of a wide variety of chemicals. With a shift
on how we perceive platform molecules, new chemical (and biological) pathways
can be envisioned. In order to induce this shift, several important bio-products
unique from petrol-based ones were identified in a 2004 US Department of Energy
report [44] later updated by Bozell and Petersen [45] and further reviewed by
Gallezot [46]. Bio-based platform chemical families and their respective processes,
industrial applications and current technical challenges, are summarized in
Table 1.1 [44–47]. For more information on the industrial challenges for biomass
valorization, the reader is referred to Chapter 13 of this book.
Table 1.1 represents only a small fraction of all the molecules that could be identi-
fied as valuable platform chemicals, opening a significant number of possibilities for
the synthesis of petrol-like or new molecules. However, apart from established pro-
cesses such as those of sorbitol and glycerol, all other biomolecules generally suffer
from high production costs that might be caused by
(i) high price of feedstocks (depending on the required sugar purity).
(ii) low resource efficiency (e.g. synthesis of by-products that lower conversions
and intensify purification/separation processes).
(iii) high investment and operational cost required for the reactor volumes or
design, or need to maintain sterile conditions during production.
(iv) inefficient catalysts, which could be (a) biological (enzyme and bacteria), which
require metabolic engineering for higher efficiency and durability; (b) homoge-
neous, which tend to be corrosive, toxic, or difficult to reuse and recycle; or (c)
heterogeneous, which have lower conversions even if they can be recovered and
reused, but are prone to irreversible adsorption of organic molecules, leading
to coke and thus reactor fouling.
Particularly, when compared to petrol-like compounds, the disadvantages of
chemicals from biomass processing become increasingly apparent in terms of
overall costs. Even when only considering feedstock transportation, the advantage
goes to petroleum, as it is a fluid that can be pumped (or natural gas through
pipelines). Biomass tends to occupy larger volumes, given its physical nature, and
is much more difficult to transport as a result. Nevertheless, the most notable
difference that gives petrol-like compounds the slight edge is the absence of oxygen
functionalities (aliphatics/aromatics/olefins), which reduces their reactivity but
yields larger production volumes by the addition of heteroatoms. In fact, although
fossil compounds are modified via oxidation, bio-derived compounds often require
oxygen removal. In this sense, larger initial volumes are required for biomass to
reach the same final product volume, making it economically inefficient. Moreover,
the reactivity of oxygen groups in biomass gives inefficient processes, especially if
targeting petrol-like compounds. In this regard, a better route is to build off these
different functionalities and explore new platform chemicals that are specific for
biomass products. Most of the advances have been achieved largely because of
catalytic pathways that allow for lower energy requirements and higher resource
efficiency.
Table 1.1 Key examples of the possible bio-based products, state-of-the-art processes, and
challenges [44–47].
Bio-product Industrial Technological

platform (example) Process application challenge
1,4-Diacid (succinic Anaerobic Pharmaceutical, Separation/purification of

acid) fermentation food, polymers, products
solvents
Furanics (HMF) Acid-catalyzed Food/cosmetics, Low resource efficiency
dehydration of C-5 polymers,
and C-6 construction,
sugars/oxidation textiles, fuels
3-Hydroxypropionic Aerobic Polymers, textiles Low resource efficiency
acid (acrylic acid) fermentation Under metabolic engineering
research
Amino acid (aspartic Microbial process Biodegradable Need of sterile conditions
and glutamic acids) polymers, Complex separation
pharmaceuticals
Under metabolic engineering
research
Gluconic acid Aerobic fermenta- Food, Low resource
(methylglucoside) tion/catalytic pharmaceuticals efficiency/catalyst
oxidation deactivation
Itaconic acid (itaconic Aerobic Specialty polymers Low resource efficiency
anhydride) fermentation (including Under metabolic engineering
biodegradable) research
Glycerol By-product of Cosmetics, food, Low market price
(dihydroxyacetone) biodiesel/soap pharmaceuticals, Expensive purification
manufacture lubricants,
polymers, Li Catalyst
batteries separation/deactivation in
upgrade
Levulinates Acid-catalyzed Fragrances, food, Low resource efficiency
(γ-valerolactone) dehydration of C-6 fuels, solvents,
sugars pharmaceuticals,
polymers
Sorbitol (isosorbide) Hydrogenation of Food, Established technology
C-6 sugars pharmaceuticals Low market price
Lactones (3-hydroxy- Oxidative Pharmaceuticals, Inefficient oxidation
butyrolactone) degradation of C-5 chiral building Low resource efficiency
and C-6 sugars block, polymers unless starch is used
Inhibitory effect of biomass
Lactic acid Anaerobic Cosmetics, High feedstock cost
(oxalic acid) fermentation pharmaceutical, (high-purity lignocellulosic
biodegradable sugars or food derived)
polymers Separation/purification of
products
(continued)
Table 1.1 (Continued)
Bio-product Industrial Technological

platform (example) Process application challenge
Biohydrocarbons Aerobic Polymers Investment cost (reactors)

(isoprene) fermentation High feedstock cost
(high-purity lignocellulosic
sugars or food derived)
ABE (acetone, ABE fermentation Fuels, solvents High feedstock cost
butanol, ethanol) Low resource efficiency
Lignin Catalytic Polymers, food, Low resource efficiency
decomposition pharmaceuticals,
fuels
Sources: Werpy et al. [44], Bozell et al. [45], Gallezot [46], Isikgor et al. [47].
For instance, by taking the case study of plastic production from biomass, a
variety of options can be imagined [47], giving strong environmental benefits.
If traditional plastics (e.g. PE, polyamides, and PET) are produced starting from
biomass, a possible reduction of ca. 310 Mt of CO2 -equiv per year could be achieved
with the substitution of less than 66% of the current fossil-based plastics [48]. This
footprint reduction is solely based on the process and not on the product as the
degradation characteristics of these plastics (i.e. nonbiodegradable) are the same
regardless of the feedstock type (e.g. biomass and petroleum). At the same time,
new and innovative platform chemicals can be produced with fewer chemical
steps (e.g. furanics as opposed to aromatics), opening new opportunities in the
production of bio-based plastics. For instance, a furan-based plastic was synthesized
via the polymerization of 2,5-furandicarboxylic acid (FDCA), an oxidized product
of 5-hydroxymethylfurfural (HMF) (see Table 1.1), and ethylene glycol [49, 50].
This plastic, known as polyethylene furanoate (PEF), can be conceived as the
bio-based parallelism of the common PET, where the C-6 aromatic functionality is
substituted by a furan ring. Further, the furan-based polymer was found to perform
better compared to PET in terms of physical properties such as gas barrier [49].
The production of PEF relies on the acid-catalyzed dehydration of lignocellulosic
biomass and/or sugars (e.g. glucose) into HMF with subsequent oxidation to FDCA
(Figure 1.2) (see further Chapter 13).
However, this process is hindered by the coproduction of substances known as
humins (at times, referred to as coke) in the dehydration step [51–53]. The lower
resource efficiency of the first step increases the overall cost of PEF, limiting its com-
petition with fossil-based PET regardless of the improved properties. This low atom
economy is common to many bio-based processes.
Generally, when producing chemicals from whole lignocelluloses, the yields of
conversion processes are lower compared to the same synthesis starting from the
sugar (e.g. fructose, xylose, and glucose); hence, process costs tend to increase.
Predominantly, the differences of lignin content and feedstock density depending
on the considered biomass (e.g. grasses vs. softwood vs. hardwood) cause variation
on the process yields as well as the amount of volumes to be processed (e.g. grasses
HO O O O
+ HO OH HO +
OH O
O OH HO OH
O O O O O
O
HO O
O O O O
PET n PET n
OH
CH3 O OH
CH3 C ru de HO OH
OH
BTX C6-sugars
(Benzene, toluene,
xylenes)
Figure 1.2 Parallelism between the production of PET (left) and PEF (right).
require bigger volumes). In particular, the hydrogen bonding between the different
components (i.e. lignin, hemicellulose, and cellulose) reduces the available surface
to processing, increasing the structural complexity and the recalcitrant nature of
lignocellulosic feedstocks. Furthermore, the inorganic metals (e.g. Mg and Ca)
naturally present in plants may induce reactor fouling by induced precipitation of
salts or heterogeneous catalyst (e.g. zeolites) deactivation by ion exchange [54, 55].
Above all, the aforementioned large presence of heteroatoms (particularly oxygen)
increases the moieties’ reactivity, leading to low atom efficiency and occurrence
of undesired side reactions, such as the synthesis of humins that act as a catalyst
deactivator (in a similar way to coke) and promote reactor fouling.
In order to overcome these challenges, strategies include the use of unconven-
tional solvents, milder conditions, and various pretreatment methods in order to sep-
arate the single components (e.g. decompose cellulose to glucose) and allow targeted
valorization.
1.5 Solvents
Solvent selection is an important factor in the viability of biomass processes. Aque-

ous solvents are advantageous for high solubility with most biomass feedstocks.
Other desirable factors of aqueous solvents are low cost and low environmental
impact, especially when compared to other solvents. Water, for instance, is the
ideal solvent for biocatalytic routes as they have fewer chances to denature the
used microorganism [56]. However, a downside of using water is usually the higher
energy-intensive separation processes, hence higher cost [57]. From the chemical
point of view, aqueous solvents typically facilitate many side reactions that lower
yields, including decomposition and polymerization [58–61]. In fact, many of
the mechanisms of humin formation (i.e. sugar platform chemical polymer with
low current market value) are attributed to ring-opening hydrolysis [62]. The use
1.5 Solvents 11
of organic solvents can overcome this type of mechanism and maintain a low
environmental impact if the process is designed to recycle said solvents. Polar
aprotic solvents can offer higher yields of the desired products compared to aqueous
systems thanks to high sugar solubility and suppression of side reactions [63, 64].
However, most polar aprotic solvents, such as dimethyl sulfoxide (DMSO), have
high boiling points that make product separation more difficult and significantly
increase production costs.
Other conventional solvents have certainly been employed in biomass appli-
cations as well, but focus has been placed on coupling biomass processes with
bio-based or green solvents. These include bio-based conventional solvents, ter-
penes, ionic liquids, switchable solvents, fatty acid/glycerol-based solvents, and
liquid carbon dioxide.
Conventional bio-based solvents can mostly be used as a drop-in replacement.
Common examples of this are glycerol, ethyl lactate, and 2-methyltetrahydrofuran.
In addition, acetone and various linear alcohols (e.g. methanol, ethanol, and
butanol) can be derived from bio-based sources, but current technology is not
the most efficient [65]. The use of these solvents may offer an advantage, given
the chemical affinity to the desired platform biomolecules. These solvents alone,
however, have also induced the formation of humins.
Terpenes can be extracted from various materials in nature and subsequently used
as a bio-based solvent. Cis-rich pinane can be extracted from pine tree by-products
and used as a suitable replacement for n-hexane [66]. Another example, D-limonene,
has similar properties and comes from orange peels. It has been safely designated by
the USFDA for use in home and personal products [65]. However, the small volumes
of these potential solvents limit their use to specialty applications (e.g. cosmetics).
Ionic liquids (ILs) are also being explored as solvents for biomass processes.
Recently, they have been a major focus in biomass applications for their potential
to overcome other solvent limitations because of their versatility (i.e. large working
temperature range, acidic or basic capabilities, and compatibility with different
materials) and non-volatility. Initial studies show that ionic liquids can offer
satisfactory product yields when combined with metal halides. In fact, whereas
the ionic liquid provides a stable medium for sugar conversion, the halide acts as
Brønsted acid catalyzing the system. Another advantage of using ionic liquids is
that they are generally considered to have high stability. However, application of
ionic liquids is still a relatively new field and the physicochemical properties are not
properly defined, in the end causing safety concerns [67]. The major issue related to
the use of ionic liquids, however, is the hindered separation of oxygenated products
such as furanics, given the higher stability of these molecules in charged media [68].
Switchable solvents are attractive for coupling desirable solvent properties that
would otherwise be on the opposite ends of the spectrum. Switchable solvents
are able to quickly undergo reversible property switches that are activated by an
external change. The external trigger is typically a change in pH, temperature or
concentration [65]. Switchable solvents are like biphasic solvents in that they both
can possess two different solvent properties in just one system. One highly desirable
solvent property for manipulation is hydrophilic character [69]. A switchable
hydrophilic solvent (SHS) has been used for extracting different fractions such
as proteins, lipids, and carbohydrates from microalgal biomass [69] and also for
extracting phenols from lignin pyrolysis oil [70]. The SHS employed in both of
these studies was N,N-dimethylcyclohexylamine [69, 70]. However, limitations are
present with switchable solvents as it is a newer field lacking in research.
Other solvents worth noting are fatty acid/glycerol-based solvents, advantageous
for chemical inertness, and liquid/supercritical CO2 , advantageous for wide avail-
ability, good solubility, and low toxicity [65]. The high boiling point of the glycerol
mixtures (higher than DMSO) may be used as an advantage for separating volatile
molecules but hinders their recyclability if nonvolatile molecules are coproduced
(e.g. humins). Alternatively, employing liquid/supercritical CO2 as a solvent indi-
cates costly high-pressure systems/vessels and additional safety requirements.
Another solvent approach is the use of biphasic systems. With two different
phases, reactions take place in the aqueous phase but extraction and separation
in the organic phase [59, 71–74]. Hydrophobic extracting phases (e.g. cyclopentyl
methyl ether, CPME) in the presence of a chloride salt (e.g. NaCl) can enhance the
partitioning coefficient of the organic solvent, favoring extraction [71]. Otherwise,
polar solvents with low water solubility (e.g. methyl isobutyl ketone, MIBK) can be
used in the sugar conversions. Even so, the addition of multiple solvents increases
the production costs even if recycled (small loss of solvents, specialty molecules)
and reduces the greenness of the overall process.
By using these (mixtures of) solvents, one-pot transformation of lignocelluloses
via different methodologies has been attempted [50]. However, one-step procedures
are difficult to achieve with biomass processes because of the intricacies associated
with solvent selection, catalyst, and other operating conditions. With this in mind,
biomass processes that focus on individual bio-components as opposed to entire sys-
tems could be more effective.
1.6 Pretreatment of Lignocelluloses

Pretreatment is a necessary measure for handling biomass on an individual com-
ponent basis. One of the main functions for pretreatment is to facilitate separation
and allow for improved access of the different biomass fractions, particularly from
the rigid components that make up the plant wall [75]. In lignocellulose, these rigid
components that significantly hinder solubilization are lignin and cellulose. Pecu-
liarly, the separation of each bio-component without further decomposition (e.g.
to by-products) could greatly contribute to the development of efficient conversion
strategies, improving the competitiveness of a bio-economy.
Biomass pretreatments can be classified as physical, chemical, physicochemical,
or biological [75–77]. Physical pretreatment is reserved mainly for less complex
applications where only an increased surface area is mostly desired. Some com-
mon physical pretreatment methods are sheer mixing, milling, and grinding that
physically break apart the plant wall components [76]. Chemical pretreatment
is widely used for its ability to greatly improve solubilization in order to make
subsequent biomass processes possible. Chemical methods include acid/alkali
1.6 Pretreatment of Lignocelluloses 13
treatment, ozonolysis, and organosolv [77]. Many researchers have been utilizing
acid treatment as a simple chemical transformation route that is particularly
useful for releasing some of the bio-sugars that are locked behind the more rigid
components. Furthermore, if the targeted reaction is acid-catalyzed dehydration
of the sugars to furanics or levulinics, the plausible residual presence of acids
may only enhance the rate of said reaction. On the other hand, most biological
treatments are safe and green processes that utilize fungi or other microorganisms.
The enzymes break down hemicellulose and lignin rather well, while leaving
intact cellulose. However, biological processes proceed at rather slow rates and
the microorganisms typically only thrive in a fine-tuned aqueous environment.
A majority of the innovative pretreatment methods fall under physicochemical,
as many benefits from the combinatory approach. These combination treatments
include steam explosion, ammonia fiber expansion, carbon dioxide explosion, and
wet oxidation with steam explosion being one of the most used. Steam explosion
uses high-pressure steam that creates a self-reacting autohydrolysis environment
for transforming biomass mechanically and chemically [25].
With current progress, pretreatment is a necessary measure for processing ligno-
cellulosic biomass. The lignin content is largely responsible for complicating the
heterogeneous nature of lignocelluloses and for contributing recalcitrant properties
that make it difficult to handle. Without pretreatment, most valorization approaches
are not cost effective [78].
Ideally, a pretreatment step would efficiently separate lignocellulose into its single
components. If this is achieved, biomass processes could be standardized (based on
each component) to greatly alleviate the issues of biomass inconsistency. It would
also contribute to optimized processes that maximize process conditions such as
yields and overall costs. When contemplating biocatalytic conversion of biomass
(e.g. yeast fermentation), typical yields are low (<20%) without pretreatment. This
phenomenon is given by the barrier effect of lignin to enzyme, physically hindering
the hydrolysis of the digestible components (i.e. sugars) [79, 80]. Improvements
of product yields have been obtained with either biological [81], physical [82],
and chemical steps [78, 83] or physicochemical [84, 85] pretreatments, thus giving
higher resource efficiency. Cost-effective solutions would ideally remove lignin
without affecting the desired carbohydrates, hence being energy effective while
having a simple reactor design and low production of waste compounds (including
solvents) [86]. Nevertheless, improvement of the current pretreatment technologies
is still required to obtain economical solutions. Various pretreatment strategies and
their advantages and disadvantages are illustrated in Table 1.2.
Overall, different pretreatment methods will be preferred for different applica-
tions. For example, applications requiring low toxicity would be better suited with
microbial conversions. Alternatively, applications requiring high sugar yields would
probably utilize chemical conversions. The main challenge for selective biomass
processes is achieving a reasonable balance between cost considerations and effi-
cient separation of each component. In addition, pretreatment requirements with
current technologies further complicate the processes [87]. Innovative solutions
Table 1.2 Advantages and disadvantages of pretreatment methods for lignocelluloses.
Method Pretreatment Advantages Disadvantages
Biological Fungi Energy effective Low hydrolysis rate

Degrades
lignin/hemicellulose
network
Physical Milling Reduces cellulose Energy intensive
crystallinity
Chemical Ozonolysis Lignin reduction Cost ineffective (ozone)
Low microbial inhibitors
Organosolv Lignin and hemicellulose Big solvent volumes
hydrolysis Requires solvent recycle
Alkali Lignin removal Inefficient for softwoods
Large amounts of water
Reduces cellulose Long pretreatment times
crystallinity
Limited hemicellulose Base recycle
degradation
Concentrated High glucose yield Large amounts of acids
acid Energy effective Requires acid recycle
Reactor corrosion
Diluted acid Low microbial inhibitors Low sugar yields
Lower corrosion issues Degradation products
Ionic liquids Reduces cellulose Cost ineffective (ionic
crystallinity liquids)
Higher accessible surface Difficult
area recovery/separation of
desired products
Lignin removal Potential toxicity and
Degrades thermal instability of ionic
lignin/hemicellulose liquids
network
Physicochemical Steam explosion Lignin removal High microbial inhibitors
Hemicellulose
solubilization
Fair sugar yields Partial hemicellulose
Economical degradation
Ammonia fiber Higher accessible surface Inefficient with lignin-rich

expansion area biomass
(AFEX) Low microbial inhibitors Big ammonia volumes
(cost)
(continued)
References 15
Method Pretreatment Advantages Disadvantages
CO2 explosion Higher accessible surface No effect on

area lignin/hemicelluloses
network
Low microbial inhibitors High pressure (cost,
Economical reactor)
Wet oxidation Lignin removal Cost ineffective (oxygen

Low microbial inhibitors and alkaline catalyst)
Energy effective
that address these challenges will help push biomass processes closer to practical
implementation.
1.7 Conclusions and Perspectives
The search of a true sustainable chemical industry is driven by the development

of processes that rely on not only renewable feedstocks associated with low
environmental impact techniques but also economic viability to compete with
the well-established oil and gas markets. To recede the dependency on polluting
resources, creative solutions following a green design in the most restringing way are
required. The following chapters in this book discuss various methods of biomass
valorization, along with their respective challenges and innovative solutions, as
means to progress toward chemical sustainability.
References
1 United Nations Sustainable Development Knowledge Platform. (2019). Sustain-

able development goals. https://sustainabledevelopment.un.org/sdgs (accessed 20
November 2019).
2 International Council of Chemical Associations. (2019). Sustainable development.
https://www.icca-chem.org/sustainable-development/ (accessed 10 September
2019).
3 Speight, J.G. (1999). The Chemistry and Technology of Petroleum. New York: Mar-
cel Dekker.
4 Filiciotto, L. and Luque, R. (2018). Nanocatalysis for green chemistry. In: Ency-
clopedia of Sustainability Science and Technology (ed. R.A. Meyers), 1–28. New
York: Springer.
5 Eerkes-Medrano, D., Thompson, R.C., and Aldridge, D.C. (2015). Microplastics in
freshwater systems: a review of the emerging threats, identification of knowledge
gaps and prioritisation of research needs. Water Research 75: 63–82. https://doi
.org/10.1016/j.watres.2015.02.012.
6 Law, K.L. and Thompson, R.C. (2014). Microplastics in the seas. Science 345
(6193): 144–145. https://doi.org/10.1126/science.1254065.
7 Aboudah, M. (2015). Dealing with economic sustainability challenges evolv-
ing from declining oil production in Saudi Arabia. Master thesis. Michigan
Technological University.
8 Campbell, C.J. (2013). Campbells Atlas of Oil and Gas Depletion. New York, NY:
Springer.
9 Climate Change: Vital Signs of the Planet. (2018). https://climate.nasa.gov/
(accessed 14 November 2019).
10 World population projected to reach 9.8 billion in 2050, and 11.2 billion in 2100
| UN DESA Department of Economic and Social Affairs. (2017). https://www
.un.org/development/desa/en/news/population/world-population-prospects-2017
.html (accessed 14 November 2019).
11 Anastas, P.T. and Warner, J.C. (1998). Green Chemistry Theory and Practice. New
York: Oxford University Press.
12 Keijer, T., Bakker, V., and Slootweg, J.C. (2019). Circular chemistry to enable
a circular economy. Nature Chemistry 11 (3): 190–195. https://doi.org/10.1038/
s41557-019-0226-9.
13 Lanzafame, P., Centi, G., and Perathoner, S. (2014). Catalysis for biomass and
CO2 use through solar energy: opening new scenarios for a sustainable and
low-carbon chemical production. Chemical Society Reviews 43 (22): 7562–7580.
https://doi.org/10.1039/C3CS60396B.
14 Sheldon, R.A. (2016). Green chemistry and resource efficiency: towards a
green economy. Green Chemistry 18 (11): 3180–3183. https://doi.org/10.1039/
c6gc90040b.
15 Cong, W.-F., Jing, J., Rasmussen, J. et al. (2017). Forbs enhance productivity of
unfertilised grass-clover leys and support low-carbon bioenergy. Scientific Reports
7 (1): 1–10, Article ID 1422. doi: https://doi.org/10.1038/s41598-017-01632-4.
16 Mauser, W., Klepper, G., Zabel, F. et al. (2015). Global biomass production
potentials exceed expected future demand without the need for cropland expan-
sion. Nature Communications 6 (1): 1–11, Article ID 8946. doi: https://doi.org/10
.1038/ncomms9946.
17 Woodward, F.I., Lomas, M.R., and Kelly, C.K. (2004). Global climate and the
distribution of plant biomes. Philosophical Transactions of the Royal Society of
London. Series B: Biological Sciences 359 (1450): 1465–1476. https://doi.org/10
.1098/rstb.2004.1525.
18 Abdel-Shafy, H.I. and Mansour, M.S.M. (2018). Solid waste issue: sources, com-
position, disposal, recycling, and valorization. Egyptian Journal of Petroleum 27
(4): 1275–1290.
19 European Commission (2019). Renewable Energy: Bioenergy. http://ec.europa
.eu/research/energy/index.cfm?pg=area&areaname=renewable_bio (accessed 10
November 2019).
References 17
20 Obermeier, W.A., Lehnert, L.W., Kammann, C.I. et al. (2016). Reduced CO2
fertilization effect in temperate C3 grasslands under more extreme weather
conditions. Nature Climate Change 7 (2): 137–141. https://doi.org/10.1038/
nclimate3191.
21 Wu, L., Moteki, T., Gokhale, A.A. et al. (2016). Production of fuels and chemicals
from biomass: condensation reactions and beyond. Chem 1 (1): 32–58. https://doi
.org/10.1016/j.chempr.2016.05.002.
22 Mousdale, D.M. (2008). Biofuels: Biotechnology, Chemistry and Sustainable Devel-
opment. Boca Raton, FL: CRC Press.
23 Ho, D.P., Ngo, H.H., and Guo, W. (2014). A mini review on renewable sources
for biofuel. Bioresource Technology 169: 742–749. https://doi.org/10.1016/j
.biortech.2014.07.022.
24 Rulli, M.C., Bellomi, D., Cazzoli, A. et al. (2016). The water-land-food nexus of
first-generation biofuels. Scientific Reports 6 (1) https://doi.org/10.1038/srep22521.
25 Achinas, S. and Euverink, G.J.W. (2016). Consolidated briefing of biochemical
ethanol production from lignocellulosic biomass. Electronic Journal of Biotechnol-
ogy 23: 44–53. https://doi.org/10.1016/j.ejbt.2016.07.006.
26 Lee, W.C. and Kuan, W.C. (2015). Miscanthusas cellulosic biomass for bioethanol
production. Biotechnology Journal 10 (6): 840–854. https://doi.org/10.1002/biot
.201400704.
27 Stoffel, R.B., Neves, P.V., Felissia, F.E. et al. (2017). Hemicellulose extraction from
slash pine sawdust by steam explosion with sulfuric acid. Biomass and Bioenergy
107: 93–101. https://doi.org/10.1016/j.biombioe.2017.09.019.
28 Wilkinson, S., Smart, K.A., James, S. et al. (2016). Bioethanol production
from brewers spent grains using a fungal consolidated bioprocessing (CBP)
approach. BioEnergy Research 10 (1): 146–157. https://doi.org/10.1007/s12155-
016-9782-7.
29 Prasetyo, J., Naruse, K., Kato, T. et al. (2011). Bioconversion of paper sludge
to biofuel by simultaneous saccharification and fermentation using a cellu-
lase of paper sludge origin and thermotolerant Saccharomyces cerevisiae TJ14.
Biotechnology for Biofuels 4 (1): 35. https://doi.org/10.1186/1754-6834-4-35.
30 Sims, R.E., Mabee, W., Saddler, J.N. et al. (2010). An overview of second genera-
tion biofuel technologies. Bioresource Technology 101 (6): 1570–1580. https://doi
.org/10.1016/j.biortech.2009.11.046.
31 Pierobon, S.C., Cheng, X., Graham, P.J. et al. (2018). Emerging microalgae tech-
nology: a review. Sustainable Energy Fuels 2: 13–38. https://doi.org/10.1039/
C7SE00236J.
32 Koller, M., Salerno, A., Tuffner, P. et al. (2012). Characteristics and potential of
micro algal cultivation strategies: a review. Journal of Cleaner Production 37:
377–388. https://doi.org/10.1016/j.jclepro.2012.07.044.
33 Singh, A. and Olsen, S.I. (2011). A critical review of biochemical conversion,
sustainability and life cycle assessment of algal biofuels. Applied Energy 88 (10):
3548–3555. https://doi.org/10.1016/j.apenergy.2010.12.012.
34 Aro, E.-M. (2015). From first generation biofuels to advanced solar biofuels.
AMBIO 45 (S1): 24–31. https://doi.org/10.1007/s13280-015-0730-0.
35 Moravvej, Z., Makarem, M.A., and Rahimpour, M.R. (2019). The fourth gener-
ation of biofuel. In: Second and Third Generation of Feedstocks-The evolution of
biofuels (eds. A. Basile and F. Dalena), 557–597. Amsterdam: Elsevier.
36 Camia, A., Robert, N., Jonsson, R. et al. (2018). Biomass production, supply, uses
and flows in the European Union. JRC Science for policy report https://doi.org/10
.2760/539520.
37 Xu, C., Nasrollahzadeh, M., Selva, M. et al. (2019). Waste-to-wealth: biowaste
valorization into valuable bio(nano)materials. Chemical Society Reviews 48:
4791–4822. https://doi.org/10.1039/C8CS00543E.
38 Lin, C.S.K. (2018). Chemistry and Chemical Technologies in Waste Valorization.
Cham: Springer.
39 Seyboth, K., Matschoss, P., Kadner, S. et al. (2012). Intergovernmental panel
on climate change. In: Renewable Energy Souces and Climate Change Mitiga-
tion (eds. O. Edenhofer, R.P. Madruga and Y. Sokona), 161–208. New York:
Cambridge University Press.
40 Wang, M., Dewil, R., Maniatis, K. et al. (2019). Biomass-derived aviation fuels:
challenges and perspective. Progress in Energy and Combustion Science 74: 31–49.
41 Vassilev, S.V., Baxter, D., Andersen, L.K. et al. (2012). An overview of the organic
and inorganic phase composition of biomass. Fuel 94: 1–33. https://doi.org/10
.1016/j.fuel.2011.09.030.
42 Zabed, H., Sahu, J., Suely, A. et al. (2017). Bioethanol production from renewable
sources: current perspectives and technological progress. Renewable and Sustain-
able Energy Reviews 71: 475–501. https://doi.org/10.1016/j.rser.2016.12.076.
43 Bruyn, M.D., Fan, J., Budarin, V.L. et al. (2016). A new perspective in
bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydroly-
sis lignin by selective conversion of residual saccharides. Energy & Environmental
Science 9 (8): 2571–2574. https://doi.org/10.1039/c6ee01352j.
44 Werpy, T.A., Holladay, J.E., and White, J.F. (2004). Top Value Added Chemicals
From Biomass: I. Results of Screening for Potential Candidates from Sugars and
Synthesis Gas. Oak Ridge (TN): Pacific Northwest National Laboratory (PNNL)
and the National Renewable Energy Laboratory (NREL).
45 Bozell, J.J. and Petersen, G.R. (2010). Technology development for the production
of biobased products from biorefinery carbohydrates – the US Department of
Energy’s “Top 10” revisited. Green Chemistry 12 (4): 539. https://doi.org/10.1039/
b922014c.
46 Gallezot, P. (2012). Conversion of biomass to selected chemical products. Chemi-
cal Society Reviews 41 (4): 1538–1558. https://doi.org/10.1039/c1cs15147a.
47 Isikgor, F.H. and Becer, C.R. (2015). Lignocellulosic biomass: a sustainable plat-
form for the production of bio-based chemicals and polymers. Polymer Chemistry
6 (25): 4497–4559. https://doi.org/10.1039/c5py00263j.
48 Spierling, S., Knüpffer, E., Behnsen, H. et al. (2018). Bio-based plastics – a
review of environmental, social and economic impact assessments. Journal of
Cleaner Production 185: 476–491. https://doi.org/10.1016/j.jclepro.2018.03.014.
49 YXY Technology. (2019). https://www.avantium.com/renewable-polymers/yxy-
technology/ (accessed 10 September 2019).
References 19
50 Liu, B. and Zhang, Z. (2016). One-pot conversion of carbohydrates into furan

derivatives via furfural and 5-hydroxylmethylfurfural as intermediates. Chem-
SusChem 9 (16): 2015–2036. https://doi.org/10.1002/cssc.201600507.
51 Van Zandvoort, I., Wang, Y., Rasrendra, C.B. et al. (2013). Formation, molecular
structure, and morphology of humins in biomass conversion: influence of feed-
stock and processing conditions. ChemSusChem 6 (9): 1745–1758. https://doi.org/
10.1002/cssc.201300332.
52 Rice, F.A.H. (1958). Effect of aqueous sulfuric acid on reducing sugars. V.
Infrared studies on the humins formed by the action of aqueous sulfuric acid
on the aldopentoses and on the aldehydes derived from them. Journal of Organic
Chemistry 23 (3): 465–468. https://doi.org/10.1021/jo01097a036.
53 Hoang, T.M.C., van Eck, E.R.H., Bula, W.P. et al. (2015). Humin based
by-products from biomass processing as a potential carbonaceous source for
synthesis gas production. Green Chemistry 17 (2): 959–972. https://doi.org/10
.1039/c4gc01324g.
54 Girisuta, B. (2007). Levulinic acid from lignocellulosic biomass. PhD thesis.
University of Groningen.
55 Tang, P. and Yu, J. (2014). Kinetic analysis on deactivation of a solid Brønsted
acid catalyst in conversion of sucrose to levulinic acid. Industrial & Engineering
Chemistry Research 53 (29): 11629–11637. https://doi.org/10.1021/ie501044c.
56 Ferreira-Leitão, V., Cammarota, M., Aguieiras, E.G. et al. (2017). The protago-
nism of biocatalysis in green chemistry and its environmental benefits. Catalysts
7 (12): 9. https://doi.org/10.3390/catal7010009.
57 Scott, E. L., Bruins, M. E., and Sanders, J. P. M. (2013). Rules for the biobased
production of bulk chemicals on a small scale. Wageningen UR Report BCH
2013/016.
58 Asghari, F.S. and Yoshida, H. (2006). Acid-catalyzed production of
5-hydroxymethyl furfural from D-fructose in subcritical water. Industrial &
Engineering Chemistry Research 45 (7): 2163–2173. https://doi.org/10.1021/
ie051088y.
59 Roman-Leshkov, Y. (2006). Phase modifiers promote efficient production of
hydroxymethylfurfural from fructose. Science 312 (5782): 1933–1937. https://doi
.org/10.1126/science.1126337.
60 Watanabe, M., Aizawa, Y., Iida, T. et al. (2005). Glucose reactions with acid and
base catalysts in hot compressed water at 473 K. Carbohydrate Research 340 (12):
1925–1930. https://doi.org/10.1016/j.carres.2005.06.017.
61 Choudhary, V., Mushrif, S.H., Ho, C. et al. (2013). Insights into the interplay
of Lewis and Brønsted acid catalysts in glucose and fructose conversion to
5-(hydroxymethyl)furfural and levulinic acid in aqueous media. Journal of
the American Chemical Society 135 (10): 3997–4006. https://doi.org/10.1021/
ja3122763.
62 Filiciotto, L. (2019). Structural insights and valorization of humins: a catalytic
approach. PhD thesis. Universidad de Córdoba.
63 Morales, G., Melero, J.A., Paniagua, M. et al. (2014). Sulfonic acid heterogeneous
catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in
dimethyl sulfoxide. Chinese Journal of Catalysis 35 (5): 644–655. https://doi.org/

10.1016/s1872-2067(14)60020-6.
64 Dias, A.S., Pillinger, M., and Valente, A.A. (2005). Liquid phase dehydration of
D-xylose in the presence of Keggin-type heteropolyacids. Applied Catalysis A:
General 285 (1–2): 126–131. https://doi.org/10.1016/j.apcata.2005.02.016.
65 Soh, L. and Eckelman, M.J. (2016). Green solvents in biomass processing. ACS
Sustainable Chemistry & Engineering 4 (11): 5821–5837. https://doi.org/10.1021/
acssuschemeng.6b01635.
66 Yara-Varón, E., Selka, A., Fabiano-Tixier, A.S. et al. (2016). Solvent from forestry
biomass. Pinane a stable terpene derived from pine tree byproducts to substitute
n-hexane for the extraction of bioactive compounds. Green Chemistry 18 (24):
6596–6608. https://doi.org/10.1039/c6gc02191c.
67 Diallo, A.O., Len, C., Morgan, A.B. et al. (2012). Revisiting physico–chemical
hazards of ionic liquids. Separation and Purification Technology 97: 228–234.
https://doi.org/10.1016/j.seppur.2012.02.016.
68 Menegazzo, F., Ghedini, E., and Signoretto, M. (2018). 5-Hydroxymethylfurfural
(HMF) production from real biomasses. Molecules 23 (9): 2201. https://doi.org/10
.3390/molecules23092201.
69 Cicci, A., Sed, G., Jessop, P.G. et al. (2018). Circular extraction: an innovative
use of switchable solvents for the biomass biorefinery. Green Chemistry 20 (17):
3908–3911. https://doi.org/10.1039/c8gc01731j.
70 Fu, D., Farag, S., Chaouki, J. et al. (2014). Extraction of phenols from lignin
microwave-pyrolysis oil using a switchable hydrophilicity solvent. Bioresource
Technology 154: 101–108. https://doi.org/10.1016/j.biortech.2013.11.091.
71 Wang, C., Zhang, L., Zhou, T. et al. (2017). Synergy of Lewis and Brønsted acids
on catalytic hydrothermal decomposition of carbohydrates and corncob acid
hydrolysis residues to 5-hydroxymethylfurfural. Scientific Reports 7 (1): 1, , Article
ID 40908–9. https://doi.org/10.1038/srep40908.
72 Yu, I.K., Tsang, D.C., Yip, A.C. et al. (2016). Valorization of food waste into
hydroxymethylfurfural: dual role of metal ions in successive conversion steps.
Bioresource Technology 219: 338–347. https://doi.org/10.1016/j.biortech.2016.08
.002.
73 Cai, C.M., Nagane, N., Kumar, R. et al. (2014). Coupling metal halides with a
co-solvent to produce furfural and 5-HMF at high yields directly from ligno-
cellulosic biomass as an integrated biofuels strategy. Green Chemistry 16 (8):
3819–3829. https://doi.org/10.1039/c4gc00747f.
74 Choudhary, V., Sandler, S.I., and Vlachos, D.G. (2012). Conversion of xylose to
furfural using Lewis and Brønsted acid catalysts in aqueous media. ACS Catalysis
2 (9): 2022–2028. https://doi.org/10.1021/cs300265d.
75 Agbor, V.B., Cicek, N., Sparling, R. et al. (2011). Biomass pretreatment: funda-
mentals toward application. Biotechnology Advances 29 (6): 675–685. https://doi
.org/10.1016/j.biotechadv.2011.05.005.
76 Behera, S., Arora, R., Nandhagopal, N. et al. (2014). Importance of chemical
pretreatment for bioconversion of lignocellulosic biomass. Renewable and Sus-
tainable Energy Reviews 36: 91–106. https://doi.org/10.1016/j.rser.2014.04.047.
References 21
77 Kumar, A.K. and Sharma, S. (2017). Recent updates on different methods of pre-
treatment of lignocellulosic feedstocks: a review. Bioresources and Bioprocessing 4
(1): 1–19, Article ID 7: doi: https://doi.org/10.1186/s40643-017-0137-9.
78 Den, W., Sharma, V.K., Lee, M. et al. (2018). Lignocellulosic biomass trans-
formations via greener oxidative pretreatment processes: access to energy and
value-added chemicals. Frontiers in Chemistry 6: 1–23, Article ID 141. doi:
https://doi.org/10.3389/fchem.2018.00141.
79 Satari, B., Karimi, K., and Kumar, R. (2019). Cellulose solvent-based pretreat-
ment for enhanced second-generation biofuel production: a review. Sustainable
Energy & Fuels 3 (1): 11–62. https://doi.org/10.1039/c8se00287h.
80 Mosier, N., Wyman, C., Dale, B. et al. (2005). Features of promising technolo-
gies for pretreatment of lignocellulosic biomass. Bioresource Technology 96 (6):
673–686. https://doi.org/10.1016/j.biortech.2004.06.025.
81 Wagner, A., Lackner, N., Mutschlechner, M. et al. (2018). Biological pretreat-
ment strategies for second-generation lignocellulosic resources to enhance biogas
production. Energies 11 (7): 1797. https://doi.org/10.3390/en11071797.
82 Kucharska, K., Rybarczyk, P., Hołowacz, I. et al. (2018). Pretreatment of ligno-
cellulosic materials as substrates for fermentation processes. Molecules 23 (11):
2937. https://doi.org/10.3390/molecules23112937.
83 Hou, Q., Ju, M., Li, W. et al. (2017). Pretreatment of lignocellulosic biomass
with ionic liquids and ionic liquid-based solvent systems. Molecules 22 (3): 490.
https://doi.org/10.3390/molecules22030490.
84 Kumar, G., Dharmaraja, J., Arvindnarayan, S. et al. (2019). A comprehensive
review on thermochemical, biological, biochemical and hybrid conversion meth-
ods of bio-derived lignocellulosic molecules into renewable fuels. Fuel 251:
352–367. https://doi.org/10.1016/j.fuel.2019.04.049.
85 Basso, T.P. (2019). Emerging physiochemical methods for biomass pretreatment.
In: Fuel Ethanol Production from Sugarcane (eds. T.P. Basso and L.C. Basso),
41–62. London: IntechOpen.
86 Alvira, P., Tomás-Pejó, E., Ballesteros, M. et al. (2010). Pretreatment technologies
for an efficient bioethanol production process based on enzymatic hydrolysis:
a review. Bioresource Technology 101 (13): 4851–4861. https://doi.org/10.1016/j
.biortech.2009.11.093.
87 Guragain, Y.N. and Vadlani, P.V. (2016). Importance of biomass-specific pretreat-
ment methods for effective and sustainable utilization of renewable resources.
In: Biotechnology and Biochemical Engineering (eds. S. Gummadi and P. Vadlani),
207–215. Singapore: Springer.
23
Section I
Catalytic Strategies
25
Biomass Processing via Acid Catalysis

Iurii Bodachivskyi 1 , Unnikrishnan Kuzhiumparambil 2 , and D. Bradley G.
Williams 1
1 University of Technology Sydney, School of Mathematical and Physical Sciences, PO Box 123, Broadway,
NSW 2007, Australia

2
University of Technology Sydney, Climate Change Cluster (C3), PO Box 123, Broadway, NSW 2007, Australia
2.1 Introduction
Biomass consists of one or more of high-molecular-weight carbohydrates, such as
lignin (aromatic polymers), lipids, and proteins, and is a viable renewable alternative
substrate (to fossil materials) for the industrial synthesis of bulk and fine chemicals
[1–5]. Model reactions of individual substances that constitute biomass show that all
native (macro)molecules are convertible into a large range of low-molecular-weight,
value-added products through a variety of acid-catalyzed processing steps [1–13].
Catalysis is a major pillar upon which a major portion of the global chemical industry
rests, and it is estimated that catalysts are used to generate nearly 75% of all chemi-
cals produced worldwide [14]. The value and role of catalysts in the industry cannot
be overstated. The valorization of biomass is no exception [1–5].
As explained in Section 2.1.1., lignocellulose can be considered to be the main, or
only, appropriate substrate for large-scale, acid-catalyzed processing into platform
chemicals, and it accordingly holds significant industrial potential [4]. The net pro-
duction of terrestrial plant cell walls alone has been estimated to be 150–170 billion
tons per year [15]. There already exists a very significant industry revolving around
lignocellulosic materials [16]. Of these, forestry is one of the largest with a mature
global supply chain from sustainable forests through to saw mills, pulp and paper
manufacturing, and distribution networks. This industry, along with paper and card-
board recycling, is ready and poised to supply large volumes of feedstocks to indus-
tries focused on the valorization of lignocellulose to produce platform and other
chemicals. Logging slash (the side branches and other woody debris left during log-
ging operations) would be an excellent source material for industrial processes, given
the volumes of its production, the zero or negative cost associated with slash, and
the existing environmental issues relating to slash [17]. Other potential high-volume
sources of materials for the sustainable acid-catalyzed production of green chemi-
cals, without disrupting any existing business or facilities, include waste streams of
Biomass Valorization: Sustainable Methods for the Production of Chemicals, First Edition.
Edited by Davide Ravelli and Chiara Samorì.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
26 2 Biomass Processing via Acid Catalysis
marine and fresh water algae aquaculture and nonedible and waste residues from
agriculture, horticulture, and food production [4].
A goal of this chapter is to define efficient methods for the acid-catalyzed conver-
sion of biomass into targeted value-added products. It analyzes current technologies,
underpinning the relation of the method to the sustainability of the process. It also
discusses the chemistry accompanying catalytic transformations of carbohydrates
and lignin into specific products, defining the overall role of the acidic catalyst, sol-
vent, and processing parameters. This is to strengthen the foundation for future
sustainable developments of biorefineries.
2.1.1 Is an Acid the Best Catalyst?

Acid catalysts can be classified as Lewis acids or Brønsted acids and may be further
classified as heterogeneous or homogeneous [18]. Brønsted acid-catalyzed reactions
are those in which molecules are activated by protonation of the substrate. A wide
range of sites may be protonated, including carbonyl systems, alcohols, ethers, dou-
ble bonds, etc., but not all protonation steps lead to chemical reactions. Often, the
strength of the Brønsted acid, in combination with other reaction conditions, deter-
mine how and where a given substrate molecule reacts. This point will become clear
as this chapter unfolds.
Conversely, Lewis acid-catalyzed reactions are those in which the electron-
deficient center of a Lewis acid coordinates to a Lewis basic site on the substrate.
The site and strength of the bonding may be predicated based on Pearson’s HSAB
(hard and soft [Lewis] acids and bases) principles, which predict that soft Lewis acids
interact preferentially with soft Lewis bases and hard with hard [19]. When it comes
to biomass, the majority of the active sites are hard Lewis bases, and so it is most
common to encounter the application of hard Lewis acids to valorization chemistry.
In a third type of acid catalyst system, the mixtures of two different acid catalysts
produce synergistic effects to deliver enhanced catalytic activity (Brønsted or Lewis)
via an assisted acidity mechanism [20, 21]. The assisted acid systems can be con-
structed from mixtures of two Brønsted acids (Brønsted acid-assisted Brønsted acid
catalysts), two Lewis acids (Lewis acid-assisted Lewis acid catalysts), or Brønsted
and Lewis acids (Brønsted acid-assisted Lewis acid catalysts or Lewis acid-assisted
Brønsted acid catalysts) [20]. Under specific types of conditions, these mixtures can
turn into superacidic systems [22], imparting very significant catalyst activity. A
pictorial manifestation of the activation of the substrate by different types of acid
catalysts is represented in Scheme 2.1, and throughout this chapter, we will make
reference to the different types of acidity that are, or may be, at play.
As is evident from Scheme 2.2, acids can promote the valorization of all main
classes of biomacromolecules. Only a few existing acid-catalyzed processes can
be considered to be sustainable, usually because of the nature of the substrates
employed. Most methods that show promise in the laboratory are based on
transformations of refined edible substances, such as low-molecular-weight sac-
charides and oligosaccharides, vegetable oils, or refined proteins [1, 2, 4, 23]. The
use of food products for the production of chemicals fails to meet sustainability
requirements and must be avoided in large volume manufacturing, even though
2.1 Introduction 27
Brønsted acid
H + Sub
O
O
H M
O H + Sub O H Sub Sub + H O
Brønsted acid assisted Brønsted acid Lewis acid assisted
brønsted acid activation brønsted acid
O Lewis acid
H activation M
M + Sub M Sub Sub + M
Brønsted acid assisted Lewis acid assisted

lewis acid lewis acid
+ Sub
M
Lewis acid
Scheme 2.1 Types of acid catalysts and acid-catalyzed activations. Sub, substrate. H+ ,
hydrogen ion; although Brønsted acids are conventionally denoted as H+ , the hydrogen ion
is known to form Lewis acid–Lewis base complexes, for instance, H13 O6 + in aqueous
solutions. M, electron-deficient center of the Lewis acid catalyst. Source: Bodachivskyi
et al. [4, 7].
Brønsted and lewis acids OH

Dehydration
Rehydration
HO O
OH
Isomerization Glyceraldehyde Levulinic acid or
RO alkyl levulinates
Lactic acid or alkyl lactate O O
O HO OH OR
Dihydroxyacetone
O
Lewis acids Retro-aldol condensation
Brønstedacids
OH rehydration
Brønsted acids
OH OH Lewis acids OH O Brønsted acids
OH hydrolysis isomerization dehydration O
O O HO O OH
O HO HO HO O
HO O
OH OH OH OH OH
OH Fructose HMF
Glucans Glucose
Brønsted acids OH Lewis acids Brønsted acids
isomerization
OH dehydration
O HO OH hydrolysis
O O HO O HO OH O
HO O O
OH OH OH OH O
Xylans Xylose Xylulose FF
OH
O O OH OH OH
O Brønsted and
lewis acids O OH
HO O O
Lignin HO O
O
O Phenol derivatives
OH OH OH
O O
Brønsted and O O O O
R O O R lewis acids
Triacylglycerides O O R O OH R RNR2 R OR O Estolides O
O OH Fatty acid Fatty acid R OR
R R OH Monoacylglycerides
alkyl esters amides
Fatty acids
S O R O Brønsted acids S O O
H H hydrolysis H O
N N N H3 N H3N
N N H3N O O O
H H
O R O S O R R S
Proteins Peptides and amino acids
Scheme 2.2 Acid-catalyzed valorization of biomacromolecules. R, H or organyl.

certain biorefinery processes have been readily engineered on a sizeable scale, such
as production of lactates from sugar-derived lactic acid (LacA), alkyl glucoside
surfactants from mono- and oligosaccharides, or biodiesel fuel from edible seed
oils [1, 2]. In contrast, nonfood competitive materials, such as plant cell walls
(lignocellulose), or oleaginous and keratinous waste are sustainable feedstocks
for industrial chemical processing [4, 24, 25]. Examples of sustainable feedstocks
include non-food-competitive waste products and side streams of forestry, horticul-
ture and agriculture, vegetable oil refinery, animal husbandry, along with animal
feather, wool, horns, and other indigestible fibrous proteins (keratinous feedstocks).
Although acid catalysis prevails in most processes with, for example, lignocellu-
lose, it is not the only means that adds value to biomass, especially with noncellulosic
substances. Sometimes, other strategies are more advantageous, brought about in
large part because of the limitations of the chemistry under acid-catalyzed condi-
tions. For example, lipids, such as triacylglycerides and free fatty acids, can form
manifold oleochemicals (functional products based on oleaginous materials) in the
presence of an appropriate acid catalyst (Brønsted or Lewis) [1, 2, 10–12]. In par-
ticular, acid-catalyzed esterification of free fatty acids with low-molecular-weight
alcohols is beneficial for the production of biodiesel fuel from waste cooking oils
[26, 27]. However, base catalysts or transition metal catalysts are more efficient for
the transformation of triacylglycerides into fuel products (fatty acid alkyl esters or
varied hydrocarbons) and other functional oleochemicals [24, 26–28]. Acid catalysts
fare less well for such transformations [26, 27]. Additionally, the proteinaceous por-
tion of biomass may be hydrolyzed into amino acids in solutions of concentrated
Brønsted acids [13]. Nevertheless, the depolymerization of keratinous waste is often
more efficient by other means than acid catalysis [25].
Polysaccharides, such as glucans and xylans, can be depolymerized into monomer
sugars in the presence of Brønsted acid catalysts [4, 6]; such monosaccharides have
many applications from organic synthesis [29] to energy sources for fermenta-
tion [30]. In the context of valorization chemistry toward platform molecules,
for example, the depolymerization step is followed by the Lewis acid-catalyzed
aldose–ketose isomerization of monosaccharides, or their retro–aldol reactions,
into other derivative carbohydrates [4, 7]. These intermediate products are typically
convertible into furan-type molecules or carboxylic acid derivatives under suitable
processing parameters (catalyst, solvent, and reaction temperature). Indeed, the
reaction conditions can be determinative of the selectivity toward specific types of
products [4, 7].
Apart from carbohydrate polymers, lignin is known to transform into a range of
useful phenol derivatives under acid-catalyzed conditions, but the overall role of
the catalysis is less well understood for these processes [5, 8, 9]. These bio-based
molecules may potentially generate a renewable platform that produces large vol-
umes of green replacements to crude oil-based products, such as fuels, monomers
for plastics, detergents, and other commodity products [1–13]. In the rest of this
chapter, we will concentrate only on those transformations where acid catalysts
display notable advantages over other types of catalysts. Effectively, this approach
focuses on lignocellulosic materials.
2.2 Acid-Catalyzed Processing of Cellulosic

Polysaccharides
The valorization of lignocellulose is an intricate chemical problem. The challenge
relates largely to the rigid supramolecular structure of native plant cell walls, formed
by inter- and intramolecular bonding of polysaccharides, lignins, and sometimes
other macromolecules [31]. A common strategy to improve reactivity is to separate
carbohydrate polymers and lignin [32]. Fractionation of biomass is performed on
large scale during commercialized pulping processes and may also be conducted by
the selective catalytic transformation of one particular class of biomacromolecules
[16, 32–35]. For example, a carbohydrate fraction can be recovered by catalytic
hydrogenolysis of lignin into low-molecular-weight phenolic substances [33]. It is
also possible to retain the lignin fraction by the direct acid-catalyzed processing
of polysaccharides present in native biomass [34, 35]. To complicate matters, the
acid-catalyzed transformation of individual macromolecules is a complex cascade
of reactions that require both Brønsted acid and Lewis acid catalysts (Scheme 2.2)
[4, 7]. In addition, acidic catalysts may simultaneously promote side reactions of
the products into undesirable by-products, compromising selectivity of the targeted
processes [4, 7]. Consequently, judicious selection of the catalysts and processing
conditions are essential to ensure the efficient processing of biomass into targeted
value-added products. This section will deal with major developments in the
processing of cellulosic substances.
Cellulose is the most naturally abundant macromolecule on the Earth [36]. Even
if this view is contested, lignocellulose is the only large volume biomass to which
we have ready access on large industrial scale and where there is a globally dis-
tributed large volume industry and supply chain [4]. Cellulose consists of β(1 → 4)
linearly linked glucose units and is a principal portion of plant cell walls. Hemicel-
lulose is another polysaccharide present in lignocellulose and is often made of struc-
turally branched xylose units and sometimes other moieties [6, 16, 31]. The past few
decades have witnessed a significant interest in the acid-catalyzed processing of cel-
lulosic substances into organic building block chemicals (platform molecules), such
as 5-(hydroxymethyl)furfural (HMF), furfural (FF), levulinic acid (LevA), LacA, and
their many derivatives [4].
A key first step in the valorization of polysaccharides is the depolymerization
thereof into low-molecular-weight sugars, from which other value-added chemicals
are generated (Scheme 2.2) [6, 37]. In their own right, low-molecular-weight saccha-
rides are valuable ingredients in the food manufactory and also used as substrates
for the fermentative production of ethanol or LacA [38–40]. Polysaccharides are
commonly hydrolyzed in aqueous mineral acids in industrial processes [41]. Most
technologies are based on thermal hydrolysis of cellulosic biomass in dilute aqueous
sulfuric acid solution in batch or percolation reactors, with a typical glucose yield
of 55–70% [41]. The glucose yield may be improved to 85%, when conducting the
hydrolytic processing of biomass in a countercurrent shrinking bed reactor system
at elevated temperatures (up to 225 ∘ C) [42]. This technology has been engineered
at National Renewable Energy Laboratory (NREL) by designing a cascade of
percolation reactors simulating countercurrent. The available information suggests

that this specific process has been demonstrated to bench scale at present [42]. The
sustainability of such methods at industrial scale may be compromised by the need
for forcing processing parameters [40, 43]. On the other hand, complexities arise
because of the formation of large amounts of acidic wastewater and solid waste
(typically, calcium sulfate after neutralization of sulfuric acid) and also because of
the requirement for corrosion-resistant manufacturing equipment [4, 40]. These
ongoing challenges have led to the exploration of new efficient methods for the
hydrolytic processing of polysaccharides into low-molecular-weight derivatives,
where high yields and selectivities, accompanied by low levels of waste production,
are key parameters.
Solid acid-catalyzed reactions of polysaccharides in aqueous media have drawn
particular interest [40]. The use of solid catalysts is attractive because of the ease of
their recovery and sometimes recyclability. An interesting strategy has been devised
using a cellulase mimetic catalyst [44], containing both cellulose binding and
cellulose hydrolyzing sites, similar to cellulase enzymes. The catalyst is a sulfonated
chloromethyl polystyrene resin (CP-SO3 H) bearing chloride groups (–Cl) with
which saccharides and sulfonic groups (–SO3 H) are coordinated to generate the
Brønsted acidity requisite for the hydrolysis of the glycosidic linkages (Scheme 2.3)
[44]. The catalyst CP-SO3 H demonstrated impeccable activity during the processing
of microcrystalline cellulose (MCC), or starch (a mixture of α(1 → 4) linearly linked
glucose polymer amylose and branched α-glucose polymer amylopectin), in high
yields of glucose (up to 100%). CP-SO3 H is significantly more efficient than a diluted
solution of sulfuric acid under identical processing conditions, or many other
reported solid acid catalysts, such as acidic resins, zeolites, carbonaceous acids, or
functionalized silicas [44, 45]. This success has spread the adoption of cellulase
mimetic catalysts based on varied sulfonated chloroorganic materials [46]. Table 2.1
provides a summary of the outcomes of several acid-catalyzed processes.
OH Cellulose
OH
O O HO O
HO O O
OH
H OH
O
O
Cl S O Cl
Catalyst
Scheme 2.3 Proposed structure and mechanism of catalytic action of the cellulase
mimetic catalyst. Source: Based on Shuai and Pan [44].
The sustainability of solid acids is somewhat undermined by the insolubility

of both the cellulose and the catalyst, the latter by design, in aqueous reaction
mixtures [4, 40]. The heterogeneity of the system limits the number of effective
substrate–catalyst interactions during the processing, leading to several technical
and economical hurdles. Firstly, there is a need for high loadings of the catalyst
Table 2.1 Conditions and results of the acid-catalyzed processing of cellulosic biomass into carbohydrates and furansa).
Yield Yield Yield Yield Yield

Substrate Reaction media Catalyst T (∘ C) t (h) glucans (%) glucose (%) xylose (%) HMF (%) FF (%) References
MCC Water CP-SO3 H 120 10 — 93 — — — [44]

Starch 2 — 100 — — —
MCC H2 SO4 — 1 — — —
Ball-milled Water Carbonaceous Cl− , 120 24 — 85 — — — [46]
MCC SO3 H-containing
material
Ball-milled Water Si33 C66 -823-SO3 H 150 24 4 50 — 0 — [45]
MCC
Sulfonated 6 27 — 1 —
pyrolyzed sucrose
Beechwoodb) Water H2 SO4 145 1 2 76 74 2 6 [47]
Poplar woodb) 2 78 82 2 8
Cotton linters [C2 mim]Clc) HCl 105 3d) — 87 — 6 — [34]
Corn stover [C2 mim]Clc) — 70 79 — —
Sigmacell [C4 mim]Cl H2 SO4 100 0.75d) — 38 — — — [48]
[C4 mim]Cl HCl 100 0.18d) — 21 — — —
Eucalyptus [C4 mim]Cl/ — 120 10 19 48 — 4 — [49]
cellulose ChCl/oxalicc)
Pinus cellulose 120 10 21 50 — 6 —
Corncob 100 2 0 54 35 10 —
120 4
P. cruentum 100 2 0 55 40 0 —
120 4
(continued)
Yield Yield Yield Yield Yield

Substrate Reaction media Catalyst T (∘ C) t (h) glucans (%) glucose (%) xylose (%) HMF (%) FF (%) References
Cellulose [C2 mim]Cl/ CrCl2 /HCl 140 2d) — — — 54 — [50]

Corn stover DMA/LiCl CrCl3 /HCl 47 37
MCC [C2 mim]Clc) CuCl2 /CrCl2 120 8 — — — 58 — [51]
MCC [C2 mim]OAc/ CuCl2 160 3.5 — — — 70 — [52]
[C4 SO3 Hmim]-
CH3 SO3
Wood chipse) [C4 mim]Cl CrCl3 120 2 — — — 79 — [53]
Rice strawe) — — — 76 —
Corn husk ZnCl2 ⋅3.0 — 120 1d) — — — — 26 [54]
P. cruentum H2 O/anisole — — — — 42
Corncob ZnCl2 ⋅4.25 H2 O HCl 120 1d) — 61 — 30 22 [35]
P. cruentum — 49 — 35 29
Softwood — 26 — 22 11
Ulva lactuca — 52 — 25 15
Inulin ChCl/oxalic/EtOAc — 80 2 — — — 64 — [55]
Xylans ChCl/citric/MIBK AlCl3 140 0.58 — — — — 69 [56]
P. cruentum ChCl/oxalic — 80 2 0 42 73 1 25 [57]
P. cruentum ChCl/oxalic/MIBK — 100 2 0 68 13 9 44
4 0 32 0 5 72
Softwood ChCl/oxalic/MIBK — 100 5 0 0 0 1 55
a) We note that this table show yields of products either in mol% or in wt%; it is recommended to refer to the given references if the accurate evaluation of yields is
sought. “—” = not specified; “0” = not detected, or detected in trace amounts; T, reaction temperature; t, reaction time; HMF, 5-(hydroxymethyl)furfural; FF,
furfural; MCC, microcrystalline cellulose; [C2 mim]Cl, 1-ethyl-3-methylimidazolium chloride; [C2 mim]OAc, 1-ethyl-3-methylimidazolium acetate; [C4 mim]Cl,
1-butyl-3-methylimidazolium chloride; [C4 SO3 Hmim]CH3 SO3 , 1-(4-sulfobutyl)-3-methylimidazolium methanesulfonate; ChCl, choline chloride; DMA,
dimethylacetamide; EtOAc, ethyl acetate; and MIBK, methyl isobutyl ketone.
b) The substrate was subjected to sulfuric acid-assisted ball milling.
c) ILs were diluted with water during processing to a total water up to 10–43 wt% based on the reaction system.
d) t does not include the time for the dissolution of the substrate.
e) Substrate was treated with aqueous sodium hydroxide.
[4, 44–46]. This may lead to the production of solid deactivated catalyst waste,
if it is not fully recyclable. Another downside relates to the use of pretreated
cellulose, instead of largely available lignocellulosic biomass. Pretreatment helps
to ameliorate issues pertaining to mass transfer in heterogeneous systems, owing
to the reduced physical size and sometimes lower molecular weight of pretreated
polysaccharides. Examples of pretreated substrates are MCC, a medium value
product obtained by the treatment of wood pulp in diluted aqueous acids, and
ball-milled cellulose [16, 58]. Ball milling is arguably the most commonly used
method for the pretreatment of cellulosic biomass. Although this approach is
efficient at the bench scale and quite effectively depolymerizes cellulose to some
extent, it becomes highly energy demanding at the larger scale and remains mostly
unemployed in the industry [4]. Some studies, however, claim that some of the
significant energy implications associated with this method of pretreatment may
be avoided for acid-assisted mechanochemical depolymerization [47, 59]. For
instance, mechanochemical depolymerization of beechwood and poplar wood
may be realized at kilogram scale by ball milling of biomass in the presence of
sulfuric acid [47]. Nevertheless, these processes require subsequent dilution of the
pretreated acidified systems with water and hydrolytic treatment under forcing
reaction conditions, which does not significantly differ from other processes in
aqueous solvents (Table 2.1). Considering the energy costs accompanied by a need
for corrosion-resistant equipment, such means of depolymerization cannot be
accepted as sustainable, unless the energy demands of ball milling can somehow be
reduced.
The rates and (often) selectivities of the chemical process improve if the process
can be performed under homogeneous conditions. As mentioned above, cellulosic
materials are essentially insoluble in aqueous systems and most common organic
solvents. However, ionic liquids (ILs) in their many manifestations are potentially
key to improved chemical transformations of cellulosic materials. ILs are a class of
green solvents that consist solely of ions and, under certain conditions, are able to
fully dissolve cellulosic polysaccharides [48, 60, 61]. This ability enables significant
progress toward milder reaction conditions and better yields of some targeted prod-
ucts, making ILs outstanding reaction systems for the acid-catalyzed valorization of
native carbohydrates [4, 61]. For example, quaternary ammonium salts, especially
imidazolium derivatives such as 1-alkyl-3-methylimidazolium chloride ([Cn mim]Cl,
n = integer), have been effectively employed in the catalytic hydrolysis of cellulose
and cellulosic biomass of diverse origin [34, 49, 62, 63]. A seminal study [34] explored
transformations of polysaccharides into monomer sugars (glucose and xylose) in a
range of ILs in the presence of hydrochloric acid, a Brønsted acid catalyst. The study
identifies that the molecular formula of ILs substantially influences the reaction out-
comes, mostly related to the solubility of the substrate. There is an apparent need
for the chloride anion to coordinate hydroxyl groups and to disrupt the extensive
hydrogen bonding between polysaccharides, thus promoting their dissolution. In
contrast, non-coordinating, or weakly coordinating, anions, such as tetrafluorobo-
rate (BF4 − ), nitrate (NO3 − ), bromide (Br− ), and trifluoromethanesulfonate (triflate,
OTf− ), dissolve cellulose only poorly, slowing or preventing reactions from taking
place [34, 64]. The cation component of the ILs also influences the chemical reactiv-
ity of the cellulose in ILs: imidazolium salts or alkylpyridinium-based solvents with
longer alkyl chains reduce the solubility of cellulose in such ILs, hampering the reac-
tivity [58, 64]. Interestingly, imidazolium ILs with acetate (OAc− ) and dimethylphos-
phate ((MeO)2 P(O)O− ) counterions, which are excellent solvents for cellulose [64],
provide zero yield of glucose after exposure to intended hydrochloric acid-catalyzed
processing of cellulose [34]. This is likely because of the reaction between the strong
Brønsted acidic hydrochloric acid and the conjugate base of weaker acids, leading
to formation of imidazolium chloride and a weaker Brønsted acid (acetic acid or
dimethylphosphoric acid) that is unable to promote the hydrolysis under the selected
processing conditions [62].
Another important finding is that acid-catalyzed conversion of cellulosic biomass
in IL media can be improved and effectively promoted by the gradual addition
of water [34]. The optimized method provides impressive yields of glucose (up to
87 mol% based on the glucose content in the substrate) and xylose (up to 79 mol%
based on the xylose component of the substrate) in [C2 mim]Cl solvent in the
presence of hydrochloric acid catalyst at 105 ∘ C, whose mixture was gradually
diluted with 43 wt% of water (Table 2.1). Previous methods, which were based
on the processing of cellulose in [C4 mim]Cl without addition of water, provided
significantly lower yields of monosaccharides [48]. Although glucose is the terminal
product of hydrolysis chemistry of cellulose, the hydrolysis of cellulose proceeds
predominantly into glucose oligomers (cellotetraose, cellotriose, and cellobiose)
from which glucose emerges (Scheme 2.4) [49]. There is also evidence that water
suppresses the subsequent acid-catalyzed conversion of saccharides into furanoids
and by-products in ionic solvents [34, 49, 62], thereby enhancing the yields of
the desirable monosaccharides. The addition of water enhances the high yielding
and selective transformation of polysaccharides into monomer sugars in ILs: it
helps to promote the formation of monosaccharides and suppresses unwanted
processes. However, care must be taken as to the timing of the addition of water. If
this is done at the start of the process, then the substrate can remain undissolved
because of the negative influence of the added water on the ability of ILs to dissolve
biomass [34, 62]. Finally, the processing of lignocellulose in imidazolium ILs leaves
a lignin-rich residue as the unreacted portion that can be potentially employed
for subsequent valorization [34]. Table 2.1 provides processing conditions and
outcomes of several instances, as described above.
ILs are highly tunable systems, and their physical and chemical characteris-
tics can be modulated for specific tasks, providing high levels of flexibility for
[Cn mim]Cl
OH Brønsted acid OH OH OH
OH H2O OH
HO O O O HO O
H2O HO O
O HO O OH
O HO HO O O HO OH HO
OH OH m OH OH
OH Cellulose HO Glucose
Scheme 2.4 Acid-catalyzed hydrolysis of cellulose into low-molecular-weight

carbohydrates in ILs via oligosaccharides. n, integer; m, 0, 1, and 2 for cellobiose, cellotriose,
and cellotetraose, respectively.
Another random document with
no related content on Scribd:
VIII
Jelisein jäädessä mökkiin sairaiden luokse odotti Jefim häntä

kokonaisen päivän. Hän astui vain lyhyen matkan eteenpäin ja jäi
maantien reunalle istumaan; hän odotti odottamistaan, nukahti,
heräsi, istui vielä hetken — mutta toveria ei vieläkään näkynyt. Hän
tähysteli melkein silmät päästään. Aurinko laski — Jeliseitä ei
vieläkään näkynyt.
Jefim ajatteli itsekseen:— Onkohan hän mahtanut kävellä minun

ohitseni tahi ajanut ohitse (jos joku on ottanut hänet rattailleen), kun
nukuin, eikä ole minua huomannut? Mutta olisihan hänen pitänyt
minut nähdä! Arolla näkee hyvin kauas. Jos minä nyt käännyn
takaisin, voi hän joutua kauas edelleni. Vielä pahempi on eksyä
toisistaan.
Parasta lienee mennä eteenpäin ja odottaa häntä ensi

majapaikassa.
Hän tuli kylään ja pyysi kymmenniekkaa heti ilmoittamaan, jos

kylään tulisi pieni kaljupäinen ukko. Mutta Jeliseitä ei kuulunut. Jefim
astui eteenpäin ja kyseli kaikilta, eivätkö olleet nähneet vanhaa
kaljupäistä miestä. Kukaan ei ollut nähnyt. Jefim oli ihmeissään ja
lähti yksin eteenpäin. Hän arveli tapaavansa Jelisein Odessassa tahi
laivalla eikä ajatellut asiaa sen enempää.
Matkalla hän sai seuralaisekseen erään pyhiinvaeltajan. Tällä oli

yllään munkin hilkka ja kaapu ja hänen hiuksensa olivat pitkät kuin
papin. Hän oli käynyt pyhän Athos-vuoren luostarissa ja matkasi jo
toista kertaa Jerusalemiin. He tapasivat toisensa eräässä
majatalossa, alkoivat puhella keskenään ja läksivät yhdessä
eteenpäin.
Terveinä ja reippain mielin he saapuivat Odessaan. Täällä heidän

täytyi odottaa kolme päivää laivan lähtöä. Moni muu pyhiinvaeltaja
— niitä oli tullut kaikilta suunnilta — odotti siellä heidän kanssaan.
Jefim kyseli jokaiselta Jeliseitä, mutta kukaan ei ollut häntä nähnyt.
Pyhiinvaeltaja neuvoi Jefimille, miten merimatka voitaisiin tehdä

maksutta. Jefim ei tahtonut kuitenkaan häntä kuunnella, vaan virkkoi:
— Minä maksan mieluummin rehellisesti merimatkasta; sitä

vartenhan minä olen juuri säästänytkin.
Hän maksoi neljäkymmentä ruplaa meno- ja paluulipusta ja osti

leipää ja silliä evääksi matkalle. Kun laiva oli lastattu, pääsivät
pyhiinvaeltajat sinne. Jefim ja hänen uusi matkatoverinsa astuivat
myöskin laivaan. Ankkuri nostettiin, ja laiva lähti aavalle merelle.
Ensimmäisenä päivänä meni matka varsin hyvin, mutta illalla nousi
tuuli, alkoi sataa, laiva keinui puolelle ja toiselle, ja aallot huuhtelivat
usein kantta. Matkustajat kävivät levottomiksi, naiset parkuivat, ja
moni arkaluontoinen mies juoksenteli sinne tänne turvaa etsien.
Jefim oli myös peloissaan, mutta ei tahtonut sitä näyttää; hän istui
koko yön ja koko seuraavan päivän samassa paikassa, minne oli
laivaan tullessaan istuutunut. Hänen vieressään istui useita miehiä
Tambovin tienoilta. Hän, kuten tambovilaisetkin, piteli
matkalaukkuaan käsissään eikä puhunut sanaakaan. Kolmantena
päivänä oli tyyni, viidentenä laiva laski Konstantinopolin satamaan.
Jotkut pyhiinvaeltajista menivät maihin katsomaan pyhän Sofian
temppeliä, jonka herroina turkkilaiset nyt ovat. Mutta Jefim ei
mennyt, vaan jäi istumaan laivaan. Vuorokauden oli laiva
Konstantinopolissa, sitten se jatkoi matkaansa. Se poikkesi vielä
Smyrnaan ja Aleksandriaan ja saapui onnellisesti Jaffan kaupunkiin.
Jaffassa täytyi pyhiinvaeltajien astua laivasta ja kulkea
seitsemänkymmentä virstaa jalan Jerusalemiin. Laivasta astuminen
oli pyhiinvaeltajista kovin pelottavaa: laiva oli korkea, ja
pyhiinvaeltajien täytyi hypätä laivan kannelta veneeseen. Vene
keinui sinne tänne, niin että helposti saattoi pudota veteen. Pari
pyhiinvaeltajaa kastuikin perinpohjin, mutta kaikki pääsivät kuitenkin
onnellisesti maihin. Astuttiin eteenpäin ja neljäntenä päivänä
saavuttiin Jerusalemiin. Lähdettiin venäläiseen majataloon, joka oli
kaupungin portin edustalla, näytettiin passit ja syötiin päivällistä.
Sitten Jefim lähti pyhiinvaeltajan opastamana pyhiin paikkoihin.
Vapahtajan hautaa katsomaan ei vielä päästetty. He joutuivat
patriarkan luostariin, jonne kaikki pyhiinvaeltajat kerääntyivät; siellä
asetettiin miespuoliset ja naispuoliset eri ryhmään. Kaikkien
käskettiin riisua jalkineet ja istuutua piiriin. Munkki pyyhinliinoineen
saapui pesemään jalkoja; hän pesi, pyyhki ja suuteli ja teki niin
jokaiselle. Jefiminkin jalkoja hän pyyhki ja suuteli. He olivat ilta- ja
aamujumalanpalveluksessa, rukoilivat, asettivat kynttilöitä
pyhäinkuvain eteen ja antoivat uhrilahjoja vanhempainsa puolesta.
Siellä heille annettiin ruokaa ja tarjottiin viiniä. Aamulla he menivät
kammioon, jossa Neitsyt Maria varustautui pakenemaan Egyptiin. He
toivat kynttilöitä pyhäinkuvain eteen ja olivat läsnä
jumalanpalveluksessa. He lähtivät täältä Abrahamin luostariin ja
näkivät puutarhan, ja kohdan, missä Abraham aikoi uhrata poikansa
Herralle. Sitten he kävivät paikassa, missä Kristus ilmestyi Maria
Magdalenalle, ja Jakobin, Herran veljen, kirkossa. Pyhiinvaeltaja
näytti Jefimille kaikki pyhät paikat ja sanoi hänelle kaikkialla, kuinka
paljon rahaa oli uhrattava. Kun he olivat palanneet majataloon ja
päässeet jo levolle, alkoi pyhiinvaeltaja äkkiä voihkia ja kopeloida
vaatteitaan. Lopulta hän valitti:
— Minulta on viety kukkaro. Siinä oli kaksikymmentäkolme ruplaa:

kaksi kymmenen ruplan seteliä ja kolme ruplaa pientä rahaa.
Hän valitteli vielä kauan. Asia ei kuitenkaan ollut autettavissa, ja

kaikki rupesivat levolle.
IX
Jefim pani myös pitkäkseen. Mutta syntiset ajatukset alkoivat kiusata

häntä. Hän ajatteli itsekseen, ettei hänen toveriltaan pyhiinvaeltajalta
ole tainnut kukaan ryöstää rahoja ja ettei hänellä ole niitä ollutkaan.
Sillä hän ei ollut missään maksanut mitään. Hän on antanut minun
maksaa joka paikassa, itse ei ole penniäkään hellittänyt, onpa vielä
lainannutkin minulta ruplan.
Ja tätä miettiessään hän alkaa soimata itseään: — Minkätähden

minä rupean toista ihmistä epäilemään? Se on suuri synti. Minun
täytyy olla ajattelematta koko asiaa.
Mutta sittenkin tulee taas mieleen, miten pyhiinvaeltaja pälyili

hänen rahojaan ja miten uskomattomalta tuntui koko juttu, että
häneltä, oli kukkaro varastettu. Ja Jefim ajattelee jälleen: — Hänellä
ei ole varmaankaan rahaa ollutkaan. Se on petkutusta.
Seuraavana päivänä mentiin isoon Ylösnousemuksen kirkkoon

Pyhälle
Haudalle. Pyhiinvaeltaja pysyy koko ajan Jefimin seurassa.
Tultiin temppeliin. Suuri joukko pyhiinvaeltajia seisoi ulkopuolella:

venäläisiä ja kaikenlaisia muita kansallisuuksia, kreikkalaisia,
armenialaisia, turkkilaisia ja syyrialaisia. Heitä oli tavattoman paljon.
Jefim kulki väkijoukossa Pyhästä portista. Munkki opasti heitä. Hän
vei heidät turkkilaisen vahdin ohi paikkaan, missä Vapahtaja oli
otettu ristiltä ja hänen ruumiinsa voideltu. Siinä kohdassa oli
yhdeksän suurta haarakynttiläjalkaa palavin kynttilöin. Opas näytteli
ja selitteli kaikki. Jefim lahjoitti tännekin kynttilän. Matkatoveri vei
hänet sitten oikealle portaita ylös siihen kohtaan Golgataa, missä
risti oli seisonut. Jefim vaipui täällä rukoukseen. Sitten näytettiin
hänelle halkeama, joka oli syntynyt, kun maa oli auennut manalaan
saakka, ja kohta, missä Vapahtaja oli ristiinnaulittu. Hänelle näytettiin
Aatamin hauta, missä Kristuksen veri vuoti Aatamin luille. He tulivat
sitten kivelle, missä Kristus oli istunut, kun hänen päähänsä pantiin
orjantappurakruunu; sitten paalun luo, mihin hänet oli sidottu, kun
häntä piestiin. Jefim näki myös kiven, missä oli kaksi syvennystä,
Vapahtajan jalkain jäljet. Hänelle olisi tahdottu vielä jotakin näyttää,
mutta muut kiiruhtivat Kristuksen haudan kappeliin, missä
vierasuskoisten jumalanpalvelus juuri oli päättynyt ja oikeauskoisten
alkoi. Jefim tuli muun väen mukana tänne.
Hän olisi tahtonut päästä pyhiinvaeltajasta eroon, syntiset

ajatukset kun yhä vielä häntä ahdistivat, mutta matkatoveri oli joka
askeleella hänen kintereillään ja seisoi nytkin hänen vieressään
päiväjumalanpalveluksessa hautakappelissa. He olisivat halunneet
tunkeutua lähemmäksi eteenpäin, mutta eivät enää päässeet; tungos
oli niin suuri, ettei voinut liikkua eteen- eikä taaksepäin. Ja kun Jefim
siinä seisoo, katsoo eteenpäin ja rukoilee, haparoi hän samalla koko
ajan rahakukkaroaan. Hän ajattelee kahta asiaa: ensiksikin, että
matkatoveri pettää häntä; toiseksi, että ellei tämä ole valehdellut,
vaan rahakukkarojuttu onkin tosi, niin kuka takaa, ettei hänelle
itselleen käy samoin.
X
Jefim seisoo keskellä tungosta, rukoilee ja katsoo eteenpäin

kappeliin, missä on pyhä hauta, jonka yläpuolella palaa
kolmekymmentäkuusi lamppua. Jefim seisoo siinä katsellen ihmisten
päiden yli… Mitä ihmettä! Kaikkien pyhiinvaeltajien edessä, aivan
lamppujen alla, on lyhyt, vanha mies karkeasta kankaasta tehdyssä
kauhtanassa; kalju päälaki hohtaa suurena pälvenä aivan kuin
Jelisei Bodrovin pää. — Hän on todellakin aivan Jelisein näköinen,
— ajattelee Jefim mielessään. — Mutta Jelisei se ei voi mitenkään
olla. Mitenkä hän olisi ehtinyt Jerusalemiin ennen minua! Odessasta
oli laiva lähtenyt viimeksi viikkoa aikaisemmin kuin meidän
laivamme. Sillä laivalla hän ei ole mitenkään voinut tulla. Meidän
laivassamme hän ei ainakaan ollut. Minähän näin kaikki
pyhiinvaeltajat.
Jefim oli tuskin ehtinyt näin päätellä, kun tuo mies alkoi rukoilla.
Hän kumartui kolme kertaa: kerran eteenpäin Jumalalle ja sitten
oikealle ja vasemmalle oikeauskoiselle kristikunnalle. Ja kun hän
käänsi päänsä oikealle, näki Jefim todellakin ystävänsä Jelisei
Bodrovin. Hän tunsi tämän mustan kiharan parran, josta pilkisti
harmaata poskien kohdalla, silmäkulmat, silmät, nenän ja koko
kasvot — Jelisei Bodrov ilmielävänä.
Jefim tuli hyvin iloiseksi, kun oli jälleen tavannut
matkakumppaninsa, ja ihmetteli samalla, miten tämä oli päässyt
perille ennen häntä.
— Kas sitä Bodrovia, kuinkahan se on päässyt noin eteen! ajatteli

hän itsekseen. — On varmaan saanut sellaisen toverin, joka on
toimittanut hänet sinne. Minäpä tapaan hänet ulko-ovella. Annan
matkapassit pyhiinvaeltajalle ja yhdyn Jeliseihin. Hän toimittaa
varmasti minutkin lähemmäksi.
Jefim koetti nyt pitää varansa, ettei Jelisei pääsisi näkyvistä.

Jumalanpalvelus oli päättynyt, ihmisjoukko tunkeutui eteenpäin
saadakseen suudella ristiä, ja Jefim työntyi väkijoukossa syrjään.
Hänet valtasi taaskin pelko, että häneltä viedään rahakukkaro. Koko
ajan hän koetteli kukkaroaan ja ponnisteli päästäkseen tungoksesta
ulkoilmaan. Hän pääsi ulos ja kierteli etsien Jeliseitä sekä
ulkopuolelta että sisältä. Temppelin kammioissa oli paljon
kaikenlaista väkeä: muutamat söivät täällä ja joivat viiniä, makasivat
ja lukivat. Jeliseitä ei vain näkynyt missään. Jefim palasi majataloon,
mutta ei löytänyt Jeliseitä. Tänä iltana ei pyhiinvaeltajakaan tullut
enää majapaikkaan. Hän oli kadonnut antamatta takaisin
lainaamaansa ruplaa. Jefim oli nyt yksin.
Seuraavana päivänä Jefim meni jälleen Vapahtajan haudalle

erään tambovilaisen vanhuksen seurassa — tämä tambovilainen oli
tullut samassa laivassa. Hän yritti päästä lähemmäs eteen, mutta
työntyi tungoksessa aina poispäin. Hän jäi erään pylvään ääreen
rukoilemaan. Ja katsellessaan siinä eteensä hän näkee taaskin
aivan Pyhän haudan luona, lamppujen alla, Jelisein seisovan. Hän
on levittänyt kätensä niinkuin pappi alttarilla, ja kalju päälaki hohtaa.
— No, nyt, — ajattelee Jefim, — tällä kertaa en hellitä silmiäni
hänestä. — Hän tunkeutui väkijoukon läpi ja pääsi eturiviin. Mutta
Jelisei ei ohut enää siellä.
Kolmantena päivänä Jefim menee jumalanpalvelukseen ja näkee

jälleen pyhässä paikassa Jelisein. Hän seisoo nytkin käsivarret
levällään ja katse ylöspäin suunnattuna, kuin näkisi jotakin ylhäällä.
Ja kalju päälaki hohtaa ja loistaa. — Nyt, — ajattelee Jefim, — nyt
hän ei ainakaan pääse karkuun. Minä asetun ulko-ovelle ja tartun
siellä kiinni hänen käsivarteensa. Meidän on mahdotonta siellä
sivuuttaa huomaamatta toisiamme. — Jefim seisoi ulko-ovella, seisoi
puoli päivää, koko ihmisjoukko kulki hänen ohitseen, mutta Jeliseitä
ei näkynyt.
Jefim viipyi Jerusalemissa kuusi viikkoa ja kävi kaikissa pyhissä

paikoissa: Betlehemissä, Betaniassa ja Jordanilla; Vapahtajan
haudalla hän antoi leimata sinetillä uuden paidan, missä hänet
kerran oli haudattava. Hän otti myös mukaansa pienen pullollisen
Jordanin vettä, samoin multaa ja kynttilöitä pyhistä paikoista, jakeli
rahansa ja jätti itselleen vain sen verran kuin kotimatkaan tarvittiin.
Ja Jefim lähti paluumatkalle. Hän astui jalan Jaffaan, matkusti
laivassa Odessaan ja kulki sieltä taas kotiin jalan.
XI
Jefim vaelsi samaa tietä kuin mennessäänkin. Kun hän läheni kotia,
valtasi hänet huoli omaisista: kuinkahan nämä ovat tulleet toimeen
hänen poissaollessaan? — Vuodessa ehtii paljon tapahtua, —
ajattelee hän itsekseen. Koko elämä menee ihmiseltä
kuntoonpanemiseen, mutta hävittämiseen tarvitaan hyvin vähän
aikaa. Kuinkahan poika lienee hoitanut taloa? Millainen mahtoi olla
kevät, miten on karjan laita ollut talvella, kuinka uusi rakennus on
onnistunut? Jefim tuli samoille tienoille, missä oli edellisenä vuonna
joutunut eroon Jeliseistä. Asukkaita ei voinut enää tuntea samoiksi.
Kuka edellisenä vuonna oli nähnyt nälkää, eli nyt herroiksi. Vilja oli
kasvanut hyvin, ihmiset olivat taas päässeet hyvään alkuun ja
näyttivät unohtaneen entisen surkeuden. Iltapuolella päivää Jefim
joutui samaan kylään, missä oli Jeliseistä eronnut. Hän oli tuskin
ennättänyt kylään, kun pieni valkeaan paitaan puettu tyttönen juoksi
ulos mökistä huutaen hänelle:
— Isoisä, isoisä, tulehan meille!
Jefim aikoi lähteä eteenpäin, mutta tyttönen tarttui hänen

kauhtanansa liepeisiin ja veti hymyillen hänet mökkiä kohti.
Portaille tuli myös nainen ja poika; he viittailivat hänelle ja pyysivät
häntä tulemaan sisään.
— Poikkea meille, ukko. Saat meillä illallista ja voit olla meillä yötä.
Jefim meni sisään. »Voinhan kysellä samalla Jeliseistä: eiköhän

se vain poikennutkin juuri tähän mökkiin juomaan vettä.» Jefim astui
tupaan, mökin vaimo auttoi repun hänen selästään, toi hänelle
pesuvettä ja tarjosi hänelle paikan pöydässä. Hän kantoi pöydälle
maitoa, rieskaa ja puuroa. Jefim kiitti ja kehui mökin väkeä, kun niin
vieraanvaraisesti ottivat pyhiinvaeltajia luokseen.
Vaimo pudisti päätään ja virkkoi:
— Täytyy kai meidän olla ystävällisiä jokaiselle pyhiinvaeltajalle,

sillä pyhiinvaeltajalta olemme oppineet, miten on elettävä. Elimme
synnissä ja Jumala rankaisi meitä siksi niin, että odotimme vain
kuolemaa. Viime kesänä makasimme kaikki sairaina nälästä.
Olisimme olleet hukassa, mutta Jumala lähetti luoksemme
samanlaisen vanhuksen kuin sinä. Eräänä päivänä hän tuli
luoksemme vain janoissaan juomaan, mutta kun näki meidät, tuli
hänen meitä sääli ja hän jäi luoksemme. Hän antoi meille juotavaa ja
syötävää, sai meidät virkoamaan, lunasti pantatun maan, osti
hevosen ja rattaat ja jätti ne meille.
Tupaan tuli vanha muori. Hän keskeytti vaimon puheen ja virkkoi:
— Me emme tiedä itsekään, oliko hän ihminen vai Jumalan enkeli.

Kaikkia hän rakasti, kaikkia sääli. Ja hän lähti luotamme mitään
sanomatta. Emme tiedä kenelle saisimme rukoilla Jumalan
siunausta. Näen edessäni ihan kuin tässä nyt tapahtuisi miten minä
makaan tuossa ja odotan kuolemaa, ja äkkiä tulee vanha,
kaljupäinen maalaisukko sisään pyytämään vettä juodakseen. Minä
syntinen vielä ajattelin: mokomat kuljeksijat! — Mutta tämäpäs kun
näki meidät, riisui heti repun selästään, pani sen tänne tähän
kohtaan, avasi.
Tyttönen keskeytti muorin:
— Ei, isoäiti, hän laski repun ensin maahan keskelle tupaa ja nosti
sitten penkille.
Ja niin alettiin kiistellä ja muistella kaikkea mitä ukko oli tehnyt ja

sanonut: missä hän oli istunut, missä nukkunut, mitä hän oli
toimittanut ja mitä kenellekin puhunut.
Yöksi tuli myös mökin isäntä hevosella kotiin. Hänkin kertoi

Jelisein olosta heillä.
— Ellei hän olisi tullut luoksemme, virkkoi hän, — olisimme

varmaan kuolleet kaikki synteinemme. Olimme nääntymäisillämme,
näimme kuoleman edessämme, olimme nyreissämme Jumalalle ja
ihmisille. Hän auttoi meidät jälleen pystyyn, ja hänen kauttaan tuli
Jumala taas meidän näkyviimme ja me saimme takaisin uskomme
hyviin ihmisiin. Kristus olkoon hänelle armollinen! Ennen elettiin vain
päivästä toiseen kuin mitkäkin elukat; hän teki meidät taas ihmisiksi.
Mökin väki antoi Jefimille syötävää ja juotavaa, he laittoivat

hänelle makuusijan ja laskeutuivat itsekin levolle.
Jefim makaa vuoteellaan, mutta ei saa unta; hänen täytyi siinä

maatessaan aina vain ajatella Jeliseitä, jonka hän näki kolme kertaa
Jerusalemissa Vapahtajan haudalla.
— Tässä talossa, ajatteli hän, — hän pääsi minun edelleni. En
tiedä, onko minun uhrini, kelvannut taivaassa vai eikö; hänen uhrinsa
on varmasti ollut otollinen Herralle.
Aamulla Jefim erosi mökin väestä. He antoivat hänelle evääksi

piirakoita ja menivät työhönsä. Ja Jefim jatkoi matkaansa.
XII
Jefim oli ollut poissa tasan vuoden. Kun hän palasi kotiin, oli taas
kevät.
Hän tuli kotiin iltapäivällä. Poika ei ollut kotona: hän istui

kapakassa. Kun hän vihdoin palasi kotiin vähän päissään, alkoi
Jefim tiedustella häneltä kotiasioita. Jefim huomasi heti, että poika oli
hoitanut huonosti taloutta: rahat hän oli hävittänyt ja kaikki toimet
laiminlyönyt. Kun isä nuhteli häntä, tuli poika röyhkeäksi.
— Olisit itse hoitanut asiat, virkkoi poika. — Mutta sinä läksit maita
kiertämään ja otit mukaasi kaikki rahat. Minunko niistä on tehtävä
tiliä!
Vanhus vihastui ja antoi pojalleen selkäsaunan.
Seuraavana aamuna Jefim Tarasytš meni kylänvanhimman luo

puhelemaan pojastaan. Kulkiessaan Jelisein talon ohitse hän näki
Jelisein vaimon seisovan portailla. Tämä tervehti häntä virkkaen:
— Hyvää päivää, naapuri! Hyvin on tainnut matka mennä?
Jefim Tarasytš pysähtyi ja sanoi:

— Matkani meni. Jumalan kiitos, onnellisesti; sinun ukostasi vain
eksyin matkalla, mutta hän kuuluu tulleen kotiin.
Muori oli hyvin puhelias ja alkoi kertoa:
— Hän on jo aikoja sitten palannut, hyvä mies. Taisi tulla siinä

kohta Marian päivän jälkeen. Me tulimme iloisiksi, kun Jumala toimitti
hänet jälleen kotiin; meillä oli niin ikävä, kun hän oli poissa. Ei
hänestä tosin enää paljon työhön ole, parhain ikä on jo ohi. Mutta
talon pää hän yhä on, meidän on nyt taas paljon hupaisampaa.
Poikakin tuli, niin iloiseksi. Isän poissa ollessa, sanoi hän, tuntuu
elämä samalta kuin silmät vailla valoa. Kun hän ei ole kotona, ei
elämä ole meille mikään ilo, ystäväiseni, niin me rakastamme häntä
ja olemme häneen kiintyneet.
— No, onko hän nyt kotona?
— Kotona on, mehiläistarhassa parvea korjaamassa. Mehiläiset

menestyvät nykyjään hyvin, sanoo hän. Niin kuuluvat höystyvän,
ettei ukko ole semmoista ennen nähnyt. Jumala ei varmaankaan
katso ensinkään syntejämme, kun niin on armollinen, sanoo hän.
Käy häntä katsomaan, ystävä; jo nyt ukko tuleekin iloiseksi!
Jefim astuu pihamaan poikki mehiläistarhaan Jelisein luo. Hän

tulee tarhaan ja näkee Jelisein seisovan koivun suojassa verkotta ja
käsineittä, harmaa kauhtana yllään, käsivarret levitettyinä, ja
katsovan ylöspäin kalju päälaki hohtaen. Aivan samalla tavalla hän
oli seisonut Jerusalemissa Vapahtajan haudalla; ja samoin kuin
Jerusalemissa valo loisti häneen, paistoi nyt aurinko koivun lehvistön
lävitse; hänen päänsä yllä liitelee kultaisia mehiläisiä, muodostaen
kultaseppeleen, eivätkä ne pistä häntä.
Jefim jää seisomaan.
Jelisein muori huusi miehelleen:
— Naapuri on tullut sinua katsomaan!
Jelisei katsoi ympärilleen, ilostui kovin ja meni Jefimiä kohti.

Kulkiessaan hän otti varovasti parrastaan muutamia mehiläisiä.
— Jumalan rauha, Jefim! Jumalan rauha, ystävä, miten kävi

matka?
— Jalat tekivät matkan; toin sinulle myös vettä Jordanista. Mutta

lienevätkö vaivani olleet Herralle otolliset.
Jefim vaikeni hetkiseksi, sitten hän sanoi:
— Jalkani olivat Jerusalemissa, mutta oliko minun sieluni myöskin,

vai jonkun muun.
— Anna Jumalan päättää, Jefim, anna Jumalan päättää.
— Kotimatkalla poikkesin mökkiin, jossa eksyin sinusta

menomatkalla..
Jelisei säikähti ja keskeytti Jefimin:
— Anna Jumalan päättää, ystävä, anna Jumalan päättää. Käyhän

tupaan, niin kestitsen hunajalla.
Jelisei sekoitti pois koko jutun ja alkoi jutella kotiasioista.
Jefim huokasi eikä enää puhunut vähävenäläisen mökin väestä

eikä myöskään siitä, että oli nähnyt Jelisein Jerusalemissa. Ja hän
käsitti, että Jumala on määrännyt jokaiselle ihmiselle veron, jota
meidän on kuolemaamme asti suoritettava rakkaudella ja hyvillä
töillä.
KOIRANI
I
BULJKA.
Minulla oli Buljka-niminen pieni verikoira. Se oli aivan musta,

etukäpälän päät vain olivat valkoiset. Kaikilla verikoirilla on alaleuka
pitempi kuin yläleuka ja ylähampaat jäävät alahampaiden taakse,
mutta Buljkalla työntyivät alahampaat niin kauas eteenpäin, että
saattoi pistää sormen ylä- ja alahampaiden väliin. Buljkan kuono oli
leveä, silmät olivat suuret, mustat ja kiiluvat, valkeat hampaat
törröttivät aina näkyvissä. Se oli neekerin näköinen. Buljka oli
rauhaarakastava eikä purrut, mutta samalla se oli vahva ja sitkeä.
Kun se kävi johonkin kiinni, puri se hampaat yhteen ja jäi riepuna
riippumaan, joten sitä ei saanut temmatuksi irti; se oli pureutunut
kiinni lujasti kuin punkki.
Kerran se päästettiin karhun kimppuun. Se tarttui lujasti

hampaineen karhun korvaan ja jäi iilimadon tavoin riippumaan
siihen. Karhu löi sitä käpälillään, heitteli sitä puolelta toiselle, mutta ei
saanut sitä irtautumaan; vihdoin se teki kuperkeikan rutistaakseen
Buljkan kuoliaaksi allensa. Buljka pysyi sittenkin karhussa kiinni ja
hellitti vasta, kun sitä oli kylmällä vedellä valeltu.
— Minä olin saanut sen nuorena pentuna ja kasvattanut itse
isoksi. Kun matkustin Kaukasiaan, en tahtonut ottaa sitä mukaan;
läksin huomaamatta matkalle ja annoin sulkea Buljkan lukon taakse.
Kun ensimmäisessä majatalossa siirryin toisille rattaille, näin äkkiä
jotakin mustaa ja kiiltävää kiitävän maantietä pitkin. Se oli Buljka
messinkisine kaulaketjuineen. Tupruna se kiiri majataloa kohti. Se
syöksyi minun kimppuuni, nuoli kättäni ja ojentautui pitkäkseen
rattaiden varjoon. Kieli riippui kämmenen pituudelta kuonosta. Milloin
koira veti kielensä sisään niellen sylkeä, milloin pisti sen taas
kämmenen verran ulos. Se huohotti hengästyneenä, ja sen kyljet
suorastaan hytkyivät. Se kiemurteli puolelle ja toiselle ja koputteli
maata hännällään.
Sain myöhemmin tietää, että se minun lähdettyäni oli särkenyt

ikkunan, hypännyt ulos ja juossut keskipäivän paahteessa
parikymmentä virstaa jäljestäni maantietä pitkin.
II
BULJKA JA METSÄKARJU.
Läksimme kerran Kaukasiassa villisikoja metsästämään, ja Buljka

juoksi minun mukaani. Ajokoirat olivat tuskin päässeet riistan jäljille,
kun Buljka kirmasi metsään haukuntaa kohti ja katosi näkyvistä. Oli
marraskuu, jolloin villisiat ja karjut tavallisesti ovat hyvin lihavia.
Kaukasian metsissä, missä villisiat asustavat, on paljon herkullisia

hedelmiä ja marjoja: viinirypäleitä, käpyjä, omenia, päärynöitä,
vaapukoita, tammenterhoja, tuomenmarjoja. Kun kaikki nämä
hedelmät ovat kypsiä ja ensimmäisen pakkasen puremia, syövät
villisiat niitä minkä jaksavat ja tulevat lihaviksi.
Tuollainen villisika on tällöin usein niin lihava, ettei se kauan jaksa

juosta koiria pakoon. Kun sitä on ajettu pari tuntia takaa, tunkeutuu
se pensaikkoon ja jää paikoilleen. Metsästäjät rientävät sitten sille
paikalle, johon se on pysähtynyt, ja ampuvat. Koirien haukunnasta
saattaa huomata, vieläkö villisika juoksee vai onko se jo pysähtynyt.
Niin kauan kuin se juoksee, uikuttavat koirat niinkuin niitä piestäisiin;
kun se pysähtyy, haukkuvat ne taas sitä kuin ihmistä ja ulvahtelevat.

Biomass Valorization Sustainable Methods For The Production of Chemicals Davide Ravelli Full Chapter PDF

Uploaded by

Copyright:

Available Formats

You might also like

Biomass Valorization Sustainable Methods For The Production of Chemicals Davide Ravelli Full Chapter PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Biomass Valorization Sustainable Methods For The Production of Chemicals Davide Ravelli Full Chapter PDF

Uploaded by

Copyright:

Available Formats

Biomass Valorization: Sustainable

Methods for the Production of

Biomass, Biofuels, Biochemicals – Biochemicals and

Valorization of Microalgal Biomass and Wastewater

Strategic Planning for the Sustainable Production of

Genetic and Metabolic Engineering for Improved Biofuel

Hydrocarbon Biorefinery: Sustainable Processing of

Agri-Waste and Microbes for Production of Sustainable

Sustainable Production System: Eco-development versus

Heating, Cooling, Lighting: Sustainable Design Methods

Sustainable Methods for the Production of Chemicals

© 2021 WILEY-VCH GmbH, Boschstr.

All rights reserved (including those of

Print ISBN: 978-3-527-34717-9

Typesetting SPi Global, Chennai, India

Printed on acid-free paper

1 Role of Biomass in the Production of Chemicals 1

Section I Catalytic Strategies 23

2 Biomass Processing via Acid Catalysis 25

3 Biomass Processing via Base Catalysis 57

3.2.3 Aldol Condensation Between Alcohols: Guerbet Coupling Reaction 64

4 Biomass Processing via Metal Catalysis 81

5 Biomass Processing with Biocatalysis 113

5.6 Enzymatic Hydrolysis of Starch to Glucose 121

Section II Thermal Strategies 147

6 Biomass Processing via Pyrolysis 149

7 Biomass Processing via Thermochemical–Biological Hybrid

Section III Advanced/Unconventional Strategies 225

8 Biomass Processing via Electrochemical Means 227

8.4.1.2 5-HMF Reduction 238

9 Biomass Processing via Photochemical Means 265

10 Biomass Processing via Microwave Treatment 289

11 Biomass Processing Assisted by Ultrasound 315

11.7 Conclusions and Perspectives 332

12 Biomass Processing via Mechanochemical Means 343

Section IV Closing Remarks 367

13 Industrial Perspectives of Biomass Processing 369

Why bother with biomass conversion? It seems so difficult compared to converting

● evaluate new conversion processes and products in terms of potential environ-

conversion to platform chemicals, all the way to manufacture finished products,

their potential availability at industrial scale and the environmental impact of

discarded, and do not themselves lead to environmental crises,

stocks become the norm.

August 2020 Philip Jessop

November 2020 Chiara Samorì, University of Bologna, Italy

Role of Biomass in the Production of Chemicals

Chemistry is a fundamental part of everything around us. Nature is largely responsi-

1.2 Biomass Valorization

The sustainable production of chemicals and products can be achieved from

(3) Third-generation biomass: This includes nonedible feedstocks that do not

promising alternative to the fossil-based industry. From an energetic perspective,

1.3 Lignocellulosic Biomass

Figure 1.1 Schematic representation of the components of lignocelluloses.

lignocellulose. Further, lignocellulosic bio-feedstocks include variable quantities of

1.4 Key Biomolecules

Alternatively, another approach is to obtain different platform molecules from

Bio-product Industrial Technological

1,4-Diacid (succinic Anaerobic Pharmaceutical, Separation/purification of