Bio-Based Solvents E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Wiley Series in Renewable Resources
- Sprache: Englisch
A multidisciplinary overview of bio-derived solvent applications, life cycle analysis, and strategies required for industrial commercialization
This book provides the first and only comprehensive review of the state-of-the-science in bio-derived solvents. Drawing on their own pioneering work in the field, as well as an exhaustive survey of the world literature on the subject, the authors cover all the bases—from bio-derived solvent applications to life cycle analysis to strategies for industrial commercialization—for researchers and professional chemists working across a range of industries.
In the increasingly critical area of sustainable chemistry, the search for new and better green solvents has become a top priority. Thanks to their renewability, biodegradability and low toxicity, as well as their potential to promote advantageous organic reactions, green solvents offer the promise of significantly reducing the pernicious effects of chemical processes on human health and the environment.
Following an overview of the current solvents markets and the challenges and opportunities presented by bio-derived solvents, a series of dedicated chapters cover all significant classes of solvent arranged by origin and/or chemical structure. Throughout, real-world examples are used to help demonstrate the various advantages, drawbacks, and limitations of each class of solvent.
Topics covered include:
- The commercial potential of various renewably sourced solvents, such as glycerol
- The various advantages and disadvantages of bio-derived versus petroleum-based solvents
- Renewably-sourced and waste-derived solvents in the design of eco-efficient processes
- Life cycle assessment and predictive methods for bio-based solvents
- Industrial and commercial viability of bio-based solvents now and in the years ahead
- Potential and limitations of methodologies involving bio-derived solvents
- New developments and emerging trends in the field and the shape of things to come
Considering the vast potential for new and better products suggested by recent developments in this exciting field, Bio-Based Solvents will be a welcome resource among students and researchers in catalysis, organic synthesis, electrochemistry, and pharmaceuticals, as well as industrial chemists involved in manufacturing processes and formulation, and policy makers.
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Table of Contents
Cover
Title Page
Copyright
List of Contributors
Series Preface
Foreword
Chapter 1: Glycerol as Eco-Efficient Solvent for Organic Transformations
1.1 Introduction
1.2 Metal-Free Organic Transformations in Glycerol
1.3 Metal-Promoted Organic Transformations in Glycerol
1.4 Conclusions and Perspectives
Acknowledgements
References
Chapter 2: Aromatic Bio-Based Solvents
2.1 Introduction
2.2 Resorcinolic Lipids
2.3 Cashew Nut Shell Liquid
2.4 Conclusion
References
Chapter 3: Solvents from Waste
3.1 Introduction
3.2 Lignocellulosic Waste as a Feedstock for the Production of Solvents
3.3 Solvents from Used Cooking Oil
3.4 Terpenes and Derivatives
3.5 Conclusion
References
Chapter 4: Deep Eutectic and Low-Melting Mixtures
4.1 Introduction
4.2 Deep Eutectic and Low-Melting Mixtures: Definition and Composition
4.3 Deep Eutectic and Low-Melting Mixtures in Metal-Catalysed Organic Reactions
4.4 Conversion of Carbohydrates
4.5 Extraction with or from Deep Eutectic Solvents
4.6 Conclusion
References
Chapter 5: Organic Carbonates: Promising Reactive Solvents for Biorefineries and Biotechnology
5.1 The Quest for Sustainable Solvents and the Emerging Role of Organic Carbonates
5.2 Carbonate Solvents in Biorefineries
5.3 Biotechnology: from Enzymatic Synthesis of Organic Carbonates to Enzyme Catalysis in these Non-Conventional Media
5.4 Concluding Remarks
References
Chapter 6: Life Cycle Assessment for Green Solvents
6.1 Introduction
6.2 Life Cycle Assessment: An Overview
6.3 Application of Life Cycle Assessment for Conventional Solvents
6.4 Critical Review of Life Cycle Assessment Applied to Green Solvents
6.5 Discussion: Methodological Challenges
6.6 Conclusion
References
Chapter 7: Alkylphenols as Bio-Based Solvents: Properties, Manufacture and Applications
7.1 Introduction
7.2 Properties of Alkylphenols
7.3 Manufacture of Alkylphenols
7.4 Alkylphenols as Solvent
7.5 Other Applications of Alkylphenols
7.6 Stability and Toxicity of Alkylphenols
7.7 Conclusions and Perspectives
Acknowledgements
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Series Preface
Foreword
Begin Reading
List of Illustrations
Chapter 1: Glycerol as Eco-Efficient Solvent for Organic Transformations
Figure 1.1 Reaction for biodiesel production.
Figure 1.2 Commercial consumption of glycerol (industrial sectors and volumes).
Scheme 1.1 Catalyst-free selective synthesis of 2-phenylbenzoxazole.
Scheme 1.2 Green synthesis of benzimidazoles and benzodiazepines in glycerol.
Scheme 1.3 Catalyst-free synthesis of isomeric mixtures of octahydroacridines.
Scheme 1.4 One-pot synthesis of furanoquinolines by green method.
Scheme 1.5 Microwave-assisted synthesis of phenyl disulfide.
Scheme 1.6 Green synthesis of 2,3-diphenyl-quinoxaline in glycerol.
Scheme 1.7 Triacetylborate-catalysed green synthesis of 2-styryl-1
H
-benzimidazole.
Scheme 1.8 Glycerol-mediated synthesis of
N
-aryl phthalimides.
Scheme 1.9 Metal-free synthesis of thioethers at room temperature.
Scheme 1.10 Green synthesis of 4
H
-pyrans.
Scheme 1.11 Glycerol-promoted synthesis of triazolo[1,2-
a
]indazole-triones.
Scheme 1.12 Synthesis of dimethyl-(4-phenylsulfanyl-phenyl)-amine.
Scheme 1.13 Catalyst-free green protocol for synthesis of vanillin semicarbazone.
Scheme 1.14 Glycerosulfonic acid-promoted synthesis of 1-amidoalkyl-2-naphthol.
Scheme 1.15 Preparation of glycerosulfonic acid.
Scheme 1.16 Synthesis of 2,3-dihydroquinazoline-4(1
H
)-one.
Scheme 1.17 Catalyst-free green synthesis of di(indolyl)methane.
Figure 1.3 Development of the model reaction in glycerol [32]: (a) beginning of the reaction as an identical mixture; (b) partial precipitation of the reaction; (c) the end of the precipitation of the reaction. From He
et al.
(2009)
Green Chem.
,
11
, 1767–1773.
Scheme 1.18 Metal-free synthesis of 4-arylselanylpyrazoles.
Scheme 1.19 Direct cyclocondensation reaction between phenylhydrazine and pentane-2,4-dione in glycerol–water system.
Scheme 1.20 Huisgen cycloaddition reaction for preparing 1,2,3-triazoles.
Scheme 1.21 PBM reaction for preparing complex tertiary morpholine derivatives.
Scheme 1.22 Preparation of 1-(morpholinomethyl)naphthalen-2-ol through the Betti reaction.
Scheme 1.23 Glycerol-mediated, one-pot synthesis of dihydropyrano[2,3-
c
]pyrazoles.
Scheme 1.24 Catalyst-free synthesis of spirooxindole-indazolones.
Scheme 1.25 Multi-component tandem synthesis of pyrido[2,3-
d
]pyrimidine.
Scheme 1.26 Friedel–Crafts alkylation of indoles in glycerol.
Scheme 1.27 Catalyst-free ring-opening reaction of styrene oxide with
p
-anisidine.
Scheme 1.28 Coupling reaction for synthesis of the functionalized indoles.
Scheme 1.29 Multi-component reactions of 1,3-cyclohexanediones and formaldehyde in glycerol.
Scheme 1.30 Copper acetate-promoted
N
-arylation of aromatic amine.
Scheme 1.31 CuI-promoted green synthesis of phenyl selenide derivatives.
Scheme 1.32 Synthesis of 2-phenylselanyl-pyridine.
Scheme 1.33 Green solvent and catalyst promoted the synthesis of a
Z
and
E
mixture of organylthioenynes.
Scheme 1.34 Green synthesis of β-aryl-β-sulfanyl ketones.
Scheme 1.35 Copper(i)-catalysed synthesis of 1-benzyl-4-phenyl-1
H
-[1–3]triazole.
Scheme 1.36 Copper nanoparticle-promoted synthesis of 4-
p
-tolylsulfanyl-phenylamine.
Scheme 1.37 Palladium nanoparticle-catalysed synthesis of
N
-substituted phthalimides.
Scheme 1.38 Metal ligand-promoted green synthesis of bis(2-pyridyl)diselenoethers.
Scheme 1.39 Ultrasound-promoted green synthesis of phenyl-methanol.
Scheme 1.40 Copper-catalysed cross-coupling between
N
-tosylhydrazones and 4-methoxyaniline.
Scheme 1.41 Microwave-assisted ring-closing metathesis of diethyl diallylmalonate.
Scheme 1.42 Iridium-catalysed selective hydrogen transfer of acetophenone in glycerol.
Scheme 1.43 Copper/glycerol catalytic system for the synthesis of
N
-aryl indoles.
Scheme 1.44 Synthesis of diarylselenides using glycerol as solvent.
Scheme 1.45 Synthesis of 1,3-diphenyl-3-(phenylselanyl)propan-1-one under a green protocol.
Scheme 1.46 Oxazoline synthesis using glycerol as solvent.
Scheme 1.47 Suzuki coupling of phenyl boronic acids in glycerol.
Scheme 1.48 Suzuki–Miyaura coupling reaction of aryl halides in glycerol.
Scheme 1.49 Rearrangement of (
E
)-benzaldoxime into benzamide in glycerol.
Chapter 2: Aromatic Bio-Based Solvents
Figure 2.1 General structures of alkylresorcinols and oxygenated chain analogues.
Figure 2.2 Structures of common alkylresorcinols found in cereals [7, 13, 14].
Figure 2.3 Accelerated solvent extraction.
Figure 2.4 Schematic diagram of the supercritical extraction system: 1, CO
2
cylinder; 2, cooling heat exchanger; 3, flowmeter; 4, cooling bath; 5, CO
2
pump; 6, co-solvent reservoir; 7, co-solvent pump; 8, mixer; 9, heat exchanger; 10, extraction vessel; 11, pressure gauge; 12, temperature sensor; 13, automated back-pressure pump; 14, pressure gauge; 15, cyclone separator [22].
Figure 2.5 Some examples of bio-based aromatics that can be derivatized from the alkylresorcinols occurring in cereals.
Scheme 2.1 Synthesis of daurichromenic acid using an alkylresorcinol as the starting material [42].
Figure 2.6 Components of cashew nut shell liquid.
Scheme 2.2 Synthesis of 3-propylphenol via isomerizing metathesis of 3-(non-8-enyl)phenol [69].
Scheme 2.3 Synthesis of 1-octene and (
E
)-3-(non-8-enyl)phenol [69].
Scheme 2.4 Synthesis of a detergent from cardanol [68].
Figure 2.7 Preparation of porous materials employing CNSL as a templating agent.
Figure 2.8 Preparation of anacardic acid-capped PbS and PbSe nanoparticles.
Chapter 3: Solvents from Waste
Figure 3.1 Solvents from waste: some already established solvents as well as some more recent developments categorized by waste source. Boiling points have been given for each solvent.
Figure 3.2 Lignocellulosic waste solvents produced by chemical transformations.
Figure 3.3 The production of the bio-based solvent 2-MeTHF from furfural.
Figure 3.4 The synthesis pathway of cyrene from cellulose waste.
Figure 3.5 Synthetic routes to GVL from the HMF and furfural platforms.
Figure 3.6 The production of levulinic acid and levulinic acid esters from HMF and furfural.
Figure 3.7 Synthesis of dimethyl isosorbide from glucose.
Figure 3.8 Low-molecular-weight alcohols, acids and olefins that can be produced by fermentation of waste cellulose and which can be further modified to make solvents.
Figure 3.9 Potential solvents derived from glycerol, with their corresponding boiling points.
Figure 3.10 Various terpenes and derivatives with solvent applications and their corresponding boiling points.
Figure 3.11
p
-Cymene production from d-limonene using a silica–alumina catalyst and microwave irradiation.
Figure 3.12 The synthesis of
p
-menthane from d-limonene.
Figure 3.13 Map of current bio-based solvents using HSP hydrogen-bonding versus polarity scales. Current bio-based hydrocarbons (purple circles) are high-boiling. There is a need to develop lower-boiling bio-derived solvents as alternatives. There is also an empty space where dipolar aprotic solvents such as NMP, DMF and DMSO would be located, which must be filled with bio-based solvents.
Chapter 4: Deep Eutectic and Low-Melting Mixtures
Figure 4.1 Hydrogen-bond acceptors (HBAs) usually employed in the synthesis of DESs and LMMs.
Figure 4.2 Hydrogen-bond donors (HBD) usually employed in the synthesis of DESs and LMMs.
Scheme 4.1 Ru(iv)-catalysed isomerization of allylic alcohols into saturated carbonyl compounds in ChCl-based eutectic mixtures.
Scheme 4.2 Au(i)-catalysed cycloisomerization of γ-alkynoic acids into saturated enol-lactones in ChCl-based eutectic mixtures.
Scheme 4.3 Au(i)-catalysed cycloisomerization of (
Z
)-enynols and one-pot tandem cycloisomerization/Diels–Alder cycloaddition in ChCl-based eutectic mixtures.
Scheme 4.4 Synthesis of tetrahydroisoquinolines catalysed by copper(ii) oxide impregnated on magnetite using ChCl/EG (1 : 2) as green solvent.
Scheme 4.5 Pd(0)-catalysed Stille C–C coupling reaction in sugar-based LMMs.
Scheme 4.6 CuFeO
2
-catalysed synthesis of imidazole[1,2-
a
]pyridines in the LMM citric acid/DMU.
Scheme 4.7 Rh-catalysed hydroformylation of alkenes and Pd-catalysed Tusji–Trost reaction in the eutectic mixture RAME-β-CD/DMU.
Scheme 4.8 Synthesis of HMF from cellulose.
Scheme 4.9 Synthesis of HMF in LMM.
Scheme 4.10 Formation of an LMM between ChCl and fructose. (A colour version of this scheme appears in the plate section.)
Scheme 4.11 Conversion of microcrystalline cellulose to HMF in the presence of ChCl/H
2
O/MIBK solvent.
Scheme 4.12 Conversion of fructose to HMF in organic solvents using a supported LMM.
Scheme 4.13 Acid-catalysed dehydration of fructose in ChCl-derived LMM. (A colour version of this scheme appears in the plate section.)
Scheme 4.14 Mechanism for the dehydration of fructose to HMF in ChCl catalysed by acid–base HPA catalyst [100].
Scheme 4.15 Conversion of fructose to HMF in the presence of ChCl/carboxylic acid DES.
Scheme 4.16 Conversion of lignocellulosic biomass to HMF and furfural in DES. (A colour version of this scheme appears in the plate section.)
Scheme 4.17 Extraction of DFF using DES.
Scheme 4.18 Removal of excess glycerol in biodiesel production using a eutectic salt/glycerol mixture.
Chapter 5: Organic Carbonates: Promising Reactive Solvents for Biorefineries and Biotechnology
Figure 5.1 Selected examples of organic carbonates that may be used as solvents.
Scheme 5.1 Lipase-mediated lignin oxidation with
in situ
peracid formation in DMC (as acyl donor and solvent) [34]. Possible oxidative and de-aromatization pathways in lignin mediated by peracids are shown [33].
Scheme 5.2 Production of methyl levulinate and dimethyl succinate via a DMC-based catalysed process using LA derived from biomass [40].
Scheme 5.3 Base-catalysed methylation/transesterification of cinnamyl alcohol (
9
) and 4-(3-hydroxypropyl)phenol (
10
) using DMC as reagent/solvent [42].
Scheme 5.4 Synthesis of carbonate solvents using DMC as reaction medium and CAL-B [46],
Aspergillus niger
lipase [47] or K
2
CO
3
[48] as catalysts. Dashed lines depict the observed formation of secondary products.
Scheme 5.5 Lipase-catalysed transesterification of DMC with HMF to afford HMF-based carbonates [56].
Chapter 6: Life Cycle Assessment for Green Solvents
Figure 6.1 The life cycle of a solvent.
Figure 6.2 Main impact pathways in LCA. Adapted from Impact World+ (http://www.impactworldplus.org/en/index.php).
Chapter 7: Alkylphenols as Bio-Based Solvents: Properties, Manufacture and Applications
Figure 7.1 Bio-based solvents manufactured from biomass by using bio- and chemocatalysis. EG, ethylene glycol; THF, tetrahydrofuran; 2-MeTHF, 2-methyltetrahydrofuran; GVL, gamma-valerolactone.
Figure 7.2 The water solubility and boiling point (
T
b
) of selected mono-alkylated phenols as a function of molecular weight (MW) [20–32]. The hollow symbols represent the water solubility and the filled symbols represent the boiling points of selected mono-alkylated phenols at 25°C.
Figure 7.3 Methods to produce alkylphenols from different substrates. BTX, benzene, toluene and xylene.
Figure 7.4 Factors that control the selectivity of desired alkylphenols in alkylation of phenol with alkylating agents. Temp., temperature.
Figure 7.5 Catalytic conversion of lignin into (methoxylated) alkylphenols using different approaches. The typical catalysts used for these processes are as follows. Oxidation: CuO, TiO
2
, LaMnO
3
, H
3
PMo
12
O
40
, etc. Pyrolysis: none, zeolite, etc. Base (base-catalysed depolymerization): NaOH, KOH, NiO-hydrotalcite, etc. Hydrogenation: Ni/C, NiMo, Ru/C, NiRu, etc. Transfer hydrogenation: Pt/Al
2
O
3
, MoC
1−
x
/AC, Cu-PMO (porous metal oxides), etc. Isolated lignin includes Kraft lignin, Organosolv lignin, soda lignin, steam-exploded lignin, acid-hydrolysed lignin, etc. Native lignin is the lignin of raw lignocellulose, which is also called protolignin.
Figure 7.6 The main monomers from hydrogenation of native lignin.
Figure 7.7 Alkylphenols used as solvents in the conversion of biomass. The circles represent the alkylphenols used in these steps. Solid circle: alkylphenols as solvents for this reaction. Hollow circle: alkylphenols as solvents to recycle the solvent used in this reaction. FuAl, furfural; FuOH, furfuryl alcohol; HMF, 5-hydroxymethylfurfural; GVL, gamma-valerolactone.
Figure 7.8 The 110 feasible solvents for extracting HMF from aqueous phase [139]. Each point represents a solvent: the triangles are the solvents used for verification of the computational method (COSMO-RS); the squares are the solvents identified through COSMO-RS to show improved extraction performance. The larger marked square points are alkylphenols.
Figure 7.9 Possible applications of lignin-derived aryl propenes in the fine and bulk chemistry fields [119].
List of Tables
Chapter 1: Glycerol as Eco-Efficient Solvent for Organic Transformations
Table 1.1 Physical, chemical and toxicity properties of glycerol
Chapter 3: Solvents from Waste
Table 3.1 Comparison of the Hansen solubility properties of GVL, DMAc and NMP, which were generated by the HSPiP program
Table 3.2 Kamlet–Taft solvatochromic descriptors as well as Hansen solubility parameters of eucalyptol, 2-MeTHF and THF
Chapter 5: Organic Carbonates: Promising Reactive Solvents for Biorefineries and Biotechnology
Table 5.1 Cleavage of lignin model compounds using DMC as solvent, as recently reported by the Bolm group [38]. Reactions were carried out with 0.05 eq. of catalyst, 1.25 ml DMC at 180°C. The reaction times for catalysis by Cs
2
CO
3
and LiO
t
-Bu were for 8 h and 12 h, respectively
Chapter 6: Life Cycle Assessment for Green Solvents
Table 6.1 Brief overview of green chemistry criteria and options, and their correlation to the 12 principles of green chemistry (based on Capello et al. [3])
Table 6.2 Criteria of the review according to the different LCA phases
Table 6.3 Goal and studied solvents from the literature
Table 6.4 Key points of the analysis of the reviewed papers
Wiley Series in Renewable Resources
Series Editor
Christian V. Stevens – Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium
Titles in the Series
Wood Modification: Chemical, Thermal and Other Processes
Callum A. S. Hill
Renewables-Based Technology: Sustainability Assessment
Jo Dewulf, Herman Van Langenhove
Biofuels
Wim Soetaert, Erik Vandamme
Handbook of Natural Colorants
Thomas Bechtold, Rita Mussak
Surfactants from Renewable Resources
Mikael Kjellin, Ingegärd Johansson
Industrial Applications of Natural Fibres: Structure, Properties and Technical Applications
JÖrg Müssig
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power
Robert C. Brown
Biorefinery Co-Products: Phytochemicals, Primary Metabolites and Value-Added Biomass Processing
Chantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy
Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals
Charles E. Wyman
Bio-Based Plastics: Materials and Applications
Stephan Kabasci
Introduction to Wood and Natural Fiber Composites
Douglas D. Stokke, Qinglin Wu, Guangping Han
Cellulosic Energy Cropping Systems
Douglas L. Karlen
Introduction to Chemicals from Biomass, 2nd Edition
James H. Clark, Fabien Deswarte
Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications
Francisco G. Calvo-Flores, Jose A. Dobado, Joaquín Isac-García, Francisco J. Martín-Martínez
Sustainability Assessment of Renewables-Based Products: Methods and Case Studies
Jo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga
Cellulose Nanocrystals: Properties, Production and Applications
Wadood Hamad
Fuels, Chemicals and Materials from the Oceans and Aquatic Sources
Francesca M. Kerton, Ning Yan
Forthcoming Titles
Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste
Erik Meers, Gerard Velthof
Nanoporous Catalysts for Biomass Conversion
Feng-Shou Xiao, Liang Wang
The Chemical Biology of Plant Biostimulants
Danny Geelen
Bio-Based Packaging
Mohd Sapuan Salit, Muhammed Lamin Sanyang
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power, 2nd Edition
Robert Brown
Bio-Based Solvents
Edited by
François Jérôme
Institut de Chimie des Milieux et Matériaux de Poitiers Université de Poitiers, ENSIP France
Rafael Luque
Departamento de Química Orgánica Universidad de Córdoba Spain
This edition first published 2017
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Library of Congress Cataloging-in-Publication Data
Names: Jérôme, François, 1974- editor. | Luque, Rafael, editor.
Title: Bio-based solvents / edited by François Jérôme, National Higher Engineering School of Poitiers (ENSIP), University of Poitiers, France, Rafael Luque, Departament of Quimica Organica, University of Cordoba, Spain.
Other titles: Biobased solvents
Description: Hoboken, NJ : John Wiley & Sons, Inc., 2017. | Series: Wiley series in renewable resources | Includes bibliographical references and index.
Identifiers: LCCN 2017007717 (print) | LCCN 2017008295 (ebook) | ISBN 9781119065395 (cloth) | ISBN 9781119065432 (pdf) | ISBN 9781119065449 (epub)
Subjects: LCSH: Solvents. | Green chemistry.
Classification: LCC TP247.5 .B56 2017 (print) | LCC TP247.5 (ebook) | DDC 660/.29482-dc23
LC record available at https://lccn.loc.gov/2017007717
Cover Design: Wiley
Cover Images: (Top Image) © herjua/Gettyimages; (Bottom Left) Ingram Publishing / Alamy Stock Photo
List of Contributors
Paula Bracco
Biocatalysis, Department of Biotechnology, TU Delft, The Netherlands
Fergal Byrne
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
James H. Clark
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
Annelies Dewaele
Centre for Surface Chemistry and Catalysis, KU Leuven, Belgium
Pablo Domínguez de María
Sustainable Momentum SL, Las Palmas de Gran Canaria, Spain
Thomas J. Farmer
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
Amandine Foulet
Institut des Sciences Moléculaires, Université de Bordeaux, France
Joaquín García-Álvarez
CSIC, Laboratorio de Compuestos Organometálicos y Catálisis, Centro de Innovación en Química Avanzada, Universidad de Oviedo, Spain
Eskinder Gemechu
Institut des Sciences Moléculaires, Université de Bordeaux, France
Yanlong Gu
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, China
Andrew J. Hunt
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
François Jérôme
CNRS, Institut de Chimie des Milieux et Matériaux de Poitiers, Université de Poitiers, ENSIP, France
Saimeng Jin
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
Yuhe Liao
Centre for Surface Chemistry and Catalysis, KU Leuven, Belgium
Philippe Loubet
Institut des Sciences Moléculaires, Université de Bordeaux, France
Rafael Luque
Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Spain
C. Rob McElroy
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
James Mgaya
Chemistry Department, University of Dar es Salaam, Tanzania
Egid B. Mubofu
Chemistry Department, University of Dar es Salaam, Tanzania
Joan J. E. Munissi
Chemistry Department, University of Dar es Salaam, Tanzania
Karine de Oliveira Vigier
CNRS, Institut de Chimie des Milieux et Matériaux de Poitiers, Université de Poitiers, France
Palanisamy Ravichandiran
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, China
Bert F. Sels
Centre for Surface Chemistry and Catalysis, KU Leuven, Belgium
James Sherwood
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK
Guido Sonnemann
Institut des Sciences Moléculaires, Université de Bordeaux, France
Michael Tsang
Institut des Sciences Moléculaires, Université de Bordeaux, France
Danny Verboekend
Centre for Surface Chemistry and Catalysis, KU Leuven, Belgium
Series Preface
Renewable resources, their use and modification are involved in a multitude of important processes with a major influence on our everyday lives. Applications can be found in the energy sector, chemistry, pharmacy, the textile industry, paints and coatings, to name but a few.
The area interconnects several scientific disciplines (agriculture, biochemistry, chemistry, technology, environmental sciences, forestry …), which makes it very difficult to have an expert view on the complicated interaction. Therefore, the idea to create a series of scientific books, focusing on specific topics concerning renewable resources, has been very opportune and can help to clarify some of the underlying connections in this area.
In a very fast changing world, trends are not only characteristic for fashion and political standpoints; also, science is not free from hypes and buzzwords. The use of renewable resources is again more important nowadays; however, it is not part of a hype or a fashion. As the lively discussions among scientists continue about how many years we will still be able to use fossil fuels – opinions ranging from 50 to 500 years – they do agree that the reserve is limited and that it is essential not only to search for new energy carriers but also for new material sources.
In this respect, renewable resources are a crucial area in the search for alternatives for fossil-based raw materials and energy. In the field of energy supply, biomass and renewable-based resources will be part of the solution alongside other alternatives such as solar energy, wind energy, hydraulic power, hydrogen technology and nuclear energy.
In the field of material sciences, the impact of renewable resources will probably be even bigger. Integral utilization of crops and the use of waste streams in certain industries will grow in importance, leading to a more sustainable way of producing materials.
Although our society was much more (almost exclusively) based on renewable resources centuries ago, this disappeared in the Western world in the nineteenth century. Now it is time to focus again on this field of research. However, it should not mean a ‘retour à la nature’, but it should be a multidisciplinary effort on a highly technological level to perform research towards new opportunities, to develop new crops and products from renewable resources. This will be essential to guarantee a level of comfort for a growing number of people living on our planet. It is ‘the’ challenge for the coming generations of scientists to develop more sustainable ways to create prosperity and to fight poverty and hunger in the world. A global approach is certainly favoured.
This challenge can only be dealt with if scientists are attracted to this area and are recognized for their efforts in this interdisciplinary field. It is, therefore, also essential that consumers recognize the fate of renewable resources in a number of products.
Furthermore, scientists do need to communicate and discuss the relevance of their work. The use and modification of renewable resources may not follow the path of the genetic engineering concept in view of consumer acceptance in Europe. Related to this aspect, the series will certainly help to increase the visibility of the importance of renewable resources.
Being convinced of the value of the renewables approach for the industrial world, as well as for developing countries, I was myself delighted to collaborate on this series of books focusing on different aspects of renewable resources. I hope that readers become aware of the complexity, the interaction and interconnections, and the challenges of this field and that they will help to communicate on the importance of renewable resources.
I certainly want to thank the people of Wiley's Chichester office, especially David Hughes, Jenny Cossham and Lyn Roberts, in seeing the need for such a series of books on renewable resources, for initiating and supporting it and for helping to carry the project to the end.
Last, but not least, I want to thank my family, especially my wife Hilde and children Paulien and Pieter-Jan, for their patience and for giving me the time to work on the series when other activities seemed to be more inviting.
Christian V. Stevens, Faculty of Bioscience Engineering Ghent University, Belgium Series Editor ‘Renewable Resources’ June 2005
Foreword
The present-day solvent market is of the order of 20 million tonnes and worth tens of billions of US dollars annually to the global economy. European solvent production provides about one-quarter of the worldwide market. The sheer volumes involved, the diversity of applications and the prevalence of small, functional compounds that often contain heteroatoms helps make the solvent sector a top candidate for switching to safer and more sustainable alternatives under the pressure of regional and global chemical regulation, notably REACh (Registration, Evaluation, Authorisation & restriction of Chemicals). A critical stage in the REACh process is imminent as the small- to medium-volume chemicals are registered in time for the 2018 deadline. As several commonly used solvents like NMP (N-methyl-2-pyrrolidone) are under close scrutiny at the time of writing, we can assume that the number of problematic solvents identified under REACh (and possibly other legislation) will be far greater at the time of reading.
The search for “greener” solvents is not new. If we go back to the early days of green chemistry in the 1990s, “alternative solvents” was one of the most popular research areas, with more and more articles reporting uses for known alternatives, including liquid and supercritical carbon dioxide, and an ever-increasing number of newly reported ionic liquids. These represented potentially positive step changes to chemical manufacturing technologies. Supercritical CO2 enables rapid and easy separation after reaction (since separations are commonly a major contributor to the low environmental impact of many chemical processes) and ionic liquids can avoid the critical environmental concerns around using volatile organic compounds (these being threats to human health and causes of atmospheric damage). Research in these areas has continued, though few industrial processes have changed to incorporate these step-change technologies. The costs of such major changes to the processes, the added energy and capital expenditure costs of working with supercritical fluids, and the toxicity, separation and purification challenges associated with some ionic liquids have inhibited progress. Among the most likely ionic liquids to have a future in industrial chemistry are deep eutectic mixtures as well as other low-melting mixtures that are constructed from bio-based compounds. These are the subject of a book chapter here. Other “green solvent” approaches including greater use of water as a reaction solvent; and no-solvent processes have had some impact, but the vast majority of solvent applications have remained essentially unchanged. In the meantime, the rapidly growing number of synthetic transformations used by the pharmaceutical industry have effectively increased the breadth and complexity of the problems (e.g. more metal-catalysed processes and more processes that need polar aprotic solvents). Other, newer industries, such as advanced materials, are creating additional problems (e.g. the current use of solvents like NMP to process graphene). The need for safer, cost-effective solvents has never been greater.
Bio-based organic solvents are another way to make chemical processes more sustainable, and despite the infancy of the area of bio-based chemicals, the annual bio-based solvent use in the European Union is projected to grow to over one million tonnes by 2020.
In the European Union, for example, a strategy for implementing and encouraging a bio-based economy has been launched and a mandate issued specifically addressing the development of standards relating to bio-based solvents. As a tool to support and enhance the bio-based economy, the purpose of standards is to increase market transparency and establish common requirements for products in order to guarantee certain characteristics, such as a minimum value of bio-based content. Bio-based solvents must also compete economically with established petrochemical solvents in order to gain a significant market share. It is also important to note that standards for bio-based products will increasingly include considerations of feedstocks – their renewability and sustainability, as well as end-of-life issues, potentially extending to the recovery of resources consistent with the “circular economy”. Life cycle assessments for greener solvents are described in a chapter in this book.
But what should future bio-based solvents look like? Is it sufficient for them to provide the advantages of sustainability and biodegradability? The problem with replacing petroleum-derived solvents with the same bio-based solvent is that any safety or toxicity issues are not resolved. Environmental issues occurring at the end of use will also persist. With the REACh European regulation starting to influence solvent selection, manufacturers will be forced to investigate alternative solvents. At least bio-based solvents are compatible with the development of environmentally sustainable processes. We must assume that new solvents will be needed to meet the highly demanding requirements of the current breadth of solvent properties. Nature provides few naturally occurring compounds that can act as solvents, though modern biotechnology enables access to large volumes of a number of useful small molecules, some of which can be directly used as solvents (e.g. ethanol) and others that can be easily converted into solvents (e.g. lactates from lactic acid). But the creation of new bio-based solvents with properties similar to many existing solvent types, including aromatics, halogenated solvents and amides, will be challenging. In this book we look at bio-based aromatic solvents in some detail.
Regarding the origin of bio-based solvents, it is important that bio-waste streams, including forestry wastes and food supply chain wastes (from farm to fork), should be the source of chemical products where at all possible. This is because two substantial issues detract from the advantages of solvent substitution in favour of “first-generation” sugar-derived bio-based solvents, especially those made by fermentation. This feedstock competes with our food supply, therefore creating a strongly objectionable conflict. Extending this argument, non-food crops for use in the chemical feedstock or biofuel sectors also require arable land, thus still creating pressure on food production (as well as biodiversity and other sustainability issues). Nonetheless, biofuels have quickly become a major part of the bio-economy, in regions from the Americas to Europe as well as in Asia and beyond. The success of the petrochemical industry is largely based on the availability of large quantities of inexpensive feedstock, and this has been enabled by the emergence and continued strength of the (petroleum) oil industry. We must learn to do the same in the bio-economy. The chapter on glycerol illustrates this by considering this major by-product from bio-diesel manufacturing as a solvent, while the broader coverage in “Solvents from waste” addresses the wider issue of waste valorization to make sustainable solvents.
When we consider wastes as feedstocks, it is important that we do not forget carbon dioxide. This major natural chemical that is a vital part of our life cycles and of the critical interaction between animal and plant life, has become regarded as a threat to civilization through its overproduction resulting from our uncontrolled burning of fossil fuels. From a biorefinery perspective, CO2 is a potential C1 feedstock, and a number of synthesis pathways have been developed to make compounds from it. In particular, organic carbonates can be synthesized using CO2 and alcohols, making them potentially 100% bio-based, at least for those small alcohols that are currently made from biomass. The resulting carbonates are considerably more attractive, at least from an environmental perspective, than those made using phosgene. The use of organic carbonates as solvent is the subject of a chapter in this book.
Solvents continue to play a key role in almost every industry sector. In the last 50 or so years we have built up an impressive array of solvents that offer a remarkable diversity of properties to suit an equally diverse range of applications. The challenge for “green chemistry” is to find safe, sustainable and effective replacements so that we can continue to enjoy the benefits of solvents without the environmental harm. Bio-based solvents will play an essential role in this quest, and this book helps to show us how.
James Clark University of York Green Chemistry Centre of Excellence April 2017
Chapter 1Glycerol as Eco-Efficient Solvent for Organic Transformations
Palanisamy Ravichandiran and Yanlong Gu
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, China
1.1 Introduction
Organic solvents are used in the chemical and pharmaceutical industries [1]. The global demand for these solvents has reached 20 million metric tons annually [2]. Solvents are unreactive supplementary fluids that can dissolve starting materials and facilitate product separation through recrystallization or chromatographic techniques. In a reaction mixture, the solvent is involved in intermolecular interactions and performs the following: (i) stabilization of solutes, (ii) promoting the preferred equilibrium position, (iii) changing the kinetic profile of the reaction, and (iv) influencing the product selectivity [3]. Selection of appropriate solvents for organic transformations is important to develop green synthesis pathways using renewable feedstock. In the past two decades, green methodologies and solvents have gained increasing attention because of their excellent physical and chemical properties [4–6]. Green solvents should be non-flammable, biodegradable and widely available from renewable sources [7].
Biodiesel production involves simple catalytic transesterification of triglycerides under basic conditions (Figure 1.1) [8]. This process generates glycerol as a by-product (approximately 10% by weight). The amount of glycerol produced globally has reached 1.2 million tons and will continue to increase in the future because of increasing demand for biodiesel [9]. Glycerol has more than 2000 applications, and its derivatives are highly valued starting materials for the preparation of drugs, food, beverages, chemicals and synthetic materials (Figure 1.2) [10].
Figure 1.1 Reaction for biodiesel production.
Figure 1.2 Commercial consumption of glycerol (industrial sectors and volumes).
The biodiesel industries generate large amounts of glycerol as a by-product. As such, the price of glycerol is low, leading to its imbalanced supply. Currently, a significant proportion of this renewable chemical is wasted. This phenomenon has resulted in a negative feedback on the future economic viability of the biodiesel industry and adversely affects the environment because of improper disposal [11]. In this regard, the application of glycerol as a sustainable and green solvent has been investigated in a number of organic transformations (Table 1.1). Glycerol is a colourless, odourless, relatively safe, inexpensive, viscous, hydroscopic polyol, and a widely available green solvent. Glycerol acts as an active hydrogen donor in several organic reactions. Glycerol exhibits a high boiling point, polarity and non-flammability and is a suitable substitute for organic solvents, such as water, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). Thus, glycerol is considered a green solvent and an important subject of research on green chemistry. This review provides new perspectives for minimizing glycerol wastes produced by biomass industries.
Table 1.1Physical, chemical and toxicity properties of glycerol
Melting point
17.8°C
Boiling point
290°C
Viscosity (20°C)
1200 cP
Vapour pressure (20°C)
<1 mm Hg
Density (20°C)
1.26 g cm
−3
Flash point
160°C (closed cup)
Auto-ignition temperature
400°C
Critical temperature
492.2°C
Critical pressure
42.5 atm
Dielectric constant (25°C)
44.38
Dipole moment (30–50°C)
2.68 D
LD
50
(oral, rat)
12600 mg kg
−1
LD
50
(dermal, rabbit)
>10 000 mg kg
−1
LD
50
(rat, 1 h)
570 mg m
−3
Our research group has contributed a comprehensive review on green and unconventional bio-based solvents for organic reactions [12]. However, enthusiasm for using glycerol as a green solvent for organic transformations in particular continues to increase. The present paper thus summarizes recent developments on metal-free and metal-promoted organic reactions in glycerol between 2002 and 2016.
1.2 Metal-Free Organic Transformations in Glycerol
The synthesis of complex organic molecules utilizes harsh reaction conditions, expensive reagents and toxic organic solvents. Most organic transformations use expensive metal catalysts, such as Pd(OAc)2, PdCl2, PtCl2 and AuCl2
