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LEVULINIC ACID
An essential overview of this renewable platform chemical with growing commercial applications
Use of fossil fuels and their derivatives has been one of the major drivers of climate change. This ongoing crisis has driven a global search for biofuels and biomass-derived chemicals which can serve as the basis for sustainable and renewable industry. One such ‘platform molecule’ is levulinic acid, whose derivatives are increasingly replacing traditional fossil-derived chemicals. The importance of levulinic acid for renewable industry is therefore only growing.
Levulinic Acid: A Sustainable Platform Chemical for Value-Added Products provides a book-length introduction to this chemical and its derivatives, like the levulinates, for which applications include fuel additives, food and cosmetic preservatives, flavors, solvents, and more. The book surveys the production routes and necessary technologies involved in the production of levulinic acid, as well as its current and potential applications and typical chemical reactions. It provides a critical introduction to a potentially rich source of alternative industrial material.
Levulinic Acid readers will also find:
- Production routes from different biomass materials
- Treatment of both organic and inorganic levulinates
- Extensive discussion of levulinic acid hydrogenation
- Other derivatives formed upon reaction at the keto-functionality
Levulinic Acid is the first book on this subject, ideal for researchers and industry professionals in green chemistry and sustainable/renewable production, as well as regulators and policymakers with a focus on the relevant industries.
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Veröffentlichungsjahr: 2022
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Table of Contents
Cover
Title Page
Copyright
About the Authors
Preface
1 Levulinic Acid – History, Properties, Global Market, Direct Uses, Safety
1.1 History and Properties
1.2 Global Market
1.3 Direct Uses
1.4 Toxicity of Levulinic Acid and Inorganic Levulinates
1.5 Concluding Remarks
References
2 Production and Technological Routes
2.1 Production and Technological Routes from Biomass
2.2 Pretreatment of Lignocellulosic Biomass
2.3 Production of Levulinic Acid from Lignocellulosic Biomass
2.4 Commercial Plants for the Production of LA
2.5 Conclusion
References
3 Levulinate Derivatives – Main Production Routes and Uses of Organic and Inorganic Levulinates Derivatives
3.1 Main Production Routes
3.2 Importance and Market of the Levulinate Derivatives
3.3 Uses of Organic Levulinate Derivatives
3.4 Uses of Inorganic Levulinate Derivatives
3.5 Conclusion
References
4 Levulinic Acid Hydrogenation
4.1 Levulinic Acid Hydrogenation Products
4.2 Performance of GVL as Fuel Additive
4.3 Levulinic Acid to γ‐Valerolactone
4.4 Homogeneous and Heterogeneous Catalysts for the Efficient Conversion of LA to GVL
4.5 Heterogeneous Catalysts for the Conversion of LA and GVL to 1,4‐PDO and 2‐MTHF
4.6 Types of Hydrogenating Agents
4.7 Patent Search of LA Hydrogenation
4.8 Conclusion
References
5 Carbonyl Reactions of Levulinic Acid – Ketals and Other Derivatives Formed Upon Reaction with the Carbonyl Group of Levulinic Acid. Production Routes, Technologies, and Main Uses
5.1 Levulinc Acid Ester Ketals Main Routes
5.2 Succinic Acid
5.3 δ‐Aminolevulinic Acid (DALA) Main Routes
5.4 5‐Methyl‐N‐Alkyl‐2‐Pyrrolidone Main Routes
5.5 Diphenolic Acid Main Routes
5.6 Conclusion
References
6 Levulinic Acid in the Context of a Biorefinery
6.1 Biorefinery
6.2 Sugar‐Based Biorefinery
6.3 Levulinc Acid and Levulinates from a Sugar Cane Biorefinery
6.4 Production of γ‐Valerolactone in a Sugar Cane Biorefinery
6.5 LA in the Context of a Biodiesel Plant
6.6 Conclusions
References
Index
End User License Agreement
List of Tables
Chapter 1
Table 1.1 Selected properties of levulinic acid.
Table 1.2 Main industrial producers of levulinic acid.
Table 1.3 Typical concentration of levulinic acid and sodium levulinate in c...
Chapter 2
Table 2.1 Typical general composition of different biomasses.
Table 2.2 Some common ionic liquids applied in biomass pretreatment.
Table 2.3 Selected literature works on biological pretreatment applied for d...
Table 2.4 Production of LA from biomass‐derived feedstocks and homogeneous a...
Table 2.5 Production of LA from biomass‐derived feedstocks and heterogeneous...
Table 2.6 Advantages and limitations of different recovery processes for lev...
Table 2.7 Leading producers of levulinic acid in the world.
Chapter 3
Table 3.1 Esterification of levulinic acid with alcohols in the presence of ...
Table 3.2 Alcoholysis of sugars to ALs over solid acid catalysts.
Table 3.3 Alcoholysis of furfural to ALs in the presence of bifunctional cat...
Table 3.4 Alcoholysis of furfuryl alcohol to alkyl levulinates in the presen...
Table 3.5 Alcoholysis of 5‐HMF to levulinate esters in the presence of acid ...
Table 3.6 Selected properties of some alkyl levulinate esters.
Table 3.7 Patents and products containing inorganic levulinate in their form...
Chapter 4
Table 4.1 Selected properties of GVL and ethanol.
Table 4.2 Selected properties of 2‐MTHF and 1,4‐PDO.
Table 4.3 Catalytic hydrogenation of LA to GVL on Ru‐based catalysts.
Table 4.4 Hydrogenation of LA to GVL over copper‐based catalysts.
Table 4.5 Nickel‐based catalysts for the hydrogenation of LA to GVL.
Table 4.6 Zirconium‐based catalysts for the hydrogenation of LA to GVL.
Table 4.7 Iron‐based catalysts for the hydrogenation of LA to GVL.
Table 4.8 Hydrogenation of levulinic acid using various supported metal cata...
Chapter 5
Table 5.1 Succinic acid production by different microorganisms.
Table 5.2 Main companies producing bio‐based succinic acid.
Table 5.3 Selected examples of microbial production of DALA.
Table 5.4 Reductive amination of levulinic acid with amines in the presence ...
Table 5.5 Selected properties of DPA.
Table 5.6 Industrial application of DPA.
Chapter 6
Table 6.1 LA hydrogenation to GVL using formic acid (FA) as hydrogen source ...
Table 6.2 Average composition of soy flour (soy meal) per 100 g.
List of Illustrations
Preface
Figure 1 Number of published scientific articles with levulinic acid as keyw...
Chapter 1
Figure 1.1 Faustino Jovita Malaguti (1802–1878) (https://www.redalyc.org/jat...
Figure 1.2 Structure of levulinic acid.
Figure 1.3 Flow diagram of levulinic acid production process.
Scheme 1.1 Schematic reaction pathway for the production of levulinic acid f...
Figure 1.4 Advertisement of the contest for uses of levulinic acid in 1959....
Scheme 1.2 Schematic reaction pathway for the production of levulinic acid f...
Scheme 1.3 Biotechnological route for the synthesis of levulinic acid.
Scheme 1.4 Synthesis of levulinic acid from fossil sources; use of maleic ac...
Scheme 1.5 Main levulinic acid transformations.
Figure 1.5 Ingredients of a commercial baby moistening cosmetic, including l...
Scheme 1.6 Decarboxylation of sodium levulinate to methyl ethyl ketone (MEK)...
Figure 1.6 Veterinary supplement containing calcium levulinate (https://shop...
Figure 1.7 Three‐dimensional structure of calcium levulinate, highlighting t...
Figure 1.8 Renewable chemical platforms listed by the US DOE.
Chapter 2
Scheme 2.1 Reaction pathways for renewable fuels and chemicals from lignocel...
Figure 2.1 Schematic structure of cellulose, hemicellulose, and lignin.
Figure 2.2 Structural alterations of lignocellulosic biomass after pretreatm...
Figure 2.3 Main types of lignocellulosic biomass pretreatments.
Figure 2.4 Supercritical CO
2
pretreatment.
Figure 2.5 Main steps involved in the production of LA from lignocellulosic ...
Scheme 2.2 Synthesis of 5‐hydroxymethyl furfural and levulinic acid.
Scheme 2.3 Route of levulinic acid production from pentoses.
Scheme 2.4 Routes for the formation of LA from simple sugars.
Scheme 2.5 Hydrolysis of sugars to LA and formic acid.
Scheme 2.6 Biphasic systems in LA production.
Scheme 2.7 Reactions of the Biofine process.
Figure 2.6 Schematic diagram of the Biofine process of levulinic acid produc...
Figure 2.7 GF Biochemicals LA plant in Italy.
Chapter 3
Figure 3.1 Chemical structure of levulinate derivatives, where R is an alkyl...
Scheme 3.1 Synthetic routes for alkyl levulinate esters from cellulose and h...
Scheme 3.2 Esterification routes of levulinic acid to alkyl levulinate ester...
Figure 3.2 Proposed structure for the protonation of the carboxyl group of l...
Figure 3.3 Proposed structure for the protonation of the hydroxyl group of l...
Scheme 3.3 Mechanistic pathway of the acid‐catalyzed esterification of the c...
Scheme 3.4 Synthesis of alkyl levulinate esters from furfural.
Scheme 3.5 Possible pathway of furfuryl alcohol formation from furfural via ...
Scheme 3.6 Proposed mechanistic pathway for the acid‐catalyzed alcoholysis o...
Scheme 3.7 Possible mechanistic pathway of the acid‐catalyzed alcoholysis of...
Scheme 3.8 Ethanolysis of 5‐HMF to 5‐ethoxymethyl furfural and ethyl levulin...
Scheme 3.9 Decarbonylation of 5‐hydroxymethyl furfural (HMF) in the methanol...
Scheme 3.10 Synthesis of AL from chloromethyl furfural.
Figure 3.4 Overall utilization of levulinate derivatives.
Figure 3.5 Possible application of methyl levulinate in the production of gl...
Figure 3.6 Synthetic route for the production of levulinate‐derived plastici...
Chapter 4
Scheme 4.1 Possible products of catalytic hydrogenation of LA.
Figure 4.1 Number of published scientific articles on LA hydrogenation to GV...
Scheme 4.2 Possible products of GVL conversion.
Figure 4.2 Some applications of GVL.
Scheme 4.3 Reaction pathways of LA to GVL.
Scheme 4.4 Possible mechanistic pathway for the production of GVL from 4‐hyd...
Scheme 4.5 GVL hydrogenation to 1,4‐PDO.
Scheme 4.6 1,4‐PDO hydrogenation to other products.
Scheme 4.7 One‐pot catalytic hydrogenation of LA to aliphatic alcohols.
Scheme 4.8 Pathways and applications of the catalytic upgrading of levulinic...
Scheme 4.9 Pathways to convert GVL to liquid fuels.
Figure 4.3 Main differences between LA hydrogenation to GVL using H
2
and for...
Scheme 4.10 Possible routes of FA decomposition.
Chapter 5
Scheme 5.1 Main derivatives formed upon reaction with the carbonyl group of ...
Scheme 5.2 Reaction pathways for the formation of levulinic acid ester ketal...
Scheme 5.3 Possible levulinic acid ester ketals formed from glycerol and lev...
Scheme 5.4 Synthesis of branched oleochemicals from epoxidized methyl oleate...
Scheme 5.5 Formation of glycerol levulinate ketal ester (GLK‐ester) from the...
Figure 5.1 Applications of levulinic acid ester ketals (LEKs), where R
1
corr...
Figure 5.2 Examples of (A) diol and (B) dicarboxylic acid esters monomers ba...
Scheme 5.6 Synthesis of polyester from an AB monomer containing a cyclic ace...
Scheme 5.7 Succinic acid production from maleic anhydride. The petrochemical...
Scheme 5.8 Succinic acid production from maleic and fumaric acid.
Scheme 5.9 Simplified biochemical pathway for the production of succinic aci...
Figure 5.3 Overview of the process to produce succinic acid: (a) ammonia pre...
Scheme 5.10 Baeyer–Villiger oxidation of LA to succinic acid and other produ...
Figure 5.4 Main applications of succinic acid.
Scheme 5.11 Conversion of succinic acid into products of industrial applicat...
Scheme 5.12 Conventional synthesis of DALA [65].
Scheme 5.13 NREL‐route to the synthesis of DALA [65].
Scheme 5.14 Synthesis of DALA hydrochloride [66].
Scheme 5.15 Two main pathways for DALA biosynthesis in living organisms [84]...
Scheme 5.16 Reductive amination of levulinic acid over supported metal catal...
Scheme 5.17 Schematic pathway for the formation of 5‐methyl‐2‐pyrrolidone fr...
Scheme 5.18 Suggested reaction pathway for the reductive amination of levuli...
Figure 5.5 Application of N‐substituted‐5‐methyl‐2‐pyrrolidone.
Figure 5.6 Examples of drugs with the pyrrolidone core.
Scheme 5.19 General synthetic route of DPA.
Scheme 5.20 Condensation of LA and phenol to afford the two DPA isomers.
Figure 5.7 Some potential applications of DPA.
Scheme 5.21 Synthesis of BPA analogs upon the amidation of DPA [131].
Chapter 6
Figure 6.1 Schematic representation of a biorefinery.
Figure 6.2 Main products obtained in sugar cane and corn‐based biorefineries...
Figure 6.3 Simplified scheme of a sugar cane biorefinery to produce bioethan...
Figure 6.4 Simplified scheme of a corn‐based biorefinery to produce bioethan...
Figure 6.5 Simplified flow diagram of the production of levulinic acid and e...
Figure 6.6 Schematic production of hydrogen on a sugar cane biorefinery.
Figure 6.7 Formic acid decomposition pathways: dehydration and dehydrogenati...
Figure 6.8 Schematic representation of hardwood pretreatment with GVL/water ...
Scheme 6.1 Transesterification of triglycerides with methanol to produce bio...
Figure 6.9 World share of feedstocks used for biodiesel production; referenc...
Figure 6.10 Simplified flow sheet for integrating the biodiesel and the LA c...
Guide
Cover
Table of Contents
Title Page
Copyright
About the Authors
Preface
Begin Reading
Index
End User License Agreement
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Levulinic Acid
A Sustainable Platform Chemical for Value‐Added Products
Claudio J.A. Mota
Ana Lúcia de Lima
Daniella R. Fernandes
Bianca P. Pinto
Federal University of Rio de Janeiro
Institute of Chemistry
Rio de Janeiro
Brazil
This edition first published 2023
© 2023 John Wiley & Sons Ltd
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The right of Claudio J.A. Mota, Ana Lúcia de Lima, Daniella R. Fernandes, and Bianca P. Pinto to be identified as the authors of this work has been asserted in accordance with law.
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Library of Congress Cataloging‐in‐Publication Data:
Names: Mota, Claudio J. A., author. | Lima, Ana Lúcia de, author. | Fernandes, Daniella R., author. | Pinto, Bianca Peres, author.
Title: Levulinic acid : a sustainable platform chemical for value‐added products / Claudio J.A. Mota, Ana Lúcia de Lima, Daniella R. Fernandes, Bianca P. Pinto.
Description: Hoboken, NJ : Wiley, 2023. | Includes bibliographical references and index.
Identifiers: LCCN 2022038112 (print) | LCCN 2022038113 (ebook) | ISBN 9781119814665 (cloth) | ISBN 9781119814689 (adobe pdf) | ISBN 9781119814696 (epub)
Subjects: LCSH: Ketonic acids.
Classification: LCC QD341.K2 M78 2023 (print) | LCC QD341.K2 (ebook) | DDC 547/.036–dc23/eng20221123
LC record available at https://lccn.loc.gov/2022038112
LC ebook record available at https://lccn.loc.gov/2022038113
Cover Design: Wiley
Cover Images: © tchara/Adobe Stock Photos; © Peggy_Marco/pixabay; © ybernardi/pixabay; © stokpic/pixabay; Molecular Structures: Courtesy of Daniella R. Fernandes
About the Authors
Claudio J.A. Mota holds a degree in chemical engineering from the Federal University of Rio de Janeiro (UFRJ), where he also obtained his PhD in chemistry. He is full professor of chemistry and chemical engineering, as well as director of the Institute of Chemistry of the UFRJ. He is a research fellow from CNPq and state scientist from FAPERJ. He is member of the Brazilian Chemical Society (SBQ), Brazilian Catalysis Society (SBCat), American Chemical Society (ACS), and fellow of the Royal Society of Chemistry (RSC). He was awarded with the TWAS Prize, given by the Mexican Academy of Science, the Technology Prize from the Brazilian Association of the Chemical Industries (ABIQUIM), the Innovation Prize of SBQ, and the Simão Mathias Medal, the highest honor of the SBQ. He is author of more than 160 scientific publications, among articles, patents, and books. He participates in the editorial boards of the Journal of CO2Utilization, Journal of Catalysis and ACS Omega, having also established several international collaborations. His current research interests are focused on biomass transformation and processes of CO2 capture and conversion, targeting applications in the fuel and chemical sectors.
Ana Lúcia de Lima received her BA degree (2011) in Chemical Sciences with Technological Assignments in Chemical Sciences from the Federal University of Uberlândia (UFU), Brazil. She received her MSc (2013) and doctoral (2017) degrees from Federal University of Rio de Janeiro (UFRJ), Brazil. She has started postdoctorate study (2017) at LMCP/IMA/UFRJ on development and evaluation of polymeric hydrogels for compliance control in oil reservoirs. At the moment, she is a professor at the Department of Analytical Chemistry at the Institute of Chemistry at UFRJ and a researcher at LARHCO/UFRJ where she researches in the area of mesoporous materials with various applications, such as heterogeneous catalysts with a focus on biomass transformation and adsorbents for CO2 capture.
Daniella R. Fernandes is an adjunct professor at the Department of Organic Chemistry at the Institute of Chemistry of the Federal University of Rio de Janeiro (UFRJ), Brazil. She holds a degree in chemistry (2001), master's (2004), and doctorate (2009) in chemistry from the same university, all with specialization in petroleum chemistry. She is a permanent professor in the Chemistry Professional Master's Program in the National Network (PROFQUI) at the Institute of Chemistry, UFRJ. She has been working at the LARHCO in the environment, energy, and catalysis areas, especially correlated to biomass valorization, biofuels production and chemicals, and material development for CO2 capture and utilization.
Bianca P. Pinto graduated in chemistry (2006) from the State University of Rio de Janeiro (UERJ) and obtained her master's (2009) and doctoral degrees (2013) in chemistry from the Federal University of Rio de Janeiro (UFRJ, Brazil). She continued to work at the same university for a postdoctoral stay (2014–2021). Her research focused on the catalytic transformation of levulinic acid into valerolactone and other products, and CO2 capture and conversion. She is also a cofounder of CarbonAir Energy, carbon capture, and utilization startup. She is currently a substitute professor at the Department of Analytical Chemistry at the UFRJ. She is the author or coauthor of 14 scientific articles in indexed journals, 3 book chapters, and 2 published books.
Preface
The climate changes caused by the use of fossil resources are driving the search for more sustainable energy sources, and the use of renewable raw material for the chemical industry. In this context, biofuels and bioderived products have emerged in the world's scenario as alternatives to decrease the carbon emissions. Bioethanol and biodiesel are commercially produced in many countries, whereas bio‐based commodity chemicals, such as ethylene obtained from ethanol, are industrially produced in large scale. The bio‐based economy will continue to grow in the twenty‐first century, especially that dealing with the valorization of lignocellulosic materials and agriculture residues of less economic value. Therefore, the development of processes for converting lignocellulosic biomass into valuable products and fuels is of great importance.
Levulinic acid (LA) emerges as an important bioderived feedstock, as it may be obtained from sugars employing thermochemical routes. Therefore, its production can be accomplished using great diversity of biomass raw materials, which makes levulinic acid a versatile bio‐based platform chemical. Today, it is still considered a specialty chemical and its industrial production is limited, as well as the applications of LA and major derivatives in different sectors. Nevertheless, as the demand for new bio‐based products increases, it is expected that levulinic acid may grow in importance, being one of the main bioderived feedstocks for the production of chemicals and biofuels.
This book intends to gather the current knowledge on levulinic acid production and conversion into major derivatives. From the best of our knowledge, this is the first book on the subject, and we hope it can motivate new scientific and technological developments, as well as new uses for levulinic acid and its derivatives. LA is a keto‐carboxylic acid; thus, it presents two functionalities that could be exploited in different reactions. Such versatility is not usually found in simple bioderived molecules, making levulinic acid an attractive bio‐based platform as pointed out by the US Department of Energy.
Figure 1 Number of published scientific articles with levulinic acid as keyword.
Figure 1 shows the number of scientific publications with levulinic acid as keyword from 1996 to 2021. The rising interest on the subject is evident, especially after 2010. The need for decreasing the CO2 emissions in the forthcoming years, to meet the goals of recent UN climate change agreements, will push forward the research on bioderived platforms, such as levulinic acid. Therefore, this book may help scientists and students around the globe in the search of new applications and processes for production and transformation of levulinic acid and its derivatives. We hope that the content would be useful, and the information needed would be easily found in one of the chapters.
Chapter 1 covers the historical context, highlighting the first studies on sugar hydrolysis that may have produced levulinic acid. It also describes the properties and first industrial processes and producers of LA. The chapter highlights the current market and companies that commercialize LA, also discussing the main applications of LA and some derivatives, as well as toxicological issues.
In Chapter 2, the processes of LA production are thoroughly discussed. Different routes, catalysts, feedstocks, and reaction conditions are presented, especially focusing on the production from lignocellulosic biomass materials. The Biofine process is also discussed, as well as the challenges on product separation and purification.
Chapter 3 is dedicated to the organic and inorganic levulinates. The production routes for the levulinate esters are detailed and discussed, together with the current market and main applications. Levulinate esters are versatile chemicals with applications going from the fuel sector to the food industry. The chapter also discusses the production route and main uses of inorganic levulinates, especially sodium and calcium levulinates. Both have uses in the food and pharmaceutical sectors.
The hydrogenation of LA is covered in Chapter 4. The different products that can be obtained from LA hydrogenation are discussed, together with information on catalysts, reaction pathways, and conditions. A particular emphasis is given to γ‐valerolactone (GVL), which has many potential applications. However, other hydrogenated derivatives, such as 1,4‐pentadediol (1,4‐PD) and 2‐methyl tetrahydrofuran (2‐MTHF), are also discussed together with their main uses.
Chapter 5 is dedicated to reactions on the carbonyl group. Formation of ketals, especially the glycerol levulinic acid/ester ketal (GLEK), is discussed, together with the main potential applications. The chapter also discusses the process of LA conversion to succinic acid and the production of δ‐aminolevulinic acid (DALA), as well as their main uses. The reaction of levulinic acid/esters with phenol derivatives is also highlighted as a bioderived strategy to replace bisphenol‐A (BPA).
Finally, Chapter 6 shows examples of LA production and uses in a sugar cane biorefinery. Production of ethyl levulinate and GVL is discussed, highlighting the integration of these chemicals with other products of the sugar cane biorefinery. In addition, integration of the biodiesel and LA fabrication chains was discussed, aiming at the production of GLEK.
We believe that the book may be a good and updated source of reference to students, scientists, and professionals in the academia, industry, and government, also motivating new technological discoveries and commercial uses of LA and its derivatives. Our aim in writing this book was to provide concise information on LA and its derivatives, covering technical aspects and major uses, together with relevant references for further consult of the interested reader.
Rio de Janeiro, May 2022 Claudio J.A. Mota
Ana Lúcia de Lima
Daniella R. Fernandes
Bianca P. Pinto
1Levulinic Acid – History, Properties, Global Market, Direct Uses, Safety
1.1 History and Properties
The first evidence for the formation of levulinic acid was obtained from the treatment of sugars with dilute acid solutions. The Italian‐French Pharmacist Faustino Jovita Malaguti (Figure 1.1) reported, in 1835 [1], the treatment of sucrose with boiling diluted acid solutions, being able to identify formic acid and other ammonia‐soluble compounds. In 1840, the Dutch chemist Gerardus Johannes Mulder reported the treatment of fructose with hydrochloric acid and was able to isolate acidic compounds [2]. Although these two scientists did not explicitly identify levulinic acid among the products, they were the first to conduct experiments in which levulinic acid would be formed. Nevertheless, the first identification of levulinic acid from the acid treatment of sugars was reported by Tollens in 1875 [3].
Levulinic acid (LA) is a keto‐carboxylic acid bearing carbonyl and carboxyl groups in its structure (Figure 1.2). Therefore, the double functionalization makes it an interesting chemical for multiple purposes. Reactions involving levulinic acid are known since the 1870s, but the development of commercial processes and uses were not significant until the 1940s, mostly because of the high costs of the raw materials at the time, high capital costs, and low yields. With the use of cellulose‐based feedstocks [4], the production of levulinic acid became more attractive motivating its general use.
Levulinic acid is the 4‐oxo‐pentanoic acid according to the International Union of Pure and Applied Chemistry (IUPAC) nomenclature. It may also be regarded as the 4‐oxo‐valeric acid. In the pure form, it is a solid that melts at 30–33 °C and boils at 245–246 °C at atmospheric pressure. Table 1.1 shows some selected properties of levulinic acid.
The first commercial production of levulinic acid dates from the 1940s when the A.E. Staley Manufacturing Company started a bath production using starch as raw material. The process [5] involves the initial mixing of proper amounts of starch and diluted hydrochloric acid at 100 °C in a preheater system. Then, the reaction mixture was autoclaved at 175–215 °C for a determined period. The effluent was neutralized with soda ash and the humins, which are insoluble by‐products, were separated by filtration, whereas water and formic acid, formed as a by‐product, were evaporated from the solution and the sodium chloride by centrifugation. Levulinic acid was obtained, like a light‐colored liquid, upon vacuum steam distillation (Figure 1.3).
Figure 1.1 Faustino Jovita Malaguti (1802–1878) (https://www.redalyc.org/jatsRepo/1816/181662291006/html/index.html).
Source: CITMATEL.
Figure 1.2 Structure of levulinic acid.
Starch is a biopolymer made of hexoses, mainly glucose, that may be obtained from wheat, potato, and oat among numerous other crops. The chemical pathway from C6 sugars to levulinic acid is depicted in Scheme 1.1. The acid medium dehydrates the carbohydrates to intermediate compounds, like hydroxymethyl furfural (HMF), which can then be converted into levulinic acid also releasing a molecule of formic acid in the process.
Table 1.1 Selected properties of levulinic acid.
Property
Value
Chemical formula
C
5
H
8
O
3
Molecular weight
116.11 g
CAS number
123‐76‐2
Chem Spider ID
11 091
Specific mass
1.1340 g ml
−1
(25 °C)
Melting point
30–33 °C
Boiling point
245–246 °C
Flash point
137 °C
Refractive index
1.439
pKa
4.65 (water at 25 °C)
Solubility in water
675 g l
−1
(20 °C)
Solubility in ethanol
Soluble
Solubility in hydrocarbons
Insoluble
Aspect
White to clear yellow solid or liquid
LD
50
in rats (oral)
1850 mg kg
−1
In the 1950s, the Quaker Oats Company developed a process to produce levulinic acid based on furfuryl alcohol as raw material. The company started producing furfural from sugarcane bagasse or corn cobs in 1922 [6, 7], upon heating the biomass in an aqueous solution of sulfuric or phosphoric acid. Furfural is an aromatic aldehyde mostly used in the production of resins at that time. In 1934, the company began the production of furfuryl alcohol from the high‐pressure hydrogenation of furfural in Memphis, Tennessee, United States [8]. Then, a continuous process was developed, achieving 99% conversion of furfural in furfuryl alcohol with the use of copper‐supported catalysts [9]. The production of levulinic acid from furfuryl alcohol began in 1957 and ended in 1972. The process involved the heating of furfuryl alcohol in the presence of aqueous hydrochloric acid, but small alcohol, such as methanol and ethanol, could also be employed affording the respective levulinate esters [10]. In the beginning, the company did not have enough uses for the levulinic acid produced. In 1959, Quaker Oats released [11] a contest for someone to bring a big idea on a commercial use of levulinic acid (Figure 1.4).
The overall chemical pathway to produce levulinic acid from C5 sugars is shown in Scheme 1.2. The pentoses are initially dehydrated to furfural in the acidic medium, usually hydrochloric acid. Then, in a second process, furfural is hydrogenated to furfuryl alcohol, which is further converted to levulinic acid upon acid‐catalyzed hydrolysis.
Figure 1.3 Flow diagram of levulinic acid production process.
Scheme 1.1 Schematic reaction pathway for the production of levulinic acid from hexoses.
A biotechnological route to levulinic acid involving multiple steps has also been suggested [12]. It involves the fermentation of sugars, like glucose and fructose, to pyruvic acid as the first step (Scheme 1.3). The next steps may also involve biocatalysts. For instance, acetaldehyde can be produced from pyruvic acid with the use of pyruvate decarboxylase. In the same way, aldolases may be employed in the aldol condensation step. Dehydration of the 2‐hydroxy‐4‐oxo‐pentanoic acid, followed by the selective hydrogenation of the intermediate to levulinic acid, may be carried out either through biocatalysis or homogeneous/heterogeneous catalysis. Although technically feasible, this route has not been employed industrially, probably because of the numerous steps, which may require specific reaction conditions and separation procedures, significantly increasing the production costs.
Figure 1.4 Advertisement of the contest for uses of levulinic acid in 1959.
Source: Reproduced with the permission of the American Chemical Society.
Scheme 1.2 Schematic reaction pathway for the production of levulinic acid from pentoses.
Scheme 1.3 Biotechnological route for the synthesis of levulinic acid.
A fossil‐based route to levulinic acid has also been developed [13]. The raw material is maleic acid, which is normally obtained from oxidation of benzene [14] or butenes [15]. However, recent developments point out possible routes from renewable feedstocks [16]. Scheme 1.4 shows the steps, which involve the decarboxylation of acetyl succinate.
The DSM company in Linz, Austria, has developed a small‐scale process to produce 3 tons per day of levulinic acid from maleic acid, with an overall yield of about 80%. Nevertheless, the company has moved the production of levulinic acid from bio‐based raw materials, discontinuing the fossil‐based route.
Levulinic acid is a bifunctional molecule, having a keto‐carbonyl and a carboxylic acid group. Therefore, it is expected to present the chemical properties of ketones and carboxylic acids. Scheme 1.5 shows the most common transformations of the levulinic acid molecule.
The levulinate esters find applications as fuel additives [17], as well as fragrancies. Inorganic levulinate salts are also important specialty chemicals; sodium levulinate is used in the cosmetic and food industry as preservative [18], whereas calcium levulinate is used in pharmaceutics and as a supplementary source of calcium. Hydrogenation may lead to different products. The γ‐valerolactone (GVL) is normally produced upon the hydrogenation of levulinic acid over bifunctional catalysts, having a metallic and acidic function. Angelica lactone and methyl‐tetrahydrofuran (MTHF) may also be produced depending on the catalyst and reaction conditions. GVL and MTHF are potential fuel additives [19] and green solvents [20], whereas angelica lactone may be an intermediate in the synthesis of pharmaceutical products. Hydrogenation may also form 1,5‐pentanediol, n‐pentanol, and valeric acid. This latter compound has application as plasticizer.
Scheme 1.4 Synthesis of levulinic acid from fossil sources; use of maleic acid as feedstock.
Scheme 1.5 Main levulinic acid transformations.
The reaction of levulinic acid with phenol may afford diphenolic levulinic acid, which may replace bisphenol‐A (BPA) in polymers and other uses. BPA has been suspected to have mutagenic activity and its use in polymers that may have direct contact with food is being discontinued. Levulinic acid ketals may be produced upon the acid‐catalyzed reaction with diols or triols, such as glycerol, obtained as a by‐product of biodiesel production. The oxidative degradation of the keto group may afford succinic acid, which is a product with increasing applications.
Nitrogenated compounds can be also obtained from levulinic acid. The γ‐amino levulinic acid may be synthesized in two steps from levulinic acid or levulinate esters. This compound may be useful in the synthesis of agrochemicals and used as pesticides [21]. N‐Alkyl‐pyrrolidones are also produced in two steps from levulinic acid or levulinate esters, being important intermediates in the pharmaceutical industry.
1.2 Global Market
Today, levulinic acid is industrially produced from biomass, being a renewable platform for the chemical industry. Table 1.2 shows the major producers and countries of origin. China appears as the major producer, but there are plants in the United States and Europe. The large number of companies indicates that levulinic acid is still produced on a relatively small scale, showing great potential to expand its use and, therefore, the capacity of the plants.
Although the production capacity is not always reported by the companies, Biofine Technology seems to be the largest producer of levulinic acid in the world, being able to use a variety of biomass feedstocks. GF Biochemicals, based in Italy, also appears as an important producer. The company has acquired smaller companies like Segetis and established a joint venture with the American Process Inc. to build an integrated biorefinery in the United States. More recently, it announced the formation of a joint venture with the Towell Engineering Group for the production and commercialization of levulinic acid.
Table 1.2 Main industrial producers of levulinic acid.
Company
Country
Biofine Technology LLC
United States
GF Biochemicals Co.
Italy
Bio‐on
Italy
Langfang Hawk Technology & Development
China
Heroy Chemical Industry Co.
China
Parchem Fine & Specialty Chemicals
United States
Avantium Inc.
Holland
DSM
Holland
E. I. du Pont de Nemours and Company
United States
Hebei Langfang Triple Well Chemicals Co.
China
Apple Flavor & Fragrance Group Co.
China
China Shijiazhuang Pharmaceutical Group Co.
China
Hefei TNJ Chemical Industry Co.
China
Haihang Industry Co.
China
Tokyo Chemical Industry Co.
Japan
Bio‐on is an Italian company that launched, in 2017, a project to produce levulinic acid together with the Sadam Group, which is also based in Italy and is known in the food and agroindustry sectors.
The Langfang Hawk Technology & Development Co. Ltd. is a Chinese company founded in 1992. Since 2002, it has been producing about 3 tons of levulinic acid per year from furfural. The Heroy Chemical Industry Co. produces levulinic acid in China since 1995. The other companies may produce levulinic acid as an intermediate for other processes or may simply commercialize it for resales. For instance, DSM announced a project to produce adipic acid from levulinic acid in 2016 and Avantium produces methyl levulinate in Holland.
The global market of levulinic acid was US$27.2 million in 2019, and it is expected to increase at a compound annual growth rate (CAGR) of 8.8% between 2020 and 2030 [22]. Global sales in 2030 are expected to reach US$60.2 million. The coronavirus pandemic may have changed this forecast, but levulinic acid is still a promising renewable raw material and the increasing demand will continue. In the year 2000, levulinic acid was commercialized with prices ranging from US$8.8–13.2 per kilogram. The market was relatively small, with total production around 0.5 ton per year. The market experienced a significant increase, and in 2013, the total production reached 2.6 ton, with prices ranging from US$5–8 per kilogram. North America is the world's largest consumer of levulinic acid and its derivatives, with Europe and Asia‐Pacific coming next.
1.3 Direct Uses
The main direct use of levulinic acid is in cosmetics (Figure 1.5) to help prevent microbial growth, without altering the pH and the color of the beauty products. Sodium levulinate may be produced from the reaction of levulinic acid with basic solutions of sodium hydroxide or sodium carbonate, and it is also popular as a preservative in skin cosmetic formulations. According to the Voluntary Cosmetic Registration Program (VCRP) of the Food and Drug Administration (FDA) of the United States, 131 cosmetic formulations use levulinic acid, whereas sodium levulinate is present in 402 cosmetic preparations. The maximum concentration of LA is 4.5% in hair dyes, whereas sodium salt is present in up to 0.62% in mouthwashes and breath fresheners. Levulinic acid and sodium levulinate are used in baby products, such as lotion, oil, and cream formulations.
Levulinic acid and sodium levulinate may also find applications in the food industry, especially as preservatives in meats [23] and sausages [18]. They are effective in stunting bacterial growth. For instance, the addition of 1% or 2% of sodium levulinate in beef bologna and turkey roll, respectively, prevents the growth of Listeria monocytogenes upon refrigerated storage [24].
Levulinic acid has also been reported to enhance dermal penetration of drugs [25], whereas sodium levulinate was tested as a renewable deicing agent [26]. For instance, at −2.7 °C, solutions of sodium levulinate completely melted the ice.
Figure 1.5 Ingredients of a commercial baby moistening cosmetic, including levulinic acid in its formulation (https://world.openbeautyfacts.org/product/4311596611461/baby-pflegecreme-blutezeit).
Source: Open Beauty Facts.
Decarboxylation of sodium levulinate yields methyl ethyl ketone (MEK) (Scheme 1.6), an important solvent in the chemical industry [27]. The process involves an electrochemical cell that is fed with sodium levulinate, sodium hydroxide, water or methanol, and hydrogen. The decarboxylation of sodium levulinate generates free radicals that may interact with hydrogen gas to yield MEK and octanedione.
Scheme 1.6 Decarboxylation of sodium levulinate to methyl ethyl ketone (MEK).
Calcium levulinate is another important salt of levulinic acid. It has been used as a dietary supplement of calcium for more than 80 years [28]. It may be presented as pills, capsules, or injections in the pharmaceutical industry (Figure 1.6) to serve as a food nutrition enhancer that improves bone formation and muscle excitability. Calcium levulinate has also been used in beverages [29] and vitamins [30], as a source of calcium.
Calcium levulinate is normally precipitated in the form of dihydrate of molecular formula Ca(C5H7O3)2(H2O)2, which forms a polymeric structure with the calcium cations being octacoordinated, with two aqua ligands and six oxygen atoms from the carboxylate groups [31]. The three‐dimensional arrangement presents interchain hydrogen bonds, involving the water molecules of one chain and the carboxylate groups of the other chain (Figure 1.7).
Figure 1.6 Veterinary supplement containing calcium levulinate (https://shopsi.martagaska.com/category?name=5000%20iu%20v%20ug).
Source: shopsi.martagaska.com.
Figure 1.7 Three‐dimensional structure of calcium levulinate, highlighting the unit cell and the hydrogen bonds (dotted lines) [31].
Source: Amarasekara et al. [31]/International Union of Crystallography/CC BY 2.0 UK.
1.4 Toxicity of Levulinic Acid and Inorganic Levulinates
Levulinic acid is listed by the FDA of the United States as a permitted synthetic flavoring substance and adjuvant in food for human consumption [32]. The acute dermal toxicity (LD50
