Levulinic Acid: A Sustainable Platform

Chemical for Value-Added Products

Claudio J.A. Mota
Visit to download the full and correct content document:
https://ebookmass.com/product/levulinic-acid-a-sustainable-platform-chemical-for-val
ue-added-products-claudio-j-a-mota/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Depolymerization of Lignin to Produce Value Added

Chemicals Pratima Bajpai

https://ebookmass.com/product/depolymerization-of-lignin-to-
produce-value-added-chemicals-pratima-bajpai/

Platform Chemical Biorefinery. Future Green Industry

1st Edition Satinder Kaur Brar

https://ebookmass.com/product/platform-chemical-biorefinery-
future-green-industry-1st-edition-satinder-kaur-brar/

Tools For Chemical Product Design From Consumer

Products to Biomedicine 1st Edition Mariano Martín

https://ebookmass.com/product/tools-for-chemical-product-design-
from-consumer-products-to-biomedicine-1st-edition-mariano-martin/

Relationship Between Microbes and the Environment for

Sustainable Ecosystem Services, Volume 1: Microbial
Products for Sustainable Ecosystem Services Jastin
Samuel
https://ebookmass.com/product/relationship-between-microbes-and-
the-environment-for-sustainable-ecosystem-services-
volume-1-microbial-products-for-sustainable-ecosystem-services-
Contemporary Chemical Approaches for Green and
Sustainable Drugs 1st Edition Török M. (Ed.)

https://ebookmass.com/product/contemporary-chemical-approaches-
for-green-and-sustainable-drugs-1st-edition-torok-m-ed/

Strategic Corporate Social Responsibility: Sustainable

Value Creation Fourth

https://ebookmass.com/product/strategic-corporate-social-
responsibility-sustainable-value-creation-fourth/

Edible mushrooms : chemical composition and nutritional

value 1st Edition Kala■

https://ebookmass.com/product/edible-mushrooms-chemical-
composition-and-nutritional-value-1st-edition-kalac/

Applications in Design and Simulation of Sustainable

Chemical Processes 1st Edition Dimian A.

https://ebookmass.com/product/applications-in-design-and-
simulation-of-sustainable-chemical-processes-1st-edition-
dimian-a/

Green Sustainable Process for Chemical and

Environmental Engineering and Science: Switchable
Solvents Dr. Inamuddin

https://ebookmass.com/product/green-sustainable-process-for-
chemical-and-environmental-engineering-and-science-switchable-
solvents-dr-inamuddin/
Levulinic Acid
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

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as
permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://
www.wiley.com/go/permissions.

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.

Registered Offices
John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK

For details of our global editorial offices, customer services, and more information about Wiley products visit
us at www.wiley.com.

Wiley also publishes its books in a variety of electronic formats and by print-on-demand. Some content that
appears in standard print versions of this book may not be available in other formats.

Trademarks: Wiley and the Wiley logo are trademarks or registered trademarks of John Wiley & Sons, Inc.
and/or its affiliates in the United States and other countries and may not be used without written permission.
All other trademarks are the property of their respective owners. John Wiley & Sons, Inc. is not associated
with any product or vendor mentioned in this book.

Limit of Liability/Disclaimer of Warranty

In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant
flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged
to review and evaluate the information provided in the package insert or instructions for each chemical, piece
of equipment, reagent, or device for, among other things, any changes in the instructions or indication of
usage and for added warnings and precautions. While the publisher and authors have used their best efforts in
preparing this work, they make no representations or warranties with respect to the accuracy or completeness
of the contents of this work and specifically disclaim all warranties, including without limitation any implied
warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by
sales representatives, written sales materials or promotional statements for this work. The fact that an
organization, website, or product is referred to in this work as a citation and/or potential source of further
information does not mean that the publisher and authors endorse the information or services the
organization, website, or product may provide or recommendations it may make. This work is sold with the
understanding that the publisher is not engaged in rendering professional services. The advice and strategies
contained herein may not be suitable for your situation. You should consult with a specialist where
appropriate. Further, readers should be aware that websites listed in this work may have changed or
disappeared between when this work was written and when it is read. Neither the publisher nor authors shall
be liable for any loss of profit or any other commercial damages, including but not limited to special,
incidental, consequential, or other damages.

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

Set in 9.5/12.5pt STIXTwoText by Straive, Chennai, India

 v

Contents

About the Authors ix

Preface xi

1 Levulinic Acid – History, Properties, Global Market, Direct

Uses, Safety 1
1.1 History and Properties 1
1.2 Global Market 8
1.3 Direct Uses 10
1.4 Toxicity of Levulinic Acid and Inorganic Levulinates 12
1.5 Concluding Remarks 13
References 15

2 Production and Technological Routes 19

2.1 Production and Technological Routes from Biomass 19
2.2 Pretreatment of Lignocellulosic Biomass 23
2.2.1 Physical Pretreatment 23
2.2.1.1 Mechanical 24
2.2.1.2 Microwave 25
2.2.1.3 Ultrasound 25
2.2.2 Chemical Pretreatment 25
2.2.2.1 Acid Hydrolysis 25
2.2.2.2 Alkaline Hydrolysis 26
2.2.2.3 Ionic Liquids 27
2.2.2.4 Organosolv 27
2.2.3 Physicochemical Pretreatment 28
2.2.3.1 Steam Explosion (SE) 29
2.2.3.2 Liquid Hot Water (LHW) 29
2.2.3.3 Ammonia Fiber Expansion (AFEX) 30
2.2.3.4 Supercritical CO2 Explosion 30
vi Contents

2.2.4 Biological Pretreatment 31

2.3 Production of Levulinic Acid from Lignocellulosic Biomass 32
2.3.1 Processes for LA Production: Homogeneous Catalysts 35
2.3.2 Processes for LA Production: Heterogeneous Catalysts 38
2.3.3 Processes for LA Production: Biphasic Systems 40
2.3.4 The Biofine Process of LA Production 41
2.3.5 Downstream Process of LA Recovery 42
2.4 Commercial Plants for the Production of LA 44
2.5 Conclusion 47
References 47

3 Levulinate Derivatives – Main Production Routes and Uses

of Organic and Inorganic Levulinates Derivatives 65
3.1 Main Production Routes 65
3.1.1 Esterification of Levulinic Acid 65
3.1.2 Direct Production from the Alcoholysis of Polyschacarides 71
3.1.3 Alcoholysis of Furfural 76
3.1.4 Alcoholysis of 5-Hydroxymethyl Furfural 82
3.1.5 Production of Levulinate Inorganic Salts 86
3.2 Importance and Market of the Levulinate Derivatives 87
3.3 Uses of Organic Levulinate Derivatives 88
3.3.1 Food and Cosmetic 88
3.3.2 Fuel Additives 89
3.3.3 Plasticizers 90
3.3.4 Solvents 91
3.4 Uses of Inorganic Levulinate Derivatives 93
3.4.1 Antifreeze Additive 93
3.4.2 Cosmetic, Pharmaceutical, and Food 93
3.4.3 Miscellaneous Applications 94
3.5 Conclusion 95
References 96

4 Levulinic Acid Hydrogenation 107

4.1 Levulinic Acid Hydrogenation Products 107
4.1.1 γ-Valerolactone (GVL) 107
4.1.1.1 GVL Versus Ethanol 111
4.1.1.2 2-Methyl-tetrahydrofuran (2-MTHF) 111
4.1.1.3 1,4-Pentanediol (1,4-PDO) 112
4.1.1.4 Alkyl Valerates 113
4.2 Performance of GVL as Fuel Additive 113
4.3 Levulinic Acid to γ-Valerolactone 114
 Contents vii

4.3.1 Conversion of GVL into 1,4-PDO and 2-MTHF 115

4.3.2 GVL to Butenes and Hydrocarbons 117
4.4 Homogeneous and Heterogeneous Catalysts for the Efficient
Conversion of LA to GVL 121
4.4.1 Precious Metal Catalysts 121
4.4.2 Nonprecious Metal Catalyst 125
4.4.2.1 Copper-Based Catalysts 125
4.4.2.2 Nickel-Based Catalysts 127
4.4.2.3 Zirconium-Based Catalysts 130
4.4.2.4 Iron-Based Catalysts 130
4.5 Heterogeneous Catalysts for the Conversion of LA and GVL to
1,4-PDO and 2-MTHF 132
4.6 Types of Hydrogenating Agents 135
4.7 Patent Search of LA Hydrogenation 137
4.8 Conclusion 138
References 138

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 149
5.1 Levulinc Acid Ester Ketals Main Routes 150
5.1.1 Levulinic Acid Ester Ketals Main Uses 153
5.2 Succinic Acid 158
5.2.1 Petrochemical and Biotechnological Routes 158
5.2.2 Levulinic to Succinic Acid 163
5.2.3 Succinic Acid Main Uses 164
5.3 δ-Aminolevulinic Acid (DALA) Main Routes 167
5.3.1 δ-Aminolevulinic Acid Main Uses 169
5.4 5-Methyl-N-Alkyl-2-Pyrrolidone Main Routes 171
5.4.1 5-Methyl-N-Alkyl-2-Pyrrolidone Main Uses 177
5.5 Diphenolic Acid Main Routes 179
5.5.1 Diphenolic Levulinic Acid Main Uses 181
5.6 Conclusion 185
References 185

6 Levulinic Acid in the Context of a Biorefinery 197

6.1 Biorefinery 197
6.2 Sugar-Based Biorefinery 198
6.3 Levulinc Acid and Levulinates from a Sugar Cane Biorefinery 200
6.4 Production of γ-Valerolactone in a Sugar Cane Biorefinery 201
viii Contents

6.5 LA in the Context of a Biodiesel Plant 204

6.6 Conclusions 206
References 207

Index 209
 k

ix

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
k Industries (ABIQUIM), the Innovation Prize of SBQ, and the Simão Mathias k
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 CO2 Utilization, 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 develop-
ment 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 Chem-
istry at UFRJ and a researcher at LARHCO/
UFRJ where she researches in the area of meso-
porous materials with various applications, such as heterogeneous catalysts with
a focus on biomass transformation and adsorbents for CO2 capture.

k
 k

x About the Authors

Daniella R. Fernandes is an adjunct profes-

sor at the Department of Organic Chemistry at
the Institute of Chemistry of the Federal Univer-
sity 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
k (UERJ) and obtained her master’s (2009) and k
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 transfor-
mation 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 Depart-
ment 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.

k
 k

xi

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
k k
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 applica-
tions 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 technolog-
ical 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.

k
 k

xii Preface

700

600
Number of publications

500

400

300

200

100

0
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
2019
2020
2021
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
k after 2010. The need for decreasing the CO2 emissions in the forthcoming years, k
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 proper-
ties 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. Differ-
ent 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 produc-
tion 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

k
 k

Preface xiii

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 tetrahy-
drofuran (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 deriva-
tives 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.
k k
We believe that the book may be a good and updated source of reference to stu-
dents, 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

k
 1

Levulinic 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
Levulinic Acid: A Sustainable Platform Chemical for Value-Added Products, First Edition.
Claudio J.A. Mota, Ana Lúcia de Lima, Daniella R. Fernandes, and Bianca P. Pinto.
© 2023 John Wiley & Sons Ltd. Published 2023 by John Wiley & Sons Ltd.
2 1 Levulinic Acid – History, Properties, Global Market, Direct Uses, Safety

Figure 1.1 Faustino Jovita Malaguti

(1802–1878) (https://www.redalyc
.org/jatsRepo/1816/181662291006/
html/index.html). Source: CITMATEL.

O Figure 1.2 Structure of levulinic acid.

OH

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 dis-
tillation (Figure 1.3).
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 dehy-
drates 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.
 1.1 History and Properties 3

Table 1.1 Selected properties of levulinic acid.

Property Value

Chemical formula C5 H8 O3
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
LD50 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 fur-
fural 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 alde-
hyde 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 fur-
furyl alcohol in the presence of aqueous hydrochloric acid, but small alcohol, such
as methanol and ethanol, could also be employed affording the respective levuli-
nate 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
4 1 Levulinic Acid – History, Properties, Global Market, Direct Uses, Safety

73.5 kg
Starch Steam
Water 147 L Pre-heater 200 °C
28% HCl14.5 kg 100 °C Digester

NaOH
Neutralizer

Humin filter Humins

Evaporator Water and

Formic Acid

Centrifuge NaCl

Vacuum steam Levulinic

distillation Acid

Figure 1.3 Flow diagram of levulinic acid production process.

O
O
CHO
H3 O+ HO H3O+
C6H12O6 OH + HCO2H
–3H2O +2H2O
hexose
HMF Formic
O acid
Levulinic acid

Scheme 1.1 Schematic reaction pathway for the production of levulinic acid from
hexoses.

is hydrogenated to furfuryl alcohol, which is further converted to levulinic acid

upon acid-catalyzed hydrolysis.
A biotechnological route to levulinic acid involving multiple steps has also been
suggested [12]. It involves the fermentation of sugars, like glucose and fructose,
 1.1 History and Properties 5

Figure 1.4 Advertisement of the contest for uses of levulinic acid in 1959. Source:
Reproduced with the permission of the American Chemical Society.

O
O O
CHO H CH2OH H O+
H3O+ 2 3 OH
C5H10O5 catalyst +H2O
–3H2O
Pentose
Furfural Furfuryl alcohol Levulinic acid O

Scheme 1.2 Schematic reaction pathway for the production of levulinic acid from
pentoses.

to pyruvic acid as the first step (Scheme 1.3). The next steps may also involve bio-
catalysts. 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, fol-
lowed by the selective hydrogenation of the intermediate to levulinic acid, may be
6 1 Levulinic Acid – History, Properties, Global Market, Direct Uses, Safety

CH2OH
O O
HO
O OH
Glycolysis Pyruvate + CO2
H
Decarboxylase
HO OH Acetaldehyde
O
Pyruvic acid
OH

O
O OH O OH OH

OH +
OH OH
H

O
O O

O
O
O OH
OH
OH
OH

O
O
Levulinic acid O

Scheme 1.3 Biotechnological route for the synthesis of levulinic acid.

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 con-
ditions and separation procedures, significantly increasing the production costs.
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 decar-
boxylation of acetyl succinate.
The DSM company in Linz, Austria, has developed a small-scale process to pro-
duce 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 prop-
erties 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 fra-
grancies. Inorganic levulinate salts are also important specialty chemicals; sodium
 1.1 History and Properties 7

HOOC COOH HOOC COOH

O2 EtOH
Naphta
Cat. “H+”

Maleic acid Diethyl maleate

O O

OH H3O+ OEt
EtO

O O
O
Levulinic acid
Acetyl succinate

Scheme 1.4 Synthesis of levulinic acid from fossil sources; use of maleic acid as
feedstock.
R

N
O

O
O
N-Alkyl-pyrrolidone
OR
OH
NR H2
HO
Succinic acid OH O
O
Levulinate esters
ROH
Oxidation “H+” OH
RNH2 O
O O OH
O O O
1,5-Pentanediol
H2 H2 OH
OH
Angelicalactone γ-Valerolactone “H+” n-Pentanol
O (GVL) OH
O
Levulinic acid Valeric Acid
“H+”
Br2 O
Methyl-tetrahydrofuran 2 PhOH 1,2-Diols
R
O (MTHF) O

Br
HO O O
CO2H OH
NH3

O
O
HO OH H2N Levulinic acid ketal
Diphenolic levulinic acid CO2H
δ -Amino-levulinic acid

Scheme 1.5 Main levulinic acid transformations.

Another random document with
no related content on Scribd:
For tis not styles far-fetched from Greece or Rome,
But just the Fireside, that can make a home;
None of your spindling things of modern style,
Like pins stuck through to stay the card-built pile,
It rose broad-shouldered, kindly, debonair,
Its warm breath whitening in the October air,
While on its front a heart in outline showed
The place it filled in that serene abode.

“When first I chanced the Eagle to explore,

Ezra sat listless by the open door;
One chair careened him at an angle meet,
Another nursed his hugely-slippered feet;
Upon a third reposed a shirt-sleeved arm,
And the whole man diffused tobacco’s charm.
'Are you the landlord?' 'Wahl, I guess I be,'
Watching the smoke, he answered leisurely.
He was a stoutish man, and through the breast
Of his loose shirt there showed a brambly chest;
Streaked redly as a wind-foreboding morn,
His tanned cheeks curved to temples closely shorn;
Clean-shaved he was, save where a hedge of gray
Upon his brawny throat leaned every way
About an Adam’s-apple, that beneath
Bulged like a boulder from a brambly heath.
The Western World’s true child and nursling he,
Equipt with aptitudes enough for three:
No eye like his to value horse or cow,
Or gauge the contents of a stack or mow;
He could foretell the weather at a word,
He knew the haunt of every beast and bird,
Or where a two-pound trout was sure to lie,
Waiting the flutter of his home-made fly;
Nay, once in autumns five, he had the luck
To drop at fair-play range a ten-tined buck;
Of sportsmen true he favored every whim,
But never cockney found a guide in him;
A natural man, with all his instincts fresh,
Not buzzing helpless in Reflection’s mesh,
Firm on its feet stood his broad-shouldered mind,
As bluffly honest as a northwest wind;
Hard-headed and soft-hearted, you’d scarce meet
A kindlier mixture of the shrewd and sweet;
Generous by birth, and ill at saying 'No,'
Yet in a bargain he was all men’s foe,
Would yield no inch of vantage in a trade,
And give away ere nightfall all he made.

“'Can I have lodging here?' once more I said.

He blew a whiff, and, leaning back his head,
'You come a piece through Bailey’s woods, I s’pose,
Acrost a bridge where a big swamp-oak grows?
It don’t grow, neither; it’s ben dead ten year,
Nor th' ain’t a livin' creetur, fur nor near,
Can tell wut killed it; but I some misdoubt
’Twas borers, there’s sech heaps on ’em about.
You did n' chance to run ag’inst my son,
A long, slab-sided youngster with a gun?
He’d oughto ben back more ’n an hour ago,
An' brought some birds to dress for supper—sho!
There he comes now. 'Say, Obed, wut ye got?
(He’ll hev some upland plover like as not.)
Wal, them’s real nice uns, an’ll eat A 1,
Ef I can stop their bein' over-done;
Nothin' riles me (I pledge my fastin' word)
Like cookin' out the natur' of a bird;
(Obed, you pick ’em out o' sight an' sound,
Your ma’am don’t love no feathers cluttrin' round;)
Jes' scare ’em with the coals,—thet’s my idee.'
Then, turning suddenly about on me,
'Wal, Square, I guess so. Callilate to stay?
I’ll ask Mis' Weeks; ’bout thet it’s hern to say.'

“Well, there I lingered all October through,

In that sweet atmosphere of hazy blue,
So leisurely, so soothing, so forgiving,
That sometimes makes New England fit for living.
I watched the landscape, erst so granite glum,
Bloom like the south side of a ripening plum,
And each rock-maple on the hillside make
His ten days' sunset doubled in the lake;
The very stone walls draggling up the hills
Seemed touched, and wavered in their roundhead wills.
Ah! there’s a deal of sugar in the sun!
Tap me in Indian summer, I should run
A juice to make rock-candy of,—but then
We get such weather scarce one year in ten.

“There was a parlor in the house, a room

To make you shudder with its prudish gloom.
The furniture stood round with such an air,
There seemed an old maid’s ghost in every chair,
Which looked as it had scuttled to its place
And pulled extempore a Sunday face,
Too smugly proper for a world of sin,
Like boys on whom the minister comes in.
The table, fronting you with icy stare,
Strove to look witless that its legs were bare,
While the black sofa with its horse-hair pall
Gloomed like a bier for Comfort’s funeral.
Each piece appeared to do its chilly best
To seem an utter stranger to the rest,
As if acquaintanceship were deadly sin,
Like Britons meeting in a foreign inn.
Two portraits graced the wall in grimmest truth,
Mister and Mistress W. in their youth,—
New England youth, that seems a sort of pill,
Half wish-I-dared, half Edwards on the Will,
Bitter to swallow, and which leaves a trace
Of Calvinistic cholic on the face.
Between them, o’er the mantel, hung in state
Solomon’s temple, done in copperplate;
Invention pure, but meant, we may presume,
To give some Scripture sanction to the room
To give some Scripture sanction to the room.
Facing this last, two samplers you might see,
Each, with its urn and stiffly-weeping tree,
Devoted to some memory long ago
More faded than their lines of worsted woe;
Cut paper decked their frames against the flies,
Though none e’er dared an entrance who were wise,
And bushed asparagus in fading green
Added its shiver to the franklin clean.

“When first arrived, I chilled a half-hour there,

Nor dared deflower with use a single chair;
I caught no cold, yet flying pains could find
For weeks in me,—a rheumatism of mind.
One thing alone imprisoned there had power
To hold me in the place that long half-hour:
A scutcheon this, a helm-surmounted shield,
Three griffins argent on a sable field;
A relic of the shipwrecked past was here,
And Ezra held some Old-World lumber dear.
Nay, do not smile; I love this kind of thing,
These cooped traditions with a broken wing,
This freehold nook in Fancy’s pipe-blown ball,
This less than nothing that is more than all!
Have I not seen sweet natures kept alive
Amid the humdrum of your business hive,
Undowered spinsters shielded from all harms,
By airy incomes from a coat of arms?”

He paused a moment, and his features took

The flitting sweetness of that inward look
I hinted at before; but, scarcely seen,
It shrank for shelter ’neath his harder mien,
And, rapping his black pipe of ashes clear,
He went on with a self-derisive sneer:
“No doubt we make a part of God’s design,
And break the forest-path for feet divine;
To furnish foothold for this grand prevision
Is good and yet to be the mere transition
Is good, and yet—to be the mere transition,
That, you will say, is also good, though I
Scarce like to feed the ogre By-and-by.
Raw edges rasp my nerves; my taste is wooed
By things that are, not going to be, good,
Though were I what I dreamed two lustres gone,
I’d stay to help the Consummation on,
Whether a new Rome than the old more fair,
Or a deadflat of rascal-ruled despair;
But my skull somehow never closed the suture
That seems to knit yours firmly with the future,
So you ’ll excuse me if I’m sometimes fain
To tie the past’s warm nightcap o’er my brain;
I’m quite aware ’tis not in fashion here,
But then your northeast winds are so severe!

“But to my story: though ’tis truly naught

But a few hints in Memory’s sketchbook caught,
And which may claim a value on the score
Of calling back some scenery now no more.
Shall I confess? The tavern’s only Lar
Seemed (be not shocked!) its homely-featured bar.
Here dozed a fire of beechen logs, that bred
Strange fancies in its embers golden-red,
And nursed the loggerhead whose hissing dip,
Timed by nice instinct, creamed the mug of flip
That made from mouth to mouth its genial round,
Nor left one nature wholly winter-bound;
Hence dropt the tinkling coal all mellow-ripe
For Uncle Reuben’s talk-extinguished pipe;
Hence rayed the heat, as from an in-door sun,
That wooed forth many a shoot of rustic fun.
Here Ezra ruled as king by right divine;
No other face had such a wholesome shine,
No laugh like his so full of honest cheer;
Above the rest it crowed like Chanticleer.

“In this one room his dame you never saw,

Wh i db t ld S li l
Where reigned by custom old a Salic law;
Here coatless lolled he on his throne of oak,
And every tongue paused midway if he spoke.
Due mirth he loved, yet was his sway severe;
No blear-eyed driveller got his stagger here;
'Measure was happiness; who wanted more,
Must buy his ruin at the Deacon’s store;'
None but his lodgers after ten could stay,
Nor after nine on eves of Sabbath-day.
He had his favorites and his pensioners,
The same that gypsy Nature owns for hers:
Loose-ended souls, whose skills bring scanty gold,
And whom the poor-house catches when they ’re old;
Rude country-minstrels, men who doctor kine,
Or graft, and, out of scions ten, save nine;
Creatures of genius they, but never meant
To keep step with the civic regiment.
These Ezra welcomed, feeling in his mind
Perhaps some motions of the vagrant kind;
These paid no money, yet for them he drew
Special Jamaica from a tap they knew,
And, for their feelings, chalked behind the door
With solemn face a visionary score.
This thawed to life in Uncle Reuben’s throat
A torpid shoal of jest and anecdote,
Like those queer fish that doze the droughts away,
And wait for moisture, wrapt in sun-baked clay;
This warmed the one-eyed fiddler to his task,
Perched in the corner on an empty cask,
By whose shrill art rapt suddenly, some boor
Rattled a double-shuffle on the floor;
'Hull’s Victory' was, indeed, the favorite air,
Though 'Yankee Doodle' claimed its proper share.

“'Twas there I caught from Uncle Reuben’s lips,

In dribbling monologue ’twixt whiffs and sips,
The story I so long have tried to tell;
The humor coarse, the persons common,—well,
From Nature only do I love to paint,
Whether she send a satyr or a saint;
To me Sincerity’s the one thing good,
Soiled though she be and lost to maidenhood.
Quompegan is a town some ten miles south
From Jethro, at Nagumscot river-mouth,
A seaport town, and makes its title good
With lumber and dried fish and eastern wood.
Here Deacon Bitters dwelt and kept the Store,
The richest man for many a mile of shore;
In little less than everything dealt he,
From meeting-houses to a chest of tea;
So dextrous therewithal a flint to skin,
He could make profit on a single pin;
In business strict, to bring the balance true
He had been known to bite a fig in two,
And change a board-nail for a shingle-nail.
All that he had he ready held for sale,
His house, his tomb, whate’er the law allows,
And he had gladly parted with his spouse.
His one ambition still to get and get,
He would arrest your very ghost for debt.
His store looked righteous, should the Parson come,
But in a dark back-room he peddled rum,
And eased Ma’am Conscience, if she e’er would scold,
By christening it with water ere he sold.
A small, dry man he was, who wore a queue,
And one white neckcloth all the week-days through,—
On Monday white, by Saturday as dun
As that worn homeward by the prodigal son.
His frosted earlocks, striped with foxy brown,
Were braided up to hide a desert crown;
His coat was brownish, black perhaps of yore;
In summer-time a banyan loose he wore;
His trousers short, through many a season true,
Made no pretence to hide his stockings blue;
A waistcoat buff his chief adornment was,
Its porcelain buttons rimmed with dusky brass
Its porcelain buttons rimmed with dusky brass.
A deacon he, you saw it in each limb,
And well he knew to deacon-off a hymn,
Or lead the choir through all its wandering woes
With voice that gathered unction in his nose,
Wherein a constant snuffle you might hear,
As if with him ’twere winter all the year.
At pew-head sat he with decorous pains,
In sermon-time could foot his weekly gains,
Or, with closed eyes and heaven-abstracted air,
Could plan a new investment in long-prayer.
A pious man, and thrifty too, he made
The psalms and prophets partners in his trade,
And in his orthodoxy straitened more
As it enlarged the business at his store;
He honored Moses, but, when gain he planned,
Had his own notion of the Promised Land.

“Soon as the winter made the sledding good,

From far around the farmers hauled him wood,
For all the trade had gathered ’neath his thumb.
He paid in groceries and New England rum,
Making two profits with a conscience clear,—
Cheap all he bought, and all he paid with dear.
With his own mete-wand measuring every load,
Each somehow had diminished on the road;
An honest cord in Jethro still would fail
By a good foot upon the Deacon’s scale,
And, more to abate the price, his gimlet eye
Would pierce to cat-sticks that none else could spy;
Yet none dared grumble, for no farmer yet
But New Year found him in the Deacon’s debt.

“While the first snow was mealy under feet,

A team drawled creaking down Quompegan street.
Two cords of oak weighed down the grinding sled,
And cornstalk fodder rustled overhead;
The oxen’s muzzles, as they shouldered through,
Were silver fringed; the driver’s own was blue
Were silver-fringed; the driver s own was blue
As the coarse frock that swung below his knee.
Behind his load for shelter waded he;
His mittened hands now on his chest he beat,
Now stamped the stiffened cowhides of his feet,
Hushed as a ghost’s; his armpit scarce could hold
The walnut whipstock slippery-bright with cold.
What wonder if, the tavern as he past,
He looked and longed, and stayed his beasts at last,
Who patient stood and veiled themselves in steam
While he explored the bar-room’s ruddy gleam?

“Before the fire, in want of thought profound,

There sat a brother-townsman weather-bound:
A sturdy churl, crisp-headed, bristly-eared,
Red as a pepper; ’twixt coarse brows and beard
His eyes lay ambushed, on the watch for fools,
Clear, gray, and glittering like two bay-edged pools;
A shifty creature, with a turn for fun,
Could swap a poor horse for a better one,—
He’d a high-stepper always in his stall;
Liked far and near, and dreaded therewithal.
To him the in-comer, 'Perez, how d’ye do?'
'Jest as I’m mind to, Obed; how do you?'
Then, his eyes twinkling such swift gleams as run
Along the levelled barrel of a gun
Brought to his shoulder by a man you know
Will bring his game down, he continued, 'So,
I s’pose you’re haulin' wood? But you’re too late;
The Deacon’s off; Old Splitfoot couldn’t wait;
He made a bee-line las' night in the storm
To where he won’t need wood to keep him warm.
’Fore this he’s treasurer of a fund to train
Young imps as missionaries; hopes to gain
That way a contract that he has in view
For fireproof pitchforks of a pattern new.
It must have tickled him, all drawbacks weighed,
To think he stuck the Old One in a trade;
His soul, to start with, wasn’t worth a carrot,
And all he’d left ’ould hardly serve to swear at.'

“By this time Obed had his wits thawed out,

And, looking at the other half in doubt,
Took off his fox-skin cap to scratch his head,
Donned it again, and drawled forth, 'Mean he’s dead?'
'Jesso; he’s dead and t’other d that follers
With folks that never love a thing but dollars.
He pulled up stakes last evening, fair and square,
And ever since there’s been a row Down There.
The minute the old chap arrived, you see,
Comes the Boss-devil to him, and says he,
“What are you good at? Little enough, I fear;
We callilate to make folks useful here.”
“Well,” says old Bitters, “I expect I can
Scale a fair load of wood with e’er a man.”
“Wood we don’t deal in; but perhaps you’ll suit,
Because we buy our brimstone by the foot:
Here, take this measurin'-rod, as smooth as sin,
And keep a reckonin' of what loads comes in.
You’ll not want business, for we need a lot
To keep the Yankees that you send us hot;
At firin' up they’re barely half as spry
As Spaniards or Italians, though they’re dry;
At first we have to let the draught on stronger,
But, heat ’em through, they seem to hold it longer.”

“'Bitters he took the rod, and pretty soon

A teamster comes, whistling an ex-psalm tune.
A likelier chap you wouldn’t ask to see,
No different, but his limp, from you or me'—
'No different, Perez! Don’t your memory fail?
Why, where in thunder was his horns and tail?'
'They’re only worn by some old-fashioned pokes;
They mostly aim at looking just like folks.
Sech things are scarce as queues and top-boots here;
’Twould spoil their usefulness to look too queer.
 p q
Ef you could always know ’em when they come,
They’d get no purchase on you: now be mum.
On come the teamster, smart as Davy Crockett,
Jinglin' the red-hot coppers in his pocket,
And clost behind, ('twas gold-dust, you’d ha' sworn,)
A load of sulphur yallower’n seed-corn;
To see it wasted as it is Down There
Would make a Friction-Match Co. tear its hair!
“Hold on!” says Bitters, “stop right where you be;
You can’t go in athout a pass from me.”
“All right,” says t’other, “only step round smart;
I must be home by noon-time with the cart.”
Bitters goes round it sharp-eyed as a rat,
Then with a scrap of paper on his hat
Pretends to cipher. “By the public staff,
That load scarce rises twelve foot and a half.”
“There’s fourteen foot and over,” says the driver,
“Worth twenty dollars, ef it’s worth a stiver;
Good fourth-proof brimstone, that’ll make ’em squirm,—
I leave it to the Headman of the Firm;
After we masure it, we always lay
Some on to allow for settlin' by the way.
Imp and full-grown, I’ve carted sulphur here,
And given fair satisfaction, thirty year.”
With that they fell to quarrellin' so loud
That in five minutes they had drawed a crowd,
And afore long the Boss, who heard the row,
Comes elbowin' in with “What’s to pay here now?”
Both parties heard, the measurin'-rod he takes,
And of the load a careful survey makes.
“Sence I’ve bossed the business here,” says he,
“No fairer load was ever seen by me.”
Then, turnin' to the Deacon, “You mean cus,
None of your old Quompegan tricks with us!
They won’t do here: we’re plain old-fashioned folks,
And don’t quite understand that kind o' jokes.
I know this teamster, and his pa afore him,
And the hard working Mrs D that bore him;
And the hard-working Mrs. D. that bore him;
He wouldn’t soil his conscience with a lie,
Though he might get the custom-house thereby.
Here, constable, take Bitters by the queue,
And clap him into furnace ninety-two,
And try this brimstone on him; if he’s bright,
He’ll find the masure honest afore night.
He isn’t worth his fuel, and I’ll bet
The parish oven has to take him yet!” ’

“This is my tale, heard twenty years ago

From Uncle Reuben, as the logs burned low,
Touching the walls and ceiling with that bloom
That makes a rose’s calyx of a room.
I could not give his language, wherethrough ran
The gamy flavor of the bookless man
Who shapes a word before the fancy cools,
As lonely Crusoe improvised his tools.
I liked the tale,—’twas like so many told
By Rutebeuf and his brother Trouvères bold;
Nor were the hearers much unlike to theirs,
Men unsophisticate, rude-nerved as bears.
Ezra is gone and his large-hearted kind,
The landlords of the hospitable mind;
Good Warriner of Springfield was the last;
An inn is now a vision of the past;
One yet-surviving host my mind recalls,—
You’ll find him if you go to Trenton Falls.”

THE ORIGIN OF DIDACTIC POETRY.

When wise Minerva still was young
And just the least romantic,
Soon after from Jove’s head she flung
That preternatural antic,
’Tis said, to keep from idleness
Or flirting, those twin curses,
She spent her leisure, more or less,
In writing po——, no, verses.

How nice they were! to rhyme with far

A kind star did not tarry;
The metre, too, was regular
As schoolboy’s dot and carry;
And full they were of pious plums,
So extra-super-moral,—
For sucking Virtue’s tender gums
Most tooth-enticing coral.

A clean, fair copy she prepares,

Makes sure of moods and tenses,
With her own hand,—for prudence spares
A man-(or woman-)-uensis;
Complete, and tied with ribbons proud,
She hinted soon how cosy a
Treat it would be to read them loud
After next day’s Ambrosia.

The Gods thought not it would amuse

So much as Homer’s Odyssees,
But could not very well refuse
The properest of Goddesses;
So all sat round in attitudes
Of various dejection,
As with a hem! the queen of prudes
Began her grave prelection.

At the first pause Zeus said, “Well sung!—

I k Ph b h k ”
 I mean—ask Phœbus,—he knows.”
Says Phœbus, “Zounds! a wolf’s among
Admetus’s merinos!
Fine! very fine! but I must go;
They stand in need of me there;
Excuse me!” snatched his stick, and so
Plunged down the gladdened ether.

With the next gap, Mars said, “For me

Don’t wait,—naught could be finer,
But I’m engaged at half past three,—
A fight in Asia Minor!”
Then Venus lisped, “I’m sorely tried,
These duty-calls are vip’rous;
But I must go; I have a bride
To see about in Cyprus.”

Then Bacchus,—“I must say good bye,

Although my peace it jeopards;
I meet a man at four, to try
A well-broke pair of leopards.”
His words woke Hermes. “Ah!” he said,
“I so love moral theses!”
Then winked at Hebe, who turned red,
And smoothed her apron’s creases.

Just then Zeus snored,—the Eagle drew

His head the wing from under;
Zeus snored,—o’er startled Greece there flew
The many-volumed thunder.
Some augurs counted nine, some, ten;
Some said ’twas war, some, famine,
And all, that other-minded men
Would get a precious——.

Proud Pallas sighed, “It will not do;

Against the Muse I’ve sinned, oh!”
And her torn rhymes sent flying through
Ol ’ b k i d
 Olympus’s back window.
Then, packing up a peplus clean,
She took the shortest path thence,
And opened, with a mind serene,
A Sunday-school in Athens.

The verses? Some in ocean swilled,

Killed every fish that bit to ’em;
Some Galen caught, and, when distilled,
Found morphine the residuum;
But some that rotted on the earth
Sprang up again in copies,
And gave two strong narcotics birth,
Didactic verse and poppies.

Years after, when a poet asked

The Goddess’s opinion,
As one whose soul its wings had tasked
In Art’s clear-aired dominion,
“Discriminate,” she said, “betimes;
The Muse is unforgiving;
Put all your beauty in your rhymes,
Your morals in your living.”

THE FLYING DUTCHMAN.

Don’t believe in the Flying Dutchman?

I’ve known the fellow for years;
My button I’ve wrenched from his clutch, man:
I shudder whenever he nears!

He’s a Rip van Winkle skipper,

A Wandering Jew of the sea,
Who sails his bedevilled old clipper
In the wind’s eye, straight as a bee.

Back topsails! you can’t escape him;

 The man-ropes stretch with his weight,
And the queerest old toggeries drape him,
The Lord knows how long out of date!

Like a long-disembodied idea,

(A kind of ghost plentiful now,)
He stands there; you fancy you see a
Coeval of Teniers or Douw.

He greets you; would have you take letters:

You scan the addresses with dread,
While he mutters his donners and wetters,—
They’re all from the dead to the dead!

You seem taking time for reflection,

But the heart fills your throat with a jam,
As you spell in each faded direction
An ominous ending in dam.

Am I tagging my rhymes to a legend?

That were changing green turtle to mock:
No, thank you! I’ve found out which wedge-end
Is meant for the head of a block.

The fellow I have in my mind’s eye

Plays the old Skipper’s part here on shore,
And sticks like a burr, till he finds I
Have got just the gauge of his bore.

This postman ’twixt one ghost and t’other,

With last dates that smell of the mould,
I have met him (O man and brother,
Forgive me!) in azure and gold.

In the pulpit I’ve known of his preaching,

Out of hearing behind the time,
Some statement of Balaam’s impeaching,
Giving Eve a due sense of her crime.
 I have seen him some poor ancient thrashing
Into something (God save us!) more dry,
With the Water of Life itself washing
The life out of earth, sea, and sky.

O dread fellow-mortal, get newer

Despatches to carry, or none!
We’re as quick as the Greek and the Jew were
At knowing a loaf from a stone.

Till the couriers of God fail in duty,

We sha’n’t ask a mummy for news,
Nor sate the soul’s hunger for beauty
With your drawings from casts of a Muse.

CREDIDIMUS JOVEM REGNARE.

O days endeared to every Muse,

When nobody had any Views,
Nor, while the cloudscape of his mind
By every breeze was new designed,
Insisted all the world should see
Camels or whales where none there be!
O happy days, when men received
From sire to son what all believed,
And left the other world in bliss,
Too busy with bedevilling this!

Beset by doubts of every breed

In the last bastion of my creed,
With shot and shell for Sabbath-chime,
I watch the storming-party climb,
Panting (their prey in easy reach),
To pour triumphant through the breach
In walls that shed like snowflakes tons
Of missiles from old-fashioned guns,
B t bl ’ th th t th t
But crumble ’neath the storm that pours
All day and night from bigger bores.
There, as I hopeless watch and wait
The last life-crushing coil of Fate,
Despair finds solace in the praise
Of those serene dawn-rosy days
Ere microscopes had made us heirs
To large estates of doubts and snares,
By proving that the title-deeds,
Once all-sufficient for men’s needs,
Are palimpsests that scarce disguise
The tracings of still earlier lies,
Themselves as surely written o’er
An older fib erased before.

So from these days I fly to those

That in the landlocked Past repose,
Where no rude wind of doctrine shakes
From bloom-flushed boughs untimely flakes;
Where morning’s eyes see nothing strange,
No crude perplexity of change,
And morrows trip along their ways
Secure as happy yesterdays.
Then there were rulers who could trace
Through heroes up to gods their race,
Pledged to fair fame and noble use
By veins from Odin filled or Zeus,
And under bonds to keep divine
The praise of a celestial line.
Then priests could pile the altar’s sods,
With whom gods spake as they with gods,
And everywhere from haunted earth
Broke springs of wonder, that had birth
In depths divine beyond the ken
And fatal scrutiny of men;
Then hills and groves and streams and seas
Thrilled with immortal presences,
Not too ethereal for the scope
Of human passion’s dream or hope.

Now Pan at last is surely dead,

And King No-Credit reigns instead,
Whose officers, morosely strict,
Poor Fancy’s tenantry evict,
Chase the last Genius from the door,
And nothing dances any more.
Nothing? Ah, yes, our tables do,
Drumming the Old One’s own tattoo,
And, if the oracles are dumb,
Have we not mediums? Why be glum?

Fly thither? Why, the very air

Is full of hindrance and despair!
Fly thither? But I cannot fly;
My doubts enmesh me if I try,—
Each lilliputian, but, combined,
Potent a giant’s limbs to bind.
This world and that are growing dark;
A huge interrogation mark,
The Devil’s crook episcopal,
Still borne before him since the Fall,
Blackens with its ill-omened sign
The old blue heaven of faith benign.
Whence? Whither? Wherefore? How? Which? Why?
All ask at once, all wait reply.
Men feel old systems cracking under ’em;
Life saddens to a mere conundrum
Which once Religion solved, but she
Has lost—has Science found?—the key.

What was snow-bearded Odin, trow,

The mighty hunter long ago,
Whose horn and hounds the peasant hears
Still when the Northlights shake their spears?
Science hath answers twain, I’ve heard;
Choose which you will, nor hope a third;
 y p
Whichever box the truth be stowed in,
There’s not a sliver left of Odin.
Either he was a pinchbrowed thing,
With scarcely wit a stone to fling,
A creature both in size and shape
Nearer than we are to the ape,
Who hung sublime with brat and spouse
By tail prehensile from the boughs,
And, happier than his maimed descendants,
The culture-curtailed independents,
Could pluck his cherries with both paws,
And stuff with both his big-boned jaws;
Or else the core his name enveloped
Was from a solar myth developed,
Which, hunted to its primal shoot,
Takes refuge in a Sanskrit root,
Thereby to instant death explaining
The little poetry remaining.

Try it with Zeus, ’tis just the same;

The thing evades, we hug a name;
Nay, scarcely that,—perhaps a vapor
Born of some atmospheric caper.
All Lempriere’s fables blur together
In cloudy symbols of the weather,
And Aphrodite rose from frothy seas
But to illustrate such hypotheses.
With years enough behind his back,
Lincoln will take the selfsame track,
And prove, hulled fairly to the cob,
A mere vagary of Old Prob.
Give the right man a solar myth,
And he’ll confute the sun therewith.

They make things admirably plain,

But one hard question will remain:
If one hypothesis you lose,
Another in its place you choose,