Table Of ContentArno Behr
Thomas Seidensticker
Chemistry
of Renewables
An Introduction
Chemistry of Renewables
Arno Behr
Thomas Seidensticker
Chemistry
of Renewables
An Introduction
Arno Behr Thomas Seidensticker
Laboratory of Industrial Chemistry Laboratory of Industrial Chemistry
Department of Biochemical Department of Biochemical
and Chemical Engineering and Chemical Engineering
TU Dortmund University TU Dortmund University
Dortmund, North Rhine-Westphalia Dortmund, North Rhine-Westphalia
Germany Germany
ISBN 978-3-662-61429-7 ISBN 978-3-662-61430-3 (eBook)
https://doi.org/10.1007/978-3-662-61430-3
Translation from the German language edition: Einführung in die Chemie nachwachsender Rohstoffe by
Arno Behr and Thomas Seidensticker, © Springer-Verlag GmbH Deutschland, ein Teil von Springer Nature
2018. Published by Springer Spektrum. All Rights Reserved.
© Springer-Verlag GmbH Germany, part of Springer Nature 2020
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V
Foreword
What are we going to do now? Nobody knows the answer to the second
question but, if you have been hooked
With an exponential increase in popula- into wanting to set out on this journey
tion, major concerns about global warm- and do not know where to start, this
ing leading to climate change and with book, The Chemistry of Renewables, which
oil and gas becoming scarcer and more gives a snapshot of where we are at pres-
expensive to extract, we stand at a point ent and a hint at directions we might take,
in the world’s history where everything is the book for you.
we do needs to change - and quickly. We
need to turn to renewable resources and There are some major differences between
to make sure that we have enough land oil and naturally occurring feedstocks.
to grow food as well as to provide all the Oil contains only carbon and hydrogen
essential and luxury items that are cur- whilst feedstocks like natural oils, cellu-
rently produced from fossil fuel based lose, lignin, etc also contain significant
starting materials. Most of our static amounts of oxygen and sometimes other
energy needs will be provided by wind, elements especially nitrogen, phospho-
solar, wave and tidal power. Cars will be rus and sulphur. Oil is mostly a mixture
powered by electricity from renewable of various chain length hydrocarbons so
resources but how will we continue to fly? is relatively simple. It has only C-H and
How will we provide all the essential and C-C bonds and is mostly easy to handle
luxury items that are so familiar to us and as a liquid, which can be pumped from
we love to have without using fossil fuel- well-defined reservoirs. Natural resources
based resources whilst at the same time are chemically much more complex and
increasing the amount of food we pro- diverse often occurring naturally as sol-
duce. ids, sometimes spread thinly over large
areas making handling trickier but not
The United Nations 17 Sustainable Devel impossible. Most of the many thousands
opment Goals provide a road map to a of effect chemicals we use on everyday
future of peace, justice, equality and pros- life contain oxygen or nitrogen as well as
perity in a pollution-free world espousing carbon and hydrogen so, to make them
a circular economy. They hint at the end from oil, we must add these elements gen-
point but how will we actually get there? erally in oxidative-type chemistry whilst
Many grandiose schemes are proposed the chemistry of the future will require
but who will actually bring them into removal of oxygen or reductive chemistry.
practice?
One possible way to solve the problem
Much of the work will be done by chem- would be to gasify biomass to give car-
ists and chemical engineers working with bon monoxide and hydrogen then carry
a whole myriad of end users to provide out Fischer-Tropsch chemistry to make a
solutions to all the problems. There has mixture of hydrocarbons rather like the
never been a better time to be starting out oil that we use already and feed it into a
on a career in chemistry or chemical engi- standard oil refinery. However, taking all
neering. The challenges are huge, address- the oxygen out of biomass and putting
ing them will require the most creative of some of it back in again is not only inel-
minds and the rewards, intellectual, social egant, it is massively energy intensive and
and financial will be enormous. Are you expensive so we really have to look for the
up for this exciting journey? Where will direct production of effect chemicals from
it start and what is the final destination? biomass. A whole new chemical industry
VI Foreword
is begging to be invented and you could chemical advances have already been
be in the forefront of that exciting devel- made. Then come amino acids and their
opment. condensation to form the elements of life,
polypeptides and proteins followed by
One of the great things about this book compounds which can be extracted from
is that it is easy to read with its quirky nature for use as dyes, flavours, vitamins,
titles, interesting anecdotes and liberal drugs or polymers, many of which are
sprinkling of lovely colour pictures. You biodegradable.
can dip in and out of it to find nuggets of
information, what is been done already Every chapter is peppered with some his-
and what still needs to be done or you tory, finds some interesting character,
could read it as a bedtime story. Just to comprehensively explores some really
make sure you have not fallen asleep exciting chemistry, shows applications
whilst reading there are “Quickie’s” at and potential uses and explains how all of
the end of each chapter; questions which this can be done. In the end, the authors
check what you have learnt and that you take a comprehensive look at the possi-
have retained it. Do not worry, though, bility of integrating many processes in a
the answers are collected at the end of biorefinery. Here, agriculture, chemistry
the book, but you should really try to get and chemical engineering are brought
them without looking them up - just use together to make everything else in the
them to check you were right! book a reality. One or more bio-feeds
are transformed into a range of different
The book starts like Under Milk Wood useful chemicals and products just as in
or the song Do Ray Me at the beginning an oil refinery using oil as the feedstock.
with an excellent overview of the field Biorefineries are usually more complex
and a critical appraisal of the advantages than oil refineries but they must become
and disadvantages of the feedstocks that commonplace exploiting different feed-
are available, before moving on to indi- stocks according to local availability. They
vidual feedstocks starting with fats and must be run in a clean environmentally
oils because they are currently the most friendly way so it is a bit sad that the pic-
exploited. The discussion moves to gly- ture of the plant producing bio-ethanol as
cerol, a coproduct when making many a platform chemical or fuel from sugar in
derivatives from natural oils and sugar Brazil appears to show dense grey smoke
before things get much more complicated emanating from the chimneys. The pilot
with cellulose, the world’s most abundant plant for biomass to liquid products in
organic polymer, starch and other carbo- Karlsruhe looks much more environmen-
hydrates. It then moves on to the toughest tally friendly!
nut of all, lignin. Masses of lignin is avail-
able from trees but it is hardly exploited When you finish reading this book, you
because its structure is complex; it is will be full of facts, ideas and enthusiasms
difficult to dissolve or break down and - and you will be exhausted but I hope
really hard to get single products form that you will be inspired to get involved,
it. It can be done, for example, in a com- solve the major problems and really make
plex process for making vanillin, a fla- a difference to our world by giving it a cir-
vouring compound that can also be used cular, sustainable and clean future.
as a starting material for pharmaceutical
production. However, this work is in its As a bonus, you will also have read a prize
infancy. There is so much more to do. It is winning text book because the origi-
difficult but the rewards will be extremely nal German version of The Chemistry of
high. Things get a bit easier with the nat- Renewables won the prize from the Ger-
urally occurring hydrocarbons, terpenes man Chemical Industry Association for
and their polymers, where significant the best German chemistry textbook of
VII
Foreword
2020. Well done to the authors for win- 7. What problems would there be in
ning the richly deserved prize and to you making all the chemicals we need
for reading the book! through hydrocarbons made by
Fischer-Tropsch Chemistry using
Quickies (You may have to read the book carbon dioxide and hydrogen pro-
to answer some of these!) duced by electrolysis of water using
1. What are the two most abundant renewable electricity during periods
renewable natural resources from of overproduction of electricity?
which effect chemicals might be
made? Scotland, UK,
2. What are the two most difficult natu- June 2020
ral resources from which to make
effect chemicals? David Cole-Hamilton
3. Why can’t we just grow plants in
order to produce all the chemical
feedstocks we need?
4. Where can you find renewable hydro-
carbons in nature?
5. Name two resources where you can
find aromatic rings in nature.
6. Cashew nut shell liquid is a non-
food oil which is available at 800,000
tonnes per year. Can you find it in
this book?
IX
Preface
This book is the English version of a text- important raw materials, products and
book on renewable raw materials that processes, and can familiarize themselves
was published in German by Springer more deeply with individual topics from
Spektrum at the beginning of 2018. Due the references.
to the great success in the German-speak-
ing world, the two authors have decided What is the structure of the book?
to publish an extended and updated ver- 5 The book is divided into 20 chapters
sion in English. The content of the book of similar size. Each of these chap-
is based on a lecture that the authors have ters starts with a chapter timetable,
been giving at the TU Dortmund Univer- which roughly announces the content
sity (Germany) for many years. The book and closes with a compact summary.
offers the reader an introduction to the Detailed illustrations, photos, flow
different groups of renewable raw materi- diagrams and chemical equations
als, especially fats and oils, carbohydrates illustrate the text.
and terpenoids. Also, more specific topics 5 At the end of each chapter, there are
such as lignin and natural pharmaceuti- 10 test questions, so-called Quickies.
cals, as well as colorants and fragrances, In the appendix, the reader will find
are addressed. Individual chapters are the answers to the 200 test questions.
dedicated to current topics such as 5 There is a short literature overview for
biopolymers or biorefineries. All sections each chapter. It consists mainly of ref-
focus on the chemical conversion of raw erences to textbooks and reviews but
materials into valuable products. Also, also includes some important current
technical aspects such as the methods of original references.
recovery or the industrial processing of 5 In addition, the text contains numer-
the reactions are discussed. ous “boxes” that describe exciting
aspects, such as historical back-
One of the authors, Prof. Behr, worked in grounds or current developments.
the chemical industry for several years
and acquired considerable experience in The authors would like to thank Springer
the process development of new processes Verlag, especially Dr. Charlotte Holling-
with fats and oils, carbohydrates and terpe- worth and Dr. Rainer Münz, for their sup-
nes. In addition, he has successfully carried port in the realization of this book project
out numerous research projects on these and Miss Andréia Bracht for her help
topics at the Technical University of Dort- drawing the figures and formulas.
mund over the past 20 years. This unique
knowledge from practice and research is In recent decades, renewable raw materials
passed on to the readers in this book. have become increasingly important, and
this trend continues. This book provides
This textbook is intended for students of the basis for a better understanding of this
natural and engineering sciences as well future top topic. Have fun reading it!
as for practitioners. The book is unique
in such a way that students can follow up Arno Behr
well on their lectures or acquire the cur- Thomas Seidensticker
riculum chapter by chapter in self-study. Dortmund, Germany
Practitioners can quickly learn about August 2020
X Preface
Prof. Dr. Arno Behr (right) and Dr. Thomas Seidensticker (left)
XI
Contents
1 The Overview - Introduction .............................................. 1
1.1 Definitions ................................................................... 2
1.2 The Different Types of Renewable Raw Materials ............................... 2
1.3 Comparison with Fossil Raw Materials ......................................... 4
1.4 Advantages and Disadvantages of Renewable Raw Materials .................. 8
References .................................................................... 13
I Fats and Oils
2 The Raw Materials of Oleochemistry - Oil Plants ........................ 17
2.1 Introduction to Oleochemistry ................................................ 18
2.2 Overview of Important Vegetable Oils and Animal Fats ........................ 21
2.2.1 Coconut Oil ................................................................... 21
2.2.2 Palm Oil and Palm Kernel Oil ................................................... 23
2.2.3 Rapeseed Oil .................................................................. 25
2.2.4 Sunflower Oil .................................................................. 25
2.2.5 Soybean Oil ................................................................... 26
2.2.6 Linseed Oil from Flax Plants .................................................... 26
2.2.7 Castor Oil ..................................................................... 27
2.2.8 Olive Oil ...................................................................... 28
2.2.9 Safflower Oil .................................................................. 29
2.2.10 Jatropha Oil ................................................................... 29
2.2.11 Other Fats and Oils ............................................................ 31
2.3 Some Numbers ............................................................... 31
References .................................................................... 34
3 The Basics of Oleochemistry - Basic Oleochemicals ..................... 37
3.1 Production of Basic Oleochemicals ............................................ 38
3.1.1 Fat Splitting ................................................................... 38
3.1.2 Transesterification ............................................................. 42
3.1.3 Saponification ................................................................. 43
3.1.4 Direct Hydrogenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2 Reactions at the Carboxy Group of Fatty Acids ................................. 45
3.2.1 Hydrogenation to Fatty Alcohols ............................................... 45
3.2.2 Conversions of Fatty Alcohols .................................................. 50
3.2.3 Conversions to Fatty Amines ................................................... 56
3.2.4 Other Fatty Acid Derivatives ................................................... 57
References .................................................................... 59
4 There is More to Oleochemistry - Reactions
at the Fatty Acid Alkyl Chain .............................................. 61
4.1 Synthesis of Substituted Fatty Acids ........................................... 62
4.2 Reactions at the C=C Double Bond of Unsaturated Oleochemicals ............. 63
4.2.1 Linkage of New C–O Bonds .................................................... 63
4.2.2 Linkage of New C–C Bonds ..................................................... 66
