Tatsiana Savitskaya
Iryna Kimlenka
Yin Lu et al.

Green
Chemistry
Process Technology and Sustainable
Development


Green Chemistry

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Tatsiana Savitskaya · Iryna Kimlenka · Yin Lu ·
Dzmitry Hrynshpan · Valentin Sarkisov · Jie Yu ·
Nabo Sun · Shilei Wang · Wei Ke · Li Wang

Green Chemistry
Process Technology and Sustainable
Development

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Tatsiana Savitskaya
Belarusian State University
Minsk, Belarus

Iryna Kimlenka

Belarusian State University
Minsk, Belarus

Yin Lu
Zhejiang Shuren University
Hangzhou, China

Dzmitry Hrynshpan
Belarusian State University
Minsk, Belarus

Valentin Sarkisov
Belarusian State University
Minsk, Belarus

Jie Yu
Zhejiang Shuren University
Hangzhou, China

Nabo Sun
Zhejiang Shuren University
Hangzhou, China

Shilei Wang
Zhejiang Shuren University
Hangzhou, China

Wei Ke
Zhejiang Shuren University
Hangzhou, China


Li Wang
Zhejiang Shuren University
Hangzhou, China

ISBN 978-981-16-3745-2
ISBN 978-981-16-3746-9 (eBook)
/>Jointly published with Zhejiang University Press
The print edition is not for sale in China (Mainland). Customers from China (Mainland) please order the
print book from: Zhejiang University Press.
ISBN of the Co-Publisher’s edition: 978-7-308-21580-0
© Zhejiang University Press 2021
This work is subject to copyright. All rights are reserved by the Publishers, whether the whole or part of the
material is concerned, specifically the rights of reprinting, reuse of illustrations, recitation, broadcasting,
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or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
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The publishers, the authors, and the editors are safe to assume that the advice and information in this book
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The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721,
Singapore

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Preface

Green chemistry and technology is a new interdisciplinary subject with significant
social needs and clear scientific objectives, which emerged in the 1990s. It is the
forefront and important field of international chemical and chemical research. The
development of traditional chemistry to green chemistry has become the inevitable
trend of chemical industry from “extensive” to “intensive”. It is the only way for
China’s environmental protection to adopt the environmental protection concept of
treating both symptoms and root causes.
Under the guidance of one belt, one road to respond to the call of the national “13th
Five-Year plan”, “Green is the necessary condition for sustainable development”,
Zhejiang Shuren University and Belarus National University signed a memorandum
of cooperation in education and research, and set up the “Belarus research center”
and awarded the Ministry of education’s national and regional research center. The
two sides jointly discussed how to protect the ecological environment and realize
the construction of an ecological country while vigorously applying green chemical
technology to promote the economic development of the two countries. In order
to publicize the concept of green chemistry and sustainable development, and let
environmental education actively penetrate into chemical education, scholars from
both sides jointly compiled “Green Chemistry—Process Technology and Sustainable
Development”.
Based on the principle of green chemistry, this paper reviews the progress of
green chemistry at home and abroad, and systematically introduces the advanced,
practical, and prospective green chemistry technology and its sustainable development in modern chemical industry. It comprehensively discusses the major sources
of practice, principle, sustainable development, and the methodology of ecological
chemistry. The development of green chemistry in Belarus and China is introduced,
which fully embodies the connotation and extension of green chemistry, and shows
the brilliant prospects of green chemistry. The book consists of seven chapters. Chapters 1 and 2 is the background of green chemistry, which mainly introduces principles

and aims of green chemistry. Chapter 3 mainly introduces the applications of green
chemistry, including the concept of green chemical synthesis, green chemistry in
catalysis, and green solvents. Chapter 4 is about green activation methods. Chapter 5
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Preface

introduces sustainable development concept and green management of chemicals.
Chapter 6 introduces renewable raw materials and energy, expounds the advantages
of biomass as green chemical synthesis raw materials, and introduces the relevant
commercial products. Chapter 7 takes the development status of green chemistry in
Belarus and China as an example, and advocates the education mode that integrates
the truth of green chemistry science with the rationality of human needs.
This book is comprehensive in content, illustrated, and highly targeted. It has
been designed as a series of lectures delivered for Belarusian and Chinese students.It
is suitable for teachers, students, and researchers engaged in the research of chemistry,
chemical engineering, and environment. This book shows readers a continuous development of a complete green chemical system, so that more scholars and the public
have a relatively clear understanding of green chemistry and chemical industry, so
as to promote the healthy development of green chemistry.
Authors of Green Chemistry
Tatsiana Savitskaya
Iryna Kimlenka
Yin Lu
Dzmitry Hrynshpan
Valentin Sarkisov

Jie Yu
Nabo Sun
Shilei Wang
Wei Ke
Li Wang

Minsk, Belarus
Minsk, Belarus
Hangzhou, China
Minsk, Belarus
Minsk, Belarus
Hangzhou, China
Hangzhou, China
Hangzhou, China
Hangzhou, China
Hangzhou, China
November 2020

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Contents

1 Principle of Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1 Green Economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 The Sustainable Development Concept . . . . . . . . . . . . . . . . . . . . . . . .
1.3 Cleaner Production Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 Green Chemistry: Principles, Current State, and Development
Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1
1
2
4
5
13
14

2 Aims of Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1 Global Product Strategy (GPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Responsible Care (RC) Initiative . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 REACH Regulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Globally Harmonized System of Classification and Labeling
of Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

15
15
16
18

3 Applications of Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1 Green Chemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1 Chemical Reaction Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2 E-Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.3 The Strategy of Organic Synthesis . . . . . . . . . . . . . . . . . . . . . .
3.1.4 General Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Green Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.2.1 Catalysis and Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2 Homogeneous Green Catalysis . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3 Heterogeneous Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.4 Biocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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3.3 Green Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.3.1 Chemical Reactions Under Solvent-Free Conditions . . . . . .
3.3.2 Dimethylcarbonate: Green Solvent and Ambident
Reagent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.3 Reactions at Supercritical Conditions . . . . . . . . . . . . . . . . . . .
3.3.4 Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.5 Fluorinated Biphasic Solvents . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Green Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.1 Twelve Principles of Green Engineering . . . . . . . . . . . . . . . . .
3.4.2 Transfer from Green Reaction to Green Industrial
Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.3 Process Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.4 Inherently Safer Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.5 Process Intensification as Green Design Concept . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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75
75
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83
86
91

4 Green Chemistry Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

4.1 Ultrasound Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2 Microwave Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.3 Photochemical Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
5 Green Chemistry and Sustainable Development . . . . . . . . . . . . . . . . . . .
5.1 Sustainable Development (SD) Strategy Genesis
and Evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 National SD Strategy in Belarus and in China . . . . . . . . . . . . . . . . . . .
5.3 Development of Ecological Policy and Natural Resource
Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Ecological Management System (EMS) . . . . . . . . . . . . . . . . . . . . . . . .
5.5 Ecolabel System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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119
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6 Renewable Sources of Raw Material and Energy . . . . . . . . . . . . . . . . . .
6.1 Renewable Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2 Biomass as a Source of Raw Materials for Chemical Synthesis . . . .
6.3 Basic Chemical Products of Biomass Conversion . . . . . . . . . . . . . . .
6.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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7 Green Chemistry in China and Belarus . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1 National Strategy of Green Economy Development in Belarus . . . .
7.2 Green Chemistry as an Educational Platform for Green
Economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.1 Benefits of Green Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2.2 Some Examples of Green Chemistry in Belarus . . . . . . . . . .

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7.3 Achievements in Green Chemistry Research and Technologies
in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3.1 Background and Premise of Green Chemistry in China . . . .
7.3.2 Current Situation of Green Chemistry in China . . . . . . . . . . .
7.3.3 Strategies and Outlook of Green Chemistry in China . . . . . .
7.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Chapter 1

Principle of Green Chemistry

Abstract The need of ecological civilization gives a thorough exploration of
resources and ecological environment in the world. The author makes an active
attempt to seek available ways to keep the sustainable development of green economy,
resources, environment, and green chemistry to change the pattern of rising and
sustainable development of the economy. To develop the green industry means industrial ecologicalization. To depend on the law and economic means to strengthen
national consciousness of environmental protection.
Keywords Sustainable development · Cleaner production · Green chemistry


1.1 Green Economy
Green has always symbolized life, hope, and recently has come to mean welfare
and prosperity as well. That’s why ecological civilization is considered a result of
sustainable development. The term sustainable development has become firmly
entrenched in the professional vocabulary in economic, social, ecological, and other
spheres. A conceptual definition of this term, although interpreted by linguists
as continuous steady growth, implies the further development, which does not
contravene the continued existence of mankind and its development in the same
direction.
Economists, such as Daniel Bell, have suggested a new term to describe the current
stage of development of society—a so-called post-industrial society or knowledge
society [1]. Its sustainable development is based on the knowledge economy. This
relatively new term means that the economy encompasses not only technologies
but also the whole process of knowledge production. The knowledge triangle,
which embodies a key driver of a knowledge-based economy, refers to the interaction between research, education, and innovation. The use of scientific knowledge and technological ideas does not lead to their depletion, but rather facilitates
the accumulation of intellectual potential of a nation. Knowledge, unlike gas and
oil, may be considered a renewable resource. Knowledge economy has also been
proclaimed as a top priority of Belarusian economic development in the coming
years. President Alexander Lukashenko noted that “there’s only one way namely
© Zhejiang University Press 2021
T. Savitskaya et al., Green Chemistry,
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1 Principle of Green Chemistry

an expedited transition to innovative, knowledge-based, resource-saving, globally
competitive economy.” [2].
Economic growth and environmental protection complement each other on the
path toward sustainable development. In this connection, the term green economy has
been coined. President of the People’s Republic of China Xi Jinping has pointed out
that “green is gold” and that moving toward a new era of Ecocivilization and building
a “Beautiful China” are key to realizing the “Chinese Dream” of rejuvenating the
nation [3].
The Green Economy Initiative, supported by more than 20 states, was put forward
by the United Nations Environment Programme (UNEP) in 2008 [4]. It defined
a green economy as low carbon, resource efficient, and socially inclusive. This
economy also enhances social welfare, ensures social equality, while mitigating
environmental risks and diminishing the prospects of environmental degradation.
Three years after Irina Bokova, UNESCO Director-General, looking back on 2011
and setting some priorities for 2012, emphasized that it’s necessary to build up not
only green economy but also green society [5]. Even though little time has passed,
there’s no doubt the green strategy affected all spheres of life and our world is well
on the way toward the new ecological civilization. This way in its turn more and
more seldom resembles attempts of NGOs to combat environmental pollution and
pollutants. For instance, at the United Nations Conference on Sustainable Development—Rio + 20—held in Rio de Janeiro, Brazil, on June 20–22, 2012, member
states spotlighted the exigencies of technological innovation and also laid down some
particular criteria for green technologies. On September 25, 2015, the 193 countries
of the UN General Assembly adopted the 2030 Development Agenda titled Transforming our world: the 2030 Agenda for Sustainable Development which renewed
hope for a bold transition toward a low-carbon economy, greater efficiency of natural
resources, inclusive green economic growth, and overall sustainable development.
To take the next step—moving from commitment to action—countries must have
an integrated approach to implementation that harmonizes environmental integrity,
social inclusiveness, and economic prosperity. For instance, the National Communication (2012) specified the main trends and principles of Belarus’s transition toward

a green economy, as an essential tool for ensuring sustainable development and
environmental security. According to the Country Report “China’s Path to Green
Economy” (2015), the current period can be considered as the “great leap-forward”
of China’s green economy agenda both conceptually and implementation-wise.

1.2 The Sustainable Development Concept
In recent years, green development trends ceased being the subject of popular publications only and shifted toward actual use. For example, green building, as a special
system for construction solutions assessment, in many countries is already regulated
by the set of national standards. The development of this system is primarily stimulated by those who engage in investment and further facility operation, those who

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1.2 The Sustainable Development Concept

3

wish to have a comprehensive assessment of the expediency of the made decision,
of the convenience of buildings in the process of operation, of their impact on the
environment and the economy. For instance, if the construction takes place in an
area, which has some clean water issues, any solution enabling to save water will be
rated higher. The European Union even adopted Directive 2010/31/EU of 19 May
2010 on the energy performance of buildings. Under this Directive, Member States
must ensure that by December 31, 2020 all new buildings shall be nearly zero-energy
consumption buildings. Much attention is paid to the reuse of materials. An example
of the use of a green building is Sochi Olympic facilities. The consumption, output
expansion, and active advertising of green goods accounted for the fact that an estimated 95% of the European respondents are ready to purchase green goods, 75% of
them are aware of this type of goods, and 63% try to find them on store shelves.
Public polls revealed the dependence of green goods consumption level on the
level of education. Meanwhile, modern education in different regions around the

world is gradually turning toward greenness. Bypassing various types of labor activities, it becomes apparent that content, approaches, and methods of green economy
education coincide with that of sustainable development education. Sometimes
green economy education is interpreted in a more narrow sense, defining it as a
type of education focused on changing the employment structure. It’s also targeted
at increasing demand for professionals in environmental technology, goods and
services, and training of specialists of new professions, so-called green collars,
along with the specific specialists, for instance, specialists in biofuel production.
In fact, sustainable development education is generally expected to conduct effective
training of creative individuals capable of solving uphill tasks through innovative
techniques. At the same time, it’s necessary to be conscious of its interdisciplinarity
and social responsibility to society. The first ones to recognize it from this perspective
were chemists, who faced the public outcry, while regarded as being accounted for
environmental contamination. Their consequent actions targeted toward changing
the negative image resulted in that chemistry became the first natural science to be
granted the green status. Perhaps, if biology developed in such a way as chemistry
did, it would potentially become green.
The diversity of shades of green in the higher education system is instantiated by
green university and green campus conceptions, which are implemented in several
countries. The United Nations Environment Programme (UNEP) has defined the
goals and objectives of green universities in “Green University Toolkit” publication. Green university works toward environmental protection, namely carbon emission reduction, separate waste collection, water and electricity saving, ecological
infrastructure development, and outreach campaigns. Green students participate in
eco-projects and events, carry out researches and project works on environmental
protection. In 2009, Grist, an American online magazine, issued the list of Top Green
Colleges and Universities. The green cohort comprised educational institutions of
the USA, the UK, Canada, Costa Rica, and Scotland. Such institutions as Harvard
University, the London School of Economics, and the University of Copenhagen have
been for years committed to the green principles of their economic and sustainable
development. The Centre for Bioeconomy and Eco-innovations (CBE) at Moscow

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1 Principle of Green Chemistry

State University named after Lomonosov together with Tetra Pak and World Wildlife
Fund has started the “Green universities for Green economy” project in Russia. The
main objective of the project is to educate the new generation of professionals, who
will take into account environmental factors in their activities.
There is another green university ranking—UI Green Metric World University Racking—which aims to draw the attention of the academic community to the
problems of ecology. In 2013, 301 universities from 61 countries tried out for this
ranking. As in the academic rankings, the leading positions were occupied by universities of the UK and the USA. Among those universities, that made it to the Top-10,
were the University of Nottingham (UK), University College Cork (UCC) (Ireland),
Northeastern University (USA), the University of Bedford (UK), the University of
Connecticut (USA), etc. However, the makeup of the Top-10 green university ranking
differs from the established global academic university rankings. In the former, the
assessment is carried out on the basis of criteria, such as specific eco-indicators,
delineating campus attitude to the environment, the use of energy-efficient appliances, facing the waste recycling university program, etc. There’s no doubt that
the assessment of greenness of laboratory practical works must be appended to the
number of these indicators. The researchers conducted in American and European
universities show that an estimated 90% of all emission is accounted for by university
labs, with about 88% of it being toxic substances of various types.
At the present moment, by all accounts, chemistry does not correlate with the
concept of green science. The survey data submitted by Lomonosov Moscow State
University in 2010 attest to the fact that biology is generally recognized by the public
as the main green science [6]. No wonder, as in the chemical sector of the economy
there is a direct correspondence between the benefit of goods and the damage, caused
to the environment and human health by the manufacturing process. Many major
industrial areas around the globe are now subject to significant chemical pollution.

Considerable funds are spent on the establishment of wastewater treatment plants
and hazardous substances disposal. Such a method of solving ecological issues at
the end of the production process is called the end-of-pipe approach.
Parallel to this method, another one, a so-called precautionary approach, has
become increasingly prominent over the past two decades. It focuses on prevention
rather than dealing with the consequences of environmental degradation. In practice,
the precautionary approach encompasses the optimization of production processes,
energy-saving technologies implementation, the selection of more environmentally
friendly raw materials, new product design, internal and external waste recycling,
reducing the use of toxic and hazardous substances.

1.3 Cleaner Production Strategy
A Cleaner Production (CP) strategy, coined in 1989 by UNEP, has firmly established
itself as revolutionary, as it enables chemists to produce required substances in a
more environmentally friendly way, which is harmless to the environment at any

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1.3 Cleaner Production Strategy

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stage of the manufacturing and is safe for those who engaged in this process. In fact,
Cleaner Production represents a systematic approach to environmental protection,
dealing with all the phases of manufacturing, as well as disposal process, i.e., the
entire lifecycle “from cradle to grave,” aimed at prevention or decreasing short and
long-run risks, threatening human health and the environment. In addition to “Cradle
to Grave” mentality, “Cradle to Cradle” concept has been recently introduced as an
innovative way of creating products. William McDonough, co-author of the book

“Cradle to Cradle: Remaking the Way We Make Things,” said “Cradle to cradle is a
strategy of hope; it’s about sharing the resources and the planet we have. It’s about
rethinking our role in our planet and on the environment.” [7].
Cleaner Production strategy has led to the emergence of a brand new branch of
chemistry, termed green chemistry, which can be regarded as one of the Cleaner
Production methods.

1.4 Green Chemistry: Principles, Current State,
and Development Trends
Green chemistry in the 21st century is not just a fashionable trend, it is an urgent
need. Green chemistry is an essential tool for achieving sustainable development
goals. In 2017, within the IUPAC the Interdivisional Committee on Green Chemistry
for Sustainable Development was created. In Fig. 1.1 the phrase “Green Chemistry”
is written using symbols of chemical elements. It was molded in the USA, then
outspread to Europe, seeped into Russia, and has reached Belarus and China. It’s also
been recently given prominence in the developing countries. For instance, the Green
Chemistry Congress held in Addis Ababa (Ethiopia) in November 2010 featuring
Prof. Paul T. Anastas, co-founder of green chemistry, resulted in launching the Pan
Africa Chemistry Network.

Fig. 1.1 “Green chemistry” written by the symbols of the chemical elements of the Periodic Table

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The main historical milestones in green chemistry development are the following:

1962—Rachel Carson, writer, biologist, and environmental conservation icon,
published the first of three installments of “Silent Spring”. The publication helped
spread public awareness of the hazards of environmental pollution and pesticides
to the environment.
1969—President Richard Nixon established the Citizen’s Advisory Committee
on Environmental Quality and a Cabinet-level Environmental Quality Council
( Later that year, Nixon expanded his environmental efforts by appointing the White House Committee to determine whether
an environmental agency should be developed.
1970—The Environmental Protection Agency (EPA) was launched.
1980s/1988—Shift from end-of-pipeline control to pollution prevention was
recognized, leading to the Office of Pollution Prevention and Toxics in 1988. In
the same years, safe chemistry activities were performed in Great Britain, Japan,
France, yet they were not regulated at the state level, as in the United States.
1990—The Pollution Prevention Act under the George H. W. Bush Administration
was passed.
1993—The EPA implemented the Green Chemistry Program, which served as
a precedent for the design and processing of chemicals that lessen the negative
environmental impact.
1995/1996—In 1995, President Bill Clinton established the Presidential Green
Chemical Challenge Awards, which served to encourage those involved with the
manufacture and processes of chemicals to incorporate environmentally sustainable design and processes in their practices. The following year, the first recipient
received the award, the only award issued by the president that honors work in
chemistry. Source: />1997—The Green Chemistry Institute was launched. It was created to advance
the broader chemistry enterprise and its practitioners for the benefit of Earth and
its people. Source: />1998—“Twelve Principles of Green Chemistry” was published by Paul Anastas
and John Warner. Within the same year, Green Chemistry Network was formed
by the Royal Society of Chemistry, backed by the Department of Chemistry,
University of York.
2000s–Present—Some major green chemistry achievements include the California Green Chemistry Initiative. In 2006, the first International IUPAC Conference on Green Chemistry as a Chemistry for Sustainable Development was held
in Dresden, 2 years later the second one takes place in St. Petersburg. In 2008,

Governor Arnold Schwarzenegger signed the bills, which served to develop policy
options for green chemistry (). One year later, President
Obama nominated Paul Anastas as head of Research and Development at the EPA.
The concept was first introduced by Paul Anastas and John Warner in 1998 [8].
Today, any type of advancement in chemistry contributing to the improvement of
environmental conditions is called green chemistry. Paul Anastas once noted that the
best chemists go in for green chemistry, and that green chemistry is just a part of

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doing good chemistry. Green chemistry has also prompted the change in the equation: “Risk = Hazard * Dose (Exposure),” by excluding the hazard component for its
impact time. In other words, it has reduced the risk by making reactants and processes
less dangerous. It all boils down to the formal definition of green chemistry “as a
philosophy of chemical synthesis that minimize the use and generation of hazardous
substances.” The notion, however, is not quite accurate, if it’s treated solely as a
branch of chemistry that embeds new safe manufacturing processes which help to
reduce or eliminate the use of hazardous substances. Green chemistry is a revolutionary concept invented to minimize and prevent environmental contamination.
Before people often used the same definitions for green and sustainable chemistry
calling green chemistry is sustainable chemistry. But as once Joaquin Barroso, the
Italian chemist said we need to differentiate Green Chemistry and Sustainable Chemistry or we take the risk of confusing purpose and procedure. Green Chemistry is
oriented toward the way we perform chemistry in order to achieve a sustainable
chemical industry. Sustainable Chemistry is the philosophical approach with which
the ongoing transformations can still be performed while the damage to the environment, namely our ecosystems, is brought to a minimum in order to maintain our
industry and the benefits there from for generations to come and spread to a larger
scale. But this is not only a matter of environmentalist nature; it is also an economical

matter. Qing-shi Zhu, a physical chemist and manufacturer of methanol automobile
fuel from biomass sources, during a press conference said: “The ‘green’ in green
chemistry is also the color of money.”
Green chemistry requires in-depth consideration, as the basis for a systematic
approach to the chemical products manufacturing. The novelty of this approach lies
in the fact that a manufacturer is responsible not only for manufacturing process to
be ecologically friendly, but also for the entire “life cycle” of the product, controlled
at various stages. In 2010, the International Standard ISO 26000:2010 was released,
providing guidelines for social responsibility including environmental issues, which
can be thus named green.
Green chemistry concept can be imaged by a mnemonic, PRODUCTIVELY,
which captures the essence of the twelve principles of green chemistry: P—Prevent
wastes; R—Renewable materials; O—Omit derivatization steps; D—Degradable
chemical products; U—Use of safe synthetic methods; C—Catalytic reagents; T—
Temperature, pressure ambient; I—In-process monitoring; V—Very few auxiliary
substances; E—E-factor, maximize feed in product; L—low toxicity of chemical
products; Y—Yes, it is safe.
These 12 principles display the current situation in the USA and Europe. The
influence of national features on the formulation of the green chemistry principles can
be observed in the greening principles, stated at the 1st Green Chemistry Congress,
held in Africa in 2010.
G—generate wealth not waste;
R—regard for all lives and human health;
E—energy from the sun;
E—ensure degradability and no hazards;

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N—new ideas and different thinking;
E—engineer for simplicity and practicality;
R—recycle whenever possible;
A—appropriate materials for function;
F—fewer auxiliary substances and solvents;
R—reactions using catalysts;
I—indigenous renewable feedstocks;
C—cleaner air and water;
A—avoid the mistakes of others.
Working according to green chemistry principles is clearly demanding and
involves great responsibility. Sometimes, it is necessary to go off the beaten track
to solve the problem. Scientists at Lomonosov Moscow State University have thus
elaborated the 13th principle of green chemistry saying “working the way it is usually
done will get you only so far.”
Green chemistry particularly offers new quantitative parameters (metrics) to
assess the degree of “greenness” of the process, such as E-factor (Environment
factor), introduced by Roger Sheldon, defined as the mass ratio of waste to desired
product mass, and atom efficiency, calculated by dividing the molecular weight of
the product by the sum total of the molecular weights of all substances formed in
the stoichiometric equation for the reaction involved. The smaller E-factor and the
closer atom efficiency to 100% are the greener process or reaction is. These two
parameters differ significantly, since E-factor indicates the amount of waste generated per kg of product. It takes the chemical yield into account and includes reagents,
used catalysts, waste, solvents losses, and all process aids, which are not included
in the stoichiometric equation used to calculate atom efficiency. It is important as
the amount of waste at the end of the process can exceed the amount of production
residue. The E-Factor concept has played a major role in processes of fine organic
synthesis in the pharmaceutical industry (from 25 to 100), and was the least valuable

for bulk chemicals synthesis (<1–5).
There are three driving forces that facilitated the advancement of green chemistry. The first one is national legislation, which monitors the hazard level of the
materials, establishes fines for improper waste disposal and manufacturer’s liability
for ecological standards violation. The second one, community, influences the image
of chemistry and chemical industry, facilitates small and, thus, safer enterprises, and
exercises control over waste management. The last one, economic benefit, can be
attained by reducing investments and the cost of production facilities.
Current green chemistry trends can be reduced to three directions: new
synthesis methods, organic solvents retirement, and renewable (biomass-based)
initial reagents.
It is abundantly clear that green chemistry requires green reactions (sometimes
called “dream reactions”). Green reactions are usually carried out at nonstandard
conditions replacing high temperatures and pressure with microwave radiation, ultraviolet, ultrasound, mechanoactivation, etc. In this context, microwave radiation is

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often named a neoteric Bunsen burner. New conditions of synthesis commonly
implicate new reaction mechanisms.
For instance, upon exposure to microwaves instead of the conventional heating
mode, benzyl alcohol forms benzaldehyde via iron (III) nitrate oxidization, leaving
no by-products (Scheme 1.1). The best solvent for green reactions is without solvent
or in water (Fig. 1.2).
Besides non-ordinary conditions, special equipment is also used in green
synthesis. Specifically, C. Ramshau suggested miniaturization as the final stage of
intensification of the process procedure. Since then, various chemical reactor designs

have thronged the industry: spinning disk reactor; cross-corrugated membranes
module, selectively expelling reactants from reaction; high exothermic reactor (HEX
reactor), drawing the heat off as it comes up.
Certainly, green reactants are required in green reactions. Hydrogen peroxide is
one of them. It is often synthesized in situ from oxygen and hydrogen, in the presence
of a supported palladium catalyst. The practical use of hydrogen peroxide obtained
in this reaction has been demonstrated in the one-pot green synthesis of propylene
oxide from propylene by using compressed (supercritical or liquid) carbon dioxide
as the solvent and small amounts of water and methanol as co-solvents. The addition
of an inhibitor effectively suppressed a number of common side reactions, including
Scheme 1.1 Oxidization of
benzyl alcohol

Fig. 1.2 Green chemistry requires green reactions

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the hydrogenation of propylene, the hydrolysis of propylene oxide, and the reaction
between propylene oxide and methanol (Scheme 1.2).
Hydrogen peroxide has successfully replaced nitric acid in the synthesis of
adipic acid from cyclohexene wherein it undergoes oxidation, in the presence of
sodium tungstate and methyltricetylammonium hydrosulfate as catalysts at 90 °C
(Scheme 1.3). Adipic acid is also used as a food additive (E355) to give a sour taste
to soft drinks and as a basic component in limescale remover.
Green chemistry uses the advantage of catalytic reaction. The implementation of

12 principles of green chemistry is illustrated in a full range in the catalytic technologies when in use. Biocatalytic systems, along with chemical ones, are involved in
the catalytic process. For instance, m-chloroperbenzoic acid assisted transformation
from ketone to lactone (Baeyer–Villiger oxidation). Biocatalyst can be represented
in the form of bakery yeast with air oxygen as an oxidizing agent (Principle 2, 6,
11), as has been demonstrated recently (Scheme 1.4).
Another green chemistry trend is the replacement of solvents in technical
processes. The majority of currently used solvents are volatile organic petroleumderived substances. Hence, these resources are exhaustible, while they are fire
hazardous, explosive, and environmentally hostile.

Scheme 1.2 Synthesis of propylene oxide

Scheme 1.3 Synthesis of adipic acid

Scheme 1.4
Baeyer–Villiger oxidation

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Supercritical fluids were offered as an alternative to usual solvents. They have
been inviting the attention of chemists for the past 150 years. In 1822, Baron Charles
Cagniard de la Tour discovered the critical point of a substance, while conducting
experiments involving a sealed cannon barrel filled with various fluids at various
temperatures. However, it was not until the end of the nineteenth century that this
phenomenon gained currency after Thomas Andrews had carried out a very complete
inquiry into the carbon dioxide characteristics, e.g., carbon dioxide is liquefied only

at rising pressures. He deduced that the meniscus (gas–liquid interface) disappears
and milky-white liquid uniformly fills up the space at 31 °C and 7.2 MPa. With a
further increase in temperature, the liquid quickly becomes mobile and translucent,
consisting of constantly alternating streams similar to hot air flows over a heated
surface. Further increase in temperature and pressure has not caused any visible
changes. Andrews termed the temperature of such transition as critical, and the state
of matter at higher temperatures as supercritical.
It is not only supercritical fluids that are involved in the development of new
solvents for chemical processes. The use of ionic liquids is also considered to be
one of the key green chemistry trends. Ionic liquids contain only ions. Broadly, an
ionic liquid is a salt in the liquid state. In some contexts, ionic liquids have been
restricted to salts whose melting point is below some arbitrary temperature, such as
100 °C (212 °F). At present, the term typically pertains to salts that melt at room
temperature, thus, called RTILs (Room-Temperature Ionic Liquid). An example of
an ionic liquid is 1-methyl-3-alkyl imidazolium hexafluorophosphate.
The properties of ionic liquids are diverse: many have low combustibility, excellent
thermal stability, non-volatility, and favorable solvating properties. Ionic liquids are
also water-miscible; many of them are highly conductive. Essentially, ionic liquids
have been reported to solve cellulose, while it is insoluble in water and most organic
solvents, due to its extensive hydrogen bonding.
The third direction, targeting at green chemistry goals, is the production of
biomass-derived (non-petroleum) hydrocarbon and fuel materials. This green
chemistry trend based on renewable feedstocks came to be called white chemistry.
However, it remains a part of biochemical technology.
Biomass is biologically degradable material derived from agricultural products
and wastes of vegetable and animal origin, forestry and related industries, and
biodegradable industrial residue and household waste. At present, such biomass
components as starch, cellulose, and lignin are at the heart of the recycling process.
The further transformation chain can be represented in the form: conversion of
starch to glucose (monosaccharide), which later undergoes fermentation to ethanol. A

variety of biomass components can be converted to organic compounds (also known
as platform chemicals) and also to biofuel. This fuel is basically hydrocarbon fuel,
although derived not from oil, but from renewable biomass grown from numerous
types of plants, including sugarcane, oilseed rape, and Jerusalem artichoke. Zest and
seafood are also contemplated as a biofuel source. The current technologies enable to
obtain both liquid biofuel (ethanol, methanol, biodiesel) and biogas. Full deployment
of biofuels had been expected by 2030, although the crisis has changed the situation.

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Sugarcane and corn fuels are worse in quality than petroleum, they require substantial modification of engine construction and most crucially they are more expensive.
It cannot be ruled out that biofuel switch will remain a distant perspective. Prof.
Sergey Varfolomeev, Corresponding Member RAS (Institute of Biochemical Physics
RAS, Moscow), reported that the oil deposit of recent origin formed approximately
50 years. This striking conclusion was the work of scientists, who were exploring
petroleum seeps discovered 10 years ago in the caldera of volcano Uzon, Kamchatka,
Russia. The oil was produced by thermophilic bacteria through anaerobic synthesis
on the surface of hot springs: carbon dioxide–lipids–carbohydrates. Swiss scientists
have calculated its conventional age using radiocarbon dating procedures. The scale
of such natural manufacturing is utterly small, approximately 10 L in 5 years. Will
it be the basis for the future industrial technology? Time will tell.
In 2002, Belarus began to develop an industrial engineering sphere targeting at
pollution-free fuel processing. Beginning in 2006–2007, The Research Institute for
Physical and Chemical Problems of the Belarusian State University in conjunction
with Belneftekhim and Grodno Azot launched a biofuel production unit that produces

biodiesel from rapeseed oil with a capacity of 5 million tons per year. At current, the
Belarusian State University Research Institutes for Physical and Chemical Problems
elaborates on new process technology for biobutanol production.
“Chinese-Belarusian Joint Laboratory for environmental-friendly products development and technologies transfer” was founded between Zhejiang Shuren University and Belarusian State University for the cooperation in green technologies and
products area.
The green manufacturing strategy requires a new chemical management policy.
In 2007, the European Union regulation REACH—Registration, Evaluation, Authorization and Restriction of Chemicals—entered into force. At present time more than
17 Belarusian corporations, such as Belshina and Himvolokno, have successfully
undergone preliminary registration in conformity with the provisions of REACH.
In 2010, the Ministry of Environmental Protection (MEP) of China released the
revised version of the Provisions on Environmental Administration of New Chemical Substances. The new regulation replaced the old regulation issued in 2003 and
came into force on October 15, 2010. This regulation is similar to EU REACH and is
also known as “China REACH”. It stipulates that new chemical substances have to be
notified to the Chemical Registration Center (CRC), irrespective of annual tonnage.
One of the main driving forces of conversion to green strategy in chemical manufacturing is the negative public image of chemistry influenced by mass media. The
great public concern about chemistry issues resulted in the establishment of the
Responsible Care initiative that is currently practiced in more than 50 countries that
share a common commitment to monitoring occupational and environmental health
at their enterprises. According to the Globally Harmonized System of Classification and Labeling of Chemicals (GHS) aimed at advancing the safe and secure
management of chemical products and processes, all chemical compounds and chemical mixtures will have been classified and marked by 2015. The main elements of
the information system to be harmonized are hazard rating, pictograms, signaling
words, hazard statement and its preventive measures.

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The new approach to chemical manufacturing—green chemistry—requires the
training of specialists who are conversant with this chemistry trend. The first university to introduce a green chemistry course for students and chemists-technologists
was the University of Nottingham (UK). Such courses are also offered in Middlesex
University (UK), Columbia College (USA), the University of Scranton (USA), the
University of York (UK), the University of Leicester (UK), the University of Zaragoza
(Spain), etc.
In Russia, recognized among CIS as a leading green chemistry country, close
attention is being paid to environmental training, familiarization with current perspectives, and green chemistry blueprints. In 2006, the Scientific-Educational Center
“Sustainable-Green Chemistry” (SEC GC) was established at Lomonosov Moscow
State University. This center aims at creating master programs, specific seminars,
and lectures for school teachers and students. It also carries out research in the field
of catalytic action, atmospheric chemistry, and humic substances.
The first Belarusian institution to pioneer green chemistry was Belarusian State
University (BSU). In 2009 the lecture course on green chemistry was introduced
at the Faculty of Chemistry of BSU. In 2012, it earned the international status and
changed its name to “Introduction to Green Chemistry: Belarus and V4 countries”
due to the number of outsourced foreign experts from Slovakia, Poland, the Czech
Republic, and Hungary who gave the lectures on green chemistry as part of the
International Visegrad Fund project (www.visegradfund.org).
The cooperation between BSU and Zhejiang Shuren University (ZHSRU) in
the research area has awakened the cooperation in education and the program
“Construction of the Internationalization Course of Green Chemistry” started
in 2015. ZSU students were introduced to Green Chemistry basics.

1.5 Conclusion
The goal of the current lecture course on green chemistry is to show the possibility of
safe chemical manufacturing, to initiate you into the implemented green technologies
and strategy for sustainable development of society.
The main objectives of the course are the following:
(1)

(2)

To introduce students to the key green chemistry trends, to take a proactive
approach to problem-solving in safe chemical manufacturing;
To build a vision of basic guidelines on safe and environmentally friendly
industrial- and research-scale chemical processes.

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References
1. John JC (1974) Reviewed work: the coming of post-industrial society by Daniel Bell. Annal Am
Acad Polit Soc Sci 413:174–175
2. Lukashenko A (2015) Speech at the plenary session of the UN Summit on Sustainable
Development. www.belta.by/president
3. Ryan M (2015) Clearing up some misconceptions about Xi Jinping’s ‘China Dream’. HuffPost
4. Pickard J, Pilmer G (2013) UK government revives infrastructure drive. Financial Times
5. Arico S (2015) Ocean sustainability in the 21st century. Cambridge University Press, London
6. Istvan H (2019) Structural chemistry at Lomonosov Moscow State University: a special issue.
Struct Chem. />7. William MD, Michael B (2010) Cradle to Cradle: remaking the Way We make things. North
Point Press, Berkeley
8. Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press,
New York
9. Clark JH (1999) Green chemistry: challenges and opportunities. Green Chemistry 1:1–8

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Chapter 2

Aims of Green Chemistry

Abstract One of the key steps to the realization of the aims of Green Chemistry
lies in the sound management of chemicals that call for the implementation of global
product strategy, which itself in turn constituents a significant part of the content
of the Responsible Care Program, a voluntary commitment of the global chemical
industry to continuously improve health, safety, and environmental management
as well as production and manufacturing processes. REACH Regulation and GHS
Classification and Labeling are two important legislations involved in the process
of chemical management. REACH takes its letters from Registration, Evaluation,
Authorisation of Chemicals and is an EU legislative initiative oriented to control the
production, usage, and placing of the chemicals, including those in mixtures and in
goods, on the EU market, whereas the GHS is launched by the UN in order to raise
awareness of the risks of chemicals and to ensure the safe production, transportation,
and disposal of these substances.
Keywords Global product strategy · Responsible care initiative · REACH
regulation · GHS labeling

2.1 Global Product Strategy (GPS)
Production and use of chemical substances contribute to economic growth and overall
development of both industrially advanced and less developed countries. Chemicals,
directly or indirectly, exert influence on the existence of all living beings, food supply
(fertilizers, pesticides, food additives, and packaging), population health (pharmaceuticals, cleaning agents), and daily life (appliances, fuel, etc.). However, the use of
chemical substances may have an adverse impact on human health and the environment. The first step toward safe handling of the chemicals is to estimate the hazards
they pose to human life and the environment. For instance, some of them are known
or suspected to increase the incidence of a particular cancer or constitute long-term

threats to aquatic habitat. Another essential step is to raise safety awareness, by both
theory and practical inputs, as to the safe and correct handling of the chemicals
and emergency management, for example, through sharing information on chemical
hazards.
© Zhejiang University Press 2021
T. Savitskaya et al., Green Chemistry,
/>
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Studying the chemical substances in terms of the threat they pose to the environment and humans is considered a global issue. In 1980, the chemical classification was
introduced according to which all chemicals are divided into two categories: existing
(grandfathered) and new (produced after 1981). New chemicals required hazard
assessment. However, the problem seemed to be that the “old” chemicals accounted
for an estimated 99% of all chemicals of which only 8% are thoroughly studied. In
1981, when Europe adopted its regulation for new chemicals, 141 chemicals were
expected to pass the toxicity tests and be approved for use.
In 1992,the UN Conference on the Environment and Development established
six programme areas to strengthen national and international efforts related to the
management of chemicals:
•
•
•
•

•
•

Expanding and accelerating international assessment of chemical risks;
Harmonization of classification and labeling of chemicals;
Information exchange on toxic chemicals and chemical risks;
Establishment of risk reduction programmes;
Strengthening of capabilities and capacities for management of chemicals;
Prevention of illegal international traffic in toxic and dangerous products.

In 1998, at an informal meeting of the Environment Ministers of EU Member
States in Chester, UK, the ministers highlighted the need for a new policy on chemicals. White Paper on the Strategy for a Future Chemicals Policy was adopted. As
a result of long discussions and wide-ranging overhaul of the chemical policy, in
October 2003, the European Commission tabled a proposal for a new Regulation on
Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)
and submitted their proposals aimed at revision of the current chemical legislation.
EU lawmakers reached the milestone when, in December 2006, they completed the
process of shaping the European chemical policy.
The International Council of Chemical Associations (ICCA) launched the Global
Product Strategy (GPS), in 2006, designed to highlight the best methods of product
stewardship performance of individual companies and the global chemical industry
as a whole. It incorporates the most effective and advanced management initiatives, facilitates transparency and upgrading of the product to international standards.
Drafting short guidelines for product stewardship, GPS targets to enhance product
quality control of the chemical industry and to provide information to the public on
handling, hazards, and risks associated with all commercially produced chemical
substances.

2.2 Responsible Care (RC) Initiative
In its turn, baseline GPS activities constitute a part of the Responsible Care program
(RC). RC is a voluntary commitment by the global chemical industry to drive continuous improvement in the performance of the pharmaceutical and chemical sector in

all aspects, which directly and indirectly impact the environment, employees, or

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