Green chemistry for environmental remediation

Sharma 1.1 The Environmental Concern 3 1.2 The Role of Chemistry 5 1.3 Sustainable Development 7 1.4 Era of Green Chemistry 8 1.4.1 Twelve Principles of Green Chemistry [1] 10 1.4.2 Obj

Green Chemistry

for Environmental Remediation

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Green Chemistry for Environmental

Remediation

Edited by

Rashmi Sanghi

and Vandana Singh

Scrivener

©WILEY

Co-published by John Wiley & Sons, Inc Hoboken, New Jersey, and Scrivener Publishing LLC, Salem, Massachusetts

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Library of Congress Cataloging-in-Publication Data:

ISBN 978-0-470-94308-3

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Contents

Foreword by Robert Peoples xix

PART 1 Green Chemistry and Societal

Sustainability 1

1 Environment and the Role of Green Chemistry 3

Rashmi Sanghi, Vandana Singh and Sanjay K Sharma

1.1 The Environmental Concern 3

1.2 The Role of Chemistry 5

1.3 Sustainable Development 7

1.4 Era of Green Chemistry 8

1.4.1 Twelve Principles of Green Chemistry [1] 10

1.4.2 Objectives of Green Chemistry 11

1.4.3 Views of Green Chemistry Experts 12

1.4.4 Concepts Related to Green Chemistry:

Cause of Confusion 17 1.4.5 International Initiatives for Green Chemistry

Awareness 18 1.5 Concluding Remarks 29

Acknowledgement 30

References 30 Suggested Reading: Some Books on Green Chemistry 32

Useful Resources for Green Chemistry

and their Links 33

2 The Greening of the Chemical Industry: Past, Present

and Challenges Ahead 35

Fernando J Diaz Lopez and Carlos Montalvo

2.1 Introduction 36 2.2 From Greening Technologies to Greening

the Economy 38

v

2.3 A Brief Note on Business Strategy

and Corporate Greening 44

2.4 The Past: An Account of the Historical Relationship

Between the Chemical

Industry and the Environment 46

2.5 The Present: From Pollution Control to Corporate

Environmental Sustainability 51

2.6 The Future: Environmentally Sustainable

Manufacturing and Eco-innovation 64

2.7 Conclusion: Greening or Sustainability

in Chemical Manufacturing? 69

References 71

Designing Sustainable Chemical Synthesis:

The Influence of Chemistry on Process Design 79

Laura A Anderson and Michael A Gonzalez

3.1 Introduction 79

3.2 Green Chemistry 83

3.3 Green Engineering 85

3.4 Sustainability Metrics 88

3.5 Designing a Sustainable Process 89

3.6 Merck Case Study 100

3.7 Conclusion 103 References 104

Green Chemical Processing in the Teaching

Laboratory: Microwave Extraction

4.4.1 Green Production Rapidity 114

4.4.2 Green Production Efficiency 115

4.4.3 Green Production Courses 115

4.4.4 Green Production Messages 116

4.4.5 Safety Considerations 116

Norita Mohamed, Mashita Abdullah

and Zurida Ismail

5.1 Introduction to Microscale Chemistry

5.2 Development of Microscale Chemistry Experiments

for Upper Secondary Schools

5.2.1 Microscale Chemistry Experiments

6 Capability Development and Technology Transfer

Essential for Economic Transformation 137

Surya Pandey and Amit Pandey

6.1 Introduction 138

6.2 The Importance of R&D 138

6.2.1 Research and Development

Expenditure 141 6.3 Knowledge Creation and Technology Transfer 145

6.3.1 Development of an RDT Voucher

System 146 6.3.2 External Engagement 146

6.3.3 Organizational RDT Planning 147

6.3.4 Structural Changes 148

6.4 Technology Transfer Future 148

6.5 Applications to Green Chemistry 149

6.6 Conclusions 150 Acknowledgements 150

References 151

PART 2 Green Lab Technologies 153

7 Ultrasound Cavitation as a Green Processing Technique

in the Design and Manufacture of Pharmaceutical

Nanoemulsions in Drug Delivery System 155

Siah Ying Tang, Khang Wei Tan

and Manickam Sivakumar

7.1 Introduction 156

7.2 Types of Emulsion and Principles

of Nanoemulsion Formation 157

7.3 Formulation Aspects of Nanoemulsion 159

7.4 The Ultrasonic Domain 160

7.5 What is Ultrasound Cavitation? 163

7.9 Advantages of Ultrasound Emulsification 171

7.10 General Reviews of Ultrasound Emulsification 173

7.11 Nanoemulsion in Pharmaceutical Application 180

7.12 Characterization of Nanoemulsion

Drug Delivery System 184

7.12.1 Particle Surface Morphology and Size

Distribution 184 7.12.2 Solubility Enhancement 187

7.12.3 Drug Encapsulation and Loading

Efficiency 188 7.12.4 Drug Release 189

7.12.5 Ultrasonic-mediated Drug Release 190

7.12.6 Site Specific Drug Targeting 193

7.12.7 Stability 194

7.13 Practical and Potential Applications of Nanoemulsion

in Different Administration Routes 194

7.13.1 Parenteral Drug Delivery 195

7.13.2 Oral Drug Delivery 196

7.13.3 Topical Drug Delivery 199

7.14 Conclusion 200

Acknowledgement 201

References 201

CONTENTS ix

8 Microwave-Enhanced Methods for Biodiesel

Production and Other Environmental Applications 209

Veera Gnaneswar Gude, Prafulla D Patil,

Shuguang Deng, Nirmalakhandan

Feedstock 218 8.3.1 Biodiesel Production from Edible and

Non-edible Oils 218 8.3.2 Biodiesel Production from Algae 221

8.4 Energy Consumption 229

8.4.1 Kinetics Study 231

8.4.2 Comparison Between Supercritical and

Microwave Assisted Algal Biodiesel Production 233 8.5 Analysis of Algal Biomass and Biodiesel 235

8.5.1 TEM Analysis of Algal Biomass 235

8.5.2 GC-MS Analysis of Algal Biodiesel

from Wet Algae 236 8.5.3 TLC Analysis of Algal Biodiesel

from Dry Algae 237 8.6 Current Status of the Microwave Technology for

Large Scale Biodiesel Production 238

8.7 Other Microwave-enhanced Applications 240

8.7.1 Microwave Applications in

Organic Synthesis 240 8.7.2 Microwave Applications for Green

Environment 242 8.8 Summary 244 References 246

9 Emergence of Base Catalysts for Synthesis of Biodiesel 251

B Singh, S.N Upadhyay, Dinesh Mohan,

Y.C Shartna

9.1 Introduction 252 9.2 Mechanism of Heterogeneous Catalysis 252

9.3 Calcium Oxide and Magnesium Oxide

9.4 Hydrotalcite Doped Compounds

9.5 Alumina Loaded Compounds

9.6 Zeolite

9.7 Conclusions

Acknowledgement

References

Hydrothermal Technologies for the Production

of Fuels and Chemicals from Biomass

D.W Racketnann, L Moghaddam, T.J Rainey,

CF Fellows, P.A Hobson and W.O.S Doherty

Biocrude 10.5.3 Bio-oil Emulsification

10.5.4 Steam Reforming Bio-oil

10.5.5 HTU® technology

10.5.6 Thermal Depolymerization Process (TDP)

Technology 10.6 Conclusions

Ionic Liquids in Green Chemistry

-Prediction of Ionic Liquids Toxicity Using

Different Models 343

Raquel F M Frade

11.1 Introduction 343 11.1.1 Ionic Liquids 343

11.1.2 Ionic Liquids: Applications 345

CONTENTS xi 11.1.3 Ionic Liquid Toxicity

12.2 Nanocatalyst: An Origin of a Green Concept

12.3 Recent Advances in Nanocatalysis

13.2.1 Free Radical Homopolymerization 386

13.2.2 Free Radical Copolymerizations 387

13.2.3 Synthesis of Composites by Free Radical

Polymerization 390 13.2.4 Emulsion Polymerization 391

13.2.5 Controlled Radical Polymerization 392

13.3 Step Growth Polymerization 394

13.3.7 Synthesis of Poly(amide-imide)s,

Poly (amide-ester)s, Poly(ether-ester)s, Poly(ester-imide)s, Poly (ether-imide)s, Poly(amino-quinone) and other

Polycondensation Reactions 400 13.3.8 Copolymerization 402

13.4 Ring Opening Polymerization 402

13.4.1 Ring Opening Polymerization of

Cyclic Esters 403 13.4.2 Enzyme Catalyzed Ring Opening

Polymerization 405 13.4.3 Cationic/Anionic Ring

Opening Polymerizations 406 13.4.4 Ring Opening Copolymerization 407

13.6 Miscellaneous Polymer Synthesis 414

13.6.1 Syntheses of Polypeptides 415

13.7 Conclusions and Perspectives 415

References 417 PART 3 Green Bio-energy Sources 425

14 Bioenergy as a Green Technology Frontier 427

Laura B Brentner

14.1 Introduction 427

14.2 Bioenergy Life Cycles 431

14.2.1 Land-use Changes 431

14.2.2 Resource Demand (other inputs) 432

14.2.3 Process Contribution to Energy Demand

(fossil fuel inputs) 434 14.3 Transportation Biofuels 435

14.3.1 Oil Crops for Biodiesel 435

14.3.2 Carbohydrate Crops for Ethanol 438

14.4 Thermochemical Conversion of Biomass 440

14.5 Biogas 442 14.5.1 Anaerobic Digestion and Methane

Production 442 14.5.2 Biohydrogen 442

CONTENTS xiii

14.6 Microbial Fuel Cells

14.7 Future Prospects

References

15 Biofuels as Suitable Replacement

for Fossil Fuels

Juan Carlos Serrano-Ruiz, Juan Manuel Campelo,

Rafael Luque, Antonio A Romero

15.1 Introduction

15.2 Types of Biofuels and Technologies

for their Production

16 Biocatalysts for Greener Solutions 479

U Lakshmishri, Rintu Banerjee

and Surya Pandey

16.1 Introduction 479 16.1.1 Challenges Facing Green Chemistry 481

16.2 Enzyme-Biocatalysts in Green Chemistry 482

16.2.1 Classification of Enzymes 482

16.2.2 General Applications of Enzymes 484

16.3 Utilization of Enzymes as Tools for

Providing Greener Solutions 485

16.3.1 Paper and Pulp Industry 485

16.3.2 Textile Industry 486

16.3.3 Petrochemical Industry 488

16.3.4 Enzymes for Bioremediation

of Persistent Organic Contaminants 491 16.3.5 Enzymes in the Pharmaceutical

Industry 494 16.3.6 Tannery 496

16.4 Conclusion 501

References 502

Lignocellulosics as a Renewable Feedstock

for Chemical Industry: Chemical Hydrolysis and

Pretreatment Processes 505

Ian M O'Hara, Zhanying Zhang,

William O.S Doherty and Christopher M Fellows

17.3 Biomass Hydrolysis Processes 511

17.3.1 Concentrated Acid Hydrolysis 512

17.3.2 Dilute Acid Hydrolysis 513

17.3.3 Solid Acid Catalysts 515

17.4 Biomass Pretreatment Processes 518

17.4.1 Chemical Pretreatment 519

17.4.2 Physico-chemical Processes 531

17.4.3 Physical Pretreatment Processes 537

17.4.4 Biological Pretreatment Processes 540

Lignocellulosics as a Renewable Feedstock

for Chemical Industry: Chemicals from Lignin

Christopher M Fellows, Trevor C Brown

and William O.S Doherty

Enzymatic Depolymerisation

CONTENTS XV 18.6 Conclusions

20 Green Biotechnology for Municipal and Industrial

Wastewater Treatment 629

Balasubramanian S., R.D Tyagi, R.Y Surampalli,

and Tian C Zhang

20.1 Introduction 630 20.2 Green Biotechnology 631

20.3 Need for Efficient/Green Biotechnology for

WWT Processes 632 20.4 Application of Green Biotechnology in

WWT Processes 633 20.4.1 Nutrient Removal (Phosphorus) 634

20.4.2 Foam Control from Activated Sludge

Processes 634 20.4.3 Green Biotechnology to Improve Sludge

Dewatering 635 20.4.4 Green Biotechnology to Improve Sludge

(Aerobic and Anaerobic) Digestion 636 20.4.5 Green Biotechnology to Control

Pathogens in Wastewater Sludge 637 20.5 Bioconversion of Wastewater Sludge to Value

Added Products 638

20.5.1 Bioenzymes (Laccases, Degradative

Enzymes and Proteases) Production 20.5.2 Bioethanol and Biodiesel

Production 20.5.3 Bio-fertilizer

21.3.3 Plant-Microbial Interactions During

Phytoremediation 667 21.4 Cadmium: Properties, Toxicity

in Aqueous Media 676 21.5.3 Cadmium Hyperaccumulators 677

21.5.4 Chelating Agents in Cadmium

Phytoremediation 684 21.6 Cadmium Phtoremediation

and Genetic Engineering 688

CONTENTS xvii Acknowledgement 694

References 694

22 A Closer Look at "Green" Glass: Remediation with

Organosilica Sol-Gels Through the Application

22.3.1 Properties of Organosilica Sol-Gels 706

22.3.2 Organosilica Sol-Gels—Benign

by Design 710 22.3.3 Remediation Strategies with

Organosilica Sol-Gel 710 22.3.4 Selective Adsorption 712

22.3.5 Binding and Catalysis 714

22.4 Green Chemistry with Glasses—The "Green" side

of Organosilica Sol-Gels 714

22.4.1 Environmental Remediation 715

22.4.2 Removal of Cationic Species 715

22.4.3 Removal of Anionic Species 716

22.4.4 Removal of Neutral Species 716

22.4.5 Binding and Reduction of Chromâtes 716

22.4.6 Remediation of Greenhouse Gas Via

Conversion to Methanol 718 22.5 Green Chemistry and The Potential Impact

of Organosilica Sol-Gels 720

22.6 Conclusions and Future

Perspectives 725

References 726

23 Modification and Applications of Guar Gum

in the Field of Green Chemistry 729

Sagar Pal, Sk A Alt, G Sen, R P Singh

23.1 Introduction 729

23.2 Experimental 735

23.2.1 Materials 735

23.2.2 Synthesis 736

Foreword

In the beginning there was chemistry Some may call it physics, but within a few billionths of a second, the fundamental particles of matter began to coalesce into the building blocks that today we call atoms If we fast forward to about 5 billion years ago when, as some believe, Earth began to form as a result of the gravitational pull of matter from that primitive beginning, our planet has been under-going an amazing display of chemistry during its evolution The very concept of photosynthesis is at the root of life on this pale blue oddity we call home The very assembly of atoms that make up our photosynthesis systems allowed the capture of solar energy and its use to fuel the process of building more complex organic molecules The sequestration of carbon dioxide (a concept mankind would like

to perfect in the 21st century) evolved on our primitive planet and resulted in the release of oxygen which allowed for a more complex chemical web to evolve

Over the millennia nature has perfected the most wonderful and elegant array of solutions to the complex challenges of energy con-version, material transport (circulation), locomotion, reproduction, and cognition These evolutionary changes occurred over millions

of years and allowed nature to perfect the elegant chemistry of life and forge a balance in what we refer to as an ecosystem, our bio-sphere, today This extended time sequence allowed for adaption and the development of symbiosis among living systems

Within the last few thousand years, things began to change as homo sapiens began to exert their influence Once it became possible to ensure food supplies through agriculture and the use of tools, one species began to impact and control its surroundings for the first time in the history of our planet This ability afforded the luxury

of time and resulted in a quickened pace for the development of

xix

tools and understanding of nature Eventually homo sapiens man began to unravel the secrets of nature, of the very chemistry that is its essence That understanding blossomed and ultimately, through the process of scientific inquiry, we deciphered the code of chemis-try From that, we have learned to synthesize molecules and even design molecules and materials that do not exist in nature With the advent of the petroleum age with its abundant building blocks, new, stronger, longer lasting, non-biodegradable substances began

to be synthesized in ever-larger quantities Through the process of waste, accidents and disposal, these new, persistent "better" mol-ecules found their way into our environment, into the food chain, and eventually into us

We now call this bioaccumulation A sample of human adipose sue, blood, or urine from anyone living any place on our planet— even the most remote location—will show various levels of approximately 200 or more synthetic chemicals that we have made

tis-It is estimated there are more than 100,000 chemicals in use around our planet Less than 10% have ever been tested for their human health or environmental impact properties Yet we know there is a litany of examples of serious adverse impacts of these persistent, bioaccumulative chemicals Now modern medicine and a revolu-tion in mechanistic toxicology are providing the evidence that this collection of persistent molecules is adversely influencing life on this planet While nature had billions of years to evolve and adapt

to her expanding chemical world, people have made changes on a timescale that is impossible for biological adaptation

Adding to the issues of persistence and bioaccumulation are the relentless demands of an expanding population and recognition that providing safe drinking water, food, shelter, energy, and trans-portation for developing societies is proving more and more diffi-cult In fact, it is quite obvious that we cannot achieve a sustainable future by the linear extension of existing technologies Such a rev-elation begs the obvious questions, what should we do differently and how should we do it? These queries are the core of this publi-cation and growing numbers like it What we can do differently is adopt the proven systems approach we call green chemistry; how

we should do it is to apply the 12 principles of green chemistry After all, chemistry is the fundamental cornerstone of all life on Earth It only makes sense that we return to the chemistry of nature

FOREWORD xxi

to solve the problems we ourselves have created on this fragile planet Only when all chemistry is green chemistry can we hope to solve these challenges

Dr Robert Peoples Director of the American Chemical Society's

Green Chemistry Institute

PARTI GREEN CHEMISTRY AND SOCIETAL SUSTAINABILITY

Used with the permission of Chris Madden

Rashmi Sanghi and Vandana Singh (eds.) Green Chemistry for Environmental

Remediation, (3-34) © Scrivener Publishing LLC

1 Environment and the Role

of Green Chemistry

Rashmi Sanghi 1 , Vandana Singh 2 and Sanjay K Sharma 3

: R-3 Media Lab, Indian Institute of Technology Kanpur India

2 Department of Chemistry, University of Allahabad, Allahabad, India department of Chemistry, Jaipur Engineering College & Research Centre,

Jaipur, India

"Green Chemistry represents the pillars that hold up our

sustain-able future It is imperative to teach the value of Green Chemistry to tomorrow's chemists."

-Daryle Busch (ACS President, 1999-2001)

Abstract

The harmful side effects of industrialization, noxious and greenhouse gas emissions, smoggy air, global warming, ozone-depletion, deforestation, threat of extinction of wildlife, and urban degradation are some of the manifestations of environmental degradation with disastrous consequences Using science and technology as a success ladder, mankind has developed from Stone Age to present day modern civilization The idea of progress towards a better life began with the scientific and industrial revolutions advocating the role of humans as masters of nature and causing them to live beyond their means Is the road to such a linear and continuous progress heading towards an environmental crisis? Is there reason to worry?

Keywords: Green chemistry, environmental, renewable resources,

ecofriendly, green chemistry resources and awards

1.1 The Environmental Concern

The Earth has existed for over five billion years, humanity for about five million years, and civilization for around 10,000 years

Rashmi Sanghi and Vandana Singh (eds.) Green Chemistry for Environmental

Remediation, (3-34) © Scrivener Publishing LLC

3

Thousands of ecological species have survived over a long period

of time and consequently may be expected to continue to exist ever, but at the same time many of them have vanished due to eco-logical misbalances Is there need to worry if certain species become extinct? Won't nature take care of this crisis over a course of time? The rising population and concurrent urbanization is proving detrimental to our natural environment Most of the environmental problems are the result of deliberate or inadvertent misuse or over-use of the natural resources by human intervention Humans are consistently and increasingly consuming renewable resources at a rate much faster than that at which ecosystems can regenerate them The environment is getting polluted at a rate greater than nature's ability to revert back for sustaining the ecosystem Through ages, nature has been maintaining an ecological balance by absorbing the environmental disturbances so as to survive the many crises and cataclysms The exponential rise in human population, produc-tion and consumption of goods and services, as well as increasing buildup of carbon dioxide in the atmosphere is taking a toll on the enormous restoration capacity of nature Does this mean that the human species is facing the threat of extinction?

for-Since time immemorial firewood has been used by our tors for fuel and lumber to build homes That is how natural gas

ances-as an alternative for fuel wances-as discovered True, using firewood ances-as fuel can cause many environmental problems, including the loss of forests and damage to vegetation But it is also true that a forest is capable of self-recovery, for after a tree is chopped down more trees will re-grow from the remaining trunk, root and seeds However, regeneration of petroleum, natural gas, and coal take a very long time and that too under very special conditions Based on today's consumption rate, the known petroleum and natural gas will only last about a hundred more years, while there might be enough coal

to last for about five hundred more years Though it is difficult to predict the time range for the depletion of fossil fuels, it is high time

to shift the focus from the production of energy and carbon-based chemicals from fossil fuels to renewable resources Our excessive dependence on petroleum products for the manufacture of materi-als for daily use is clearly a cause of serious concern To meet the fast growing requirements of the modern era, mimicking nature is the best option for synthesizing materials in demand, for nature makes materials by the lowest energy route without generating any waste and, in fact, recycles every bit it produces For example,

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 5 enzymatic reactions can be a good option for synthesizing materi-als under ambient and mild reaction environments and are thus attractive alternatives to routine chemical transformations

The earth we abuse and the living things we kill will, in the

end, take their revenge; for in exploiting their presence we are

diminishing our future

~ Mary a Mannes 'More in Anger' 1958 ~

1.2 The Role of Chemistry

The past few decades have been an era of chemistry being at the forefront in the development of clean production processes and products In fact, chemistry plays an integral part of our lives and

is everywhere around us: the air we breathe, the water we drink, the plastics we use, clothes we wear, food we eat, buildings we live

in, etc Indeed, whatsoever is present or formed on earth is due to chemistry Chemistry is the heart of science, which is the founda-tion on which technology for development of any nation is based and built The role of the chemistry in environmental sustainability

is as crucial as it is diverse The chemist is increasingly engaged

in the health sector, research for recycling of waste matters and sewage, production of agrochemicals and fertilizers for foresta-tion, production of renewable energy to replace the fossil fuels and other non-renewable energies, production and application of water treatment and sanitation chemicals, environmental chemical con-trol, monitoring of environmental degradation, and much more The role of chemistry is essential in ensuring that our next genera-tion of chemicals, materials, and energy is sustainable Worldwide demand for environment-friendly chemical processes and products requires the development of novel and cost-effective approaches for preventing pollution

Developments in water treatment, waste disposal methods, cultural pesticides and fungicides, polymers, materials sciences, detergents, petroleum additives, and so forth, have all contributed

agri-to the improvement in our quality of life But unfortunately all these advances come with a price tag of pollution Gone are the days when better living through chemistry was a promise; now it

is a bitter irony that nearly everything we use depends on the rochemical industry If substantial damage to the environment has

pet-resulted from the actions of the chemists and chemical gists in the 20th century, then the responsibility of global improve-ment will also be on them as now they are realizing the importance

technolo-of preserving the natural resources, Today, with growing ness, in industry, academia and the general public, of the need for sustainable development, the international scientific community is under increasing pressure to change current working practices and

aware-to find greener alternatives In fact, present day chemistry is driven

by an unparalleled social demand for better products and services with a growing sentiment that undue exploitations of resources must be minimized Scientists and engineers from both the chemi-cal industry and the academic world have made efforts to correct pollution problems by the more extensive use of "green chemistry" concepts, i.e., development of methodologies and products that are environmentally friendly Green chemistry has essentially two parts The first, and the most fundamental part, is the development

of a principled and environmentally conscious approach to try The other is the innovative buildup of greener strategies in the chemists' tools kit The former aspect is not new, although it has found more support only recently [1]

chemis-The increasing importance of green chemistry is seen in the awards and honors bestowed on achievements in this field Professor Walter Kohn was awarded the Nobel Prize in Chemistry

in 1998 jointly with Prof J Pople for metathesis The Royal Swedish Academy of Sciences has rewarded efforts to make the world more habitable and encouraged good and environment-friendly chemi-cal practices Yves Chauvin (France), Robert Grubbs (USA), and Richard Schrock (USA) shared the prize for their contribution to the development of metathesis (meaning"change places"), an ener-getically favored and less hazardous method in organic synthesis, which has immense industrial applications Metathesis is an exam-ple of how important basic science has been exploited for the ben-efit of man, society, and environment Apart from its applications

in the polymer industry (for making stronger plastics), metathesis has also found an important role in biotechnology in recent years

It represents a great step forward for green chemistry, reducing potentially hazardous waste through smarter production

The field of chemistry has undergone revolutionary changes and development in light of increasing awareness for environment pro-tection Industries and scientific organizations have put clean tech-nology as an important research and development (R&D) concern

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 7

It is indeed a challenge before the chemists to develop synthetic methods that are less polluting, i.e., to design clean or "green" chemical transformations Chemistry is here to stay whether to cause environmental problems or to maintain and develop our quality of life and save humanity from the doomsday It is impor-tant for chemists to use their creativity and innovation to develop environment-friendly routes for the betterment of the world With proper foresight and planning, the chemist can design reactions that are economically sound, environmentally compatible and socially acceptable, that is adopting greener route to chemical transforma-tions Green chemistry is no doubt a special contribution of chem-ists to the conditions for sustainable development

pollution prevention philosophy which is: "First and foremost, reduce

waste at the origin through improved housekeeping and maintenance, and modification in product design, processing and raw material selection Finally, if there is no prevention option possible, treat and safely dispose

of the waste"

Sustainable development demands reducing the adverse sequences of the substances that we use and generate But per-haps of equal significance is the need to deal with toxicities that are threatening the welfare of essentially all living things in real time According to Martyn Poliakoff and Pete Licence, there are two main reasons for chemical manufacture becoming unsustain-able The first is that most chemical products from perfumes to plastics to pharmaceuticals are based on carbon, which currently

con-is supplied by Earth's finite petroleum feedstocks Alternative bon sources do exist; for example, coal was the basic feedstock for chemical production before oil, and could be used again But read-ily accessible coal is also in limited supply, and the conversion of coal into fine chemicals requires catalysts based on metals that are themselves becoming scarce The second issue is the safe disposal

car-of industrial waste In general, industrial chemical processes ate large amounts of waste which, when not disposed of properly, imposes an increasing burden on the environment [2]

gener-The concept of environmental space per person per country measures environmental degradation due to human activities Environmental space is the sustainable rate at which we can use environmental resources without causing irreversible environ-mental damage, depriving the future generations of the earth's inhabitants of the resources they will need [3] Clearly, such an unsustainable way of living will eventually lead to an environ-mental and social catastrophe Although the society is dependent

in many ways on the chemical industry to maintain the current standards of living and improve the quality of our lives, mankind has to shoulder the responsibility to preserve the world's natural resources The sustainability of such development at the cost of our environment needs to be questioned, and the gravity of environ-mental degeneration is something to be seriously thought about Sustainability is "working in co-operation with nature and not working against the nature"

If one way be better than another, that you may be sure is Nature's way

~ Aristotle - Nichomachean Ethics ~

Thus it is evident that to stem the currently unsustainable jectory of global development, scientists and engineers are manip-ulating matter in new ways to create chemical products that are cleaner to manufacture, safer for people and the planet, and more economically tenable than those now in use "There is a hunger

tra-in the marketplace for reliable, consistent, compelltra-ing tra-tion on which to base greener, more sustainable choices," says Neil

informa-C Hawkins, Dow Chemical's vice president of sustainability and environmental health and safety "Chemical companies need a life-cycle view—greenhouse gases, water, energy, renewables, waste reduction, recyclability—that encompasses all parts of the supply chain," he says

1.4 Era of Green Chemistry

In the U.S., interest in green chemistry began in earnest with the passage of the Pollution Prevention Act of 1990, which was the

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 9 first environmental law to focus on preventing pollution at

the source rather than dealing with remediation or capture of

pollutants—the so-called end-of-the-pipe solution The new law

led the Environmental Protection Agency (EPA) to establish its

Green Chemistry Program in 1991 within the Office of Pollution

Prevention and Toxics

Green Chemistry came into existence in early 1990's [4] by many

names, Sustainable Chemistry, Clean Chemistry, Benign by Design

Chemistry, etc [5] The term "Green Chemistry" was coined and first

used by Paul T Anastas in 1991 It was a special program for

indus-try, academia, and government [6] According to the International

Union for Pure and Applied Chemistry (IUPAC), Green Chemistry

is defined as "The invention, design and application of chemical products

and processes to reduce or to eliminate the use and generation of hazardous substances." [7] Another definition by Seldon [8] is "Green Chemistry

efficiently utilizes (preferably renewable) raw materials, eliminates waste and avoids the use of toxic and/or hazardous reagents and solvents in the manufacture and application of chemical products". It was also defined as eco-friendly practices with profit-making goals Later on, the concept

shaped and popularized as a bunch of alternative synthetic pathways

and processes The Italian definition of green chemistry is "Green

chemistry for the environment is the use of chemistry for pollutant source reduction, the definition encompasses therefore all aspects and chemical processes that reduce impact on human health and on the environment"

As the name implies the green chemistry movement aims to make

humanity's approach to chemicals, especially synthetic organic

chemicals, environmentally benign or "sustainable" By designing

of environmentally friendly chemical reactions, green chemistry

provides the alternatives to target pollution and sustainable

devel-opments at the same time [9-11] It also makes us aware about toxic

effects of a process at the designing stage of a chemical process

In a nutshell, all traditional and old synthetic routes are more or

less "Gray" in their working and obviously give adverse effects to

the mankind and all living beings Green chemistry provides green

paths for different synthetic routes using non-hazardous solvents

and environmental-friendly chemicals [12] Green chemistry is a

central issue, in both academia and industry, with regard to

chemi-cal synthesis in the 21st century Without this approach, industrial

chemistry is not sustainable Green chemistry covers recent trends

of full range of examples such as catalysis, biocatalysis,

micro-wave assisted organic synthesis, and photocatalytic reactions from

scientific research to full industrial commercialization The adoption

of green chemistry by industry using basic science and engineering improves environmental and economic performance and motivates the implementation of green chemistry technologies [13]

1.4.1 Twelve Principles of Green Chemistry [1]

Paul T Anastas and John C Warner developed and announced the Twelve Principles of Green Chemistry in 1998 This set of principles involves suggestions and instructions for chemists to use newer chemical compounds, eco-friendly synthetic alternatives, and low waste producing processes

1 Prevention: It is better to prevent waste than to treat or clean up waste after it has been created

2 Atom Economy: Synthetic methods should be designed

to maximize the incorporation of all materials used in the process into the final product

3 Less Hazardous Chemical Syntheses: Wherever ticable, synthetic methods should be designed to use and generate substances that possess little or no toxic-ity to human health and the environment

prac-4 Designing Safer Chemicals: Chemical products should

be designed to affect their desired function while imizing their toxicity

min-5 Safer Solvents and Auxiliaries: The use of auxiliary stances (e.g., solvents, separation agents, etc.) should

sub-be made unnecessary wherever possible and ous when used

innocu-6 Design for Energy Efficiency: Energy requirements

of chemical processes should be recognized for their environmental and economic impacts and should be minimized If possible, synthetic methods should be conducted at ambient temperature and pressure

7 Use of Renewable Feedstocks: A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable

8 Reduce Derivatives: Unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) should

be minimized or avoided if possible, because such steps require additional reagents and can generate waste

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 11

9 Catalysis: Catalytic reagents (as selective as possible)

are superior to stoichiometric reagents

10 Design for Degradation: Chemical products should

be designed so that at the end of their function they

break down into innocuous degradation products

and do not persist in the environment

11 Real-time Analysis for Pollution Prevention:

Analy-tical methodologies need to be further developed to

allow for real-time, in-process monitoring and control

prior to the formation of hazardous substances

12 Inherently Safer Chemistry for Accident Prevention:

Substances and the form of a substance used in a

chemical process should be chosen to minimize the

potential for chemical accidents, including releases,

explosions, and fires

1.4.2 Objectives of Green Chemistry

Industrial developments are the motivation to acquire more

knowl-edge about new chemicals, synthetic processes, and their different applications But many chemicals are very hazardous and danger-

ous for safety and health It makes the use of such chemicals costlier and problematic So it becomes the duty of local administration and government to restrict the use of such problematic substances or processes by forcing the industries to either substitute hazardous substances in their processes or reduce the volume and hazards of their waste The costs of waste to an industry are high and diverse

and it involves cost of legislation, waste disposal, hazard evaluation,

health and safety, increasing supply chain pressures, inefficient use of raw materials, local authority and neighborhood pressures [14]

The main objective of green chemistry is thus, the reduction of

this "Costs of Waste" This involves a series of reductions- reduction

of cost, materials, energy, non-renewable, waste and risk and hazard

All the practices that help us in reducing these costs are welcome

in green chemistry The challenges for the coming generation of chemists is to develop such products, processes, and services that achieve the goals of economic, societal and environmental benefits (Triple Bottom Line Benefits) at the same time [15, 16] It requires

a new approach to make a chemical synthesis ideal An ideal thesis must be simple, safe, atom efficient, one step process with 100% yield, environmentally acceptable, using available materials

syn-and without wasting reagents [14] Some selected examples for implementing the 12 Principles are presented in Table 1.1

Green chemistry is a philosophy to work for sustainable opment following 12 principles of Anastas and Warner In litera-ture, we can easily find and search many interesting examples of synthetic processes with the use of green chemistry rules It is very difficult to declare a product or process as completely green; we can just compare the alternative process with the traditional one, whether it is greener or not, this comparison has various aspects

devel-of discussion including social, economical and environmental But great efforts are still undertaken to design ideal processes to ensure nonpolluting synthesis and productions; which require no solvents

to carry out the chemical conversion or isolation of the final product The role of green chemistry can be better visualized by Figure 1.1 The progress of green chemistry so far has been a matter of tech-nical feasibility, as researchers have developed less toxic alterna-tives to conventional methods A prime example is supercritical carbon dioxide: ordinary, nontoxic carbon dioxide that has been heated and pressurized above its critical point of 31.1°C and 7.39 megapascals, beyond which it behaves like both a gas and a liquid, and readily serves as a solvent for a wide range of organic and inor-ganic reactions Other nontoxic replacements for solvents have been found among the ionic liquids: exotic cousins to ordinary table salt that happen to be liquid at or near room temperature The same

GC approach is suggested for plastic production and other tion generating industries Catalyst and reagent chemistry is one of the most important steps of GC Use of catalysts is a better option for using principles of atom economy and 100% process efficiency

pollu-in practice Similarly, for example the textile pollu-industry is one of the high revenue generating industries in India, there is need to use natural dyes and pigments to make it environmental friendly

1.4.3 Views of Green Chemistry Experts

Robert Peoples, in the capacity of Director of the ACS Green Chemistry Institute, drives the implementation of the principles of green chem-istry across the global chemical enterprise According to him "compa-nies around the world are implementing green chemistry solutions From biodegradable packaging to recycling a cadre of petroleum

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 13

Table 1.1 Examples of implementation of Green Chemistry Principles into practice [7]

Adipic acid synthesis by oxidation of cyclohexene using hydrogen peroxide New less hazardous pesticide (e.g., Spinosad)

Supercritical fluid extraction, synthesis in ionic liquids Polyolefins-polymer alterna- tive to PWC

Production of surfactants

On-fiber derivatization as derivatization in solution in sample preparation

Efficient Au(III)- catalyzed synthesis of b-enaminones from 1, 3-dicarbonyl compound and amines Synthesis of biodegradable polymers

Use of in-line analyzers for wastewater monitoring Di-Me carbonate (DMC) is an environmentally friendly substitute for di-Me sulfate and Me halides in methylation reactions

Ref

[17] [4] [18] [19] [20] [21] [22] [23] [24]

[25] [25] [26]

Figure 1.1 Environmental problems and green solutions (copyright © Rashmi Sanghi)

based polymers, new technology is finding its way out of the ratory and into scale-up and commercial practices Yes, it will take time and we will make mistakes along the way, but such is the nature

labo-of scientific progress One might think silicon based solar panels are

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 15

sustainable because they capture the free solar flux In fact, the idea

is a step in the right direction, but the manufacture of such solar cells relies on traditional, non-sustainable chemistry" [27]

Dr Paul Anastas is the Assistant Administrator for EPA's Office of Research and Development (ORD) and the Science Advisor to the Agency Known widely as the "Father of Green Chemistry" for his groundbreaking research on the design, manufacture, and use of minimally- toxic, environmentally-friendly chemicals At the time he was nominated by President Obama

to lead ORD, Dr Anastas was the Director of the Center for Green Chemistry and Green Engineering, and the inaugural Teresa and

H John Heinz III Professor in the Practice of Chemistry for the Environment at Yale University's School of Forestry and Environmental Studies Prior to joining the Yale faculty,

Dr Anastas was the founding Director of the Green Chemistry Institute, headquartered at the American Chemical Society in Washington, D.C

Dr John C Warner is one of the founders of Green Chemistry He co-authored the seminal

book Green Chemistry: Theory and Practice,

which first described the 'Twelve Principles

of Green Chemistry.' In 2009, the Council of Scientific Society Presidents honored Dr Warner with the Leadership in Science Award for found- ing the field of Green Chemistry Dr Warner

is President, Chief Technology Officer, and Chairman of the Board of the Warner Babcock Institute for Green Chemistry, which he founded with Jim Babcock in 2007 Dr Warner currently serves on the Board of Directors of the Green Chemistry Institute in Washington, DC and on the Science Advisory Board of Strategic Environmental Research and Development Program, the Department of Defense's environmental science and technology program

Dr Robert Peoples is Director of the ACS Green Chemistry Institute In this capacity, he drives the implementation of the principles of green chemistry across the global chemical enterprise

He served as Sustainability Director for the Carpet & Rug Institute and Executive Director

of The Carpet America Recovery Effort (CARE) and Director of Sustainability and Market Development at Solutia, Inc., a spin-off of Monsanto Corporation He is also President of the Environmental Impact Group, Inc Dr Peoples was a key driver

in the development of the NSF 140 Sustainable Carpet ANSI Standard He is currently facilitating the development of an ANSI standard for Greener Chemical Products and Process Information,

a B2B tool

According to Paul Anastas "since its introduction, green try has been adopted at an astounding rate, both in the United States and internationally Green chemistry now impacts every industry sector that one can name—from the automotive industry, to energy,

chemis-to materials, chemis-to agriculture, chemis-to basic chemicals and so on But the best news is that all of this adoption—all of these accomplishments that have been recognized and rewarded for their contributions in reducing hazards to humans and the environment—these repre-sent perhaps only one percent of the power and potential of green chemistry With further and more systematic adoption, green chem-istry has the potential to move us toward a more sustainable society and economy at a level that is yet to be known" [28] In the past two decades the green chemistry movement has helped industry become much cleaner But mindsets change slowly, and the revolu-tion still has a long way to go [29] The goal of green chemistry was never just clean-up and, in his conception, green chemistry is about redesigning chemical processes from the ground up It's about making industrial chemistry safer, cleaner, and more energy effi-cient throughout the product's life cycle, from synthesis to clean-up

to disposal It's about using renewable feedstocks wherever sible, carrying out reactions at ambient temperature and pressure and above all, minimizing or eliminating toxic waste from the out-set, instead of constantly paying to clean up messes after the fact

pos-ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 17

"It's more effective, it's more efficient, it's more elegant, it's simply better chemistry," says Anastas

In an interview when John Warner was asked "with nies looking at green chemistry and it becoming a bigger issue,

compa-in what areas were they havcompa-ing the biggest impact right now?"

He felt that "At this point, green chemistry is still nascent It's only been around for 12 years, 13 years It's not something that's mainstream, and so it's still evolving But every major company that I know of has a program to address certain research devel-opment and manufacturing processes around green chemistry"

On being asked about the other barriers that companies and the larger world of green chemistry are facing, he felt that the issue is perception "It's a very strained reality that we face, that change is a difficult thing to wrap our heads around Historically,

10 or 15 years ago, I think it was a valid perception that green technologies were expensive and inferior That's no longer the case I think that the science has evolved, but there are people still living in the past And immediately, when they hear green, they think more expensive and less efficient That perception is a hindrance" [30]

1.4.4 Concepts Related to Green Chemistry:

Cause of Confusion

For a common person there is still confusion between Green Chemistry and Environmental Chemistry It should be clear to all that green chemistry (also called sustainable chemistry) is a phi-losophy of chemical research and engineering that encourages the design of products and processes that minimize the use and generation of hazardous substances [31], whereas environmental chemistry is the chemistry of the natural environment and of pol-lutant chemicals in nature

Concepts related and sometimes competing with green try may cause confusion to a person These concepts are:

chemis-• Pollution Prevention [32,33] According to the Pollution

Protection Act of 1990, the term "Pollution Prevention"

involves reduction or elimination of wastes and

emis-sion of chemicals to the environment Activities such

as waste treatment and source disposal fall outside the concept of green chemistry

• Sustainability: It has been defined as meeting the needs

of today's human being, while not compromising with the needs of future generations [34] The concept of sustainability led to the concept of the triple bottom line for industry, which involves economic prosper-

ity, social well-being, and environmental protection Green chemistry is certainly an essential part of the sustainability [35, 36]

• Design for the Environment: This refers to the design and manufacture of products and processes with min-

imal impact upon the environment

• Waste Minimization: It generally refers to reduction in the amount of solid and liquid waste produced by a process (air pollution being excepted)

• Responsible Care: The responsible care program is

an initiative that the American Chemical Society began in 1988 as a means of emphasizing the con-

cern of the public about the use and manufacture of chemicals

• Industrial Ecology: It describes the science of use and reuse of natural resources in manufacturing rather than the traditional practice of extending and using resources, then discarding and disposing

1.4.5 International Initiatives for Green Chemistry

Society in the UK has a journal named Green Chemistry, exclusively

to cover research in this area

ENVIRONMENT AND THE ROLE OF GREEN CHEMISTRY 19

1.4.5.2 Awards

Presidential Green Chemistry Challenge Awards [37]

The US Environmental Protection Agency (EPA) has collaborated with academia, industry, and other government agencies to pro-mote the use of chemistry to develop new technologies for pol-lution prevention and in 1995 instituted the Presidential Green Chemistry Challenge Awards The competitive awards program, administered by the EPA and sponsored in part by the American Chemical Society and National Science Foundation, for both aca-demic researchers and industries that excel in the discovery and practice of environment-friendly chemistry, provides national recognition for incorporating the principles of green chemistry and green engineering into the design, manufacture, and use of chemical products and processes President Bill Clinton's admin-istration announced the start of the Presidential Green Chemistry Challenge Awards in 1995 and the first award was presented

in 1996 In the ten years the agency has presented the Green Chemistry Awards, the companies that won them have cut the amount of hazardous material or waste they produce by about 1.5 million tonnes

These awards are the only awards in chemistry given out on the presidential level and were established to recognize outstanding achievements in the field of green chemistry and technology The following criteria are fixed for these awards:

• Greener reaction conditions for an old synthesis (e.g., solvent free reactions or reactions in water)

• A greener synthesis for an old chemical (by use of some biomass or catalyst)

• Synthesis of a new compound that is less toxic but has the same desirable properties (e.g., harmless pesticides)

Ciba Travel Awards in Green Chemistry

The ACS Green Chemistry Institute® Ciba Travel Awards in Green Chemistry is a new annual award that sponsors the participation of students (high school, undergraduate, and graduate students) in an American Chemical Society (ACS) technical meeting, conference, or training program, having a significant green chemistry or sustainabil-ity component, to expand the students' education in green chemistry

Kenneth G Hancock Memorial Award in Green Chemistry

ACS President Dr Paul Anderson announced the Hancock Memorial Award in Green Chemistry in June of 1997 as an opportunity for undergraduate and graduate students to compete for a prestigious memorial award in recognition of undergraduate and graduate studies and/or research in green chemistry The award is in memory

of Dr Kenneth G Hancock, Director of the Division of Chemistry

at the National Science Foundation (NSF) who died unexpectedly while attending an environmental chemistry conference in Eastern Europe in the fall of 1993 Dr Hancock was an active advocate emphasizing the role of chemists and chemistry not only in solv- ing environmental problems of the past, but also more importantly

in avoiding environmental problems in the future Offered by the American Chemical Society Green Chemistry Institute® to just one student per year, the Hancock Award is awarded in conjunction with the annual Presidential Green Chemistry Challenge Awards Ceremony at the annual Green Chemistry and Engineering Conference The award provides national recognition for out- standing student contributions to furthering the goals of green chemistry

Award for Green Product and Processes

The interuniversity consortium Chemistry for the Environment was the first in Europe to institute the award for Green Product and Processes in 1999 The consortium gives the awards following the criteria of science innovation, reduced impact on the environment, and socio-economic involvement

UK Green Chemistry Award

It is sponsored by the Royal Society of Chemistry; Salters' Company; Jerwood Charitable Foundation; DTI and DETR The award of £10,000 is given to a young academic working in collabo- ration with industry

RACI Green Chemistry Challenge Awards

The Royal Australian Chemical Institute Green Chemistry Challenge awards are to recognize and promote fundamental and innovative chemical methods in Australia that accomplish pollution prevention through source reduction and that have broad applicability in indus- try, and to recognize contributions to education in green chemistry