Green &
Sustainable
DALILA G. KOVACS G R A N D VA L L E Y S TAT E U N I V E R S I T Y
A L L E N D A L E , M I , U S A
CHEMISTRY
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MWEA May 13-2014 Lansing, MI
“A novel substance is either isolated or synthesized every 2.6 seconds on the average during the past 12 months, day and night, seven days a week in the World”
Dr. Hideaki Chihara, Ph.D. chemist and former president of Japan Association for International Chemical Information.
MWEA May 13-2014 Lansing, MI
• CAS REGISTRYSM
> 87 million unique chemical substances
• CHEMLIST® (Regulated Chemicals Listing)
>310,000 substances
> 50 new substances or are added to the database each week.
http://www.cas.org/content/chemical-substances
PHARMA INDUSTRY
Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water-treatment plant
Stackelberg P.E., Furlong E.T., Meyer M.T., Zaugg S.D., Henderson A.K., Reissman D.B. (2004) Science of the Total Environment, 329 (1-3) , pp. 99-113.
2014 (20) 2013 (43) 2012 (52) 2011 (48)
2010 (45)
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• 106 organic wastewater-related contaminants (OWCs • Several of these compounds also were frequently detected in samples of finished
water • What are these compounds: selected prescription and non-prescription drugs and their metabolites, fragrance compounds, flame retardants plasticizers, cosmetic compounds, solvent.
• Drinking-water criteria currently are based on the toxicity of individual compounds
and not combinations of compounds. Little is known about potential human-health effects associated with chronic exposure to trace levels of multiple OWCs through routes such as drinking water
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ORGANIC CONTAMINANTS SURVIVE A CONVENTIONAL DWT
BLACK
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Sierra Club: Beyond Coal (Photo Essay) 2012
GREEN
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Many chemical processes in use today are
black or red, or both. The goal of the
chemical industry should be the
replacement of red and/or black chemistry
with green alternatives: Green Chemistry
Sheldon, R. Green Chem., 2, G1. 2000
GREEN
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http://www.cmu.edu/homepage/practical/20
08/summer/melanie-vrabel.shtml
http://www.greenchem.biz/?q=company-profile
clean chemistry green chemistry sustainable chemistry
are essentially the same (Leitner, 1999)
sustainable and green (Tundo, February 2008)
1st meeting of the Working Party on Green and Sustainable Chemistry (European Association for Chemical and Molecular Sciences)
CHEMISTRY: GREEN
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An overview: origins and development of green chemistry, by J. A. Linthorst, Found Chem
(2010) 12:55–68 DOI 10.1007/s10698-009-9079-4
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GREEN CHEMISTRY
• Green chemistry (also known as
sustainable chemistry) is the design,
development, and implementation of
chemical products and processes to
reduce or eliminate the use and
generation of substances hazardous to
human health and the environment.
Anastas, P. & Warner, J.
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THE TWELVE PRINCIPLES OF GREEN CHEMISTRY
Dr. Paul Anastas Dr. John Warner
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THE TWELVE PRINCIPLES OF GREEN CHEMISTRY
1. Prevention
2. Atom Economy
3. Less Hazardous Chemical Syntheses
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feedstocks
8. Reduce Derivatives
9. Catalysis
10. Design for Degradation
11. Real-time Analysis for Pollution Prevention
12. Inherently Safer Chemistry for Accident Prevention
MWEA May 13-2014 Lansing, MI
THE TWELVE PRINCIPLES OF GREEN CHEMISTRY
1. Prevention
2. Atom Economy
3. Less Hazardous Chemical Syntheses
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feedstocks
8. Reduce Derivatives
9. Catalysis
10. Design for Degradation
12. Inherently Safer Chemistry for Accident Prevention
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11. Real-time Analysis for
Pollution Prevention
REDUCING RISK
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• Design Safer Chemicals – utilize performance chemicals that have the
lowest levels of toxicity.
• Design Less Hazardous Synthesis Methods –if feasible, use
synthetic or biosynthetic methods, with little or no toxicity to human
health and the environment.
• Use Safer Solvents and Reaction Conditions –up-to-date information
on green solvents, optimize the process and provide safer working
environment.
• Accident Prevention – Select substances that minimize the potential
for explosions, fires and chemical releases into the environment.
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Designing safer chemicals for environment degrade to harmless products
Detergents Na salts of linear alkylbenzene sulfonic acids
Builders Zeolites
Pesticides Pyrethroid pesticides
Environmentally benign antibacterial agents
Mg(OOH)OAc
Mg(OOH)2
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Polycarbonates: Made from bisphenol A BPA and phosgene. Cl2CO
“ Phosgene is used as a chemical intermediate; ..used as a chemical warfare
agent. Phosgene is extremely toxic by acute inhalation exposure. Severe respiratory effects: pulmonary edema, pulmonary emphysema, and death have been reported in humans. Severe ocular irritation and dermal burns may result following eye or skin exposure. Chronic inhalation exposure to phosgene may also cause irreversible
pulmonary changes of emphysema and fibrosis. “ http://www.epa.gov/
Less hazardous chemical synthesis
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water as a solvent vs. a resource water-born paints vs. paints based on VOCs scCO2 used in extraction of caffeine from coffee
and in dry cleaning
Safer solvents No solvent: Gas phase Solventless Benign solvent: Water
Waste Minimization & Prevention – Develop chemical
synthesis techniques, which reduce or prevent waste. It is
better to prevent waste than to clean it up after its creation.
Catalysts vs. Stoichiometric Quantities – Catalytic
reactions inherently use smaller quantities of chemicals to
carry out a specified transformation.
Reduce Chemical Derivatives – The use of protecting
groups or other forms of temporary modification of a
functionality adds to the total waste incurred in a synthetic
route.
Minimizing the Environmental
Footprint
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Synthetic Efficiency (Atom Economy) – An efficient chemical
process ensures the maximum amount of your starting materials
is used in the final product so that no atom is wasted.
Designed for Degradation – Reduce the effect on the
environment by using chemicals that are designed to be
biodegradable.
In-Process Controls for Pollution Prevention – To avoid the
formation of hazardous substances, adopt real-time analysis
and in process monitoring during synthesis.
Minimizing the Environmental
Footprint
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http://www.greenchemex.org/
Renewable Feedstocks – Use raw materials or renewable
feedstocks (waste from other processes or products derived
from agricultural streams) whenever technically or
economically feasible.
Energy Efficiency – The realization of the economical and
environmental impact of energy use in a chemical process
and the development of alternative means to reduce the
impact.
Minimizing the Environmental
Footprint
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MWEA May 13-2014 Lansing, MI
Starch-based polymers: renewable resources readily degradable
Design for degradation
THE DRIVING FORCE OF GREEN CHEMISTRY
• Acceptance: Chemical industry must not adversely affect the environment for future generations: sustainability.
• Addresses:
• Resources depletion of the production of
• waste
• Reagents & risk
• Products & degradation
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MWEA May 13-2014 Lansing, MI
The chemical industry creates an immense variety of products
which impinge on virtually every aspect of our lives.
CHEMISTRY INDUSTRY: GREEN
“There are still mistakes and these are generally well publicized in the media but overall there have been significant changes in the operation of the chemical industry that are designed to reduce the impact on the environment”
http://www.essentialchemicalindustry.org/processes/green-chemistry.html (last amended: 6th April 2014; accessed May 12, 2014)
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THE INDUSTRY PUSH TOWARD SUSTAINABILITY
Green chemistry was adopted often because it is attractive and ecologically-sound
A series of examples of industrial motivation vs. principles of green chemistry in the development of new processes have been reported
Centi, G. and Perathoner, S. (2003) Catal. Today, 77, 287.
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From Green to Sustainable Industrial Chemistry, G. Centi and S. Perathoner in Sustainable
Industrial Processes. Edited by F. Cavani, G. Centi, S. Perathoner, and F. Trifiró Copyright
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31552-9
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FROM GREEN TO SUSTAINABLE
• Greener technologies --a novel business strategy for innovation.
• Sustainable industrial chemistry --effective strategies
for sustainability though chemistry. • Green and sustainable chemistry are thus not
synonymous; green chemistry is the core for new strategy for sustainable chemistry to be built around.
Sheldon, R.A., Arends, I. and Hanefeld, U. (2007) Green Chemistry and Catalysis, Wiley-VCH Verlag, Weinheim.; Clark, J. and Macquarrie, D. (eds) (2002)
Handbook of Green Chemistry and Technology, Blackwell Science, Oxford, UK. Rothenberg, G. (2008)Catalysis – Concepts and Green Applications, Wiley-
VCH Verlag, Weinheim.; Tundo, P. and Esposito, V. (eds) (2008) Green Chemical Reactions, Springer, Dordrecht. (Proceedings of the NATO Advanced Study
Institute onNew Organic Chemistry Reactions and Methodologies for Green Production Lecce Italy 29 Oct–10 Nov 2006. Doble, M. and Kruthiventi, A.K. (2007)
Green Chemistry and Engineering, Elsevier Science & Technology Books, Amsterdam.
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1990 Pollution Prevention Act 1991 Green Chemistry
EPA & Green Chemistry
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• UltimerTM Polymer Technology
• high molecular weight, water soluble polymers in
aqueous salt solution
• eliminates use of oils and surfactants in
manufacture and use
• uses ammonium sulfate, a waste by-product from
the manufacture of caprolactam
• eliminates need for expensive mixing equipment
required for water-in-oil emulsions
Nalco Chemical Company
CLEANING WATER
• Crystal Simple Green®
• Water based industrial cleaner
• Non-toxic, biodegradable surfactants
• Replaces traditional organic solvents
• Eliminates hazardous waste sludge
production and VOC pollution Sunshine Makers, Inc.
INDUSTRIAL CLEANING
Isomet Mixture of isoparaffinic hydrocarbon, propylene glycol monomethyl ether, and isopropyl alcohol
Replaces Typewash (mixture of methylene chloride, toluene, and acetone)
Excellent performance in postage stamp and overprinting presses
Acceptable properties (cleaning ability, solvent evaporation rate, odor, environmental compliance, and cost)
U.S.Bureau of Engraving and Printing
INDUSTRIAL CLEANING
u Not a solution to all environmental
problems.
u The most fundamental approach to
preventing pollution.
u Recognizes the importance of
incremental improvements.
GREEN CHEMISTRY
PROBLEM?
Copper and Lead ions can leach into drinking water
1
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Student Ashley Brady, GVSUGreen & Industrial processes W2014
ENVIRONMENTAL CHEMISTRY
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additions reduce
lead and copper
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drinking water
Concentrations
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causes
eutrophication
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Student Ashley Brady, GVSUGreen & Industrial processes W2014
BEST SOLUTION?
Environmental Chemistry
• Prevents Lead and Copper ions from leaching out
• Solution for areas not needed - eutrophication
Green Chemistry • Solves problem by removing
hazardous materials
• Involves more labor and possible costs
Student Ashley Brady, GVSUGreen & Industrial processes W2014
• Conferences and meetings http://www.gcande.org
• Journals Green Chemistry debuted 1999.
Green Chemistry since 1991
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• The Green Chemistry Institute was created.
• The Presidential Green Chemistry Challenge Awards 1995.
Green Chemistry since 1991
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Laws (passed by the US congress) place limits on pollution and timetables for compliance, however with little regard to: Could science/technology attain goals? Economic costs?
Command & Control approach
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“end of the pipe” laws control Risk by dealing with Exposure.
Often Exposure fails.
under the Toxic Release Inventory (TRI Emergency
Planning and Community Right to Know Act EPCRA), companies are required to report the use and/or release of certain hazardous substances.
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Risk=f(Hazard, Exposure)
environmental regulations = economic hardship. cost U.S. industries between $100 to 150 billion per year. adversarial and mistrust relationships between industry and regulatory bodies
Risk=f(Hazard, Exposure)
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Policies weaknesses of command & control approach
The data gap: manufacturers sell chemicals or products without
studying or sharing information about potential health or environmental hazards. Result: consumers and businesses have difficulty knowing what ingredients are in a product, if they are safe – or knowing whether a less hazardous alternative exists
Green Chemistry at Work: Leading California Businesses Demonstrate How to Make Products
Safe from the Start, March 2010 T. Madsen, R. Kerth, Frontier Group and P. King Palitz,
Environment California Research & Policy Center
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Green Chemistry at Work: Leading California Businesses Demonstrate How to Make Products
Safe from the Start, March 2010 T. Madsen, R. Kerth, Frontier Group and P. King Palitz,
Environment California Research & Policy Center
Policies weaknesses of command & control approach
The safety gap: regulators are unable to take effective action to
address known hazards. Result: businesses may be allowed to sell products made with toxic ingredients banned in other countries.
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MICHIGAN GREEN CHEMISTRY CLEARINGHOUSE (MGCC)
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An open access portal to Green Chemistry resources
www.migreenchemistry.org
WHAT
MGCC is the result of a competitive contract with MIDEQ
won in 2010 by an eclectic group of green chemistry
stakeholders including
o Center for Sustainability at Aquinas College
o Sustainability Research Group (SRG)
o Grand Valley State University (GVSU)
o Blue Sphere Solution, Inc.
o Ecology Center Ann Arbor
o Great Lakes Green Chemistry Network (GLGCN)
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WHY MGCC
• open access website & online community, a clearinghouse for green chemistry related information
• an information portal & interactive platform for industry, educators, academics, students, decision makers, and the general public
• meant to slever the economic and innovative potential of green chemistry in Michigan at all levels, promoting human and environmental health
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Michigan Green Chemistry Program
Michigan Green Chemistry Roundtable
Michigan Governor’s Green Chemistry Awards
Program
Michigan Green Chemistry Conference
Michigan Governor’s Executive Directive 2006-6: Promotion of Green Chemistry for Sustainable
Economic Development and Protection of Public Health
Michigan Green Chemistry Action Plan
Funding & Incentives Workshops
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Informational Clearinghouse
www.migreenchemistry.org
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Webinar Series
Michigan Green Chemistry Clearinghouse YouTube Channel:
http://www.youtube.com/user/migreenchemistry
Audio-visual recordings of webinars can be found at:
o More than 60 presentations from multiple sectors (Industry, Government,
Academia, NGO / Not-for-Profits)
o General and specific audiences (e.g. students)
o Diversity of topics and perspectives on green chemistry
o Fundamental concepts of green chemistry
o Toxicology and green chemistry
o Green technology innovations
o Industry-specific initiatives in green chemistry
o State and federal government programs on green chemistry
o Other green chemistry stakeholder groups and initiatives
o Regional networks
o Education programs
o Labor groups
o Public health and chemicals
o Safer chemical regulations, policies and guidelines
o Chemical assessment methodologies and tools
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Collaborative Efforts Industry o Office Furniture Industry: Business and Institutional Furniture Manufacturers
Association (BIFMA)
o Automobile industry: Society of Automotive Engineers (SAE) Green Technology
Steering Committee
o 2025 Safer Chemistry Challenge Program (National Pollution Prevention Roundtable)
Business Commitment to Green Chemistry
Education o Michigan Green Chemistry Education Network
o Great Lakes Green Chemistry Student Network
o Next Generation Science Standards
o Toxicology training for green chemistry education
o Green Chemistry Education Self-Assessment
o Green Chemistry Commitment (Beyond Benign)
o Green Chemistry and Commerce Council (GC3) Policy Statement on Green Chemistry
in Higher Education
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Collaborative Efforts continued…
Government / NGO o Michigan Green Chemistry Program
o Michigan Green Chemistry Roundtable (and Work Groups)
o Michigan Governor’s Green Chemistry Awards
o Michigan Green Chemistry & Engineering Conference
o Support initiatives of other green chemistry organizations (for
example):
o Beyond Benign
o Green Chemistry and Commerce Council
o Great Lakes Green Chemistry Network
o Network with national and international green chemistry organizations
to build, foster and support community of green chemistry advocates
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http://www2.epa.gov/green-chemistry
http://www2.epa.gov/green-chemistry#video
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http://www.greenchemistrynetwork.org
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http://greenchem.uoregon.edu/gems.html
WHAT IS GREEN CHEMISTRY?
Green chemistry can be described as:
a. Sustainable chemistry.
b. Chemistry that is benign by design.
c. Pollution prevention at the molecular level.
d. All of the above.
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GREEN CHEMISTRY IS MORE EXPENSIVE THAN TRADITIONAL CHEMISTRY?
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a. True
b. False
“I foresee the time when industry shall no longer denude the forests which require generations to mature, nor use up the
mines which were ages in the making, but shall draw its materials largely from from the annual produce of the fields.”
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