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Green Chemistry:
Environmental and health protection
through innovation
Paul T. Anastas
Yale University
1
So.
All we have is…
energy
matter
energy
2010, Bloomberg News
Wegmans stops selling reusable bags after lead tests
2010, Bloomberg News
Wegmans stops selling reusable bags after lead tests
2010, NY Times
Hydrocarbons in Cereal
Stoke New Debate Over
Food Safety
2010, The Sun Chronicle
Toxic Beauty
2010, Maine Public Broadcasting Network
Report: Cosmetic Products Contain High Levels of Toxic
Chemicals
2009, BBC News
Deet bug repellent
'toxic worry'
2009, The
Charleston
Gazette
Study finds food-
wrapper
chemicals in
blood
Persistence
Chemicals in the Environment
• Toxics Release Inventory (TRI)
• 4.44 billion lbs. of toxic chemicals were released directly
to air, water, and land in 2011
– Only 650 of toxic chemicals and toxic chemical
categories out of 78,000 in commerce are tracked by
TRI
Absurdity then.
Absurdity now.
- Developmental
delays
- Infertility
- Cancer
- Obesity
- Behavioral
problems
Mahoney et al. Toxicol and applied Pharmacol,
2010.
Soto et al. Nature Reviews: Endocrinology, 2010.
Today.
Today.
Today.
Today.
70% of Smallmouth
Bass in the
Mississippi River
are intersex.
Source, USGS: http://www.usgs.gov/newsroom/article.asp?ID=2305
Today.
Over 90% of Florida
Panthers’ sperm are
abnormal. Many are
completely sterile.
And source Facemire et al.EHP, 1995.
Today.
Source : UNEP
The total volume of water on Earth:
~1.4 billion km3
Percent of total that is freshwater:
2.5%
Percent of Freshwater locked up in
ice & snow: ~70 %
Percent freshwater that is
drinkable: <1%
Today.
In developing countries, 70% of industrial wastes are dumped
untreated into waters where they pollute the usable water
supply. Source: UNEP
Today.
--Source, US EPA
In 2010, the U.S.
generated 30
million tons of
plastic waste.
Equal to the weight of
nearly 100 Empire
State Buildings.
Only 7 % was recovered for recycling.
Today.
The Pacific Trash Vortex Today.
Marine trash kills more than 1
million seabirds and 100,000
mammals and sea turtles each
year.
Source, UN
Statement
Today.
Montcoal Mine, West Virigina
April 2011
Death Toll: 29
Deepwater Horizon, Gulf of
Mexico
April, 2010
Death Toll: 11
Fukushima
Nuclear
Disaster,
Japan
March 2011
Toll?
Today.
• Doing the right things, wrong.
water
toxics climate energy
biodiversity
Unintended Consequences
Biofuels that
compete with
food, feed,
and land use
Unintended Consequences
Purifying
water with
acutely lethal
substances
Unintended Consequences
Renewable
energy through
the use of
precious, rare,
toxic metals in
photovoltaics
Unintended Consequences
Agricultural crop
efficiency from
persistent
pesticides
Unintended Consequences
Energy saving
compact fluorescent
light bulbs reliant on
toxic metals
How did we get there?
• Urgent and necessary challenges
• Noble goals
• Exciting science and technology
• Best of intentions
• Lack of systems thinking.
Design for a Systems Context
Awareness
Problems cannot be
solved at the same level
of awareness that created
them. A. Einstein
Definition
• GREEN CHEMISTRY:
The design of chemical products and
processes that reduce or eliminate the use
and generation of hazardous substances
Principles of Green Chemistry 1. It is better to prevent waste that to treat or clean up waste after it is formed.
2. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.
3. Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment.
4. Chemical products should be designed to preserve efficacy of function while reducing toxicity.
5. The use of auxiliary substances (e.g. solvents, separation agents, etc.) Should be made unnecessary wherever possible and, innocuous when used.
6. Energy requirements should be recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure.
7. A raw material of feedstock should be renewable rather than depleting wherever technically and economically practicable.
8. Reduce derivatives - Unnecessary derivatization (blocking group, protection/ deprotection, temporary modification) should be avoided whenever possible.
9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
10. Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products.
11. Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.
12. Substances and the form of a substance used in a chemical process should be chosen to minimize potential for chemical accidents, including releases, explosions, and fires.
Twelve Principles…Isn’t that how it
is done now?
• Entire industries are geared toward cleaning up after wasteful
chemical syntheses.
• Feedstocks are seldom selected with regard to hazard.
• Industrial chemicals products do not have minimal hazard as a
performance criterion
• Persistence of chemicals in the biosphere and in our bodies is a
major global health issue. (CDC 250 chemicals since 1945)
• The vast majority of organic chemicals are made by depleting (non-
renewable) feedstocks
• Our chemical industry deals with safety through engineering and
security through barricades.
Green Chemistry Design Framework Across the life-cycle
Waste Prevention
Atom Economy
Design For
Degradation
Less Hazardous
Reagents
Renewable Feedstocks
Design for Safety and Security
Green Analytical
Methods
Benign Solvent Systems
Use of Catalysis
Benign Product Design
Unnecessary
Derivatives
Energy Considerations
Origins
Of Materials Manufacturing Distribution Use End of Life
Journals
Articles
1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009
Headlines
Research
Networks
Business?
Green Chemistry across
Industrial Sectors
• Defense and aerospace – Adhesives, coatings, corrosion
inhibitors
• Automotive – Solvents, polymers, fuels
• Household cleaners – Surfactants, fragrances, dyes
• Cosmetics – Builders, chelating agents, dyes
• Agriculture – Pesticides, fungicides, fertilizers
• Electronics – Solder, housings, displays
• Pharmaceuticals
AqueousSolvents
Biobased
Transformations
Biobased materials
Alternative Energy Science
Synthetic Methodologies
Next Generation
Catalysts
Molecular
Self-Assembly
Breakthroughs
Green Nano
RT Ionic Liquids
Degradable Polymers
Biofuels Reactor Design
Super-
critical
fluids
We know what carbon dioxide
as waste looks like.
Emissions of Carbon
Increases in Carbon Dioxide
Global Change
CO2 for Extraction (Coffee)
CO2 as a Cleaner
CO2 in Concrete
• Materials Tech - Supramics
• CO2 Solutions
• Calera
• Carbon Sense Solutions
• Drexel University
• McGill University
• MIT
CO2 and the Integrated Biorefinery Alternative technologies for extraction, transformation, isolation and purification of value-added chemicals and fuels.
Algae-to-fuel and algae-to-chemical technologies Soh, L.; Zimmerman, J., Biodiesel Production Potential of Algal
Lipids Extracted with Supercritical Carbon Dioxide. Green Chemistry 2011, 13 (6), 1422-1429. Brentner, L. B.; Eckelman, M. J.; Zimmerman, J. B., Combinatorial life cycle assessment to inform process design of industrial production of algal biodiesel. Environmental Science & Technology 2011, 45, 7060-7067. Foley, P. M.; Beach, E. S.; Zimmerman, J. B., Algae as a source of renewable chemicals: opportunities and challenges. Green Chemistry 2011, 13, 1399-1405.
Solvents • Highest Volume Chemicals
• Amongst the Most Regulated Chemicals
• Widely distributed in the Environment
• High chronic and Acute Toxicity
• Significant Strat. Ozone Depleters
• Significant Atmosph. Ozone Generators
• Potent Green House Gas Potential
A PRIME OPPORTUNITY FOR GREEN
CHEMISTRY INNOVATION
Room Temperature Ionic Liquids
• Virtually no vapor pressure
• Tailored for performance
• BASF
– The BASIL Process
Bio-Based Solvents
• Gamma Valero Lactone
• Ligno-cellulosic derived
• Equal or superior performance to
classic organic solvents
15-20% of the total economy
80% of chemical products
90% of new chemical processes
Catalysis is
involved in:
VCI,
Positionspapier Katalyse, 2002
Serenade®: An Effective,
Environmentally Friendly Biofungicide
• Non-toxic alternative to traditional chemical pesticides and is compatible with organic and conventional farming
• Feedstock includes agricultural materials (soybeans, starches, sugars) from plant-based sources, reducing petroleum-based feedstocks; fermentation products are non-hazardous
• No synthetic chemical residues; non-toxic to beneficial insects and organisms and does not cause secondary disease or insect problems
• Safe toxicology profile allows for a 4 hour re-entry period for workers and a zero day pre-harvest interval
AgraQuest, Inc.
Voutchkova-Kostal, A. M.; Kostal, J.; Connors, K. A.; Brooks, B. W.; Anastas, P. T.; Zimmerman, J. B., Towards rational molecular design for reduced chronic aquatic toxicity. Green Chemistry 2012, 14 (4), 1001-1008. Voutchkova, A. M.; Kostal, J.; Steinfeld, J. B.; Emerson, J. W.; Brooks, B. W.; Anastas, P. T.; Zimmerman, J. B., Towards rational molecular design: derivation of property guidelines for reduced acute aquatic toxicity. Green Chemistry 2011, 13, 2373-2379. Voutchkova, A. M.; Osimitz, T. G.; Anastas, P. T., Toward a Comprehensive Molecular Design Framework for Reduced Hazard. Chem. Rev. 2010, 110, 5845-5882. Voutchkova, A. M.; Ferris, L. A.; Zimmerman, J. B.; Anastas, P. T., Toward Molecular Design for Hazard Reduction-Fundamental Relationships between Chemical Properties and Toxicity. Tetrahedron 2010, 66, 1031-1039.
Molecular Design for Reduced Hazard
Developing World Green
Chemistry
Developing countries are emerging as major markets and
sources of innovation for industrial biotech. Braskem, a
Brazilian chemicals firm, has commercialised
polyethylene—a commonly used plastic resin—made from
sugarcane. It is now working with Novozymes, a
pioneering Danish biotech firm, to repeat the trick for
polypropylene, another common plastic. And Brazil's
ethanol industry, already the world's biggest, wants to
move from first-generation ethanol (made from sugarcane)
to the next-generation cellulosic variety.
Biotechnology
Chemistry goes green
Biopolymer Sorbents for Arsenic
Removal
Yamani, J. S.; Miller, S. M.; Spaulding, M. L.; Zimmerman,
J. B., Enhanced arsenic removal using mixed metal oxide
impregnated chitosan beads. Water Research 2012, 46
(14), 4427-4434.
Miller, S. M.; Spaulding, M. L.; Zimmerman, J. B.,
Optimization of capacity and kinetics for a novel bio-based
arsenic sorbent,TiO2-impregnated chitosan bead. Water
Research 2011, 45 (17), 5745-5754.
Miller, Sarah M.; Zimmerman, Julie B., Novel, bio-based,
photoactive arsenic sorbent: TiO2-impregnated chitosan
bead. Water Research 2010, 44, 5722-5729.
Developing new catalysts and
methods for controlled
transformation of lignin and
lignocellulosic materials.
Catalytic transformation of lignocellulose Hansen, T. S.; Barta, K.; Anastas, P. T.; Ford, P. C.; Riisager, A., One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol. Green Chemistry 2012, 14, 2457-2461 . Matson, T. D.; Barta, K.; Iretskii, A. V.; Ford, P. C., One-Pot
Catalytic Conversion of Cellulose and of Woody Biomass
Solids to Liquid Fuels. Journal of the American Chemical
Society 2011, 133, 14090-14097.
Renewable Specialty
Chemicals
• Based on Green
Chemistry Principles
• Bio-based oils,
sugars, starches,
and oxygen.
• Flavors, fragrances,
and suractants
Is it really all we have?
energy
matter
energy
So.
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