This document discusses green chemistry and its principles. It provides examples of companies that have implemented green chemistry approaches to reduce waste and hazardous chemicals in their products and manufacturing processes. These include substituting safer chemicals and renewable feedstocks, improving atom economy in reactions, and redesigning synthesis routes.

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The Ideal “Sustainable”Product
Green Chemistry:
Pollution Prevention by Design
• Consumable - compostable, biodegradable
• Stays in Technical Loop - product of service, reusable, recyclable
• Minimized hazard in product and manufacturing process. Hazard
includes human health, safety and ecological harm - Green Chemistry
Dr. Lauren Heine
Zero Waste Alliance
International Sustainable Development
Foundation
Portland, OR
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Societal Image of Chemistry Historical Approach to
Environmental Problems
• Chemistry was once viewed as a field of • Waste treatment, control, and disposal; pollutant
innovation resulting in medical breakthroughs monitoring; hazardous waste site cleanup.
and modern convenience. • Development of standards for emissions to air,
releases to water, and disposal by land, as well as
• Chemistry is now viewed by many as fouling the regulation of these standards.
planet. • “Command and Control.”
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EPACT
Growth in Environmental Laws FFCA
CERFA
CRAA “Command and Control”
PPA
AMFA PPVA
120
ARPAA
AJA
ASBCAA
ESAA-AECA
FFRAA
AQA
IEREA
ANTPA
GLCPA
ABA
CZARA
Cost to Industry
110 FEAPRA WRDA
IRA EDP
NWPAA NAWCA OPA
CODRA/NMSPAA RECA
100 FCRPA CAAA
MMPAA GCRA
GLFWRA
90
APA
SWDA
CERCLA
CZMIA
RCRAA
WLDI
WQA HMTUSA
NEEA
SDWAA
• Industry spent $115 billion in 1992 on waste
NWPA SARA
80
COWLDA
FWLCA
MPRSAA
CAAA
BLRA
ERDDAA
treatment, control, and disposal.
ARPA EAWA
CWA MPRSAA
NOPPA
70 SMCRA PTSA
• It was estimated at that time that it would cost as
Number of Laws
SWRCA UMTRCA
SDWAA ESAA
BLBA QGA
60 FWPCA
MPRSA
CZMA ESA
TAPA
HMTA NCPA
TSCA
FLPMA
much as $700 billion to clean up existing
NCA RCRA
50 FEPCA
PWSA
MMPA
FRRRPA
SOWA
DPA
NFMA
CZMAA hazardous waste sites.
NEPA
40 EQIA
AQA
FOIA
WRPA
FCMHSA CAA
EPA
EEA
• These costs, and the costs associated with
30 AFCA OSHA
20 TA
FHSA
NFMUA
WSRA
EA
FAWRAA
NPAA regulatory compliance, are rising.
FWCA AEPA FIFRA PAA NHPA RCFHSA
BPA WLDA
WA FWCAA
10 NBRA NPS MBCA FAWRA
IA FWA
RHA AA NLRA AEA
YA WPA
0
1870 1880 1890 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000
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“Command and Control” Chemical Releases
Cost to Industry 1994: 2.3 billion Surface
pounds of ~ 300 Water (2.9%)
Toxic Release
• DuPont’s 1996 research budget: $1,000,000,000.00. Inventory (TRI)
chemicals were Land
reported as released (12.8%)
• DuPont’s 1996 environmental compliance budget: Air (68.9%)
to the environment
$1,000,000,000.00.
by TRI-reporting
facilities.
• Dupont’s 1996 chemical sales: $18,000,000,000.00
Today ~ 650 TRI
(41percent of total sales). chemicals Underground
Injection
(15.4%)
More than 75,000 in
commerce
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Pollution Prevention Act 1990 Green Chemistry
• Pollution Prevention can be accomplished
by several approaches:
– Inventory controls.
– Process controls. Green Chemistry is the design of
– In-process recycling. chemical products and processes that
– Housekeeping changes. reduce or eliminate the use and/or
– Green Chemistry. generation of hazardous substances.
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Chemistry and Responsible Care™
Good, but Good Enough?
Risk = Hazard x Exposure
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Chemistry and Responsible Care™ Chemistry and Responsible Care™
Good, but Good Enough? Good, but Good Enough?
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The 12 Principles of Green Chemistry Atom Economy
MW of desired product
Atom economy =
1. Prevention of waste Sum of MWs of all substances produced
2. Atom Economy
3. Less Hazardous Chemical Synthesis Diels-Alder Reaction
4. Designing Safer Chemicals O O
5. Safer solvents and auxiliaries
+ 100% Atom economy
6. Energy efficient
7. Renewable feedstocks
8. Reduce derivatives Wittig Reaction
9. Catalysis O
+ _ CH2
10. Design for degradation + Ph3P CH2 + Ph3P=O
11. Real time analysis for pollution prevention
12. Safety 35% Atom economy
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Pathways to Green Chemistry Traditional Synthesis of Ibuprofen
Chemical Manufacturers O O CHCO2 C2H5
(CH3 CO)2O ClCH2 CO2 C 2H5
• Create new ways to make desired materials- AlCl3
I¯Bu
NaOC 2H5
I¯Bu
different feedstocks, different pathways CHO CH NOH
H+ H2NOH
H20
• Identify desired performance characteristics I¯Bu I¯Bu
and create new materials C N CO 2H
60% Waste
Ibuprofen
¯
I Bu
(BASF and Celanese Corporation)
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Green Chemistry Alternative Synthesis of Alternative Feedstocks
Ibuprofen Use of Biomass in the Synthesis of Animal Feed,
Chemicals, and Fuels
O
(CH3 CO)2 O H2 Acidification Acetic Acid
Propionic Acid
HF + CH 3COOH catalyst
Waste Butyric Acid
Lime Fermentatio
Biomas Concentration
Treatment n
s
OH CO2H
CO, Pd Acetone
Thermal
(Lime-Treated Biomass) MEK
Conversion Diethyl Ketone
1% Waste
Hydrogenatio Isopropanol
Animal Feed Isobutanol
Ibuprofen n Isopentanol
(BASF and Celanese Corporation)
(Mark T. Holtzapple, et al., Texas A&M
adapted from U.S.EPA Green Chemistry Program)
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Benefits of Using Biomass Traditional Feedstock in the Synthesis
of Adipic Acid
• Renewable Feedstock
O OH
• Contributes no net CO2 to the atmosphere
Ni-Al2O3 Co, O2
• Conserves fossil fuel leading to a secure +
domestic supply 370-800 psi 120-140 psi
benzene cyclohexane cyclohexanone cyclohexanol
• Platform for making an array of chemical
products from what is otherwise considered
Cu, NH 4 VO3 , CO 2 H
waste HO 2 C + N2 O
HNO 3 adipic acid
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Alternative Feedstock in the Synthesis The Use of Phosgene in the
of Adipic Acid Synthesis of Polycarbonates
OH CO 2 H HO 2 C
CH3
OH H2O/CH 2CI2
O E. coli E. coli COCI2
HO C OH +
phosgene interfacial
O CH3 polymerization
OH OH
CO 2 H
OH OH OH bisphenol A
D-glucose 3-dehydroshikimate cis, cis-muconic acid
Pt, H2 CO 2 H
HO 2 C + (n-1) NaCl
50 psi adipic acid
(John W. Frost, et al., Michigan State)
polycarbonate
(Kyosuke Komiya, et al., Asahi Chemical)
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Diphenylcarbonate as an Pathways to Green Chemistry
Alternative to Using Phosgene Non-Chemical Manufacturers
CH3
O
• Identify materials that are unsustainable and
HO C Ph—O—C —O—Ph
OH phase them out
CH3
solid-state
polymerization
• Identify benign materials that already exist
bisphenol A
and select them
• Work with vendors and manufacturers to
develop new benign and environmentally
appropriate materials. Competitive edge!
polycarbonate
(Kyosuke Komiya, et al., Asahi Chemical)
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Everything is Chemical…. Green Chemistry at IKEA-
Changing Chemistries and Business Models
• IKEA faced highly publicized
Non-chemical manufacturing businesses incidents of formaldehyde off-
gassing from glue in 1981 and from
Looking toward sustainability lacquer on bookshelves in 1992
• In a 1992 report, IKEA states:
Finding challenges based in chemistry “What we are actually measuring [at
the cash register] is the rate at
which we are transforming
resources into waste.” Changing
business models.
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US-OR-Beaverton-
Green Chemistry at Nike- Dir. of Sustainable Product Chemistry
“Big Audacious Goals” !
As our Director of Sustainable Product Chemistry, you’ll protect and enhance Nike’ s
• Developed technology to grate waste from outsole molds Global Apparel products and brand image by developing a thorough understanding of
materials, components, raw material manufacturing processes, and the application of
into REGRIND for premium performance outsoles Sustainable Chemistry. You’ll serve as our internal expert for product chemical safety
and work closely with toxicologists, vendors, chemical experts, and academia to
• Substitution of water-based solvents in adhesives, primers, understand the toxicological and legislative risks associated with existing and new
substances in apparel products. In this position, you’ll develop strategies and action
degreasers, and mold release agents for petroleum-based plans for addressing the presence of priority substances and disseminate information
solvents. Millions of dollars saved. to all regions and track existing and developing legislation and non-governmental
organization issues as they apply to chemical substances in our products. You’ll also
evaluate test procedures to determine applicability to product testing to ensure safe
• Substituting for Nike ‘AIR’, which is really sulfur and environmentally responsible apparel products, search for Green Chemistry
hexafluoride. One gram of SF6 has the global warming applications in the production of products, track advances in production of apparel
products, and leverage Nike’s position as an environmentally responsible company. In
potential of 23,900 g of CO2 (~24,000 times) addition, you’ll proactively investigate potential substance problems, work to minimize
the chances of "substance surprises," and manage the Nike "approved" list of test
laboratories and test methods used for product testing.
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Green Chemistry at Patagonia- Green Chemistry at 3M
Committed to the Core! • 3M is phasing out Scotchgard products, which contain
perfluorooctanyl sulfonate (PFOS). Studies have not
• PET from recycled 2-liter soda bottles are demonstrated any hazards to human health from the
used as the base material for Synchilla®, compound.
a signature Patagonia fleece • PFOS is persistent in nature and has been found at levels
• Eliminated chlorine bleach in fabric of 10 to 100 parts per billion (PPB) in blood banks from
several countries, 3M workers have levels of 2 parts per
• Reduced formaldehyde use million.
• Elimination of azo dyestuffs • Affected product lines account for $320 million annually
and at the time of the phase-out, there were no immediate
• Elimination of PVC in luggage fabrics, plastic
substitutes for the compound.
components and clothing labels
• Organic Cotton-using a renewable
feedstock in a more sustainable way
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Green Chemistry at Interface 1999 Presidential Green Chemistry Award -
• Pandel, an Interface foam and backing Dow Agrosciences Sentricon™
manufacturer, has eliminated all lead, cadmium
and barium stabilizers in their foam products • Innovative integrated pest management approach
• Interface has begun to make carpet made from
corn-based polylactic acid polymers • Monitors and delivers highly specific bait, in very small
• Guilford of Maine, an Interface carpet maker, quantities - interferes with termite molting.
reduced phosphorus levels in effluent water • Unmatched technical performance, environmental
from 10 parts per million to trace amounts
compatibility, and reduced human risk
through product substitution
• Just in time for an EPA ban on Dursban!
• If you demand it, it will come….
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Summary
Parting thought...
• Green Chemistry provides a technical solution to
many environmental problems
• Effective due to design stage efforts, starting at the “We do so much to prepare our children
molecular level lets you design out the hazardous
properties and design in environmentally appropriate for the future, but are we doing enough
features.
to prepare the future for our children?”
• A systematic approach can ensure effective
application.
--Larry Chalfan
• Why Green Chemistry? Because we can….
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Contact: Green Chemistry Resources-Education
• Green Chemistry: Theory and Practice, by Paul T. Anastas & John C. Warner Oxford University
Press
• The 12 Principles of Green Chemistry:
http://www.acs.org/education/greenchem/principles.html
Larry Chalfan Dr. Lauren Heine
Executive Director Director, Green Chemistry and Engineering • UMASS Boston Green Chemistry: http://green.chem.umb.edu/
One World Trade Center
One World Trade Center 121 S.W. Salmon St., Ste 210 • Green Chemistry at the University of Oregon: http://www.uoregon.edu/~hutchlab/greenchem/
121 S.W. Salmon St., Ste 210 Portland, OR 97204
Portland, OR 97204 Tel: 503-279-9383
Tel: 503-279-9383 Fax: 503-279-9381 • ACS/EPA – Case Studies, Lab Modules: http://www.acs.org/education/greenchem/
Fax: 503-279-9381
lheine@zerowaste.org
lchalfan@zerowaste.org www.zerowaste.org
• Green Chemistry Institute: http://www.chemistry.org/greenchemistryinstitute/ or
www.zerowaste.org chemistry.org/portal/Chemistry?PID=acsdisplay.html&DOC=greenchemistryinstituteind
ex.html
• Green Chemistry Network: http://www.chemsoc.org/networks/gcn/about.htm
• University of Scranton, Green Chemistry Program:
http://academic.scranton.edu/faculty/CANNM1/greenchemistry.html
• Center for Green Manufacturing: http://bama.ua. edu/~cgm/
• Univ. of Illinois – Interdisciplinary Science and Techn. Program:
http://www.scs.uiuc.edu/~shapleyp/ISTP/ISTP-top.html
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Green Chemistry & Engineering Resources Related Resources
U.S. Enivironmental Protection Agency (EPA) • Environmental Science & Technology (journal subscription): http://pubs.acs.org/journals/esthag/
• Environmental Science and Technology Magazine (free online):
– EPA Green Chemistry Page: http://www.epa.gov/greenchemistry/index.htm ttp://pubs.acs.org/journals/esthag/index_magazine.html
• ToxFAQs (from Agency for Toxic Substances and Disease Registry):
– Presidential Green Chemistry Challenge: http://www.epa.gov/greenchemistry/presgcc.htm http://www.atsdr.cdc.gov/toxfaq.html
• Right-to-Know Network: http://www.rtk.net/
– Design for the Environment Home Page: http://www.epa.gov/opptintr/dfe
• Environmental Defense Environmental Scorecard: http://www.scorecard.org
• Journal of Chemical Education: http://jchemed.chem.wisc.edu/index.html
– U.S. EPA Green Engineering - www.epa.gov/opptintr/greenengineering/
• The Journal of Green Chemistry: http://www.rsc.org/is/journals/current/green/greenpub.htm
– Technology for a Sustainable Environment www.epa.gov/ncerqa/rfa/tse01.html • United Nations' Environmental Programme - Division of Technology, Industry, & Economics:
Case Studies of the Manufacture of Chemicals and Chemical Products
– Hancock Memorial Scholarship - www.epa.gov/greenchemistry/educat.htm http://www.emcentre.com/unepweb/tec_case/chemical_24/house/casestudy.shtml
• CleanEdge: The Clean-Tech Market Authority: http://www.cleanedge.com
Green Chemistry in Oregon • GreenBiz.com: The Resource Center on Business, the Environment and the Bottom Line:
http://www.greenbiz.com
– International Sustainable Development Foundation: http://www.isdf.org • The Alliance for Environmental Innovation: http://www.environmentaldefense.org/Alliance/
• Center for Waste Reduction Technologies - www.aiche.org/cwrt/
– Zero Waste Alliance: http://www.zerowaste.org
– Green Chemistry at the University of Oregon: http://www.uoregon.edu/~hutchlab/greenchem/
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