Introduction to Green Chemistry

1
Introduction to Green Chemistry

• Mary Kirchhoff
• Associated Colleges of the Chicago Area
• 16 September 2003

2
Green Chemistry

• Green Chemistry is the design of chemical
  products and processes that reduce or eliminate
  the use and/or generation of hazardous substances.

3
Historical Approach to Environmental Problems

• Waste treatment, control, and disposal pollutant
  monitoring hazardous waste site cleanup.
• Development of standards for emissions to air,
  releases to water, and disposal by land, as well
  as regulation of these standards.
• Command and Control

4
Growth in Environmental Regulation
EPACT FFCA CERFA CRAA
PPA PPVA IEREA ANTPA GLCPA ABA CZARA WRDA EDP OPA
RECA CAAA GCRA GLFWRA HMTUSA NEEA
AMFA ARPAA AJA ASBCAA ESAA-AECA FFRAA FEAPRA IRA N
WPAA CODRA/NMSPAA FCRPA MMPAA
120 110 100 90 80 70 60 50 40 30 20 10 0
AQA
NAWCA
RCRAA WLDI
APA SWDA CERCLA CZMIA COWLDA FWLCA MPRSAA
WQA
SDWAA SARA
NWPA
BLRA ERDDAA EAWA NOPPA PTSA UMTRCA ESAA QGA NCPA
ARPA
CAAA CWA SMCRA SWRCA SDWAA
MPRSAA
BLBA FWPCA MPRSA CZMA NCA FEPCA PWSA MMPA
Number of Laws
HMTA
TSCA FLPMA RCRA NFMA CZMAA
ESA TAPA
FRRRPA SOWA DPA
NEPA EQIA CAA EPA EEA OSHA FAWRAA NPAA
AQA FOIA
FCMHSA
WRPA AFCA
FHSA NFMUA
WSRA EA RCFHSA
TA FWCA BPA
AEPA
FIFRA
NHPA
PAA
WLDA
WA
FWCAA
NBRA
MBCA
NPS
FAWRA
FWA
IA
AEA
AA
RHA
NLRA WPA
YA
1870 1880 1890 1900 1910 1920 1930 1940 1950 1960
1970 1980 1990 2000
5
Environmental Expenditures Economic
Sustainability Source R. R. Bezdek., MISI -
1999
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Pollution Prevention Act of 1990
PollutionPrevention
SourceReduction
Recycling
Treatment
Disposal
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Green Chemistry

• Green Chemistry is the design of chemical
  products and processes that reduce or eliminate
  the use and/or generation of hazardous substances.

8
Characterization of Environmental Problems
Risk f(hazard x exposure) Traditionally, risk
management has focused on exposure rather than
hazard.
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Circumstantial vs. Intrinsic Recognize hazard as
a design flaw

• Circumstantial
• Use
• Exposure
• Handling
• Treatment
• Protection
• Recycling
• Costly

• Intrinsic
• Molecular design for reduced toxicity
• Reduced ability to manifest hazard
• Inherent safety from accidents or terrorism
• Increased potential profitability

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Why Green Chemistry?

• Business is going to get significantly more
  profitable through the application of green
  technology. Proactive companies are finding the
  theme good for business to be credible and
  real.
• Paul V. Tebo, Vice President for Safety,
  Health, and Environment, DuPont
• We have found that voluntary environmental
  improvements - as encouraged by programs like
  EPAs Green Chemistry Challenge ... - can return
  as much as 53 on capital, compared with a
  negative 16 when improvements are mandated by
  law.
• William S. Stavropoulos, President and Chief
  Executive Officer, The Dow Chemical Company

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Presidential Green Chemistry Challenge

• Goal To promote pollution prevention and
  industrial ecology through a new EPA Design for
  the Environment partnership with the chemical
  industry.
• Challenge To find cleaner, cheaper, and smarter
  ways to manufacture the products that we depend
  on.

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Presidential Green Chemistry Challenge Awards

• Alternative synthetic pathways
• Alternative reaction conditions
• Designing safer chemicals
• Academic
• Small business

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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

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Principle 1It is better to prevent waste than
to treat or clean up waste after it is formed.
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Redesign of the Sertraline Process

• Sertraline active ingredient in Zoloft
• Combined process
• Doubled yield
• Ethanol replaced CH2Cl2, THF, toluene, and hexane
• Eliminated use of 140 metric tons/year TiCl4
• Eliminated 150 metric tons/year 35 HCl
• Pfizer

16
Redesign of the Sertraline Process
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Principle 1 Waste prevention

• Cytovene
• antiviral agent used in the treatment of
  cytomegalovirus (CMV) retinitis infections
• AIDS and solid-tissue transplant patients
• Improved synthesis
• reduced chemical processing steps from 6 to 2
• reduced number of reagents and intermediates from
  22 to 11
• eliminated 1.12 million kg/year liquid waste
• eliminated 25,300 kg/year solid waste
• increased overall yield by 25

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Principle 2Synthetic methods should be designed
to maximize the incorporation of all materials
used into the final product.
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Principle 2 Atom economy

• Traditional synthesis of ibuprofen
• 6 stoichiometric steps
• lt40 atom utilization

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Principle 2 Atom economy

• Catalytic synthesis of ibuprofen
• 3 catalytic steps
• 80 atom utilization (99 with recovered acetic
  acid)
• BHC

21
Principle 3Wherever practicable, synthetic
methodologies should be designed to use and
generate substances that possess little or no
toxicity to human health and the environment.
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Principle 3 Non-toxic substances

• Disadvantages
• phosgene is toxic, corrosive
• requires large amount of CH2Cl2
• polycarbonate contaminated with Cl impurities

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Principle 3 Non-toxic substances

• Advantages
• diphenylcarbonate synthesized without phosgene
• eliminates use of CH2Cl2
• higher-quality polycarbonates
• Komiya et al., Asahi Chemical Industry Co.

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Alternative Synthetic Pathways

• Sodium iminodisuccinate
• Biodegradable, environmentally friendly chelating
  agent
• Synthesized in a waste-free process
• Eliminates use of hydrogen cyanide
• Bayer Corporation and Bayer AG
• 2001 Alternative Synthetic Pathways Award
  Winner

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Principle 4Chemical products should be designed
to preserve efficacy of function while reducing
toxicity.
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Principle 4 Reduce Toxicity

• Spinosad a natural product for insect control
• produced by Saccharopolyspora spinosa
• isolated from Caribbean soil sample
• demonstrates high selectivity, low toxicity
• Dow AgroSciences

27
Designing Safer Chemicals

• Cationic electrodeposition coatings containing
  yttrium
• Provides corrosion resistance to automobiles
• Replaces lead in electrocoat primers
• Less toxic than lead and twice as effective on a
  weight basis
• PPG Industries
• 2001 Designing Safer Chemicals Award Winner

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Small Business Award

• PYROCOOL Technologies, Inc.
• PYROCOOL F.E.F. (Fire Extinguishing Foam)
• 0.4 aqueous mixture of highly biodegradable
  nonionic surfactants, anionic surfactants, and
  amphoteric surfactants
• replacement for halon gases and aqueous film
  forming foams (AFFFs)

29
ACQ Wood Preservatives

• Pressure-treated lumber
• 7 million board feet/year
• chromated copper arsenate (CCA) preservative
• 40 million pounds of arsenic
• 64 million pounds of hexavalent chromium
• Alkaline Copper Quaternary (ACQ) wood
  preservative
• Bivalent copper complex plus quaternary ammonium
  compound dissolved in ethanolamine of ammonia
• Virtually eliminates use of arsenic in US
• Avoids production, transportation, use, and
  disposal risks associated with CCA
  
• Chemical Specialties, Inc.

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Principle 5The use of auxiliary substances
(e.g. solvents, separation agents, etc.) should
be made unnecessary wherever possible and,
innocuous when used.
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Principle 5 Benign solvents

• Carbon-carbon bond formation in water
• Diels-Alder, Barbier-Grignard, pericyclic
• Indium-mediated cyclopentanoid formation
• Li, Tulane University

32
Research to Commercialization Thomas Swan Co
Ltd

• Multi-purpose plant using supercritical fluids
• First full-scale facility for continuous,
  multi-purpose synthesis, including
• Hydrogenations
• Friedel-Crafts reactions
• Hydroformylations
• Etherifications
• Technology developed with the University of
  Nottingham

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Reactions in Supercritical Fluids

• Formation of cyclic ethers
• Hydrogenation
• Poliakoff, University of Nottingham

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CO2 for Dry Cleaning

• Dry Cleaning
• current process uses perc (perchloroethylene), a
  suspected carcinogen and groundwater contaminant
• new process uses liquid carbon dioxide, a
  nonflammable, nontoxic, and renewable substance

35
Non-Fluorous CO2-Philic Materials

• Replacement for expensive, persistent fluorous
  CO2-philes
• New CO2-philes needed to expand commercial
  applications of CO2
• Poly(ether-carbonates)
• Lower miscibility pressures than
  perfluoropolyethers
• Biodegradable
• 100 times less expensive
• Beckman, University of Pittsburgh

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Principle 6Energy requirements should be
recognized for their environmental and economic
impacts and should be minimized. Synthetic
methods should be conducted at ambient
temperature and pressure.
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Principle 6 Minimize energy usage

• Catalytic synthesis of ULTEM thermoplastic resin
• 25 less energy required to produce each pound of
  resin
• volume of organic waste stream for off-site
  disposal decreased by 90
• 50 less catalyst used
• GE Plastics (General Electric Corporation)

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Alternative products

• Thermal Polyaspartic Acid (TPA)
• catalytic polymerization process
• biodegradable polymer
• substitute for non-biodegradable polyacrylic acid
  (PAC)
• Donlar Corporation

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Principle 7A raw material of feedstock should
be renewable rather than depleting wherever
technically and economically practicable.
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Adipic Acid Synthesis

• Contributes 2 anthropogenic N2O/year

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Adipic Acid Synthesis

• Recycles nitrous oxide into adipic acid synthesis
• new pathway to phenol
• Solutia, Inc.

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Adipic Acid Synthesis

• No nitrous oxide generated
• Renewable feedstock replaces petroleum-based
  feedstock
• Draths and Frost, Michigan State

43
Principle 7 Renewable feedstocks

• Conversion of waste biomass to levulinic acid
• paper mill sludge, municipal solid waste,
  unrecyclable waste paper, agricultural residues
• Biofine, Incorporated

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Principle 7 Renewable feedstocks

• CO2 feedstock in polycarbonate synthesis
• Improved Zn catalyst yields faster reaction, uses
  milder reaction conditions
• Coates et al., Cornell University

45
Principle 8Unnecessary derivatization (blocking
group, protection/deprotection, temporary
modification of physical/chemical processes)
should be avoided whenever possible.
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Boric Acid-Mediated Amidation

• Direct amidation of carboxylic acids with amines
• Boric acid nontoxic, safe, inexpensive
• Eliminates use of SOCl2, PCl3, phosgene
• Widely applicable
• Emisphere
  Technologies, Inc

47
Principle 8 Derivatization

• Enzymatic synthesis of cephalexin
• eliminates protection/deprotection of functional
  groups

48
Principle 9Catalytic reagents (as selective as
possible) are superior to stoichiometric reagents.
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Principle 9 Catalysis

• Improved synthesis of a central nervous system
  compound
• interdisciplinary approach, combining chemistry,
  microbiology, and engineering
• For every 100 kg product,
• 300 kg chromium waste eliminated
• 34,000 liters solvent eliminated
• Eli Lilly and Company

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Principle 9 Catalysis
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Principle 9 Catalysis

• Synthesis of disodium iminodiacetate (DSIDA)
• filter catalyst from waste stream, no additional
  purification required
• Replacement for the Strecker process
• utilized NH3, CH2O, HCN, HCl
• Monsanto Company

52
Principle 10Chemical 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.
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Polylactic Acid

• Manufactured from renewable resources
• Corn or wheat agricultural waste in future
• Uses 20-50 fewer fossil fuels than conventional
  plastics
• PLA products can be recycled or composted
• Cargill Dow

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Alternative solvents

• Solvent-free synthesis of polylactic acid
  polymers (PLA)
• lactic acid obtained from corn and sugar beets
• condensation of aqueous lactic acid yields PLA
  pre-polymer
• pre-polymer thermally depolymerized into L- and
  meso-lactide diastereomers
• tin-catalyzed ring opening polymerization of
  lactide produces PLA high polymer
• Cargill Dow Polymers LLC

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Alternative products

• Eastman Biodegradable Copolyester 14766
• copolyester of adipic acid, terephthalic acid,
  and 1,4-butanediol
• totally biodegrades to H2O, CO2, biomass
• reduces waste sent to landfills and incinerators
• Eastman Chemical Company

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Principle 11Analytical methodologies need to be
further developed to allow for real-time,
in-process monitoring and control prior to the
formation of hazardous substances.
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Principle 11 Real Time Analysis

• 1999 10 million environmental samples analyzed
• Analysis in support of state and federal
  regulatory programs used more than 2 million
  gallons of solvent
• Spent waste solvent disposal cost is about 51
  million

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Principle 11 Real Time Analysis

• Ion Fingerprint Detection (IFD) software
• MS peak deconvolution algorithms
• Rapidly identifies and quantifies EPA targeted
  compounds by GC/MS
• Sample cleanup not required in the presence of
  other targets and contamination
• 90 solvent reduction for GC/MS analysis
• 50 solvent elimination for LC/MS analysis
• 10-fold productivity gains
• Robbat, Jr.

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Principle 12Substances and the form of a
substance used in a chemical process should be
chosen so as to minimize the potential for
chemical accidents, including releases,
explosions, and fires.
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Principle 12 Minimize hazard
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Principle 12 Minimize hazard

• Catalytically synthesize methylisocyanate to
  reduce risk of exposure
• eliminates use of phosgene
• Manzer, DuPont

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Green Chemistry

• Not a solution to all environmental problems.
• The most fundamental approach to preventing
  pollution.
• Recognizes the importance of incremental
  improvements.

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2004 Green Chemistry Events

• 227th ACS Meeting, March 2004, Anaheim
• Joe Breen Student Poster Session
• Innovations in Green Chemistry Education
• 8th Annual Green Chemistry and Engineering
  Conference
• June 29 July 1, Washington, DC
• Gordon Research Conference on Green Chemistry
• July 4-9, Bristol, RI
• PRF Summer School on Green Chemistry

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Student Affiliates

• Host a green chemistry speaker
• Develop a green chemistry activity with a local
  school
• Organize a green chemistry poster session on
  campus
• Work with a local company on a green chemistry
  project
• Make a current lab experiment greener
• Design a green chemistry web page

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Student Affiliates

• Benefits
• Recognition at the Student Affiliates Chapter
  awards ceremony at the spring ACS meeting
• Information on green chemistry internships and
  research opportunities
• Copies of green chemistry materials
• Connections to faculty engaged in green chemistry
  research

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Green Chemistry Institute

• Working Today to Prevent Pollution Tomorrow
  Through
• Information Dissemination
• Chemical Education
• Awards and Recognition
• Conferences and Symposia
• Research and Fellowships
• International Outreach

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The Major Challenges to Sustainability

• Population
• Energy
• Global Change
• Resource Depletion
• Food Supply
• Toxics in the Environment

• Population
• Energy
• Global Change
• Resource Depletion
• Food Supply
• Toxics in the Environment

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Population

• Empirical data shows that increased quality of
  life correlates with sustainable population
  control.
• Increased quality of life, however, has
  historically resulted in increased damage to the
  biosphere and the earths ability to sustain life.

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Population

• The challenge How to increase quality of life
  while minimizing detrimental effects to human
  health, the environment and the biosphere.
• The solution Green chemistry provides a
  mechanism to addressing this challenge in very
  real terms.

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Energy

• The vast majority of the energy generated in the
  world today is from non-renewable sources that
  damage the environment.
• Carbon dioxide
• Depletion
• Effects of mining, drilling, etc
• Toxics

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Energy

• Green Chemistry will be essential in
• developing the alternatives for energy
  generation (photovoltaics, hydrogen, fuel cells,
  biobased fuels, etc.) as well as
• continuing the path toward energy efficiency
  with catalysis and product design at the
  forefront.

72
Global Change

• Concerns for climate change, oceanic temperature,
  stratospheric chemistry and global distillation
  can be addressed through the development and
  implementation of green chemistry technologies.

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Alternative Solvents/Reaction Conditions Award

• CO2 blowing agent for manufacture of polystyrene
  foam sheet packaging
• eliminates 3.5 million pounds/year of
  chlorofluorocarbon blowing agents
• carbon dioxide obtained from existing by-product
  commercial and natural sources, no net increase
  in global CO2
• The Dow Chemical Company

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Resource Depletion

• Due to the over utilization of non-renewable
  resources, natural resources are being depleted
  at an unsustainable rate.
• Fossil fuels are a central issue.

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Resource Depletion

• Renewable resources can be made increasingly
  viable technologically and economically through
  green chemistry.
• Biomass
• Nanoscience technology
• Solar
• Carbon dioxide
• Chitin
• Waste utilization

76
Food Supply

• While current food levels are sufficient,
  distribution is inadequate
• Agricultural methods are unsustainable
• Future food production intensity is needed.
• Green chemistry can address many food supply
  issues

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Food Supply

• Green chemistry is developing
• Pesticides which only affect target organisms
  and degrade to innocuous by-products.
• Fertilizers and fertilizer adjuvants that are
  designed to minimize usage while maximizing
  effectiveness.
• Methods of using agricultural wastes for
  beneficial and profitable uses.

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Toxics in the environment

• Substances that are toxic to humans, the
  biosphere and all that sustains it, are currently
  still being released at a cost of life, health
  and sustainability.
• One of green chemistrys greatest strengths is
  the ability to design for reduced hazard.