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Introduction to Green Chemistry

Introduction to Green Chemistry. Mary Kirchhoff Associated Colleges of the Chicago Area 16 September 2003. Green Chemistry. Green Chemistry is the design of chemical products and processes that reduce or eliminate the use and/or generation of hazardous substances.

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Introduction to Green Chemistry

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  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 NWPAA 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 CAAA CWA SMCRA SWRCA SDWAA ARPA MPRSAA Number of Laws BLBA FWPCA MPRSA CZMA NCA FEPCA PWSA MMPA 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 FIFRA AEPA PAA NHPA 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 SustainabilitySource: R. R. Bezdek., MISI - 1999

  6. Pollution Prevention Act of 1990 PollutionPrevention SourceReduction Recycling Treatment Disposal

  7. 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.

  9. 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

  10. 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 EPA’s 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

  11. 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.

  12. Presidential Green Chemistry Challenge Awards • Alternative synthetic pathways • Alternative reaction conditions • Designing safer chemicals • Academic • Small business

  13. 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

  14. Principle 1It is better to prevent waste than to treat or clean up waste after it is formed.

  15. 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

  17. 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%

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

  19. Principle 2: Atom economy • Traditional synthesis of ibuprofen • 6 stoichiometric steps • <40% atom utilization

  20. 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.

  22. Principle 3: Non-toxic substances • Disadvantages • phosgene is toxic, corrosive • requires large amount of CH2Cl2 • polycarbonate contaminated with Cl impurities

  23. Principle 3: Non-toxic substances • Advantages • diphenylcarbonate synthesized without phosgene • eliminates use of CH2Cl2 • higher-quality polycarbonates • Komiya et al., Asahi Chemical Industry Co.

  24. 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

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

  26. 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

  28. 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.

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

  31. 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

  33. Reactions in Supercritical Fluids • Formation of cyclic ethers • Hydrogenation Poliakoff, University of Nottingham

  34. 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

  36. 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.

  37. 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)

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

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

  40. Adipic Acid Synthesis • Contributes 2% anthropogenic N2O/year

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

  42. 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

  44. 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.

  46. 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.

  49. 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

  50. Principle 9: Catalysis

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