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Green Chemistry: Chemistry for the Long Haul Sustainable Chemistry

Green Chemistry: Chemistry for the Long Haul Sustainable Chemistry. Michael Cann Chemistry Department http://academic.scranton.edu/faculty/CANNM1/greenchemistry.html. Mission. “To advance the broader chemistry enterprise and its practitioners for the benefit of Earth and its people.”.

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Green Chemistry: Chemistry for the Long Haul Sustainable Chemistry

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  1. Green Chemistry:Chemistry for the Long HaulSustainable Chemistry Michael Cann Chemistry Department http://academic.scranton.edu/faculty/CANNM1/greenchemistry.html

  2. Mission “To advance the broader chemistry enterprise and its practitioners for the benefit of Earth and its people.” https://portal.acs.org/portal/acs/corg/memberapp?_nfpb=true&_ pageLabel=PP_ARTICLEMAIN&node id=1392&use_sec=false Michael C. Cann, University of Scranton

  3. Sustainability & Chemistry • The Chemistry Enterprise in 2015(A 2005 Report of the ACS), “By 2015, the chemistry enterprise will be judged under a new paradigm of sustainability. Sustainable operations will become both economically and ethically essential.” • “Chemical Society Presidents Pledge Support For Sustainable Development” (American, British, Japanese, German, French, Dutch), July 16, 2007, C&En • “I feel so strongly about sustainability and the vital role the chemistry enterprise will play in providing for a sustainable future that I selected "Sustainability of Energy, Food & Water" as the presidential theme for the March 2007 ACS national meeting in Chicago.” Catherine Hunt, ACS President, May 7, 2007, C&En Michael C. Cann, University of Scranton

  4. Sustainability • "Meeting the needs of the present without compromising the ability of future generations to meet their needs." (The U.N. Brundtland Commission 1987) Michael C. Cann, University of Scranton

  5. Sustainability?Consumption & WastePopulation Growth & Affluence Nature • Are we exceeding the carrying capacity of the earth? Are we using resources and creating waste faster that the earth can take our wastes and convert them back into resources? Using “natural capital” rather than just the interest. Resources Consumption Waste Humans Resources Consumption Waste Michael C. Cann, University of Scranton

  6. By Nation • There exists about 4.5 acres/person of biologically productive space on the earth http://www.earthday.net/footprint/index_reset.asp?pid=2066614043005642 Michael C. Cann, University of Scranton

  7. "I Want to be like Mike" Michael C. Cann, University of Scranton

  8. I Want to Be Like Mike! • “China's gross domestic product (GDP) surged by 10.7% in 2006 ….. fourth straight annual double-digit growth rate” • India 8.5% • World 5.1% • US 3.3% China Bureau National Statisticshttp://english.gov.cn/2007-01/25/content_507608.htm CIA World Fact Book https://cia.gov/library/publications/the-world-factbook/rankorder/2003rank.html Michael C. Cann, University of Scranton

  9. Population of the Earth • Exponential population growth ranks high on the list ofenvironmental threats • * 1 billion in 1804    * 2 billion in 1927 (123 years later)   * 3 billion in 1960 (33 years later)   * 4 billion in 1974 (14 years later)   * 5 billion in 1987 (13 years later)   * 6 billion in 1999 (12 years later)  • 2050 projections range from 7.5-11 billion • At 1% growth rate the US will double in population in 70 years Michael C. Cann, University of Scranton

  10. Sustainability -"Meeting the needs of the present generation without compromising the ability of future generations to meet their needs." • Enhanced global warming • Depletion of resources • Food shortages • Shortages of potable water • Housing • Waste How can chemistry contribute? Michael C. Cann, University of Scranton

  11. Lipitor $ 8.4 Zocor $ 4.4 Nexium $ 4.4 Prevacid $ 3.8 Plavix $ 3.5 Zoloft $ 3.1 Procrit $ 3.1 Rogaine Viagra Ibuprophen Nylon Dacron PET Polystyrene Acrylics Teflon Rayon Polyaniline “Better Things for Better Living Through Chemistry” DuPont • DNA • Recombinant • Technology • PCR Michael C. Cann, University of Scranton

  12. ENVIRONMENTAL DISASTERS • DDT • CFCs • Cuyahoga River • Love Canal Michael C. Cann, University of Scranton

  13. Chemical Ecological FootprintHow much land and water area the production, use and disposal of chemicals requires under prevailing technology.(environmental consequences of chemical products and the processes by which these products are made) We must lower our chemical ecological Footprint by improving the prevailing technology GREEN CHEMISTRY

  14. GREEN CHEMISTRY • Green Chemistry, or sustainable/environmentally benign chemistry is the design of chemical products and processes that reduce of eliminate the use and generation of hazardous substances • Minimize: • waste • energy use • resource use (maximize efficiency) • utilize renewable resources The Triple Bottom Line Michael C. Cann, University of Scranton

  15. The Twelve Principals of GREEN CHEMISTRY(Anastas and Warner 1998) 1. It is better to prevent waste than 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 whenever possible and, innocuous when used. 6. Energy requirements should recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure. Michael C. Cann, University of Scranton

  16. The Twelve Principals of GREEN CHEMISTRY (Anastas and Warner 1998) 7.A raw material feedstock should be renewable rather than depleting whenever technically and economically practical. 8. Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical processes) 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 chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires. Michael C. Cann, University of Scranton

  17. GREEN CHEMISTRY • Pollution Prevention Act 1990 • Roger Garret and Paul Anastas began the Alternative Synthetic Reactions Program in 1991 • Joe Breen coined "Green Chemistry" in 1993 • 1996 Presidential Green Chemistry Challenge Awards • 1997 Green Chemistry and Engineering Conference • 1999 Journal “Green Chemistry” • Chemical and Engineering News • 2000 GCI integrated into ACS • 2000 Journal of Chemical Education Michael C. Cann, University of Scranton

  18. 'Green chemistry' work wins Nobel –CNN 10/5/05 “France's Yves Chauvin and Americans Robert H. Grubbs and Richard R. Schrockwon the award for their development of the metathesis method in organic synthesis.” “This represents a great step forward for 'green chemistry,' reducing potentially hazardous waste through smarter production. Metathesis is an example of how important basic science has been applied for the benefit of man, society and the environment,……" Michael C. Cann, University of Scranton

  19. Examples of Green Chemistry Presidential Green Chemistry Challenge Award Winners • New syntheses of Ibuprofen and Zoloft. • Integrated circuit production. • Removing Arsenic and Chromate from pressure treated wood. • Many new pesticides; Harpin • New oxidants for bleaching paper and disinfecting water. • Getting the lead out of automobile paints. • Recyclable carpeting. • Replacing VOCs and chlorinated solvents. • Lowering of trans fats in oils. • Biodegradable polymers from renewable resources. • Replacing petroleum based polymers with cellulose (ionic liquids) Michael C. Cann, University of Scranton

  20. Consider Your Coating’s Life Cycle Green chemistry can be applied to each step of a coating’s life cycle: feedstock synthesis & formulation process & application end of life consumer Replace petroleum-based, non-renewable, toxic, etc. Replace petroleum-based, hazardous chemicals, solvents, etc. Prevent waste, reduce energy use, reduce hazards to workers, etc. Prevent exposure to VOCs, endocrine disruptors, etc. Prevent frequent re-applications of coating, waste; recycle unused materials, use biodegradable materials, etc. Consider how the 12 Principles of Green Chemistry & Green Engineering fit into your coatings work. Michael C. Cann, University of Scranton

  21. GREEN CHEMISTRY • Antifoulants (algae and seaweed; • barnacles and diatoms) Michael C. Cann, University of Scranton

  22. Antifoulants • TBTO • Half-life of TBTO in seawater is > 6 months • Bioconcentration, 104 • Chronic Toxicity • Thickness of oyster shells • Sex changes in whelks • Imposex in snails • Immune system in dolphins and others? Michael C. Cann, University of Scranton

  23. Antifoulants • DCOI(Rohm and Haas, PGCC 1996 winner) • Acutely toxic to a wide range of marine organisms (effective anitfoulant) • Rapid biodegradation to nontoxic products (½ life < 1 hour) • Low Bioconcnetration (bioconcentration =13) • Environmental Conc. < Acute Toxicity level • No Chronic Toxicity • Rapid partitioning to the sediment (low bioavailability) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one Michael C. Cann, University of Scranton

  24. Lead in Electrodeposition Coatings • Due to high toxicity of lead compounds, significant regulatory pressures on its use • Demand for corrosion resistance in automobiles has increased steadily • With no satisfactory substitute for lead electrocoat has been routinely exempted from environmental regulations Michael C. Cann, University of Scranton

  25. Yttrium in Place of Lead in Electrodeposition CoatingsPPG, PGCC winner, 2001 • Y twice as effective as Pb (use half the amount); eliminates about 1 million lb of lead • Yttrium widely distributed in earth crust in low amounts although in higher concentrations than lead or silver • Lower (by orders of magnitude) less toxic that analogous compounds of lead • e.g. Yttrium oxide (active compound in electrodeposited paint) oral LD50>10g/kg in rats • Eliminates the necessity of the use of chromium and nickel metal pretreatments –results in elimination of >25,000 lb of chrome and >50,000 lb of nickel/year Michael C. Cann, University of Scranton

  26. UV-Curable Coatings and Eco-Efficiency Tool – BASF PGCC 2005 winner • BASF has developed a new urethane acrylate oligomer that crosslinks (cures) by visible, UV, or sun light in minutes • The polymer is used as a primer (first layer) in automotive repair painting • Green attributes: reduced VOC, reduced energy consumption (no oven bake drying), reduced waste generated during application, and less safety protection required compared to traditional isocyanate-based coatings • Physical property attributes: more durable, controls corrosion better, and has unlimited shelf-life Michael C. Cann, University of Scranton

  27. Preservation of Wood • 4 billion dollar industry • Industry annually pressure treats greater than 7 billion board feet wood (about 1/5 of all softwood lumber sold) • Untreated wood rots in 3-12 years, treated wood 20-50 • Without treatment $15 billion dollar increase in lumber production (transportation, construction and utility industries) • Estimates indicate about 6.5 billion board feet of wood conserved each year in the US (435,000 new houses, or 226,000,000 trees) Michael C. Cann, University of Scranton

  28. Production of Pressure Treated Wood (PTW) • > 95% PTW was treated with CCA, 2001 7 billion board feet of PTW produced (about 1/5 of all softwood lumber sold) • 150 million pounds of CCA • 40 million pounds of arsenic • 64 million pounds of hexavalent chromium • Wood is placed in a vacuum (depletes wood cells of air and water); CCA solution is applied under pressure infiltrating the wood Michael C. Cann, University of Scranton

  29. Production of PTW • Typical CCA solution: 35.3% CrO3; 19.6% CuO; 45.1% As2O3 • Cu, Cr and As levels in the wood 1000-5000mg/kg • 8x10 deck, 4 lb metals (1.9 lb Cr, 1.36 As, 0.74 lb Cu) Michael C. Cann, University of Scranton

  30. Potential Risks Associated with PTW • Arsenic leaching from PTW • Ingestion from contact with PTW • Risk to workers in the production of PTW • Waste generated from PTW production • Disposal of PTW (burned, mulched) • Hazards associated with transportation, production, use and disposal of CCA components http://www.cnn.com/2001/HEALTH/parenting/05/23/arsenic.playgrounds/index.html Michael C. Cann, University of Scranton

  31. Michael C. Cann, University of Scranton

  32. Removing the Arsenic and Chromium from PTW 2002Chemical Specialties Inc • ACQ (Alkaline Copper Quarternary Ammonium Compound) Preserve, Chemical Specialties Inc (CSI) • Similar copper formulations are used in controlling algae in various water systems; Quaternary ammonium salts are routinely used in disinfectants and cleaners • Low mammalian toxicity to the copper and ammonium salts (LD50=730 – 800 mg/kg; about the same as salt and ethanol) in ACQ • Disposal of ACQ treated wood: may be disposed of in general landfills Michael C. Cann, University of Scranton

  33. GREEN CHEMISTRY • Major Focus: Replacement of organic solvents -VOCs, halogenated, almost 15 billion kilograms produced worldwide each year • Solvent free • Solvent alternatives: • Ionic liquids • Fluorous • Carbon dioxide Michael C. Cann, University of Scranton

  34. GREEN CHEMISTRY • Dry Cleaning • Initially gasoline and kerosene were used • Chlorinated solvents are now used, such as perc • Supercritical/liquid carbon dioxide (CO2) Michael C. Cann, University of Scranton

  35. Solubility of Substances in CO2 • Carbon dioxide a non polar molecule since the dipoles of the two bonds cancel one another. • Carbon dioxide will dissolve smaller non polar molecules • hydrocarbons having less than 20 carbon atoms • other organic molecules such as aldehydes, esters, and ketones • But it will not dissolve larger molecules such as oils, waxes, grease, polymers, and proteins, or polar molecules. Michael C. Cann, University of Scranton

  36. Surfactant Michael C. Cann, University of Scranton

  37. CO2 Surfactant:Joe DeSimone, UNC, NCSU, NSF Science and Technology Center for Environmentally Responsible Solvents and Processes, PGCC Award 1997

  38. CO2 Surfactant Michael C. Cann, University of Scranton

  39. http://www.hangersdrycleaners.com/ Michael C. Cann, University of Scranton

  40. Environmental/Economic Advantages of Liquid CO2 • Using CO2 eliminates hazardous waste generation of perc. • CO2 does not pose the environmental and human health risks associated with perc (used by 34,000 dry cleaners in US). • Using CO2 reduces environmental regulatory burdens for Hangers operators. • Uses waste CO2 from other processes. Michael C. Cann, University of Scranton

  41. Ionic Liquids & Microwave Heating to Dissolve/Process CelluloseRobin Rogers, Alabama, PGCC winner2005 30 billion tons of cellulose is produced naturally by terrestrial plants Michael C. Cann, University of Scranton

  42. Green Chemistry Endeavorsat Scranton • “Real-World Cases in Green Chemistry,” Volume I & II • Web-based Green Chemistry Modules =Spanish & Portuguese. • “Greening” existing chemistry textbooks. • “Environmental Chemistry.” Baird & Cann, 4th edition • Other Freeman texts • “Chemistry for Changing Times,” Hill & Kolb, Prentice Hall • “Organic Chemistry,” Solomons & Fryhle, Wiley • “Chemistry Foundations and Applications,” Macmillan • “Chemistry in Context,” ACS • The business side of green chemistry. • Infusion into business courses • Bringing green chemistry to the high school and secondary school level. • Integrating sustainability throughout our campus http://matrix.scranton.edu/sustainability/default.shtml Michael C. Cann, University of Scranton

  43. Acknowledgements • Marc Connelly, Tom Umile • The “Green Machine:” Trudy Dickneider, Tim Foley, David Marx, Donna Narsavage-Heald, Joan Wasilewski • Camille and Henry Dreyfus Foundation • American Chemical Society: Sylvia Ware, Mary Kirchhoff, Janet Boese, Mary Ann Ryan • Environmental Protection Agency: Tracy Williamson, Rich Engler • Green Chemistry Institute: Kathryn Parent • Center for Green Chemistry and Engineering at Yale: Paul Anastas • Universidad de Las Palmas de Gran Canaria, Maria de la Concepcion, Sebastian Perez • Universidade Federal de Pelotas (UFPel)Eder J. Lenardãoa & Colleagues Michael C. Cann, University of Scranton

  44. Michael C. Cann, University of Scranton

  45. Michael C. Cann, University of Scranton

  46. Michael C. Cann, University of Scranton

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