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  • 1. We’re not going to talk about green buildings, biodegradable packaging, or bio-based renewables – those are for other webinars
  • Mention Paul Anastas
  • Notice the safety theme here
  • Ibuprofen by the Boots Process (UK) used 43 H atoms, 20 C atoms, 1 N, 1 Cl, 1 Na, 10 O atoms to produce Ibuprofen C13H18O2. 43 out of 75 input atoms are wasted. Ibuprofen by the improved 3 step BHC Process (UK) used 22 H atoms, 15 C atoms,and 4 O atoms to produce Ibuprofen C13H18O2. only 9 out of 41 input atoms are wasted.
  • Carbon dioxide is in its supercritical fluid state when both the temperature and pressure equal or exceed the critical point of 31°C and 73 atmos. In its supercritical state, CO 2 has both gas-like and liquid-like qualities, and it is this dual characteristic of supercritical fluids that provides the ideal conditions for extracting compounds with a high degree of recovery in a short period of time. By controlling or regulating pressure and temperature, the density, or solvent strength, of supercritical fluids can be altered to simulate organic solvents ranging from chloroform to methylene chloride to hexane. This dissolving power can be applied to purify, extract, fractionate, infuse, and recrystallize a wide array of materials. Because CO 2 is non-polar, a polar organic co-solvent (or modifier) can be added to the supercritical fluid for processing polar compounds. By controlling the level of pressure/temperature/modifier, supercritical CO2 can dissolve a broad range of compounds, both polar and non-polar. SCO2 is used widescale in the decaffeination of coffee. SCO2 is a medium in which to perform safer hydrogenation reactions. Supercritical water is water at temperatures above 374 deg. C and 220 atmospheres. It behaves both as a gas and as a liquid, like other supercritical fluids. One interesting use is the supercritical water oxidation of hazardous materials such as PCBs. In supercritical conditions, the behavior of water as a solvent is altered (in comparison to that of subcritical liquid water) - it behaves much less like a polar solvent. As a result, the solubility behavior is "reversed" so that chlorinated hydrocarbons become soluble in the water, allowing single phase reaction of aqueous waste with a dissolved oxidizer. Salts also precipitate out of solution, meaning they can be treated using conventional methods for solid-waste residuals. Efficient oxidation reactions occur at low temperature (400-650 °C). Ionic liquids are low melting point salts. They have no vapor pressure, and are chemically and thermally stable. Viscosities are only slightly higher than conventional solvents. Apart from chlorinated examples most are non-corrosive. They are currently expensive Ionic liquids can be used as extremely selective solvents for liquid-liquid extraction – aromatics (BTX) from reformate aromatic/alephatic mixtures Ionic liquids can be used as a medium for a variety of organic reactions, many at room temperature
  • Note the Safety Theme Note the similarities with GC 12 Principles - Eng #1 like Chem #2, Eng #2 like Chem #1, Eng #7 like Chem #10 etc
  • Don’t design for imortality

Transcript

  • 1. American Institute of Chemical Engineers – Delaware Valley Section An Introduction to Green Chemistry and Engineering November 18 th 2011 Ken Rollins CEng, FIChemE
  • 2. American Institute of Chemical Engineers – Delaware Valley Section
    • What is green chemistry and what is green engineering?
    • Green chemistry/green engineering is concerned with the design and use of processes and products that are feasible and economical while minimizing the risk to human health and the environment, and the generation of pollution at source.
  • 3. American Institute of Chemical Engineers – Delaware Valley Section
    • The Twelve Principles of Green Chemistry
    • Prevent Waste
    • Safer Chemicals and Products
    • Less Hazardous Chemical Syntheses
    • Use Renewable Feedstocks
    • Use Catalytic Reactions
    • Avoid Chemical Derivatives
    • Maximise Atom Economy
    • Safer Solvents and Reaction Conditions
    • Increased Energy Efficiency
    • Design Chemicals to Degrade after Use
    • Pollution using Real Time Analysis
    • Minimize Accident Potential
  • 4. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #1 - Prevent Waste
    • Design chemical syntheses to prevent waste. Leave no waste to treat or to clean up
  • 5. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #2 – Safer Chemicals & Products
    • Design chemicals/products to be fully effective but with little or no toxicity
  • 6. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #3 - Less Hazardous Chemical Syntheses
    • Design reactions to use and/or generate chemicals with little or no toxicity to humans, and with low environmental impact
  • 7. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #4 - Use Renewable Feedstocks
    • Use raw materials that are renewable rather than depleting. Bio-based materials or other processes’ waste materials, rather than fossil-based materials – oil, coal
  • 8. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #5 - Use Catalytic Reactions
    • Catalysts are renewable and can be re-used many times, in preference to the use of excess stoichiometric reagents which generate wstes
  • 9. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 6 - Avoid Chemical Derivatives
    • Avoid chemical derivatives used as ‘temporary by-products’, which generate wastes
  • 10. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 7 – Maximize Atom Economy
    • The final product should contain the maximum number of atoms in the the starting materials
  • 11. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 8 – Use Safer Solvents and Reaction Conditions
    • Avoid solvents if possible. Consider using water or other innocuous materials. Minimize
  • 12. American Institute of Chemical Engineers – Delaware Valley Section
    • Alternate ‘Green’ Solvents
    • Supercritical Carbon Dioxide
    • Supercritical Water
    • Ionic Liquids
    • .
  • 13. American Institute of Chemical Engineers – Delaware Valley Section
    • Biomimicry
    • Imitate Mother Nature ?
    • How about a material with the strength of a Spider’s web ?
    • One of Paul Anastas’ examples. A glue that mimicked the adhesive power of a limpet ?
  • 14. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 9 – Increased Energy Efficiency
    • Operate at ambient temperature and atmospheric pressure where possible
  • 15. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 10- Design Chemicals to Degrade after Use
    • Choose materials that will degrade after use rather than those that will accumulate in the environment
  • 16. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 11- Analyze in Real Time
    • Use real time process analysis to monitor and control reactions rather than historical data
  • 17. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle # 12 - Minimize Accident Potential
    • Minimize the potential for fires, explosions and other hazards by selection of chemicals and their forms (gas/liquid ?)
  • 18. American Institute of Chemical Engineers – Delaware Valley Section
    • ACS – GCI Pharma Roundtable
    • Much of the work in promoting green chemistry and engineering is undertaken by the Green Chemistry Institute – an arm of the American Chemistry Society.
    • Together with most of the major pharmaceutical manufacturers, they have established the ACS GCI Pharma Roundtable to catalyze the implementation of green chemistry and green engineering within that industry
  • 19. American Institute of Chemical Engineers – Delaware Valley Section
    • Concept of Process Mass Intensity
    • One of the concepts to come out of the ACS GCI Pharma Roundtable is that of Process Mass Intensity. This is defined as the summation of the mass of all materials used in a process, including water, catalysts, solvents and reagents, divided by the mass of product. The PMI index is used as an indication of ‘greenness’
    • In the petroleum industry this PMI has a value a little over unity, and increases through general chemicals and specialty chemicals industries. The pharmaceutical industry demonstrates the highest PMIs – often over 100
  • 20. American Institute of Chemical Engineers – Delaware Valley Section
    • ACS-GCI Solvent Selection Guide
    • The Roundtable has also published, in April 2011, a Solvent Selection Guide. Industrial organic solvents are assessed in terms of safety, health, environmental impact on air, water, and waste. These assessments are ranked on a scale of 1- 10, with 1 being the most desirable and 10 the least. This guide is color coded with scores of 1-3 in green, 4-7 yellow and 8-10 in red.
  • 21. American Institute of Chemical Engineers – Delaware Valley Section
  • 22. American Institute of Chemical Engineers – Delaware Valley Section
    • GCN & NNFCC in the UK
    • Two leading promoters of Green Chemistry and Engineering in the UK
    • Green Chemistry Network – based out of the University of York
    • National Non-Food Crops Centre (NNFCC)
  • 23. American Institute of Chemical Engineers – Delaware Valley Section
    • The Twelve Principles of Green Engineering
    • Ensure Inherent Safety
    • Prevent Waste rather than Treat Waste
    • Separation & Purification to Minimize Energy and Materials Use
    • Maximize Mass, Space, Energy and Time Efficiency
    • Output Pulled rather than Input Pushed
    • Conserve Complexity
    • Durability rather than Immortality
    • Meet the Need while Minimizing Excess
    • Minimize Material Diversity
    • Integrate Material and Energy Flows
    • Design for a Commercial Afterlife
    • Renewable rather than Depleting
  • 24. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #1 - Ensure Inherent Safety
    • Strive to ensure that all materials and energy inputs/outputs are as inherently non-hazardous as possible
  • 25. American Institute of Chemical Engineers – Delaware Valley Section
    • Inherent Safety as Applied to a Chemical Process
    • A chemical process is inherently safer if it reduces or eliminates the hazards associated with materials used and operations, and that this reduction or elimination is a permanent and inseparable part of that process
    • Per Trevor Kletz and Dennis Hendershot
  • 26. American Institute of Chemical Engineers – Delaware Valley Section Concepts of Inherent Safety Intensification Using less of a hazardous material. Smaller (intensified) equipment can reduce the hazardous inventory and minimize the consequences of accidents Attenuation Using a hazardous material in a less hazardous form, for example, a diluted acid rather than a concentrated one. Larger particle size to minimize a dust explosion hazard. Substitution Using safer material. Water instead of a flammable solvent.
  • 27. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #2 - Prevent Waste rather than Treat Waste
    • Better to prevent waste streams occurring rather than treating them afterwards
  • 28. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #3 - Separation & Purification Operations Selection
    • Separation & Purification Operations Designed to Minimize Energy and Materials Use
  • 29. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #4 - Maximize Efficiencies
    • Processes and products should be designed to maximize Mass, Space, Energy and Time Efficiencies
  • 30. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #5 - Output Pulled not Input Pushed
    • Often a reaction or transformation is "driven" to completion by adding more energy/materials to shift the equilibrium to generate the desired output. However, this same effect can be achieved by designing reactions in which outputs are removed from the system, and the reaction is instead "pulled" to completion without the need for excess energy/materials.
  • 31. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #6 - Conserve Complexity
    • Value-conserving recycling, where possible, or beneficial disposition, when necessary, End-of-life design decisions for recycle, reuse, or beneficial disposal should be based on the invested material and energy and subsequent complexity
  • 32. American Institute of Chemical Engineers – Delaware Valley Section
    • Industrial Symbiosis at Kalundborg, Denmark
  • 33. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #7 - Durability rather than Immortality
    • Targeted durability should be a design goal
  • 34. American Institute of Chemical Engineers – Delaware Valley Section
    • CFCs
    • These coolant chlorofluorocarbons are:
    • Non-flammable
    • Non-toxic
    • Effective
    • Inexpensive
    • Stable – so stable that they migrate to the upper atmosphere, where UV-induced fragmentation causes ozone depletion
  • 35. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #8 - Meet the Need, Minimizing Excess
    • Designing for unnecessary overcapacity or over capability is a design flaw
  • 36. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #9 - Minimize Material Diversity
    • Material diversity in multi-component systems is to be minimized
  • 37. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #10 - Integrate Material & Energy Flows
    • Water Loop Closure
    • Integrate Heat/Cool Loops
    • Cogeneration
  • 38. American Institute of Chemical Engineers – Delaware Valley Section
    • Pinch Technology
    • Pinch technology, developed principally by Bodo Linnhoff at the University of Manchester in the UK, is a methodology for the integration of heating and cooling systems for maximizing energy efficiency.
  • 39. American Institute of Chemical Engineers – Delaware Valley Section
    • Simple Heat Exchange System
    Hot Stream 3500 lb/hr 400 deg F 70 deg F Coolant 0.98MM Btu/hr Cold Stream 4000 lb/hr 90 deg F 400 deg F Heating 0.87MM Btu/hr
  • 40. American Institute of Chemical Engineers – Delaware Valley Section
    • Integrated Heating and Cooling
    Hot Stream 3500 lb/hr 400 deg F 70 deg F Coolant 0.67MM Btu/hr Cold Stream 4000 lb/hr 200 deg F 90 deg F Heating 0.56MM Btu/hr 290 deg F 400 deg F
  • 41. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #11 - Design for a Commercial Afterlife
    • Products and processes should be designed for a commercial afterlife
  • 42. American Institute of Chemical Engineers – Delaware Valley Section
    • Principle #12 - Renewable not Depleting
    • Material and energy inputs should be from renewable resources not depleting resources
  • 43. American Institute of Chemical Engineers – Delaware Valley Section
    • Green Corrosion Inhibitors
    • Traditional corrosion protection methods often rely on hazardous substances, notably carginogenic chromates. Research in Europe is demonstrating the use of ‘intelligent’ self healing inhibitors. The controllable delivery is based on incorporating nano-containers of organic inhibitors in protective films of silica and zirconia – both benign and abundant. Release of material in triggered by pH.
    • taken from GCN Newsletter (UK) April 2007
  • 44. American Institute of Chemical Engineers – Delaware Valley Section
    • Biocatalysis – the use of enzymes or whole cells in the manufacturing process
    • .
    • Bicatalysts can simplify or enable production of complex molecules. These often eliminate the requirement for elaborate separation and/or purification steps. Reactions may be undertaken under milder conditions of temperature, pressure and pH. Such biocatalytic reactions are by nature safer.
  • 45. American Institute of Chemical Engineers – Delaware Valley Section
    • Microchannel Reactors
    • The use of microchannel reactors for catalytic hydrogenation reactions has the potential to improve a significant number of catalytic hydrogenation reactions in both the chemical and pharmaceutical industries.
    • These reactors could significantly improve the efficiency and safety of such manufacturing processes. These reactors possess small transverse dimensions with high surface-to-volume ratios and consequently exhibit enhanced heat and mass-transfer rates.
    • Taken from a Promotional Brochure from US Dept. of Energy
  • 46. American Institute of Chemical Engineers – Delaware Valley Section
    • Metabolic Pathway Engineering
    • Genetic modification of micro-organisms to make them produce the desired chemical.
    • Many examples – ethanol, 1.3 PDO, 1,4 BDO, succinic acid etc etc.
  • 47. American Institute of Chemical Engineers – Delaware Valley Section
    • Acknowledgements
    • Jacobs & KBR for supporting this webinar – hopefully they will continue throughout the series
    • My peer reviewers – Linda, Jasmine and Bob
    • Paul Anastas & David Shonnard – for their published works which have contributed so much to this material
  • 48. American Institute of Chemical Engineers – Delaware Valley Section
    • Questions ?