1. American Institute of Chemical
Engineers – Delaware Valley Section
An Introduction to Green Chemistry
and Engineering
November 18th 2011
Ken Rollins CEng, FIChemE
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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.
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3. American Institute of Chemical Engineers –
Delaware Valley Section
The Twelve Principles of Green Chemistry
1. Prevent Waste
2. Safer Chemicals and Products
3. Less Hazardous Chemical Syntheses
4. Use Renewable Feedstocks
5. Use Catalytic Reactions
6. Avoid Chemical Derivatives
7. Maximise Atom Economy
8. Safer Solvents and Reaction Conditions
9. Increased Energy Efficiency
10. Design Chemicals to Degrade after Use
11. Pollution using Real Time Analysis
12. Minimize Accident Potential
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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
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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
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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
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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
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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
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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
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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
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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
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12. American Institute of Chemical Engineers –
Delaware Valley Section
Alternate ‘Green’ Solvents
• Supercritical Carbon Dioxide
• Supercritical Water
• Ionic Liquids
.
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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 ?
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14. American Institute of Chemical Engineers –
Delaware Valley Section
Principle # 9 – Increased Energy Efficiency
Operate at ambient temperature and atmospheric pressure
where possible
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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
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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
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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 ?)
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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
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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
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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.
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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)
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23. American Institute of Chemical Engineers –
Delaware Valley Section
The Twelve Principles of Green Engineering
1. Ensure Inherent Safety
2. Prevent Waste rather than Treat Waste
3. Separation & Purification to Minimize Energy and Materials Use
4. Maximize Mass, Space, Energy and Time Efficiency
5. Output Pulled rather than Input Pushed
6. Conserve Complexity
7. Durability rather than Immortality
8. Meet the Need while Minimizing Excess
9. Minimize Material Diversity
10. Integrate Material and Energy Flows
11. Design for a Commercial Afterlife
12. Renewable rather than Depleting
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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
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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
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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.
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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
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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
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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
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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.
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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
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32. American Institute of Chemical Engineers –
Delaware Valley Section
Industrial Symbiosis at Kalundborg, Denmark
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33. American Institute of Chemical Engineers –
Delaware Valley Section
Principle #7 - Durability rather than
Immortality
Targeted durability should be a design goal
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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
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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
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36. American Institute of Chemical Engineers –
Delaware Valley Section
Principle #9 - Minimize Material Diversity
Material diversity in multi-component systems is to be
minimized
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37. American Institute of Chemical Engineers –
Delaware Valley Section
Principle #10 - Integrate Material & Energy Flows
• Water Loop Closure
• Integrate Heat/Cool Loops
• Cogeneration
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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.
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39. American Institute of Chemical Engineers –
Delaware Valley Section
Simple Heat Exchange System
Coolant 0.98MM Btu/hr
Hot Stream
3500 lb/hr 70 deg F
400 deg
F
Heating
0.87MM Btu/hr
Cold Stream
4000 lb/hr
400 deg F
90 deg
F
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40. American Institute of Chemical Engineers –
Delaware Valley Section
Integrated Heating and Cooling
Cold Stream
4000 lb/hr
Coolant
90 deg F 0.67MM Btu/hr
Hot Stream
3500 lb/hr 70 deg F
290 deg F
400 deg F
Heating
0.56MM Btu/hr
200 deg F
400 deg F
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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
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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
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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
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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.
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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.
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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.
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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
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48. American Institute of Chemical Engineers –
Delaware Valley Section
Questions ?
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