1. CHALLENGES AND OPPORTUNITIES
GREEN CHEMISTRY
GREEN CHEMISTRY
CHALLENGES AND OPPORTUNITIES BY
PRANOTO

2. PREVENTING POLLUTION SUSTAINING THE EARTH
GREEN CHEMISTRY
GREEN CHEMISTRY
PREVENTING POLLUTION SUSTAINING THE EARTH

3. GREEN CHEMISTRY GREEN CHEMISTRY IS ABOUT DEFINITION
Green Chemistry is the utilization of a set of principles that reduces or eliminates
the use or generation of hazardous substances in the design, manufacture and
application of chemical products *.
GREEN CHEMISTRY IS ABOUT
Waste Minimisation at Source
Use of Catalysts in place of Reagents
Using Non-Toxic Reagents
Use of Renewable Resources
Improved Atom Efficiency
Use of Solvent Free or Recyclable Environmentally Benign Solvent systems
* Green Chemistry Theory & Practice, P T Anastas & J C Warner, Oxford University Press 1998

4. Some Aspects of Green Chemistry
Safer Reactions
& Reagents
Catalysis
Solvent
Replacement
Separation
Processes
Green
Chemistry
Use of
Renewable
Feedstocks .
Energy
Efficiency
Waste
Minimisation
Process
Intensification

5. Green Chemistry Is About...
Waste
Materials
Hazard
Reducing
Risk
Energy
Environmental Impact
COST

6. THE COST OF WASTE

7. 12 Principles of Green Chemistry
1. Prevention. It is better to prevent waste than to treat or clean up waste after it is formed.
2. Atom Economy. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.
3. Less Hazardous Chemical Synthesis. Whenever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment.
4. Designing Safer Chemicals. Chemical products should be designed to preserve efficacy of the function while reducing toxicity.
5. Safer Solvents and Auxiliaries. The use of auxiliary substances (solvents, separation agents, etc.) should be made unnecessary whenever possible and, when used, innocuous.
6. Design for Energy Efficiency. Energy 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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8. 12 Principles of Green Chemistry
7. Use of Renewable Feedstocks. A raw material or feedstock should be renewable rather than depleting whenever technically and economically practical.
8. Reduce Derivatives. Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical processes) should be avoided whenever possible .
9. Catalysis. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
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9. 12 Principles of Green Chemistry
10. Design for Degradation. Chemical products should be designed so that at the end of their function they do not persist in the environment and instead break down into innocuous degradation products.
11. Real-time Analysis for Pollution Prevention. 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. Inherently Safer Chemistry for Accident Prevention. Substance 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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10. ENVIRONMENTAL DISASTERS
DDT
CFCs
Love Canal

11. Environmental Disasters
Cuyahoga River – Cleveland, Ohio
There were many things being dumped in the river such as: gasoline, oil, paint, and metals. The river was called "a rainbow of many different colors".
Fires erupted on the river several times before June 22, 1969, when a river fire captured national attention when Time Magazine reported it.
Some river! Chocolate-brown, oily, bubbling with subsurface gases, it oozes rather than flows. "Anyone who falls into the Cuyahoga does not drown," Cleveland's citizens joke grimly. "He decays." Time Magazine, August 1969
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12. Organic Chemistry & Percent Yield
Epoxidation of an alkene using a peroxyacid
100% yield
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13. Designing Safer Chemicals Case Study: Antifoulants (Marine Pesticides)
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14. (c) 2010 Beyond Benign - All Rights Reserved.
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15. Energy in a chemical process
Thermal (electric)
Cooling (water condensers, water circulators)
Distillation
Equipment (lab hood)
Photo
Microwave
Source of energy:
Power plant – coal, oil, natural gas
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16. Biomaterials [Carbohydrates, Proteins, Lipids]
Highly Functionalized Molecules
Petroleum Products [Hydrocarbons]
Singly Functionalized Compounds [Olefins, Alkylchlorides]
Highly Functionalized Molecules
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17. Polymers from Renewable Resources: Poly(lactic acid)
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18. Raw Materials from Renewable Resources: The BioFine Process
Paper mill
sludge
Agricultural
residues,
Waste wood
Levulinic acid
Green Chemistry Challenge Award 1999 Small Business Award
Municipal solid waste
and waste paper
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19. Levulinic acid as a platform chemical
butanediol
Acrylic acid
Succinic acid
MTHF
(fuel additive)
THF
Diphenolic acid
gamma
butyrolactone
DALA (-amino levulinic acid)
(non-toxic, biodegradable herbicide)
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20. (c) 2010 Beyond Benign - All Rights Reserved.
Real time analysis for a chemist is the process of “checking the progress of chemical reactions as it happens.”
Knowing when your product is “done” can save a lot of waste, time and energy!
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21. (c) 2010 Beyond Benign - All Rights Reserved.
Cyanide!
Phosgene!
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22. (c) 2010 Beyond Benign - All Rights Reserved.
Bhopal, India
December 3, 1984 – poison gas leaked from a Union Carbide factory, killing thousands instantly and injuring many more (many of who died later of exposure). Up to 20,000 people have died as a result of exposure (3-8,000 instantly). More than 120,000 still suffer from ailments caused by exposure
What happened?
Methyl isocyanate – used to make pesticides was being stored in large quantities on-site at the plant
Methyl isocyanate is highly reactive, exothermic molecule
Most safety systems either failed or were inoperative
Water was released into the tank holding the methyl isocyanate
The reaction occurred and the methyl isocyanate rapidly boiled producing large quantities of toxic gas.
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23. Chemical Industry Accidents
U.S. Public Interest Research Group Reports (April 2004) find that chemical industry has had more than 25,000 chemical accidents since 1990
More than 1,800 accidents a year or 5 a day
Top 3: BP, Dow, DuPont (1/3 of the accidents)
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25. “ Chemistry has an important role to play in achieving a sustainable civilization on earth.” — Dr. Terry Collins, Professor of Chemistry Carnegie Mellon University

26. WHAT IS A SUSTAINABLE CIVILIZATION?

27. WE SHOULD CONSIDER THIS QUESTION FROM SEVERAL VIEWPOINTS:
The environment and human health.
A stable economy that uses energy and resources efficiently.
Social and political systems that lead to a just society.

28. TO UNDERSTAND THE ROLE OF CHEMISTRY IN SUSTAINABILITY, WE WILL LOOK AT THE FIRST TWO POINTS…
The environment and human health.
A stable economy that uses energy and resources efficiently.

29. IN A SUSTAINABLE CIVILIZATION…
Technologies used for production of needed goods are not harmful to the environment or to human health.
Renewable resources (such as plant-based substances or solar energy) are used rather than those, like fossil fuels, that will eventually run out.

30. IN A SUSTAINABLE CIVILIZATION…
At the end of their use, materials are recycled if they are not biodegradable (easily broken down into harmless substances in the environment).

31. IN A SUSTAINABLE CIVILIZATION…
Manufacturing processes are either designed so as not to produce waste products,
– OR –
Waste products are recycled or biodegradable.

32. WHILE WE HAVE MADE SOME PROGRESS IN ACHIEVING THESE GOALS, WE STILL HAVE A LONG WAY TO GO…
Mountains of solid waste are piling up—particularly in industrialized nations.
Air and water pollution continue to be problems in many places.

33. BUT HOW CAN CHEMISTRY HELP US TO ACHIEVE A SUSTAINABLE CIVILIZATION?

34. First, let’s consider chemistry’s benefits… The chemical industry produces many products that improve our lives and upon which we depend.

35. BENEFITS OF CHEMICAL INDUSTRY:
Antibiotics and other medicines
Fertilizers, pesticides
Plastics
Nylon, rayon, polyester, and other synthetic materials
Gasoline and other fuels
Water purification

36. “Better Things for Better Living Through Chemistry” DuPont
Ibuprophen
Lipitor
Celebrex
Vioxx
Rogaine
Prozac
Viagra
Prilosec
Nylon
Dacron
PET
Polystyrene
Acrylics
Teflon
Rayon
Polyaniline
DNA
Recombinant
Technology
PCR
Prilosec heartburn
Lipitor cholesterol
Rogaine hair loss
Celebrex, Vioxx arthritis

37. “Most of the environmental problems of past centuries and decades, such as the biological contamination of drinking water, were solved only when the methods of science in general—and chemistry in particular—were applied to them. The phenomenal rise in human life expectancy and in the material quality of life that has come about in recent decades is due in no small measure to chemicals and chemistry.” — Colin Baird, Environmental Chemistry.

38. THE POLLUTION PREVENTION ACT OF 1990
This was the U.S. environmental law stating that the first choice for preventing pollution is to design industrial processes that do not lead to waste production.
This is the approach of green chemistry.

39. GREEN CHEMISTRY WORKS TOWARD SUSTAINABILITY BY:
Making chemical products that do not harm either our health or the environment,
Using industrial processes that reduce or eliminate hazardous chemicals, and

40. GREEN CHEMISTRY WORKS TOWARD SUSTAINABILITY BY:
Designing more efficient processes that minimize the production of waste materials.

41. GREEN CHEMISTRY MEANS…
Preventing pollution before it happens rather than cleaning up the mess later.

42. GREEN CHEMISTRY MEANS…
Saving companies money by using less energy and fewer/safer chemicals, thus reducing the costs of pollution control and waste disposal.

43. GREEN CHEMISTRY Pollution Prevention Act 1990
GC Began in 1991 at EPA, Paul Anastas
1996 Presidential Green Chemistry Challenge Awards
1997 Green Chemistry and Engineering Conference
1999 Journal “Green Chemistry”
Chemical & Engineering News
2001 Journal of Chemical Education
Its not easy being green

44. Examples of Green Chemistry
Presidential Green Chemistry Challenge Award Winners
For more informational on 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.
New oxidants for bleaching paper and disinfecting water.
Getting the lead out of automobile paints.
Recyclable carpeting.
Replacing VOCs and chlorinated solvents.
Biodegradable polymers from renewable resources.

45. EXAMPLES OF GREEN CHEMISTRY
Safer dry cleaning
Initially gasoline and kerosene were used
Chlorinated solvents are now used, such as perc
Supercritical/liquid carbon dioxide (CO2)

46. LEAD POLLUTION HAS BEEN DECREASED BY…
Replacing lead in paint with safe alternatives, and
Replacing tetraethyl lead with less toxic additives (e.g., “lead-free” gasoline).

47. CHEMICAL FOAMS TO FIGHT FIRES
Millions of tons of chemical fire-fighting foams used worldwide have discharged toxic substances into the environment, contaminating water supplies and depleting the ozone layer.

48. PUTTING OUT FIRES THE GREEN WAY
A new foam called Pyrocool FEF has now been invented to put out fires effectively without producing the toxic substances found in other fire-fighting materials.

49. CHEMICALS FOR DRY CLEANING
Perchloroethylene (“perc”) is the solvent most widely used in dry cleaning clothing.
Perc is suspected of causing cancer and its disposal can contaminate ground water.

50. A SAFER METHOD OF DRY CLEANING
Liquid CO2 can be used as a safer solvent if a wetting agent is used with it to dissolve grease.
This method is now being used commercially by some dry cleaners.

51. IN SUMMARY, GREEN CHEMISTRY IS…
Scientifically sound,
Cost effective, and
Leads toward a sustainable civilization.