GREEN CHEMISTRY CHALLENGES AND OPPORTUNITIES BY PRANOTO GREEN

GREEN CHEMISTRY CHALLENGES AND OPPORTUNITIES BY PRANOTO

GREEN CHEMISTRY PREVENTING POLLUTION SUSTAINING THE EARTH

GREEN CHEMISTRY 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

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

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

THE COST OF WASTE

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. (c) 2010 Beyond Benign - All Rights Reserved.

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. (c) 2010 Beyond Benign - All Rights Reserved.

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. (c) 2010 Beyond Benign - All Rights Reserved.

ENVIRONMENTAL DISASTERS • DDT • CFCs • Love Canal

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 (c) 2010 Beyond Benign - All Rights Reserved.

Organic Chemistry & Percent Yield Epoxidation of an alkene using a peroxyacid 100% yield

Designing Safer Chemicals Case Study: Antifoulants (Marine Pesticides) http: //academic. scranton. edu/faculty/CANNM 1/environmentalmodule. html

http: //www. uyseg. org/greener_industry/pages/super. CO 2/3 super. CO 2_coffee. htm (c) 2010 Beyond Benign

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 (c) 2010 Beyond Benign - All Rights Reserved.

Biomaterials [Carbohydrates, Proteins, Lipids] Highly Functionalized Molecules Petroleum Products [Hydrocarbons] Singly Functionalized Compounds [Olefins, Alkylchlorides] Highly Functionalized Molecules (c) 2010 Beyond Benign - All Rights Reserved.

Polymers from Renewable Resources: Poly(lactic acid) http: //www. natureworksllc. com/corporate/nw_pack_home. asp (c) 2010 Beyond

Raw Materials from Renewable Resources: The Bio. Fine Process Paper mill sludge Agricultural residues, Waste wood Levulinic acid Green Chemistry Challenge Award 1999 Small Business Award Municipal solid waste and waste paper (c) 2010 Beyond Benign - All Rights Reserved.

Levulinic acid as a platform chemical butanediol Acrylic acid Succinic acid MTHF (fuel additive) THF Diphenolic acid gamma butyrolactone (c) 2010 Beyond Benign - All Rights Reserved. DALA ( -amino levulinic acid) (non-toxic, biodegradable herbicide)

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! (c) 2010 Beyond Benign - All Rights Reserved.

Cyanide! Phosgene! (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. (c) 2010 Beyond Benign - All Rights Reserved.

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, Du. Pont (1/3 of the accidents) http: //uspirg. org/uspirgnewsroom. asp? id 2=12864&id 3=USPIRGnewsroom& (c) 2010 Beyond Benign - All Rights Reserved.

“ Chemistry has an important role to play in achieving a sustainable civilization on earth. ” — Dr. Terry Collins, Professor of Chemistry Carnegie Mellon University

WHAT IS A SUSTAINABLE CIVILIZATION?

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.

• 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.

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.

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).

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

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.

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

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

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

“Better Things for Better Living Through Chemistry” • • Ibuprophen Lipitor Celebrex Vioxx Rogaine Prozac Viagra Prilosec • • Nylon Dacron PET Polystyrene Acrylics Teflon Rayon Polyaniline Du. Pont • DNA • Recombinant Technology • PCR

“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.

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.

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

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

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

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

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

Examples of Green Chemistry Presidential Green Chemistry Challenge Award Winners For more informational on Presidential Green Chemistry Challenge Award Winners: http: //www. epa. gov/greenchemistry/presgcc. html • 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.

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 (CO 2)

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).

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

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.

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.

A SAFER METHOD OF DRY CLEANING • Liquid CO 2 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.

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