Green & Sustainable CHEMISTRY

Green & Sustainable CHEMISTRY DALILA G. KOVACS G R A N D V A L L E Y S T AT E U N I V E R S I T Y ALLENDALE, MI, USA MWEA May 13-2014 Lansing, MI “A...
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Green & Sustainable CHEMISTRY DALILA G. KOVACS G R A N D V A L L E Y S T AT E U N I V E R S I T Y ALLENDALE, MI, USA MWEA May 13-2014 Lansing, MI

“A novel substance is either isolated or synthesized every 2.6 seconds on the average during the past 12 months, day and night, seven days a week in the World” Dr. Hideaki Chihara, Ph.D. chemist and former president of Japan Association for International Chemical Information.

MWEA May 13-2014 Lansing, MI

• CAS REGISTRYSM

> 87 million unique chemical substances • CHEMLIST® (Regulated Chemicals Listing) >310,000 substances 
 > 50 new substances or are added to the database each week. http://www.cas.org/content/chemical-substances

MWEA May 13-2014 Lansing, MI

PHARMA INDUSTRY Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-watertreatment plant Stackelberg P.E., Furlong E.T., Meyer M.T., Zaugg S.D., Henderson A.K., Reissman D.B. (2004) Science of the Total Environment, 329 (1-3) , pp. 99-113. 2014 (20) 
2013 (43) 
2012 (52) 
2011 (48) 2010 (45)

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ORGANIC CONTAMINANTS SURVIVE A CONVENTIONAL DWT • 106 organic wastewater-related contaminants (OWCs • Several of these compounds also were frequently detected in samples of finished water • What are these compounds:      

selected prescription and non-prescription drugs and their metabolites, fragrance compounds, flame retardants plasticizers, cosmetic compounds, solvent.

• Drinking-water criteria currently are based on the toxicity of individual compounds and not combinations of compounds. Little is known about potential humanhealth effects associated with chronic exposure to trace levels of multiple OWCs through routes such as drinking water

MWEA May 13-2014 Lansing, MI

BLACK

Sierra Club: Beyond Coal (Photo Essay) 2012 MWEA May 13-2014 Lansing, MI

RED

NBC news-10/22/2010 MWEA May 13-2014 Lansing, MI

GREEN

Many chemical processes in use today are black or red, or both. The goal of the chemical industry should be the replacement of red and/or black chemistry with green alternatives: Green Chemistry

Sheldon, R. Green Chem., 2, G1. 2000 MWEA May 13-2014 Lansing, MI

GREEN

http://www.cmu.edu/homepage/practical/20 08/summer/melanie-vrabel.shtml

http://www.greenchem.biz/?q=company-profile MWEA May 13-2014 Lansing, MI

CHEMISTRY: GREEN clean chemistry green chemistry sustainable chemistry are essentially the same (Leitner, 1999)

 sustainable and green (Tundo, February 2008) 1st meeting of the Working Party on Green and Sustainable Chemistry (European Association for Chemical and Molecular Sciences)

MWEA May 13-2014 Lansing, MI

An overview: origins and development of green chemistry, by J. A. Linthorst, Found Chem (2010) 12:55–68 DOI 10.1007/s10698-009-9079-4 MWEA May 13-2014 Lansing, MI

GREEN CHEMISTRY • Green chemistry (also known as sustainable chemistry) is the design, development, and implementation of chemical products and processes to reduce or eliminate the use and generation of substances hazardous to human health and the environment. Anastas, P. & Warner, J. MWEA May 13-2014 Lansing, MI

THE TWELVE PRINCIPLES OF GREEN CHEMISTRY Dr. Paul Anastas

Dr. John Warner

MWEA May 13-2014 Lansing, MI

THE TWELVE PRINCIPLES OF GREEN CHEMISTRY   

        

1. Prevention 2. Atom Economy 3. Less Hazardous Chemical Syntheses 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis 10. Design for Degradation 11. Real-time Analysis for Pollution Prevention 12. Inherently Safer Chemistry for Accident Prevention MWEA May 13-2014 Lansing, MI

THE TWELVE PRINCIPLES OF GREEN CHEMISTRY   



1. Prevention 2. Atom Economy 3. Less Hazardous Chemical Syntheses 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis 10. Design for Degradation 12. Inherently Safer Chemistry for Accident Prevention

11.

Real-time Analysis for  Pollution Prevention     

MWEA May 13-2014 Lansing, MI

REDUCING RISK • Design Safer Chemicals – utilize performance chemicals that have the lowest levels of toxicity. • Design Less Hazardous Synthesis Methods –if feasible, use synthetic or biosynthetic methods, with little or no toxicity to human health and the environment. • Use Safer Solvents and Reaction Conditions –up-to-date information on green solvents, optimize the process and provide safer working environment. • Accident Prevention – Select substances that minimize the potential for explosions, fires and chemical releases into the environment. MWEA May 13-2014 Lansing, MI

Safer chemistry & Accident prevention

$$$ MWEA May 13-2014 Lansing, MI

Designing safer chemicals for humans less toxic & less flammable

MWEA May 13-2014 Lansing, MI

Designing safer chemicals for environment degrade to harmless products Detergents Na salts of linear alkylbenzene sulfonic acids Builders Zeolites Pesticides Pyrethroid pesticides Environmentally benign antibacterial agents Mg(OOH)OAc Mg(OOH)2 MWEA May 13-2014 Lansing, MI

Less hazardous chemical synthesis Polycarbonates: Made from bisphenol A BPA and phosgene. Cl CO 2

“ Phosgene is used as a chemical intermediate; ..used as a chemical warfare agent. Phosgene is extremely toxic by acute inhalation exposure. Severe respiratory effects: pulmonary edema, pulmonary emphysema, and death have been reported in humans. Severe ocular irritation and dermal burns may result following eye or skin exposure. Chronic inhalation exposure to phosgene may also cause irreversible pulmonary changes of emphysema and fibrosis. “ http://www.epa.gov/ MWEA May 13-2014 Lansing, MI

Safer solvents No solvent: Benign solvent:

Gas phase Solventless Water

 water as a solvent vs. a resource  water-born paints vs. paints based on VOCs  scCO2 used in extraction of caffeine from coffee and in dry cleaning MWEA May 13-2014 Lansing, MI

Less hazardous chemical synthesis

Roundup MWEA May 13-2014 Lansing, MI

Minimizing the Environmental Footprint Waste Minimization & Prevention – Develop chemical synthesis techniques, which reduce or prevent waste. It is better to prevent waste than to clean it up after its creation. Catalysts vs. Stoichiometric Quantities – Catalytic reactions inherently use smaller quantities of chemicals to carry out a specified transformation. Reduce Chemical Derivatives – The use of protecting groups or other forms of temporary modification of a functionality adds to the total waste incurred in a synthetic route. MWEA May 13-2014 Lansing, MI

Minimizing the Environmental Footprint Synthetic Efficiency (Atom Economy) – An efficient chemical process ensures the maximum amount of your starting materials is used in the final product so that no atom is wasted. Designed for Degradation – Reduce the effect on the environment by using chemicals that are designed to be biodegradable. In-Process Controls for Pollution Prevention – To avoid the formation of hazardous substances, adopt real-time analysis and in process monitoring during synthesis. MWEA May 13-2014 Lansing, MI

Minimizing the Environmental Footprint Renewable Feedstocks – Use raw materials or renewable feedstocks (waste from other processes or products derived from agricultural streams) whenever technically or economically feasible. Energy Efficiency – The realization of the economical and environmental impact of energy use in a chemical process and the development of alternative means to reduce the impact. http://www.greenchemex.org/ MWEA May 13-2014 Lansing, MI

Design for degradation

Starch-based polymers: renewable resources readily degradable MWEA May 13-2014 Lansing, MI

THE DRIVING FORCE OF GREEN CHEMISTRY • Acceptance: Chemical industry must not adversely affect the environment for future generations: sustainability. • Addresses: • Resources depletion of the production of • waste • Reagents & risk • Products & degradation MWEA May 13-2014 Lansing, MI

The chemical industry creates an immense variety of products which impinge on virtually every aspect of our lives.

MWEA May 13-2014 Lansing, MI

CHEMISTRY INDUSTRY: GREEN “There are still mistakes and these are generally well publicized in the media but overall there have been significant changes in the operation of the chemical industry that are designed to reduce the impact on the environment”

http://www.essentialchemicalindustry.org/processes/greenchemistry.html (last amended: 6th April 2014; accessed May 12, 2014)

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THE INDUSTRY PUSH TOWARD SUSTAINABILITY  Green chemistry was adopted often because it is attractive and ecologically-sound A series of examples of industrial motivation vs. principles of green chemistry in the development of new processes have been reported Centi, G. and Perathoner, S. (2003) Catal. Today, 77, 287.

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From Green to Sustainable Industrial Chemistry, G. Centi and S. Perathoner in Sustainable Industrial Processes. Edited by F. Cavani, G. Centi, S. Perathoner, and F. Trifiró Copyright 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31552-9 MWEA May 13-2014 Lansing, MI

FROM GREEN TO SUSTAINABLE • Greener technologies --a novel business strategy for innovation. • Sustainable industrial chemistry --effective strategies for sustainability though chemistry. • Green and sustainable chemistry are thus not synonymous; green chemistry is the core for new strategy for sustainable chemistry to be built around. Sheldon, R.A., Arends, I. and Hanefeld, U. (2007) Green Chemistry and Catalysis, Wiley-VCH Verlag, Weinheim.; Clark, J. and Macquarrie, D. (eds) (2002) Handbook of Green Chemistry and Technology, Blackwell Science, Oxford, UK. Rothenberg, G. (2008)Catalysis – Concepts and Green Applications, WileyVCH Verlag, Weinheim.; Tundo, P. and Esposito, V. (eds) (2008) Green Chemical Reactions, Springer, Dordrecht. (Proceedings of the NATO Advanced Study Institute onNew Organic Chemistry Reactions and Methodologies for Green Production Lecce Italy 29 Oct–10 Nov 2006. Doble, M. and Kruthiventi, A.K. (2007) Green Chemistry and Engineering, Elsevier Science & Technology Books, Amsterdam.

MWEA May 13-2014 Lansing, MI

EPA & Green Chemistry 1990 Pollution Prevention Act 1991 Green Chemistry

MWEA May 13-2014 Lansing, MI

GREENER CLEANING TECHNOLOGIES Cleaning: • Laundry • Water Purification • Industrial Cleaning

CLEANING WATER •

UltimerTM Polymer Technology • • • •

high molecular weight, water soluble polymers in aqueous salt solution eliminates use of oils and surfactants in manufacture and use uses ammonium sulfate, a waste by-product from the manufacture of caprolactam eliminates need for expensive mixing equipment required for water-in-oil emulsions Nalco Chemical Company

INDUSTRIAL CLEANING •

Crystal Simple Green® • Water based industrial cleaner • Non-toxic, biodegradable surfactants • Replaces traditional organic solvents • Eliminates hazardous waste sludge production and VOC pollution Sunshine Makers, Inc.

INDUSTRIAL CLEANING

Isomet Mixture of isoparaffinic hydrocarbon, propylene glycol monomethyl ether, and isopropyl alcohol Replaces Typewash (mixture of methylene chloride, toluene, and acetone) Excellent performance in postage stamp and overprinting presses Acceptable properties (cleaning ability, solvent evaporation rate, odor, environmental compliance, and cost) U.S.Bureau of Engraving and Printing

GREEN CHEMISTRY

Not a solution to all environmental problems. u The most fundamental approach to preventing pollution. u Recognizes the importance of incremental improvements. u

MUNICIPAL WATER SUPPLY 1

Student Ashley Brady, GVSUGreen & Industrial processes W2014

PROBLEM?

1

2 Copper and Lead ions can leach into drinking water Student Ashley Brady, GVSUGreen & Industrial processes W2014

ENVIRONMENTAL CHEMISTRY 3 P CP C CP P PO PO b a b PO C C PO a P PO P b 4 4 a b PO 4 a C Ca 4 bP P bPO PO 4 4 PO a C aC PO PbPO 4PObP 4 4 a C aC 4 b 4 PaPO PO 4 P b PO C a C bP 4PO PO 4 4 Pb PO PO aC Ca PO 4 PO 4 4 bP 4PO P b a 4 C POPO PO 4C a b aP4C Pa b 4 C 4 C4P b baP a b a b

Phosphate additions reduce lead and copper ions leaching into drinking water

Concentrations