Luigi Vaccaro
Laboratory of Green Synthetic Organic Chemistry,
Dipartimento di Chimica, Università di Perugia
Via Elce di Sotto, 8 – 06123 Perugia; Tel +39 075 5855541; Cell. +393384058969
luigi@unipg.it
http://www.chm.unipg.it/greensoc
A focus on GREEN CHEMISTRY
Number of publications where the term “Green Chemistry” appears
GREEN CHEMISTRY
PREVENTING POLLUTION
SUSTAINING THE EARTH
Slide taken from the American Chemical Society
“ Chemistry has an important role to
play in achieving a sustainable
civilization on earth.”
— Dr. Terry Collins, Professor of Chemistry
Carnegie Mellon University
Slide taken from the American Chemical Society
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.
Slide taken from the American Chemical 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.
Slide taken from the American Chemical Society
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.
Slide taken from the American Chemical Society
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).
Slide taken from the American Chemical Society
BENEFITS OF
CHEMICAL INDUSTRY:
Antibiotics and other medicines
Fertilizers, pesticides
Plastics
Nylon, rayon, polyester, and
other synthetic materials
• Gasoline and other fuels
• Water purification
• Organic Semiconductors
•
•
•
•
Slide taken from the American Chemical Society
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.
Slide taken from the American Chemical Society
EPA – US Environmental Protection Agency
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 Green Chemistry approach
“The Congress hereby declares it to be the national policy of the United
States that pollution should be prevented or reduced at the source
whenever feasible; pollution that cannot be prevented should be recycled in
an environmentally safe manner, whenever feasible; pollution that cannot be
prevented or recycled should be treated in an environmentally safe manner
whenever feasible; and disposal or other release into the environment
should be employed only as a last resort and should be conducted in an
environmentally safe manner”
THE POLLUTION
PREVENTION ACT OF 1990
US officially pointed the attention on the
‘‘millions of tons of pollution’’ and the related
cost of ‘‘tens of billions of dollars per year’’
(Pollution Prevention Act 1990, p.617).
In US specific financial support is given through calls on Green
Synthetic methodologies (SYN)
In Europe there are not specific actions for promoting
academic/industrial efforts in this direction.
US EPA Presidential Green Chemistry Award
Promotes and recognizes green chemistry
Five Categories
1. Alternative synthetic pathways
2. Alternative reaction conditions
3. Design of safer chemicals
4. Small business
5. Academic investigator
Source: http://www.epa.gov/greenchemistry
“Alternative synthetic pathways Award”
 1999 Lilly Research Laboratories (Talampanel)
 2000 Roche Colorado Corp (Cymevene®)
 2002 Pfizer, Inc (Zoloft®)
 2004 Bristol-Meyers Squibb Company (Taxol)
 2005 Merck & Co. Inc. (Emend®)
 2006 Merck & Co. Inc. (Januvia®)
 2006 Codexis, Inc. for Atorvastatin (Lipitor®)
 2010 Merck & Co. Inc. and Codexis, Inc. (Januvia™ II generation)
Horizon 2020
The EU Framework Programme for Research and Innovation
where knowledge across different fields of organic chemistry are
brought together to face the different issues that need to be
settled in the route towards a sustainable development.
Excellence in Science; Industrial Leadership; Societal Challenges
Horizon 2020 and the research search for a sustainable future
2011 European Roadmap
The European Association for Chemical and Molecular Sciences
(EuCheMS) highlighted the importance of the strategic choices
should be made for the European technological future.
The first European Sustainable Chemistry Award (Matthias Beller)
Green is the color of money …
The Chemical Manufacturers Association (CMA) launched the
Responsible Care® program in 1988 to respond to public concerns
about the manufacture and use of chemicals.
Part of the guiding principles of the Responsible Care® program is to
make health, safety, the environment, and resource conservation
critical considerations for all new and existing products and
processes.
Currently, 52 nations by their national chemical industrial societies
participate to this Program (Italy is included through Federchimica)…
Green is the color of money …
Green Chemistry is the common effort of Academia, Industry
and Government to realize a Sustainable Civilization
- Save companies money by using less energy and fewer/safer chemicals,
thus reducing the costs of pollution control and waste disposal.
-Train modern scientists and professionals who will contribute to a
sustainable development of our Planet in the immediate future
- Create new and appealing job positions in industries that contribute to the
wealth of the society
-Design more efficient processes that minimize the production of waste
materials
- Use industrial processes that reduce or eliminate hazardous chemicals
- Make chemical products that do not harm either our health or the
environment
GREEN CHEMISTRY …
The rise of term Green Chemistry in US
is related to a significant political and
economic action devoted to save money
and to promote innovative research
In Europe “Green Chemistry” is used with two
other definitions that only partially overlap:
- “Clean Chemistry”: replace toxic substances
and processes
- “Sustainable Chemistry”: economic and
industrial evaluation of a process in the current
and future perspective
12 Principles of Green Chemistry
1. Prevent Waste
2. Design Safer Chemicals
3. Less Hazardous
Chemical Synthesis
4. Use Renewable
Feedstock
5. Catalysis
6. Avoid derivatives
7. Atom Economy
8. Safer Solvents
9. Energy Efficiency
10. Design Chemicals for
Degradation
11. Real-Time Analysis for
Pollution Prevention
12. Inherently Safer Chemistry
for Accident Prevention
Design Safer Chemicals
•
Water-based acrylic alkyd paints with low VOCs that can be
made from recycled soda bottle plastic (PET), acrylics, and
soybean oil. In 2010, Sherwin-Williams manufactured enough of
these new paints to eliminate over 800,000 pounds of VOCs.
•
Foam cushioning are conventionally manufactured from
petroleum products. Cargill’s BiOH™ polyols are manufactured
from renewable, biological sources such as vegetable oils. Each
million pounds of BiOH™ polyols saves nearly 700,000 pounds
of crude oil. Cargill’s process reduces total energy use by 23
percent and carbon dioxide emissions by 36 percent.
Design Safer Chemicals
Dimethyl Carbonate Tree and Its Industrial Uses
Dialkyl Carbonates
Green solvents
Paints, adhesives
Policarbonate 53 %
Coatings and paintings 28%
Agrochemicals 12%
Aliphatic polycarbonate diols
Polyuretans
Diphenyl carbonate
Aromatic polycarbonates
Methylisocianate production
Quaternarium ammoniumcompounds
Surfactants, Softeners, Electronics
Allylcarbonates
Optical organic glasses
Oxoalcohol carbonates
Synthetic lubricants
Pharm. &
Cosmetics 5%
Electrolite
solv.2%
Phenolic ethers, Pharmaceuticals,
Flavours and Fragrances
22
F. Aricò,M. Chiurato, J. Peltier and Pietro Tundo Eur. J. Org. Chem. 2012, 3223–3228
Use Renewable Feedstock
Biodiesel
Bioethanol
E.g. Mossi & Ghisolfi (M&G)
Safer solvents
for the chemical production
80-90%of waste in a chemical process is represent by the
solvent used and mostrly dispersed in the environment
Green alternatives
Water
Ionic Liquids
Supercritical Fluids (scCO2)
Solvent-free… best choice is NO SOLVENT
Less Hazardous Chemical Synthesis
Invent novel chemical approaches by combining:
• Catalysis (better if heterogeneous)
• Safer solvents
• Multistep procedures
• Automated continuous-flow reactors
• Energy efficiency
Less Hazardous Chemical Synthesis
Synthesis of amino ketones
O
R1
R2
NH2
Classic batch approach
produces ca 3000 Kg of waste
each Kg of amino ketone
Adv. Synth. Catal. 2012, 354, 908–916
Automate flow approach using safer
solvent produces only 2.3 Kg of
waste each Kg of amino ketone
> 99.9% reduction
Energy Efficiency
New materials to exploit renewable energies
Solar Energy Applications
Solar Energy Applications
flexible
portable
flexible
flexible
Konarka’s solar cell
Power Plastic ®
portable
portable
Heck reaction
R1
X
R2 Pd(OAc)2 ; K3PO4
+
R1
DMF
R2
Negishi coupling
R1
X
PdCl2(PPh3)2 /
+
XZn
R2
R1
R2
R1
R2
2(i-Bu)2AlH
R1,R2= aryl, vinyl
Suzuki-Miyaura reaction
HO
R1
X
+
Pd(PPh3)4; Na2CO3 AQ
B
RoadmapHO
2011
R2
Benzene-EtOH
Nobel Prize in Chemistry 2010
"for challenge
palladium-catalyzed
cross
“[…] The
for chemists
is to find new methods using widely available
organic
synthesis“. alternatives to maintain access to key
metalcouplings
catalysts,inor
even metal-free
drugs and other products currently made using precious metals”.
Richard F. Heck
Ei-ichi Negishi
Akira Suzuki
Light from the Sun
current approach is to convert petrol or the solar energy into
electric energy
Eff. = 3%
Eff. = 1%
Light from the Sun
the future is to take the Sun into our houses using fibers optic
Only 3 companies in the world are developing this technology using
fibers prepared from petrol sources
Brighten your home, USA
Himawary, Japan
Parans, Sweden
http://www.brightenyourhome.net
http://www.himawari-net.co.jp
http://www.parans.com
ONE example of Italian creativity and excellence is pursuing the
millennium challenge of preparing efficient lighting using fiber optics
prepared from renewable resources
Headway Srl
Luigi Vaccaro
Laboratory of Green Synthetic Organic Chemistry,
Dipartimento di Chimica, Università di Perugia
Via Elce di Sotto, 8 – 06123 Perugia; Tel +39 075 5855541; luigi@unipg.it
http://www.chm.unipg.it/greensoc