POZP_7_EN

Sustainable Chemical

Technologies

•Green Chemistry

•Catalytic Processes

•Regeneration

•Integrated waste treatment

What is Sustainability?

1987, Brundtland Commission:

“Development that meets the needs of the

present without compromising the ability of

future generations to meet their own

needs.”

What is Sustainability?

Currently not sustainable

• Resources faster consumed then

replenished

• Global population continues to grow

• Hazardous materials are released into

environment in great amounts

History of Sustainability

1992 Rio de Janeiro UNCED

(United Nations Conference on the Environmental and Development)

Goal:

sustainable development

Dokuments:

• Agenda 21 -

EU and Agenda 21

• 5th action programm EU

• Towards Sustainability till 2000.

• Main direction

– Participation of public

– Sustainable technology

– Wastes treatment and disposal

Participation of public

New approach

Sharing of responsibility:

Public – Government – Producers

Public available information

• TRI Toxic Release Inventory (USA)

• NPRI National Pollutant Release Inventory (Canada)

• EPER European Pollutant Emission Register (EU)

USA EPA (www.epa.gov) TRI

http://www.eper.ec.europa.eu/eper/default.asp

What is Green Chemistry?

Definition:

Design of chemical products and processes

that reduce or eliminate the use and

generation of hazardous substances.

Popular since early ´90s, in opposition to

pollute-and-clean-up approach

What is Green Chemistry?

Main areas

• Use of alternative synthetic pathways

• Alternative reaction conditions

• Design of eco-compatible chemicals

Excellent tool for achieving Sustainability

Clean-up vs. Clean Technology

Benefits

• Environmental purpose

• Economic • + Material

• + Compliance

• + Clean-up costs

• + Funding

• + Consumer’s opinion

• - Investment in R & D

Involvement of the Society

• Academia

Knowledge, education, new

applications

• Industry

Bench top to commercialisation

• Government

Funding, regulatory relief for adaptation

Principles of Green Chemistry

• Atom economy

• Simple and safe process

• No waste

• Avoid toxic chemicals or solvents

• Use of renewable resources

Ways for Green Chemistry

• Biotechnology E. Coli to produce PDO, termite pest control

• Renewable resources Corn and sugar beet crops replace petroleum

• Reuse and recycling

• Cleaner solvents Supercritical fluids

• Catalysts

• Downsizing

The 12 principles of green chemistry 1. It is better to prevent waste than to treat or clean up waste after it is formed

2. Synthetic methods should be designed to maximize the incorporation of all materials used into the final product

3. Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment

4. Chemical products should be designed to preserve efficacy of function while reducing toxicity

5. The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary wherever possible and, innocuous when used

6. 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

7. A raw material of feedstock should be renewable rather than depleting wherever technically and economically practicable

8. Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical processes) should be avoided whenever possible

9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents

10. Chemical products should be designed to preserve efficacy of function while reducing toxicity

11. Analytical methodologies need to be developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances

12. Substances 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

Treatment and disposal of

wastes

• collection, assortment and recycling

• chemical treatment

• incineration

• biological treatment

• separation, stabilization and disposal

Wastes and releases

Wastes to production

Chemical specialities and pharmaceutic

*10 – 50

Chemical industry ~ 1

Fuels and petrochemistry 0.1

*many batch step operation

Wastes and releases from production

Release to

•air

•water

•earth

Waste

•incineration

•biological treatment

•disposal

•regeneration

•recycling

1997 Kyoto Protocol

• The Kyoto Protocol to the United Nations Framework Convention on Climate Change is an amendment to the international treaty on climate change, assigning mandatory targets for the reduction of greenhouse gas emissions to signatory nations.

• "The Kyoto Protocol is an agreement under which industrialised countries will reduce their collective emissions of greenhouse gases by 5.2% compared to the year 1990 (but note that, compared to the emissions levels that would be expected by 2010 without the Protocol, this target represents a 29% cut). The goal is to lower overall emissions of six greenhouse gases - carbon dioxide, methane, nitrous oxide, sulfur hexafluoride, HFCs, and PFCs - calculated as an average over the five-year period of 2008-12. National targets range from 8% reductions for the European Union and some others to 7% for the US, 6% for Japan, 0% for Russia, and permitted increases of 8% for Australia and 10% for Iceland."

Gas

Formula

Approximative

time of

residence in the

atmosphère

Carbon

dioxide

CO2

120 years

Methane

CH4

6 – 15 years

Nitrous oxide

N2O

120 years

Halocarbons Br, F, Cl, I

from several

weeks up to

50.000 years

Hydrofluoro-

carbons

CnHmFp

Sulfur

hexafluoride

SF6

Kyoto-protocoll

Carbon dioxide (CO2)

Sources - Carbon dioxide (CO2)

Difference of Carbon dioxide (CO2) of 99 - 04

Recommended solutions

Renewable bio-sources

• Energy

• Biomass incineration

• Biogas by fermentation

• Biofuels

• 1st generation (FAME, ethanol from starch)

• 2nd generation (pyrolysis, FT, ethanol from celulose)

• Chemicals

Agriculture competition with food products, logistic – small capacity

sources

Natural energy X Nuclear power stations

• Water

• Wind energy

• Fotovoltaic stations

Cost, life cycle, associated waste, geographical and

weather dependent, energy conservation

Past miracles of last? century

• 1940 insecticid DDT

Tetraethyl lead

• 1950 CFC instead of amonium

• 1960 PCB

• 1970 MTBE

• 2005 Bio fuels (price increase of

food products)

The “Laws of Sustainable

Development?”

1. Today’s problems come from yesterday’s solutions

2. The harder you push, the more the system pushes back

3. Behaviour grows better before it grows worse

4. The easy way out usually leads back in

5. The cure can be worse than the disease

6. Faster is slower

7. Cause and effect are not closely related in space and time

8. Small changes can produce big results—but the areas of highest leverage are often the least obvious

9. You can have your cake and eat it too—but not at once

10. Dividing an elephant in half does not produce two small elephants

11. There is no blame

Peter Senge: The Fifth Discipline, 1992.

Summary

• Agenda 21 Rio de Janeiro 1992

– Sustainable development

– Sharing of responsibility

– Clean technology

– Public information

– Wastes treatment

• Kyoto protocol 1997

– reduction of greenhouse gases

– biofuels, renewable energy

Supercritical Fluids

Gases compressed until density

approaches liquid density, while above

critical temperature

Ex: scCO2, scH2O

Supercritical Fluids

Advantages • Abscence of toxic residues

• Low extraction temperature

• Higher solvent power

• High diffusivity

• Low viscosity

• Intermediate density

• Non-toxic

• Non-carcinogenic

• Non-flammable

scCO2

Semiconductor industry consumes

enormous quantities of energy

Photoresist removal now with scCO2

+ no additional drying agent

+ better cleaning of chip due to low surface

tension

Catalysts

Significant role:

• Decreasing energy requirements

• Increasing selectivity

• Use of less hazardous reaction conditions

Ibuprofen production

Nylon-6,6

Fibres, bearing and gears

Synthesis requires adipic acid

Old process:

Benzene Cyclohexane

Mixture of Cyclohexanone and Cyclohexanol

Adipic acid + NO

Nylon-6,6

New catalytic process

Starting from cyclohexene and H2O2 with

catalysts

Old vs. New

• High pressure

• High temperature

• Generation of NO

• Lower yield

• No use of organic

solvents

• No generation of NO

• Higher yield

Maleic Anhydride

Polyester resin, motor oil additives, copolymers

Development of Vanadyl pyrophosphate catalyst,

with high activity and selectivity

Old vs. New

• 6 C

• Toxic reactants

• Higher selectivity

• Several by-products

• 4 C

• Non-toxic reactants

• One step, no solvent

• Carbon oxides and

acetic acid as by-

products

• Minimal waste

formation

Maleic Anhydride

NO CONVERSION TO GREEN

CHEMISTRY!

Economically driven: – Butane is cheaper than benzene

– Less expensive safety equipment

– Higher weight yield

– Reduction in fixed and variable costs

– Lower separation costs due to gas-phase reactions and

fewer formation of by-products and waste

Downsizing

Petrochemical industry

– Upscaling

– Process integration

Massive impact on little area

Downsizing

Obtaining Sustainability through

– Downsizing

– Decentralizing

Requirements

– Process miniaturization

– Sophisticated technologies

Central role for catalysts

Conclusion

• Long-term approach based on innovation

and unconventional reaction conditions

• Short-medium-term approach focussed on

improvement of current technologies

Conclusion

Partnerships among academia, government and industry to:

• Maximize use of available resources

• Minimize duplication of effort

• Accelerate adoption

• Regeneration

• Integrated waste treatment

• New production routes