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Green Chemistry: An Overview
                Part-I
What is Green Chemistry?
Principles of Green Chemistry?
Why Green Chemistry ?
Aspects of Green chemistry.
Initiatives by SIAL Team.
Conclusion.
What is green chemistry ?
DEFINITION
  Green Chemistry is the utilisation of a set of principles
 that reduces or eliminates the use or generation of
 hazardous substances in the design, manufacture and
 application of chemical product
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
      system
       Green Chemistry Theory & Practice, P T Anastas & J C Warner, Oxford University Press 1998
The 12 Principles of Green Chemistry (1-6)
1. Prevention
     It is better to prevent waste than to treat or clean up waste after it has been
     created.

2. Atom Economy
     Synthetic methods should be designed to maximise the incorporation of all
     materials used in the process into the final product.

3. Less Hazardous Chemical Synthesis
     Wherever practicable, synthetic methods should be designed to use and
     generate substances that possess little or no toxicity to people or the
     environment.

4. Designing Safer Chemicals
     Chemical products should be designed to effect their desired function while
     minimising their toxicity.

5. Safer Solvents and Auxiliaries
     The use of auxiliary substances (e.g., solvents or separation agents) should be
     made unnecessary whenever possible and innocuous when used.

6. Design for Energy Efficiency
     Energy requirements of chemical processes should be recognised for their
     environmental and economic impacts and should be minimised. If possible,
     synthetic methods should be conducted at ambient temperature and pressure.
The 12 Principles of Green Chemistry (7-12)
7.Use of Renewable Feedstock
    A raw material or feedstock should be renewable rather than depleting whenever
    technically and economically practicable.
8.Reduce Derivatives
    Unnecessary derivatization (use of blocking groups, protection/ deprotection, temporary
    modification of physical/chemical processes) should be minimized or avoided if possible,
    because such steps require additional reagents and can generate waste.
9.Catalysis
    Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
10.Design for Degradation
    Chemical products should be designed so that at the end of their function they break
    down into innocuous degradation products and do not persist in the environment.
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
    Substances and the form of a substance used in a chemical process should be chosen to
    minimize the potential for chemical accidents, including releases, explosions, and fires.
Waste and The Chemical
             Industry
Where does the waste come from?
   Industry Segment              TONNAGE                                E factor
       Oil Refining                 106 - 108                              <0.1
      Bulk Chemicals                104 - 106                              1-5
      Fine Chemicals                102 - 104                             5 - 50
      Pharmaceuticals               10 - 103                            25 - 100+



 • Areas traditionally thought of as being dirty (oil refining & bulk chemical production)
 are relatively clean - they need to be since margins per Kg are low.
 • Newer industries with higher profit margins and employing more complex chemistry
 produce much more waste relatively.

 E factors (kg waste per kg product)
                                                R A Sheldon J Chem Tech Biotechnol 1997 68
                                                                  381
Why green Chemistry ?
Green Chemistry Is About...
             Waste

            Materials
            Hazard

           Risk

           Energy
           Environmental
           Impact
           COST
Pollution Prevention Hierarchy


        Prevention & Reduction


            Recycling & Reuse


               Treatment


                  Disposal
Some Aspects of Green Chemistry


              Safer Reactions       Catalysis
             & Reagents
                                                        Solvent
                                                        Replacement
Separation
Processes
                                Green                          Use of
                             Chemistry                     Renewable

     Energy                                                Feedstocks

    Efficiency                                     Waste
                             Process            Minimisation
                          Intensification
Bhopal Tragedy - A Lesson in
        Inherent Safe Design
      CH3NH2 + COCl2         CH3NCO           OH


Union Carbide India, Limited (UCIL)
                                                       OCONHCH3
             PROCESS




            OH                                     CH3NH2
                                      OCOCl


                  + COCl2




          ALTERNATIVE ROUTE
Green chemistry Encounters during Process R&D
   Old Process:- 2-Methylbenzofuran
New Improved Process

New Method for production of dihydrobenzofuran in single step procedure:-
The reaction of a variety of 2-ally phenols with iodine in water produced the corresponding 2-
iodomethyl-2,3-dihydrobenzofuran in the absence of any additives or organic solvents.
Am-Ex-OL
     NH2    O   Cl
                                        O
                     Pyridine/                         KOH,EtOH       N
        O            NMP                  N
                                          H O                             NH
     NH2                  RT            NH2             Reflux
MW= 136.2                                                             O
                                    MW= 240.3
                                                                  MW= 222.2



                N                PCl5,POCl3       N
                     NH                                N
                                 90-100'C
                O                                 Cl
                                 DIOxane
            MW= 222.2
                                                MW= 240.7
A Greener way to Am-Ex-OL

     NH2      O

        O                         N
                    NaHSO3
     NH2           DMAc/DMF           NH

MW= 136.2                         O
                              MW= 222.2
The Learning Points:
The Principles of Green Chemistry can be applied to the
whole of chemistry
Think laterally - try the green alternative
Consider waste, toxicity & energy as well as yield & purity
‘Sell’ to industry on economic and environmental grounds
KISS

Green chemistry Not a solution to all
environmental problems But the most
fundamental approach to preventing
pollution.

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Hiren Ppt Green Chem

  • 1. Green Chemistry: An Overview Part-I What is Green Chemistry? Principles of Green Chemistry? Why Green Chemistry ? Aspects of Green chemistry. Initiatives by SIAL Team. Conclusion.
  • 2. What is green chemistry ? DEFINITION Green Chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical product 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 system Green Chemistry Theory & Practice, P T Anastas & J C Warner, Oxford University Press 1998
  • 3. The 12 Principles of Green Chemistry (1-6) 1. Prevention It is better to prevent waste than to treat or clean up waste after it has been created. 2. Atom Economy Synthetic methods should be designed to maximise the incorporation of all materials used in the process into the final product. 3. Less Hazardous Chemical Synthesis Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to people or the environment. 4. Designing Safer Chemicals Chemical products should be designed to effect their desired function while minimising their toxicity. 5. Safer Solvents and Auxiliaries The use of auxiliary substances (e.g., solvents or separation agents) should be made unnecessary whenever possible and innocuous when used. 6. Design for Energy Efficiency Energy requirements of chemical processes should be recognised for their environmental and economic impacts and should be minimised. If possible, synthetic methods should be conducted at ambient temperature and pressure.
  • 4. The 12 Principles of Green Chemistry (7-12) 7.Use of Renewable Feedstock A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable. 8.Reduce Derivatives Unnecessary derivatization (use of blocking groups, protection/ deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste. 9.Catalysis Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 10.Design for Degradation Chemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment. 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 Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires.
  • 5. Waste and The Chemical Industry Where does the waste come from? Industry Segment TONNAGE E factor Oil Refining 106 - 108 <0.1 Bulk Chemicals 104 - 106 1-5 Fine Chemicals 102 - 104 5 - 50 Pharmaceuticals 10 - 103 25 - 100+ • Areas traditionally thought of as being dirty (oil refining & bulk chemical production) are relatively clean - they need to be since margins per Kg are low. • Newer industries with higher profit margins and employing more complex chemistry produce much more waste relatively. E factors (kg waste per kg product) R A Sheldon J Chem Tech Biotechnol 1997 68 381
  • 7. Green Chemistry Is About... Waste Materials Hazard Risk Energy Environmental Impact COST
  • 8. Pollution Prevention Hierarchy Prevention & Reduction Recycling & Reuse Treatment Disposal
  • 9. Some Aspects of Green Chemistry Safer Reactions Catalysis & Reagents Solvent Replacement Separation Processes Green Use of Chemistry Renewable Energy Feedstocks Efficiency Waste Process Minimisation Intensification
  • 10. Bhopal Tragedy - A Lesson in Inherent Safe Design CH3NH2 + COCl2 CH3NCO OH Union Carbide India, Limited (UCIL) OCONHCH3 PROCESS OH CH3NH2 OCOCl + COCl2 ALTERNATIVE ROUTE
  • 11. Green chemistry Encounters during Process R&D Old Process:- 2-Methylbenzofuran
  • 12. New Improved Process New Method for production of dihydrobenzofuran in single step procedure:- The reaction of a variety of 2-ally phenols with iodine in water produced the corresponding 2- iodomethyl-2,3-dihydrobenzofuran in the absence of any additives or organic solvents.
  • 13. Am-Ex-OL NH2 O Cl O Pyridine/ KOH,EtOH N O NMP N H O NH NH2 RT NH2 Reflux MW= 136.2 O MW= 240.3 MW= 222.2 N PCl5,POCl3 N NH N 90-100'C O Cl DIOxane MW= 222.2 MW= 240.7
  • 14. A Greener way to Am-Ex-OL NH2 O O N NaHSO3 NH2 DMAc/DMF NH MW= 136.2 O MW= 222.2
  • 15. The Learning Points: The Principles of Green Chemistry can be applied to the whole of chemistry Think laterally - try the green alternative Consider waste, toxicity & energy as well as yield & purity ‘Sell’ to industry on economic and environmental grounds KISS Green chemistry Not a solution to all environmental problems But the most fundamental approach to preventing pollution.