Solid Acid Catalysts

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Solid Acid Catalysts
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ZEOLITE-CATALYZED FRIEDEL-CRAFTS ACYLATION
O
AlCl3
O
O
CH3COCl
HCl
solvent
MeO
MeO
O
H-beta
O
(CH3CO)2O
O
MeO
MeO
CH3CO2H
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ZEOLITE-CATALYZED FRIEDEL-CRAFTS ACYLATION

• Homogeneous
• AlCl3 gt1 equivalent
• Solvent (recycle) Hydrolysis of products 85-95
  yield
• 4.5 kg aqueous effluent per kg
• 12 unit operations

• Heterogeneous
• H-beta, catalytic regenerable
• No solvent
• No water necessary
• gt95 yield /higher purity
• 0.035 kg aqueous
• effluent per kg
• 3 unit operations

S. Ratton, Chem. Today (Chim. Oggi), March/April,
1998, 33
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SALT-FREE ESTERIFICATION OF AMINO ACIDS

• CONVENTIONAL
• NH3
• R

NH3
Cl -
O -
HCl (1 eq.)
OH
MeOH/HCl (cat.)
O
R
O

NH3 Cl -
OMe
H2O
R
O
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SALT-FREE ESTERIFICATION OF AMINO ACIDS
ZEOLITE-CATALYZED

• NH3

NH2
O -
OMe
MeOH, H-USY, 100 C
R
H2O
O
R
O
? R PhCH2 (aspartame intermediate) S/C 20
(w/w), 83 yield (TON 180) ? Naphtha cracking
catalyst (H-USY) ? Opt. Active amino acids
(partially) racemized
M.Wegman, J.M.Elzinga, E.Neeleman, F.van Rantwijk
and R.A.Sheldon, Green Chem., 3,61,2001
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Catalytic Oxidations
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TS-1 CATALYZED OXIDATIONS WITH H2O2

• Hydrophobic molecular sieve (5.6 x 5.3Å) / HI
  (Xoctane / XH2O) TS-13.4 Ti / SiO20.1

NOH
O
O
TS - 1 30 H2O2
NH3
PhOH
R2CHOH
R2C O

OH
OH
OH
OH
Enichem
B.Notari, Stud. Surf. Sci. Catal., 37 , 431 (1988)
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Cyclohexanone Oxime Manufacturing Process

• Current Process

• Ammoximation Process

(NH4)2SO4
NOH
O
Oximation
Oximation
NOH
O
NH3
(NH3OH)2SO4
H2
NH3
H2O2
dil H2SO4
Air
NO
O2
NH3
H2
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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
  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

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Green Chemistry Is About...
Waste
Materials
Hazard
Reducing
Risk
Energy
Cost
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Why do we need Green Chemistry ?

• Chemistry is undeniably a very prominent part of
  our daily lives.
• Chemical developments also bring new
  environmental problems and harmful unexpected
  side effects, which result in the need for
  greener chemical products.
• A famous example is the pesticide DDT.

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• Green chemistry looks at pollution prevention on
  the molecular scale and is an extremely important
  area of Chemistry due to the importance of
  Chemistry in our world today and the implications
  it can show on our environment.
• The Green Chemistry program supports the
  invention of more environmentally friendly
  chemical processes which reduce or even eliminate
  the generation of hazardous substances.
• This program works very closely with the twelve
  principles of Green Chemistry.

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It is better to prevent waste than to treat or
cleanup waste after it is formed
Chemical Process
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Human society is constantly facing such
environmental issues and problems, air pollution,
global climate change, soil and water pollution,
acid rain, depletion of natural resources and
accumulation of natural hazardous wasteGreen
chemistry preventing pollution and sustaining the
earth
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In this presentation the synthesis of ibuprofen
by Friedel-crafts alkylation of isobutyl benzene
with lactic acid and its derivatives was attmpted
using various acid catalysts like Zn-Zeolite-Y,
AlCl3/MCM-41, AlCl3/SiO2
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IBUPROFEN
Is this possible and if so how to effect this
reaction catalytic?
Lactic acid
IBUPROFEN
First synthezised By the Boots company in
Nottingham England in 1960s
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The use of auxiliary substances (e.g.
solvents,separation agents, etc.) should be made
unnecessary wherever possible, and innocuous
when used
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Energy requirements should be recognized for
their environmental impacts and should be
minimized.Synthetic methods should be conducted
at ambient pressure and temperature
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GLOBAL WARMING
Heating Cooling Stirring Distillation Compression
Pumping Separation
Energy Requirement (electricity)
Burn fossil fuel
CO2 to atmosphere
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A raw material of feedstock should be
renewablerather than depleting wherever
technically andeconomically practical
Non-renewable
Renewable
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Resource Depletion

• Renewable resources can be made increasingly
  viable technologically and economically through
  green chemistry.
• Biomass, Carbon dioxide, Nanoscience,
• Solar, Waste utilization

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Poly lactic acid (PLA) for plastics production
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Polyhydroxyalkanoates (PHAs)
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The major uses of GREEN CHEMISTRY

• Energy
• Global Change
• Resource Depletion
• Food Supply
• Toxics in the Environment

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ENERGY

• The vast majority of the energy generated in the
  world today is from non-renewable sources that
  damage the environment.
• Carbon dioxide
• Depletion of Ozone layer
• Effects of mining, drilling, etc
• Toxics

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ENERGY

• Green Chemistry will be essential in
• developing the alternatives for energy
  generation (photo-voltaics, hydrogen, fuel cells,
  bio-based fuels, etc.) as well as
• continue the path toward energy efficiency with
  catalysis and product design at the forefront.

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GLOBAL CHANGE

• Concerns for climate change, oceanic temperature,
  stratospheric chemistry and global distillation
  can be addressed through the development and
  implementation of green chemistry technologies

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RESOURE DEPLETION

• Due to the over utilization of non-renewable
  resources, natural resources are being depleted
  at an unsustainable rate.
• Fossil fuels are a central issue.

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RESOURCE DEPLETION

• Renewable resources can be made increasingly
  viable technologically and economically through
  green chemistry.
• Biomass
• Nanoscience technology
• Solar
• Carbon dioxide
• Chitin
• Waste utilization

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FOOD SUPPLY

• While current food levels are sufficient,
  distribution is inadequate
• Agricultural methods are unsustainable
• Future food production intensity is needed.
• Green chemistry can address many food supply
  issues

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FOOD SUPPLY

• Green chemistry is developing
• Pesticides which only affect target organisms
  and degrade to innocuous by-products.
• Fertilizers and fertilizer adjuvants that are
  designed to minimize usage while maximizing
  effectiveness.
• Methods of using agricultural wastes for
  beneficial and profitable uses.

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TOXICS IN THE ENVIRONMENT

• Substances that are toxic to humans, the
  biosphere and all that sustains it, are currently
  still being released at a cost of life, health
  and sustainability.
• One of green chemistrys greatest strengths is
  the ability to design for reduced hazard.

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Pollution Prevention Hierarchy
Prevention Reduction
Recycling Reuse
Increasing Greenness
Treatment
Disposal
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DDT

• However, DDT is soluble in organic solvents. and
  thus in animal fat. DDT and or DDE have been
  detected in fat deposits of all birds and fish
  that have been analyzed including from those from
  desert regions or ocean depths.
• In North America the average person has 3 ppm
  concentration of DDT/DDE in their body fat.

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DDT

• Concerns regarding its possible long term health
  effects and its demonstrated damage to the life
  cycle of birds lead to the ban in most of western
  countries.
• (U S 1973)

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CONCLUSION

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