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GREEN CHEMISTRY
Faculty of Chemical Engineering
HCMC University of Technology
Office: room 211, B2 Building
Phone: 38647256 ext. 5681
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Chapter 2: CATALYSIS AND
GREEN CHEMISTRY
Why is catalysis important in making industrial
processes more efficient and economically profitable?
Catalytic reagents reduce the energy of the
transition state, thereby reducing the energy
input required for a process
Catalysts are required in small quantities
The regeneration and reversibility of catalysts
are good for green processes
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No
catalyst
With
catalyst
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With catalyst: Less energy, less toxic reagents, less waste
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E factor
E factor: The actual amount of waste produced in
the process (everything but the desired product
except water) / kg of product
A higher E factor more waste greater
negative environmental effect
Generally, the E factor increases dramatically on
going from bulk to fine chemicals, and then
pharmaceuticals multi-step syntheses +
stoichiometric reagents rather than catalysts for
the latter
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For example:
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Waste generated in the manufacture of organic
compounds consists primarily of inorganic salts
Consequence of the use of stoichiometric
inorganic reagents
For examples: Stoichiometric reductions with
metals (Na, Mg, Zn, Fe) and metal hydride
reagents (LiAlH
4
, NaBH
4
)
Oxidation with KMnO
4
, CrO
3
/ H
2
SO
4

Sulfonations, nitrations, halogenations,
diazotizations and Friedel-Crafts acylations,
employing stoichiometric amounts of mineral
acids (H
2
SO
4
, HF, H
3
PO
4
) and Lewis acids (AlCl
3
,
ZnCl
2
, BF
3
)
Where is the waste from?
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Solution to reduce waste?
Substitution of classical stoichiometric
methodologies with cleaner catalytic alternatives
Catalyst
Stoichiometric
reagents
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Atom efficiency / economy
No
catalyst
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Atom efficiency / economy
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Classical aromatic chemistry
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Non-classical aromatic chemistry
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Two ways to hydroquinone
10 kg waste (MnSO
4
, FeCl
2
, NaCl, Na
2
SO
4
) / kg
< 1kg waste / kg
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Supported catalyst
Solid supports: polymer or silica
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Homogeneous Catalysts
High selectivity
Wide range available
High Cost
Catalyst Stability
Recycle Problem
Limited industrially
Heterogeneous Catalysts
Low Selectivity
Difficult to Functionalize
Ill-defined catalytic species
Limited Range of Reactions
Problems of Leaching
Ease of Recycle
Preferred Industrially

The Holy Grail: Immobilize a homogeneous
catalyst on an inert support to combine selectivity
with processability
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Using solid catalyst
Catalyst
separation by
filtration /
centrifugation
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Using solid catalyst
Less waste
Less energy consumed
More possibility to recycle and
reuse
Cleaner product
Reused catalyst
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Using homogeneous catalyst
Catalyst separation by column
chromatography / distillation / extraction
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Using homogeneous catalyst
More waste
More energy
consumed
Less possibility to
recycle and reuse
Product
contaminated with
toxic metals
More toxic solvents
involved
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Homogeneous Friedel-Crafts acylation
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Heterogeneous Friedel-Crafts acylation
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Homogeneous synthesis of 2,6-
dichlorobenzonitrile
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Heterogeneous synthesis of 2,6-
dichlorobenzonitrile less waste
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Catalyst
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Soluble polymer-supported catalyst
Temperature-dependent phase separation
Solvent-dependent phase separation
PEG: soluble in DMF, DCM but insoluble in
ether, iPrOH
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Superparamagnetic nanoparticle-supported catalyst
A
B
C
C
+
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Biocatalysts
Enzymes / whole-cell biocatalysts catalyse
organic reactions at pH 4-9, 10-50
o
C, without
extremes of pressure, addition of metals
environmentally acceptable








Conventional methods require highly acidic
or basic media, high energy input, toxic metals
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One area where organic chemists are still
struggling: chirality !!!
Biocatalysts: predominantly suited for optically
pure stereo-isomers
Essential for drugs & agrochemicals
Advantages of biocatalysis
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Chemo-selectivity:
Other chemically sensitive functional groups still
survive with enzyme
Biocatalytic conditions cleaner / greener
Side-reactions avoided advantageous for product
purifications
Enzyme react on a single type of functional group
only
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