Escolar Documentos
Profissional Documentos
Cultura Documentos
electronic material
Degree of high temperature material
Sophistication
Or
Knowledge per Composite material
Unit Area high strength steel
Aluminum alloys
Engineering Plastics
cement
Time
1
Chemical Industry: A Birds Eye View
2
What is this photograph? . . . . Think Over
Green PROCESS = Responsibility
4
Chemical Industry: Need of the Hour
Green
Society Demands
Technology Legislation Seeks
Less Hazardous
Good Public image
Materials
Sustainable
Safer plants Zero Waste
Development
Economy
5
Waste Management: Bottom-Up Approach
6
Clean Production should be Green Production
Reduce
7
Cleaner Production
Has to be an integrated strategy to product development
Sustainable Development
Meet the needs of the present without compromising the ability of future
Green
chemistry
Catalysis
Green
engineering Waste
Sustainable
management
development
Industrial
ecology E-factor,
atom economy
Renewable
energy
9
Energy consumption Petro Feed : As Fuel
15
oil BIOMASS +
109 tonnes of 10 other renewables
oil equivalent
gas NUCLEAR
5
coal HYDRO
0
1971 1980 1990 2000 2010 2020 2030
10
Major petrochemical building blocks
Petrochemicals: Not only as Fuel but also as Raw Material?
11
Petrochemicals:
12
Chemistry out of Petroleum: Can it Meet the Green Demand?
CH2=CH2
Cl2 H2, CO
O2 , H2O,
PdCl2 C6H6
CH2ClCH2Cl O2, Ag CH3CH2CHO
O2 AcOH,
CH2=CHCl PdCl2 -H2
H2O H2O CH3CH2CO2H H2
O2
CH3CH2CH2OH
(CH3CO)2O CH3CH2OH
13
What is Green PROCESS?
14
Green PROCESS. . . Probing deeper
Cleaner Waste
Production prevention
15
Green PROCESS: Probing deeper . . . . 12-Principles
17
Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998
18
Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998
19
Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998
20
Green Engineering:
M. Abraham 2004, Environ. Prog. 23 (4), p. 266
The design, commercialization, and use of processes and products, which are
feasible and economical while minimizing:
(i) generation of pollution at the source and
(ii) risk to human health and the environment.
21
Cleaner Production is the iterative application of an integrated strategy to
product development and allied services leading to enhancement of the
overall efficiency of the processes and reducing the risks to humans and the
environment.
Sustainability
Green Engineering
Green Chemistry
1:1
3. Coal gasification
1:1
1:0
23
From biomass to syn-gas to fine chemicals:
many opportunities for integrated cleaner production
polyethylene
aldehydes
CO, H2 -H2O esters
acids oligomers C2H4 EtOH ethers
alcohols
O2 + Ag
monomers
ethylene Biomass H2O + Rh catalyst
polymers oxide
N2 Fischer Tropsch
NH3 CO + H2 Gasoline
CO2
CO + Ir / Rh cat. CH3CO2H
HCHO
urea
MeOH zeolite H-ZSM-5
enzymatic Me
degradation CH2OH fermentation
O O OH
HO HO
HO O O
n
corn starch lactic acid
step-growth (-H2O)
condensation
O
Me O ring-opening
Me
polymerisation O heat Me
O
O O
n (chain growth) Me O
O Me n
O O
25
How Green is a Reaction?
FW of Atoms in Desired Product
Atom Utilization/Economy = x 100 %
FW of all Atoms in All Reactants
kG of Total Waste
Enviromental Factor (E-factor) = x 100 %
kG of Desired Product
E-FACTOR
FINE CHEMICALS & INTERMEDIATES 5 - 50
BULK CHEMICALS < 1- 5
REFINERY OPERATION ~ 0.1
26
How Green is a Reaction?
Esterification of n-butanol with acetic acid
Typical procedure: 37g butanol, 60 g glacial acetic acid and 3 drops of H2SO4 are
mixed together. The reaction mixture is then poured into 250 cm3 water. The
organic layer is separated and washed again with water (100 cm3), saturated
NaHCO3 (25 cm3) and more water (25 cm3). The crude ester is then dried over
anhydrous Na2SO4 (5 g), and then distilled. Yield = 40 g (69 %).
Yield 69 % Moderate
Atom Economy 86 % Good (byproduct is water)
E-factor 502 / 40 = 12.6 Poor
EMY 40/37 x 100 = 108 % Very good
27
How Green is a Reaction?
Atom economy and E-factor are often useful, simple guides to the
'greenness' of reactions, but may be overly focussed on waste.
Effective Mass Yield (EMY) values take into account the toxicity of reagents
and are therefore more likely to reflect the true 'greenness' of a process.
However, EMY values require us to decide what and what is not benign!
The only true way of judging 'greenness' is by a life cycle analysis, but this
too time consuming to be practical.
We therefore use atom economies, E-factors and EMY data as simple (but
imperfect) guides.
28
Phloroglucinol Synthesis
CH3 COOH
O2N NO2 O2N NO2 H2N NH2 HO OH
K2Cr2O7
Fe/HCl aq.HCl
H2SO4 / SO3 - CO2 DT
NO2 NO2 NH2 OH
TNT phloroglucinol
HO OH
29
GOING GREEN: PARADIGM SHIFT . . . paracetamol
Cl OH OH OH
H2SO4 OR Na 2S
NO2 NH OH OH OH
Pd - C Ac2O
H2SO4
NH2 NH COCH3
30
A) FINE CHEMICALS
CONVENTIONAL :
ROUTE 2) HYDROQUINONE
GOING GREEN: PARADIGM SHIFT . . . hydroquinone
CONVENTIONAL ROUTE
NH2 O OH
MnSO4
MnO2 Fe
NH2 O OH + (NH4)2SO4
H2SO4 HCl MnSO
FeCl24
MnO2 Fe
O OH + (NH4)2SO4
H2SO4 HCl
FeCl2
NEW ROUTE O OH
NEW ROUTE
OH OH OH
OH
H2O2
OH OH + OH
Ti - Silicalite OH
H2O2
OH +
Ti - Silicalite (SNAMPROGETTI, COMMERCIAL)
OH
(SNAMPROGETTI, COMMERCIAL)
31
B)
B) TEXTILE
TEXTILE -- NYLON
NYLON 1)
1) CAPROLACTUM
CAPROLACTUM (CONTD.)
(CONTD.)
GOING GREEN: PARADIGM SHIFT . . . caprolactum
CONVENTIONAL
CONVENTIONAL ROUTE
ROUTE
O ++ (NH3OH)
(NH3OH)2 SO ++ 2NH 22 + (NH ))2SO
O 2SO44 2NH33 N
N OH
OH + (NH4
4 2SO4 4
++ 22 H
H2 O
2O22
N ++ H SO NH (NH ) SO
N OH
OH H22SO44 ++ NH33
O
O
++ (NH44)2
2SO44
NH
NH
(-(- CAPROLACTUM
CAPROLACTUM
NEW
NEW ROUTE
ROUTE
TS
TS -- 1
1
O ++ NH
NH3 ++ H
H22O
O22 N OH
O 3 N OH
(ENICHEM,
(ENICHEM, BEING
BEING COMMERCIALISED)
COMMERCIALISED)
Pentasil
Pentasil
N OH O
O
N OH 350 (-(- CAPROLACTUM
350 0CC MeOH
0
MeOH NH CAPROLACTUM
NH
NN2 95.3% Yield
2 95.3% Yield (SUMITOMO,
(SUMITOMO, BEING
BEING COMMERCIALISED)
COMMERCIALISED)
32
Clean Production: End-Notes
New Solvents in Chemical Process : Ionic Liquids, Super-critical CO2
Bio-Catalysts & Meso-porous Catalysts : Already Entered the Arena
Nano-Catalysis: New Kid in the Block
Available Adapted
Routes Routes
Directed
Evolution
Dream Process
Dream Process
33