Chemical Industry: A Challenge in Green Tech

Material Innovation: Along the time line

electronic material
Degree of high temperature material
Sophistication
Or
Knowledge per Composite material
Unit Area high strength steel

Aluminum alloys
Engineering Plastics
cement

Time

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Chemical Industry: A Birds Eye View

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What is this photograph? . . . . Think Over
 Green PROCESS = Responsibility

Q. Why is there no Green Geology or Green Astronomy?

Ans. Because chemistry is the science that introduces new substances
into the world and we have a responsibility for their impact in the
world. - Ronald Breslow

BHOPAL OHIO SEVESO : LESSONS TO BE LEARNED

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 Chemical Industry: Need of the Hour

Green
Society Demands
Technology Legislation Seeks

Less Hazardous
Good Public image
Materials

Sustainable
Safer plants Zero Waste
Development

Pollution control Responsibility

Economy

Lower capital investment Lower operating costs

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Waste Management: Bottom-Up Approach

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 Clean Production should be Green Production

Reduce

Waste Hazardous Material

Energy Cost Risk

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 Cleaner Production
Has to be an integrated strategy to product development

Would aim to enhance overall efficiency of the processes

Must reduce the risks to humans and the environment.

Must be a Sustainable Process

Sustainable Development
Meet the needs of the present without compromising the ability of future

generations to meet their own needs

MT NOT P WCTA OF G TMT ON

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 Sustainable Development: The Links

Green
chemistry
Catalysis

Green
engineering Waste
Sustainable
management
development
Industrial
ecology E-factor,
atom economy
Renewable
energy

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Energy consumption Petro Feed : As Fuel

Energy demands will increase and so will CO2 production

Look for alternative energy

Projected Global Energy Consumption till 2030

15

oil BIOMASS +
109 tonnes of 10 other renewables
oil equivalent
gas NUCLEAR
5
coal HYDRO

0
1971 1980 1990 2000 2010 2020 2030

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Major petrochemical building blocks
Petrochemicals: Not only as Fuel but also as Raw Material?

Present industrial organic chemistry is based on Petrochemicals

US > 98 %, Europe > 90 %.

Seven major raw materials from petroleum

C2-C4 : Ethylene, Propylene, Butenes, Butadienes

BTX: Benzene (B), Toluene (T), Xylenes (X)

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 Petrochemicals:

1. Can they Meet the Green Demand?

2. Can they contribute to Sustainable Development?

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 Chemistry out of Petroleum: Can it Meet the Green Demand?

CH2=CH2
Cl2 H2, CO
O2 , H2O,
PdCl2 C6H6
CH2ClCH2Cl O2, Ag CH3CH2CHO

-HCl CH3CHO PhCH2CH3

O2, O2

O2 AcOH,
CH2=CHCl PdCl2 -H2
H2O H2O CH3CH2CO2H H2
O2

CH3CO2H CH2=CHOAc HOCH2CH2OH CH2=CHPh

CH3CH2CH2OH
(CH3CO)2O CH3CH2OH

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 What is Green PROCESS?

Green Chemcial Process is the study of how to design chemical

products and processes in ways that are sustainable and not harmful
for humans and the environment.

A new approach to designing chemicals and chemical transformations

that are beneficial for human health and the environment.

An innovative way to design molecules and chemical transformations

for sustainability.

Meeting the needs of the current generation without compromising the

ability of future generations to meet their own needs.

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 Green PROCESS. . . Probing deeper

Cleaner production at the molecular level

Benign by design
12-Principles
3-Components: catalysts, solvents, non-toxicity

Cleaner Waste
Production prevention

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 Green PROCESS: Probing deeper . . . . 12-Principles

Waste Prevention ... better prevent than clean up waste

Atom economy ... maximize incorporation of all materials used in product
Use Renewable feedstocks

Design for degradation

Real-time analysis for pollution prevention
Design for energy efficiency

Less hazardous chemical synthesis

Designing safer chemicals
Safer solvents and auxiliaries
Reduce derivatives
Selective Catalysis
Inherently safer chemistry for accident prevention
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 Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998

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 in the process 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.

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 Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998

4. Chemical products should be designed to preserve efficacy of

function while reducing toxicity.

5. The use of auxiliary substances (solvents, separation agents,

etc.) should be made unnecessary whenever possible and, when
used, innocuous.

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.

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 Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998

7. A raw material or feedstock should be renewable rather than

depleting whenever technically and economically practical.

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.

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 Green PROCESS: Probing deeper . . . . 12-Principles
Green Chemistry Theory and Practice by Paul T. Anastas, John C. Warner
Oxford University Press: New York, 1998

10. Chemical products would be designed so that at the end of their

function they do not persist in the environment and instead
break down into innocuous degradation products.

11. 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. 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.

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 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.

9-Declarations of Green Engineering:

M. A. Gonzalez, R. L. Smith, 2003, Environ. Prog. 22, 269
There is a duty to inform society of the practice of Green Engineering

12-Principles of Green Engineering:

P. Anastas, J. B. Zimmerman, Environ. Sci. Techol., vol 37 (5), p. 95A.

9-Principles of Sustainability Engineering:

B. Beloff et al. Eds. 2005, Transforming Sustainability Strategy into Action: The
Chemical Industry, Wiley-Interscience, p. 189

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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

M. Abraham, 2003, Environ. Progress 23, 261 22

 FROM BIOMASS TO SYN-GAS

SYNGAS: Three classical routes

1. Steam reforming of methane

1:3

2. Shell Gasification process

1:1
3. Coal gasification
1:1

1:0

In theory any hydrocarbon can be used, e.g.

toluene steam
dealkylation

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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

ROH CO, H2 alkanes

HCl Al2O3 / Pt
urea-formaldehyde acrylic
polymers MeCl aromatics
(Bakelite) resins acid
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FROM BIOMASS TO BIODEGRADABLE POLYMER: A GREEN ROUTE

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

polylactide, PLA lactide oligomers

The industrial process is 'catalysed' by tin(II)bis(2-ethylhexanoate)

No solvent - reaction is a melt phase polymerisation

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 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

mass of desired product

Effective Mass Yield (EMY) = x 100 %
mass of non-benign reactants

E-FACTOR
FINE CHEMICALS & INTERMEDIATES 5 - 50
BULK CHEMICALS < 1- 5
REFINERY OPERATION ~ 0.1

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 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 %).

Parameter Value Greenness

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

EMY indicates that the reaction is very 'green'

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 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.

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 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

+ Cr2 (SO4)3 + 2KHSO4 + 9FeCl2 + 3NH4Cl + CO2 + 8H2O

392 272 1143 160 44 144
OH
MW = 126 byproducts
product
Ca. 40kg of solid waste per kg phloroglucinol

Atom Utilisation = 126/2282 = ca. 5% ; E Factor = ca. 40

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GOING GREEN: PARADIGM SHIFT . . . paracetamol

Cl OH OH OH

NaOH Fe / HCl Ac2O

H2SO4 OR Na 2S

NO2 NO2 NH2 NH COCH3

NO2 NH OH OH OH

Pd - C Ac2O
H2SO4

NH2 NH COCH3

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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)

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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)

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 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

Compromise process to Adapt New Routes to

accommodate Existing Routes Optimize Dream Green
process

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