GREEN CHEMISTRY

Dr. Muhammad Irshad

 CONTENT

Green chemistry in practice:

 Introduction

 Impact of green chemistry process Technology on the chemical

industry

 Green Technologies
Introduction
 Realization of the goals of green chemistry will not occur without

their widespread, concerted adoption by the chemical industry.

 The industry is the logical interface between promising
laboratory-scale technologies and benefit to society at large
because of its pre-existing infrastructure for manufacture,
isolation and distribution of products.
 Many of these new approaches are foreign to the chemical

industry, and will be met with considerable reluctance and

scepticism.
Introduction
 The chemical industry has played a key role in the development of
the international economy and is still a vital part of the world’s
industrialized nations.
 The challenge, of course, is to demonstrate to the industry that
these technologies will simultaneously address their economic
needs as well as the environmental needs of the world.
 However, the public’s perception of huge smokestacks and
sprawling (irregularly spread) industrial complexes as being a
source of pride in a nation’s strength have given way to those
images being representative of ecological despoilment and
environmental havoc.
Introduction
 The terms ‘Black chemistry’ and ‘Red chemistry’ were coined
to describe how the public now views and fears much of the
conventional manufacturing carried out by the chemical
industry.
 Black chemistry refers to waste as pollution.

 Red chemistry refers to the toxic aspects of production, and

disasters.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Implementing new, environmentally friendly technology in

practice will go a long way towards changing the black and red
imagery to green.
 But evaluation of the impact of process change, and thus
determination of whether the technology will be adopted, is an
exceedingly complicated issue!
 12 principles of green chemistry are excellent mean for
industrial assessment.
 Developing a manufacturing route that embodies many of these
elements likely would be perceived as environmentally friendly.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Regardless of qualitative principles, the primary quantitative issue

from an industrial perspective is that of economics.
 The chemical industry exists to make profits and products, in that
order. If a process is no longer profitable, it is jettisoned, either by
elimination from the product line or by improvement through
modifications designed to return it to profitability.
 This is a reality that must be understood whenever any new green
approach is proposed. The chemical industry has been very
successful in developing high-yield economical routes for the
manufacture of a wide range of chemical building blocks and
intermediates.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 It understands and can manipulate existing technologies and

primary feedstocks with amazing control, even at incredibly
high annual production levels.
 Some of these processes have been in place for decades. Any
new methodology designed to displace them will be subjected
first to a stringent economic screen and will (in the absence of
legislation forcing replacement) be discarded if the cost is too
high, regardless of the environmental benefits.
 More frequently, the argument is being made that a ‘green’
approach is also the more economical approach.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 The industry is facing increasing regulatory and cost pressures

regarding environmental issues that are driving the industry to
more environmentally friendly processes.
 The cost for environmental controls has been estimated at
about 3% of sales revenue, or about $10 billion each year.
 Deeper evaluation of these numbers by industry has revealed
that there might be generally unrecognized and positive
economic drivers beyond simple raw material and capital costs
to encourage green chemistry growth in the industry. This is
certainly the case in the evaluation of new projects.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 For example, the cost of safety issues in the design of a new

plant is always evaluated.
 Safety costs are minimum initially at start of process but a
factor of 10 4 if an incident occurs.
 It would be reasonable to assume that similar factors also
apply to the environmental impact of a new process.
 Many other analyses have pointed out where positive economic
benefits accrue through waste minimization and capital
expenditures on green process technology rather than end-of-
pipe treatments.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Reduction of waste and elimination of toxic byproducts can be

translated directly into economic benefit.
 A useful quantitative measure of the impact of a technology
based on the amount of waste it generates was developed by
Sheldon, and measures the ratio of the weight of by-products
in a process to the weight of product formed (E value).
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 This E value has been cited in many subsequent papers and is

summarized here.
 Table indicates that the industry segment handling the largest amount of
chemical products also generates the smallest amount of waste, at least
as a function of product tonnage.
 The pharmaceutical industry with its reliance on multistep syntheses and
somewhat exotic reagents and solvents is, by this evaluation, ‘dirtiest’.
 However, in absolute terms, the oil refining industry still generates the
biggest pile of material to dispose. To address this component of the
issue, Sheldon also has tried to incorporate an ‘unfriendliness factor’
into the evaluation.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Fairly innocuous waste products (such as NaCl), which are more

common in large-scale commodity manufacture, could be given an

unfriendliness factor of 1,
 whereas the generation of heavy metal waste (e.g. Cr waste from an

oxidation step) might be given a factor of 100 or 1000. This factor

is multiplied by the E value to give an environmental quotient (EQ),
which would be a measure of the overall impact of the waste.
 Evaluation of the EQ could indicate that small-scale processes have

a very large impact. A goal for green technology would be to direct

all manufacturing routes, large and small, to the lowest possible EQ.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Quantitative evaluations of the relative greenness of a process can be

debated. If an improvement results in less waste, but not zero waste,

is it acceptable?
 If a process or product is renewables-based, is it automatically green?

 Some evaluations have projected that routes employing renewable

feedstocks actually may consume more energy and generate more

waste than those currently used.
 If an industry decides to use a biotechnological step for production,

are the cell waste or metabolic by-products less damaging to the

environment than some of those generated by the fine chemical or
pharmaceutical industries.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 what is a reasonable unfriendliness factor for newly

developing technology?
 If one uses catalysis, how many additional manufacturing

steps can be included before the effectiveness is lost?

 For example, a BASF procedure uses a catalytic
hydroformylation step in the production of vitamin-A.
 However, the process also uses a very atom-uneconomical

Wittig coupling in a subsequent step.

 What is the overall impact?
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 From a broader viewpoint, should separate technology (other than

green technology) for the manufacture of reagents needed for a

particular transformation also be evaluated?

 Reagents H 2 O 2 , O 2 and O 3 are widely considered as benign oxidants,

but the production of H 2 O 2 or O 3 is energy intensive.

 What is the environmental impact of their production?

 Electrochemistry frequently is suggested as a very clean method for

the production of new compounds, and a large-scale electrochemical

process for the production of adiponitrile (2.7 × 10 5 t year - 1 ) by
electrohydrodimerisation of acrylonitrile was developed and
commercialized by Monsanto.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 How much energy is required to run the operation? Is the source

of that energy a coal-fired power plant or a hydroelectric facility?

 Manufacture of the acrylonitrile used as a starting material also

generates large amounts of a salt as a by-product that must be

disposed of.
 Each of these questions again links directly to the overall

economics and the resulting cost to the industry.

 Long term, the clearest quantitative goal for green technology in

the chemical industry may be that of Pereira: develop processes

having 100% raw materials utilization or zero waste.
IMPACT OF GREEN PROCESS
TECHNOLOGY ON THE CHEMICAL INDUSTRY

 Questions such as these surrounding industrial adoption of green

process technology clearly highlight the need to incorporate more life-

cycle analysis for the evaluation of any supposed ‘environmentally
friendly’ routes .
 In the context of life-cycle analysis, some have proposed that green

technology eventually must provide a cradle to grave service for a

product, e.g. in the photocopier industry where the makers of toner
cartridges are also their primary recyclers.
 Research also provides answers. Improvements in the synthesis of

H 2 O 2 have been developed that could lower its cost and make it more
attractive as a green oxidant from an energy viewpoint.
Green Technologies
 The green technologies that have been employed most widely
by the industry comprise three major categories.
1. Catalysis

2. Biocatalysis/Bioprocessing

3. Renewables as chemical feedstocks

Green Technologies
Catalysis
 Catalysis is proving to be a most powerful technology for the
greening of the chemical industry.
 Most simply, catalysis is employed because of its ability to
promote reactions by adding one molecular fragment to
another, with incorporation of most or all of the atoms in both
fragments (reactants) in the final product.
 Catalysis thus embodies the goal of eliminating the
stoichiometric reagent and its associated waste from chemical
manufacturing.
Green Technologies
Catalysis
 Catalysis also encompasses efficient organic synthesis as a
subset, because conversions of high atom economy frequently
employ catalytic steps to carry out given transformations.
 This field of research continues to develop within the
chemical industry, with 80–90% of all chemical processes
involving at least one catalytic step
Green Technologies
Biocatalysis/Bioprocessing
 Biocatalysis is closely related to non-biological catalysis and
possesses many of the same features and benefits.
 In addition, bioprocesses proceed under very mild conditions,
frequently in aqueous reaction media, and can use renewable
feedstocks as starting materials.
 However, issues of separation, expense, productivity,
maintenance of organisms and new capital investment so far
have limited the use of bioprocesses in the chemical industry,
except where no other alternatives are available.
Green Technologies
Renewables as chemical feedstocks.
 Renewables will play an important role in the future evolution
of the chemical industry.
 Progress in the use of conventional chemical processing and
catalysis for the conversion of renewables to products are
areas that will see significant growth as the world turns its
attention to new carbon sources as non-renewable crude oil
feedstocks diminish.
Some Recent Developments and
Examples of Green Technology
 A continuous process and apparatus converts waste biomass
into industrial chemicals, fuels, and animal feed. Another
process converts waste biomass, such as municipal solid
waste, sewage sludge, plastic, tires, and agricultural residues,
to useful products, including hydrogen, ethanol, and acetic
acid.
 A fermentation method for the production of carboxylic acids.

 A method of partially oxidizing alcohol, such as methanol to

ethers, aldehydes, esters or acids, by using a supercritical
fluid mobile.
Some Recent Developments and
Examples of Green Technology
 A pro ces s fo r m a n u fa ct u ri n g a fl u o ro pol yme r by u s in g s u pe rcr it ica l ca r bon
dio xi de .
 A n e co no mi ca l me t ho d o f pr o du cin g e th y l la cta t e, a n on - to xic s ol ve n t der iv ed
f r om co r n .
 A va r ie ty of ‘ or ga n ic s ol ve n ts ’, for ex a mpl e, bi oe th a n o l, t h a t a r e w o rk e r
f r ie n dly a n d e n vi ro n me n t a lly s o u n d.
 A n o ve l e n vi ro n me n ta ll y f ri en dl y te ch n o lo gy i n m ix ed m eta ls r e cov er y f ro m
s pen t a cid w a s te s h a s be en u se d t o r eco ve r zin c a n d f e rr o us ch lo r ide f ro m
pick le l iq uo r .
 Th e de ma n d fo r n o n -io n ic s u rfa cta n ts is i n cr ea s in g. A n i n n ov a ti ve ex a mpl e o f
th i s is a lk yl g lyc os ide , w hi ch i s ma de f ro m sa cch a ride . Th is pro du ct ca n be
u s ed a s a re pla ce me n t fo r a lk yl a r yl s u lp ho n a te an i o n ic s u r f a cta n t s in
s h a mpo os .
 Any
Question?