Green Chemistry Application for

Sustainable Development

Lecture 4

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Principle 7 – Use of renewable raw
materials and feedstocks

Green chemists must change the

manufacturing process by discovering
renewable chemicals

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 Use of alternative basic chemicals as feedstocks in chemical
industry and research
In 2007 the U.S. Department of Energy commissioned a report for the future of
alternative and renewable feedstocks for its chemical industry. The U.S. has the
biggest chemical industry in the global arena producing almost 1/3 of chemical
products. U.S. scientists are considering from now that the time is approaching for
the natural gas and petroleum production will "peak," plateau and then decline.
Prices also increased substantially in the last decades contributing to the
uncertainty.

These trends and the uncertain future inevitably influence other industrial nations
and especially the European Union countries which produce the other 1/3 of
chemical products.

Until now, of the last 50 years the majority of raw chemicals and starting materials
not only for the chemical industry but also for other industries and workshops were
products of the petrochemical industry.

This total reliability to fossil fuels and their products (for chemicals and transport)
had a great impact on resources, sudden increase on prices, economic crisis for
certain countries and an uncertain future for availability of feedstocks. 20-25.000
basic chemicals are relying on petrochemical feedstocks due to low cost and the
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established technological means.
Green Chemistry and Green Engineering are striving to produce new
methodologies for sustainable development. Their proposals focus on:

a) Renewable feedstocks and raw materials

Green Chemistry wants to change into renewable feedstocks. The second most
desired property of basic starting materials is their lower toxicity and their
environmental impact. Health and safety protection of workers and the
environment is a top priority. Green Chemistry proposes change of direction
into biological raw materials (plant and animal waste, products from fermentation
of plant waste, biogas, etc). There are many difficulties in the use of these
materials, but in the last years there are encouraging new prospects for large
scale production and use of alternative, renewable materials.

b) Oleochemistry. New biological starting materials

Fats and oils (from plants and animals) as oleochemical raw materials can become
a new source of chemical feedstocks. Already a series of raw materials exist in
the market with many applications in cosmetics, polymers, lubricating oils and
other products.

c) Photochemistry. New chemical processes with the aid of lights

d) Photocatalytic synthetic routes with Titanium dioxide (TiO2)

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e) Photocatalytic oxidations. Waste and toxic chemicals decomposition
f) Waste Biomass as chemical feedstocks, biomaterials and biofuels
The advances of the last decade into the use of biomass for the production of various
materials was very impressive. It was known for decades that biomass from
agricultural processes was wasted. Scientists for year researched many aspect of
biomass and its effective. Biomass is considered a very important problem of
sustainability with increasing fossil fuel prices. In recent years many new
technologies showed the use of biomass as biofuel, raw material for the production of
biomaterials, polymers and various other applications.

g) Biodegradation of biomass for biogas and biodiesel

Biomass is well known for its use for biofuel, especially from organic waste in
landfills. Biomass, through chemical and physical processes can be used for the
production of biodiesel. Biomass in 2005 offered the opportunity for the production of
19% of energy on a global scale. Now, it is estimated that 4% of all fuel products in
cars is produced from biomass.

h) Biocatalysis and biotransformations in the chemical industry

i) Capture or sequestration of carbon dioxide

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 Lifecycle carbon emissions profiles of various fuels, including many synthetic
fuels. Coal and biomass co-conversion to transportation fuels, Michael E. Reed, 6
DOE NETL Office of Fossil Energy, Oct 17 2007
 SOURCES OF FEEDSTOCKS
Feedstocks - the main ingredients that go into the production of chemical products.

A feedstock should be as safe as possible.

The source of a feedstock can largely determine its environmental impact, and the
acquisition of the feedstock should not strain Earth’s resources.
For the manufacture of organic chemicals and the vast variety of products made from
them, such as textiles, plastics, and rubber, the overwhelming choice of feedstock
now is petroleum, amounting to all but about 2% of raw material is used for organic
chemical manufacture.

Much of the challenge and potential environmental harm in obtaining feedstocks is in

separating the feedstock from other materials. Cellulose from wood, which can be
converted to paper and a variety of chemicals, is mixed intimately with lignin, from
which it is separated only with difficulty. Some metals occur at levels of less than 1%
in their ores, requiring energy-intensive means of separating out the metals from
huge quantities of rock.

In evaluating the suitability of a feedstock, it is not sufficient to consider just the

hazards attributable to the feedstock itself and its acquisition. That is because
different feedstocks require different processing and synthetic operations
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downstream that may add to their hazards.
If feedstock A requires use of a particularly hazardous material to convert it to
product, whereas feedstock B can be processed by relatively benign processes,
feedstock B should be chosen. This kind of consideration points to the importance of
considering the whole life cycle of materials rather than just one aspect of them.

The ideal feedstock is renewable and poses no hazards; can be converted to

the desired product using few steps with 100% yield and 100% atom economy.
This should be done with minimum quantities of reagent using only safe media in
which the reaction occurs.

Addition reaction
All feedstock material becomes part of the product and there are no byproducts.
These are the best kinds of reactions from the viewpoint of green chemistry
because, when they work ideally, there are no wastes.
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Substitution reaction
- uses a reagent to replace a functional group on the feedstock molecule.

Elimination reaction
- removes a functional group from a feedstock molecule.

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 BIOLOGICAL FEEDSTOCKS
Biomass, the plant material generated from photosynthesis is the leading candidate
to replace petroleum as a feedstock for the organic chemicals industry. Several
major categories of biomass that can be used for feedstock:
1. Carbohydrate, which has the general formula of approximately CH2O.
Carbohydrate is the biomass that is produced initially as glucose sugar from water
and carbon dioxide during photosynthesis. It is contained in the structural parts of
plants as cellulose, a biopolymer.

2. Lignin, a biological polymer with a complex structure, which occurs with

carbohydrate cellulose in woody parts of plants, binding fibers of cellulose
together. Relatively few uses have been found for lignin, and it poses impurity
problems in extracting cellulose for feedstock use.

3. Lipid oils extracted from seeds, including soybeans, sunflowers, and corn.

4. Hydrocarbon terpenes produced by rubber trees, pine trees, and some other kinds
of plants.

5. Proteins, produced in relatively small quantities, but potentially valuable as

nutrients and other uses.
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Glucose as feedstock
The glucose molecule provides a promising platform for a
number of different organic syntheses. Glucose is
metabolized by essentially all organisms, so it serves as an
excellent starting point for biosynthesis reactions using
enzymes, and it and many of its products are
biodegradable, adding to their environmental acceptability.
The greatest use of glucose for synthesis is by fermentation with yeasts to produce
ethanol, an alcohol widely used as a gasoline additive, solvent, and chemical
feedstock.

Glucose is widely used as a starting material for the biological synthesis of a

number of different biochemical compounds. These include ascorbic acid, citric acid
and lactic acid. Several amino acids used as nutritional supplements, including
lysine, phenylalanine, threonine, and tryptophan, are biochemically synthesized
starting with glucose. The vitamins folic acid, ubiquinone, and enterochelin are also
made biochemically from glucose.

As an example of the potential of glucose for making important feedstocks, consider

the synthesis from glucose of adipic acid, a feedstock consumed in large quantities
to make nylon.
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Cellulose as feedstock
The most abundant natural material produced
by organisms is cellulose synthesized
biologically by the joining of glucose molecules
with the loss of 1 H2O molecule for each bond
formed.
Wood is about 40% cellulose, leaf fibers about
70%, and cotton, one of the purest sources of
cellulose, about 95%.

A finely divided form of cellulose called microcrystalline cellulose is produced

by appropriate physical and chemical processing of cellulose. This material has
many uses in foods in which they impart smoothness, stability, and a quality of
thickness and in pharmaceutical preparations and cosmetics.
Added to food, indigestible cellulose contributes bulk and retains moisture.

Cellulose nitrate makes transparent film and was used in the early days of moving
pictures for movie film.

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Lignin as feedstocks
Lignin, a chemically complex biopolymer that is associated with cellulose in plants
and serves to bind cellulose in the plant structure, ranks second in abundance only
to cellulose as a biomass material produced by plants.

Lignin is normally regarded as a troublesome waste in the processing and utilization

of cellulose. The characteristic that makes lignin so difficult to handle in chemical
processing is its inconsistent, widely variable molecular structure.

A significant characteristic of lignin is its resistance to biological attack.

Lignin generated as a byproduct in the
extraction of cellulose from wood is now
largely burned for fuel.

It has some uses for binders to hold

materials together in coherent masses,
fillers, resin extenders, and dispersants.

There is also some potential to use lignin as

a degradation-resistant structural material,
such as in circuit boards.
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Fatty acids as feedstock

Fatty acids are often described

by numbers such as 16:0, 18:1
or 18:3. The first number (16 or
18) is used to describe the
number of carbon atoms in the
chain whilst the second (0,1,3)
gives the number of C=C double
bonds in the molecule. Palmitic
acid can therefore be shortened
to 16:0 whilst oleic acid is 18:1.

Whilst the acids and many of their derivatives currently find niche applications in
some market sectors, factors related to price, volume of supply and consistency
have all limited commercial viability. In the longer term, reduced costs and improved
consistency through improved growing and harvesting techniques, coupled with16an
increased requirement for biodegradability, will increase demand for fatty acids.
 The current major use of erucic acid is in
the production of erucamide, a 'slip agent‘
used in the manufacture of polythene bags
to make them open more easily.

With European consumption being around

60 000 t/year; almost 40000 ha of land are
used to grow rapeseed for erucic acid
production in Europe.

The high level of erucic found in this type

of rape seed oil make it unsuitable for
human consumption, owing to the
indigestibility of such large amounts of this
acid.

Linolenic acid is also important industrially; it is the major constituent of linseed oil
(approximately 47%) which is obtained from flax. The high degree of unsaturation
present in this acid makes the oil an excellent drying agent for use in paints,
varnishes and inks.

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 CONCLUSIONS

► For long-term sustainable development and the future stability of

the economy, the world’s dependence on fossil resources must be
reduced.

► The use of renewable resources for manufacturing specific

performance and specialty chemicals, and for fibres to replace
synthetic ones, is growing. The driver for this is improved
cost/performance.

► Many technical developments in separation science as well as

improvements in the overall ‘yield’ of chemicals are required before
renewable feedstock can compete effectively with oil and gas, but the
gap will continue to narrow.

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 Principle 8. Reduce intermediate
derivatives

Chemists must aim for reducing unnecessary

derivatization (use of blocking groups,
protection/deprotection techniques and
temporary modification of physical and chemical
processes) in the synthetic routes

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 Conventional reactors
Chemical processes can be divided into two main types, batch and continuous;
most fine chemicals and pharmaceuticals are made in batch reactors whilst the
majority of bulk chemicals are made in continuous plants.
Semi-batch plants are used in some cases; these processes involve additional
ingredients being added at certain stages into an otherwise batch process. Multi-
purpose plants tend to go hand in hand with batch processing; these are relatively
common in the fine chemicals industry, most bulk processes using dedicated plant.

Reactor choice and operation can have a dramatic effect on the overall eco-
efficiency of a process. An effective reactor design can dramatically reduce
downstream processing requirements and hence costs and waste.

Continuous Stirred Tank Reactors

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Reaction profile of batch and CSTR reactors
 Inherently safer design (ISD)

Over 60% of all accidents at chemical manufacturing plants are caused by either
mechanical failure or operational error. The concept of ISD seeks to avoid accidents
and incidents by asking: ‘Can the hazard be eliminated by redesigning the process?’

At the heart of ISD is the avoidance of reliance on mechanical safety devices andor
procedures, both of which are ultimately fallible. Chemical plants are designed to be
safe but most are not designed to be inherently safe.

The concept of ISD arose as a consequence of the incidents at Flixborough and

Bhopal (the classic case study of what could have been prevented with ISD).

Convenient subdivisions of the concepts and methodology of ISD:

a) Minimization: by minimizing inventories of hazardous material, for example
through ‘just in time’ production the consequences of any accident will inevitably
be reduced. Minimization goes much hurther than storage, however. For many
processes the largest inventory of hazardous materials is in the reactor. If,
through radical reactor design, inventories and equipment size can be reduced
whilst throughput is maintained, then this presents opportunities for improved
safety and possibly reduced capital costs.
The Flixborough disaster in 1974, in which a cyclohexane oxidation plant exploded,
is a good example of what can happen when large inventories of hazardous 21
material are used.
b) Simplification: less mechanical equipment and fewer joints, both of which may
fail leading to an accident. Simplification reduces the opportunity for error and
malfunction. Frequent modification is another significant cause of complexity. Some
modifications are carried out to make the plant more versatile but others are to
overcome basic faults, such as having valves in inaccessible places.

Some possible examples of over-complexity include:

► Running long lengths of pipe with many flanges, say from a reactor to a filter,
owing to lack of attention to layout.
► Using solvent as a heat sink in a batch reaction rather than having a more
efficient cooling system or using a tubular reactor.
► Installing an excess of analytical equipment and sample ports; for example, an
online near-infrared analyser may take the place of a gas and liquid sample port and
associated GC equipment.

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c) Substitution
The substitution of hazardous materials by more benign ones is a core principle of
green chemistry, and a key feature in ISD.
Obvious examples would be the substitution of a flammable solvent by a non-
flammable one and replacement of a harmful material by a safer one, as in the case
of scC02 decaffeination of coffee.

d) Moderation
In many cases it will not be possible to substitute a hazardous material, and in these
cases the onus should be on using the hazardous material in a less hazardous form
or under less hazardous conditions.
Concern over the storage of hazardous materials has resulted in significant
moderation.

e) Limitation
Chemicals manufacture will always involve some risk and will always rely to some
extent on equipment integrity and appropriate operation. Limitation is the process of
minimizing the effects of failure (of equipment or people) or an incident by design.
One important aspect of the design process should be to limit the available energy to
an appropriate level.

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 Process intensification (PI)

Process intensification is commonly defined as ' Technologies and strategies that

enable the physical sizes of conventional process engineering unit operations
to be significantly reduced.'

This is achieved through:

► Improving mass-transfer rates to match that of the reaction.
► Improving heat-transfer rates to match the exothermicity of a rection.
► Having an appropriate residence time for the reaction.

As a general rule major equipment such as reactors and distillation columns

account for only 20% of the price of a manufacturing plant, the remainder being
pipework, instrumentation, labour and engineering charges, etc.

The scope of PI is now extensive, extending well beyond basic equipment design
into actual process methodology.

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Mike LANCASTER, GREEN CHEMISTRY. An introductory text, ISBN 0-85404-620-8, The
Royal Society of Chemistry 2002

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Example of PI - manufacture of nitroglycerine.
The reaction, originally carried out in large stirred batch reactors, involves the
nitration of propylene glycol (glycerine) with a mixture of concentrated nitric and
sulfuric acid, and is highly exothermic. If the heat is not removed quickly enough the
nitroglycerine can decompose explosively.

In the original process, external cooling was provided manually by the operator
opening cold water circulating valves when the reactor had reached a certain
temperature. In an attempt to ensure safe operator practice, one-legged stools were
provided to prevent the operator falling asleep-definitely not an inherently safe
design!
The method developed in the 1950s involved having a rapid flow of acid into a small
reactor. This created a partial vacuum (water pump) which sucked glycerine into the
acid stream, ensuring good mixing. Using this method residence time in the reactor
was reduced from 2 h to 2 min. This enabled the reactor inventory to be reduced to
1 kg, a size at which the severity of an explosion could be mitigated by building a
blast wall around the reactor. 26