Green Chemistry Application for

Sustainable Development

Lecture 3

1
The principles of green chemistry

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Principle 5. Safer solvents and auxiliary
substances

Solvents, separation agents and auxiliary

chemicals used in synthetic chemistry must
be replaced or reduced with less toxic
chemicals

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In its short history, Green Chemistry has been heavily focused on
developing new, cleaner, chemical processes using the new technologies.
Increasing legislation will force an increasing emphasis on products, but it
is important that these in turn are manufactured by green chemical methods.
Industry is becoming more aware of these issues and some companies can
see the business edge and competitive advantage that Green Chemistry can
bring.

However, the rate of uptake of Green Chemistry into commercial application

remains very small. While the reasons for this are understandably complex
and also dependent on the economic vitality of the industry, it is important
that the advantages offered by Green Chemistry can be quantified.

Legislation or supply-chain pressures may persuade a company that the use

of a chlorinated organic solvent is undesirable, but how can they select a
genuinely “greener” alternative?
How can a company add environmental data to simple cost and production
factors when comparing routes to a particular compound?

In order to make Green Chemistry happen, we need to see the concept

mature from an almost philosophical belief that it is the “right thing to do” to
one that can give hard, reliable data to prove its merits. 4
Chemical reactions are diverse and are known to occur at a wide range of
temperature and pressure conditions. In most reactions, the reaction vessel
provides the following three components:
- solvent,
- reagent/catalysts,
- energy input.

Basic components
of a reaction

Many of the commonly used solvents (benzene, chlorinated organic solvents,

etc.) are known carcinogens and many others pose hazardous threats to the
environment.
Hence, the use of solvents should be contained; when its use is inevitable,
the solvent should be nontoxic, nonflammable, and eco-compatible, like
water. Alternatives to organic solvents are needed to decrease the negative
environmental impact of these substances. One consequence is the need 5to
avoid the use of organic solvents where possible.
 Organic Solvents: Environmentally Benign Solutions
Organic solvents have played a key role in the development of many useful
products. They are used, for example, to produce pharmaceuticals of the
required purity, to ensure the easy flow and good finish of gloss paints, to
formulate inks that dry successfully and in aerosol applications.
In the latter three consumer applications all the solvent is lost to the
atmosphere whereas in industrial applications ‘end-of-pipe’ solutions can be
installed to recover much of the solvent for reuse or safe disposal and for
energy recovery.

In chemical manufacture, organic solvents are widely used in a variety of unit

operations including separation, reaction (reaction medium), degreasing,
washing, reactants, carrier, crystallization.

One of the key roles organic solvents play in the chemical industry, however,
is that of reactant solvent allowing the homogenization of a reactant mixture,
speeding up reactions through improved mixing, and in addition reducing
energy consumption.

Solvents also contribute to safety by acting as a heat sink for exothermic

reactions.
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Applications of solvent in chemical processes

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The selection of the solvent should consider the following:
• What type of application is it for?
• Can the solvent dissolve the solute(s) and can it be recycled with minimum
solvent loss?
• Is the solvent stable, low-cost, and readily available, and is its environmental
impact acceptable?
• What are the physical and chemical properties of pure solvent(s)?
• What are the interactions among different solvents used in multistep
processes?

Solvents having an average to high degree of safety - SAFE SOLVENTS

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A closer analysis of VOC emission data for solvents reveals that almost half
of the emissions come from the surface coating industry, including
automotive finishing. Non-industrial processes account for around 40% of
emissions; these include pesticide applications as well as consumer solvent
and surface coating applications, such as painting. VOC emissions from
chemical manufacturing processes are a relatively small fraction of overall
emissions, but where these materials are used they often make up a sizeable
percentage of the total process waste coming from chemical factories.

The main environmental issue concerned with VOCs is their ability to form
low-level ozone and smog through free radical air oxidation processes. The
EPA has published a list detailing a number of adverse health effects, which
are now thought to originate from the presence of VOCs in the environment,
including:
- conjunctival irritation
- nose and throat discomfort
- headache
- allergic skin reaction
- dyspnea
- declines in serum cholinesterase levels
- nausea
- fatigue
dizziness. 9
Many technical solutions to the VOC problem are being developed, each
potentially likely to find niche applications. Some of the more common
alternatives to using VOCs including the use of:
- benign non-volatile organic solvents
- solvent-free processes
- supercritical fluids: supercritical carbon dioxide (31.1°C, 73 atm) and
supercritical water (374°C, 218 atm)
- water-based processes
- ionic liquids
- fluorous biphase solvents

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Properties of volatile organic solvents

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 SOLVENT- FREE SYSTEMS

It is a misconception that most chemicals are manufactured in organic

solvents. Most high-volume bulk chemicals are actually produced in solvent-
free processes or at least ones in which one of the reactants also acts as a
solvent.

Advantages associated with the use of a solvent-free system over the use
of organic solvent:
1. There is no reaction media to collect, dispose of, or purify and recycle.
2. On a laboratory’s preparative scale, there is often no need for specialized
equipment.
3. Extensive and expensive purification procedures such as
chromatography can often be avoided due to the formation of sufficiently
pure compounds.
4. Greater selectivity is often observed.
5. Reaction times can be rapid, often with increased yields and lower
energy usage.
6. Economic considerations are more advantageous, since cost savings
can be associated with the lack of solvents requiring disposal or recycling.

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Typical examples of such large-scale processes include the manufacture of
benzene, methanol, MTBE, phenol and polypropylene.

MTBE – methyl tert-butyl ether (MTBE is almost exclusively used as a fuel

component in fuel for gasoline engines. It is one of a group of chemicals
commonly known as oxygenates because they raise the oxygen content of
gasoline).
Since 1980 MTBE has made a significant contribution to the lowering of VOC
emissions from car exhausts. This is due to its clean burn properties,
(producing fewer hydrocarbon by-products).
MTBE is commonly produced in a fixed-bed reactor by passing a mixture of
2-methylpropene and excess methanol over an acidic ion exchange resin
(Scheme 1). The reaction takes place in the liquid phase at temperatures 70 –
900C and pressures upwards of 8 atm. Depending on the feed, conversions of
over 90% are achieved.

Scheme 1

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 GREEN SOLVENTS
Green solvents are environmentally friendly solvents, or biosolvents, which
are derived from the processing of agricultural crops.

The use of petrochemical solvents is the key to the majority of chemical

processes but not without severe implications on the environment.
Green solvents were developed as a more environmentally friendly alternative
to petrochemical solvents.

Ethyl lactate
- a green solvent derived from processing corn,
- the ester of lactic acid. Lactate ester solvents are commonly used solvents
in the paints and coatings industry and have numerous attractive advantages:
- 100% biodegradable,
- easy to recycle,
- noncorrosive,
- noncarcinogenic,
- nonozone-depleting.
- is a particularly attractive solvent for the coatings industry as a result of its
high solvency power, high boiling point, low vapor pressure and low surface
tension. 14
Ethyl lactate
- is a desirable coating for wood, polystyrene and metals and also acts as a
very effective paint stripper and graffiti remover,
- has replaced solvents such as toluene, acetone and xylene, resulting in a
much safer workplace,
- is an excellent cleaner for the polyurethane industry,
- has a high solvency power (it is able to dissolve a wide range of
polyurethane resins).

The excellent cleaning power of ethyl lactate also means it can be used to
clean a variety of metal surfaces, efficiently removing greases, oils, adhesives,
and solid fuels.

The use of ethyl lactate is highly valuable, as it has eliminated the use of
chlorinated solvents.

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 WATER AS A REACTION SOLVENT
From a green chemistry viewpoint the use of water as a solvent has many
advantages but also some disadvantages.

Water has many interesting properties which are now being exploited in
synthetic chemistry; as the temperature of water is raised the ionic product
increases whilst its density and polarity decrease. Thus at temperatures above
2000C (in the liquid state) water starts to take on many of the properties of
organic solvents whilst at the same time becoming a stronger acid and base,
for example at 3000C water has solvent properties similar to acetone. These
effects are related to the reduction in hydrogen bonding of water at higher
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temperatures.
Replacement of organic solvents by water may be done for environmental,
cost (e.g. reduction in raw materials and VOC containment costs) or technical
reasons.
In the flavor and fragrance industry, where the presence of even trace
amounts of volatile impurities can be detected by the expert 'nose', significant
process costs are entailed in ensuring complete removal of solvent. If
reactions can be carried out in water then these additional costs can be saved.

Ex. Geraniol (food, cigarettes) can be isomerized to the important fragrance

intermediates α-terpinol and linalol in water at 2200C.

Isomerization of geraniol in water

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The increase in acidity and basicity of water at high temperatures often
means that lower amounts of acid or base can be used in the process, which
in turn results in lower salt waste streams.
A hydrolysis process and
highlights the synthetic
versatility and tunability that
can be obtained. At 2000C
indole carboxylic acid esters
Indole synthesis in high are rapidly hydrolysed in high
temperature water yield in the presence of small
amounts of base, but at 2550C
the resulting carboxylic acid is
decarboxylated in over 90%
Indole – used in cosmetics industry (perfumes)
yield in under 20 min.

Decarboxylation step has environmental advantages when compared to more

usual methods involving use of copper catalysts in non-volatile organic bases
at high temperatures.

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Some examples using
water as a reaction
solvent

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Most water-based paints use copolymers of polyvinyl acetate (often with butyl
acrylate). They do contain small amounts of higher-boiling organic solvents
but VOC emission and health risks are minimal; these products are now
widely accepted by the public for home use. A typical household emulsion
paint will contain around 30% polymer, 25% pigments, 15% dispersant and
20% water; the remainder is made up of a range of additives such as
antifoams and in particular around 6% high-boiling organic solvents, mainly
ethylene and propylene glycols.

Advantages and challenges faced in development of

water-based coatings

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 Ethanol - sole solvent for Sertraline manufacturing
1970 - Pfizer chemist Reinhard Sarges invented a novel series of psychoactive
compounds based on the structures of neuroleptics chlorprothixene and
thiothixene
Sertraline (trade names Zoloft - RO, Lustral) is an antidepressant of the
selective serotonin reuptake inhibitor (SSRI) class. It was introduced to the
market by Pfizer in 1991. Sertraline is primarily prescribed for major
depressive disorder in adult outpatients as well as obsessive–compulsive,
panic, and social anxiety disorders in both adults and children.
In 2011, it was the second-most prescribed antidepressant on the U.S. retail
market, with 37.208.000 prescriptions.

Redesign the sertraline manufacturing process - Pfizer received a Presidential

Green Chemistry Challenge Award in 2002.

Among other waste - minimizing improvements, a three - step sequence was

streamlined by employing ethanol as the sole solvent. This eliminated the
need to use, distill, and recover four solvents (methylene chloride,
tetrahydrofuran, toluene, and hexane) and resulted in a reduction in solvent
usage from 250 to 25 liters per kilogram of sertraline.

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The new sertraline process
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Similarly, Pfizer workers also reported impressive improvements in solvent
usage in the process for sildenafil (Viagra) manufacture, reducing the
solvent usage from 1700L/kg of product used in the medicinal chemistry
broute to 7L/kg in the current commercial process with a target for the
future of 4L/kg.
The E factor (kg waste/kg product) for the current process is 8, placing it
more in the lower end of fine chemicals rather than with typical
pharmaceutical manufacturing processes.

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 Green Chemistry and reduction of solvent toxicity
Alternative solvents or replacement

Green Chemistry is concerned with the amounts of toxic organic solvents

used in synthetic routes and overall chemical processes.

In accord to principle 5 of green chemistry is necessary to reduce the use of

solvent as much as possible, or if possible to replace with a less toxic or to
use alternative techniques in which solvents are not needed.

Solvents in the chemical industry is one of the major problems concerning

workers health and safety and environmental pollution because of waste.
Synthesis, separation of product, cleaning, drying, analysis and recycling,
etc. are some of the processes where solvents are used. Changing solvents
and technological processes is not an easy task. There are many alternatives
but can be more expensive, time consuming or difficult to implement under
the established order of chemical methodologies. Although environmental
pollution from solvents can be a serious problem for many chemical
industries, the solutions are not always there to replace solvents or to reduce
their use.

In recent years, under the influence of green chemistry principles, some

solvents have been replaced and methodologies changed to more benign 24
techniques.
a) Oxidations under Green Chemistry principles to reduce solvents

Many oxidation techniques in chemical processes have changed under green

chemistry principles. They now are performed in water, in supercritical CO2 or
with less toxic solvents and under room temperatures.

H2O2 - considered as a very good oxidative reagent that performs at normal

temperatures. There are numerous research efforts to apply oxidations with
high selectivity and as by-production only water.
Homogeneous and heterogeneous reactions in combination with catalysts are
used in many oxidations. Oxidations are very important in the pharmaceutical
industry and in many petrochemical processes.
Oxygen and nitrogen oxides (NOx) are oxidative agents with green chemistry
credentials which are used in the oxidation of benzene, cyclopentanone and
propylene.

In recent years for oxidations chemists use catalytic methods with metallic
complexes. Some of these are: metal-peroxo systems, polyoxometallates
(POM), metal oxide clusters, especially metal - W and heteroanions.
Heterogeneous catalysis for oxidations with zeolitic materials are some other
techniques used in recent years. Many research projects of these types of
oxidation agents can be found in scientific journals for selective oxidations.
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b) Catalytic selectivity in synthesis to reduce solvents

Catalytic selectivity can be another research effort for the reduction in the use
of solvents and with higher yields and lower amounts of waste. Many
industrial processes are based in new catalysts, such as inorganic polyacids
and heteropolyacids which act as green catalysts in oxidations, in the
hydration of butane mixtures and in the polymerization of tetrahydrofuran
(THF).
The heterogeneous catalytic method showed:
- cleaner products,
- minimum waste,
- easy separation of the products.

Various porous materials with small pore diameter can be used as catalytic
surfaces for the regulation of the dissipating reactants (mesoporous solid
acids). Selectivity and higher yields are achieved in this type of reactions.

Polymer chemistry and production of plastics have achieved recently green

credentials with new methodologies. Some of the achievements in the
production of well known commercial polymers:
- renewable starting materials,
- higher yields with biocatalytic methods,
- minimum use of solvents,
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- less waste.
 Applications of new methodologies in the synthesis
of chemical compounds

a) Ionic liquids in organic synthetic routes

Ionic liquids (liquid electrolytes) - used extensively in recent years as
alternative solvents in organic synthesis. These substances can be ionic melts,
ionic fluids, fused salts, liquid salts, or ionic glasses. Ionic liquids have many
applications, as powerful solvents and electrically conducting fluids
(electrolytes). Salts that are liquid at near-ambient temperature are important
for electric battery applications. Ionic liquids are mixtures of anions and
cations, fused salts with melting point less than 100 0C. Ionic liquids do no fit
to the principles of green chemistry, they are considered as good candidates
for future improvements that can give “green” credentials to their use and
applications.

b) Organic synthesis in water

Water was considered for many decades as a medium that was to avoided as
solvent for synthetic organic chemistry. Water proved to be an excellent
solvent for many synthetic methods. Water has been proved very good for
selectivity even for reagents which are not very soluble or insoluble in water.
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c) Organic synthesis in polyfluorinated phases
In these techniques chemists are using polyfluorinated two phase systems of
solvents which dissolve a catalysts with a long hyperfluorinated alcylo- or
aliphatic chain. Reagents are dissolved in an organic solvent which is
insoluble in the hyperfluorinated phase. Warming up the mixture accelerates
the reaction with excellent yield of products.

d) Supercritical carbon dioxide and supercritical water

Supercritical fluid is called any liquid substance at a temperature and pressure
above its critical point, where distinct liquid and gas phases do not exist. It
can effuse through solids like a gas, and dissolve materials like a liquid. In
addition, close to the critical point, small changes in pressure or temperature
result in large changes in density, allowing many properties of a supercritical
fluid to be "fine-tuned". Supercritical fluids are suitable as a substitute for
organic solvents in a range of industrial and laboratory processes. Carbon
dioxide and water are the most commonly used supercritical fluids. They are
use for supercritical fluid extraction (SFE). These supercritical properties can
be applied as “green chemistry” credentials in chemistry with high yields and
minimum waste.

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e) Use of microwave techniques for organic synthesis
Microwave furnaces are widespread now for food warming and cooking. Their
use in organic synthesis started many years ago and their success in organic
synthesis with “green’ criteria is very well established.
Advantages of microwave technique for organic synthesis:
- high yields,
- solvents free,
- low waste,
- very low energy requirements.

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f) Sonochemistry
The use of ultrasound for synthesis Chemical reactions can start and
enhanced by sonic waves. Sonochemical reactions by ultrasound is very
advanced “green” techniques with exceptional high yields.
There are three classes of sonochemical reactions:
- homogeneous sonochemistry of liquids,
- heterogeneous sonochemistry of liquid-liquid or solid–liquid systems,
- sonocatalysis.

The chemical enhancement of reactions by ultrasound has been explored

and has beneficial applications in mixed phase synthesis, materials
chemistry, and biomedical uses.

Other techniques advanced in the last decade in organic synthesis, with

emphasis on toxic solvent minimization:
- soluble polymers as catalysts,
- thermoregulated systems,
- enzymes.

All these techniques have been advanced with green chemistry principles
in mind, since industrial production of chemical substances is the
fundamental technology producing environmental problems, waste and
toxic by-products. 30
Short conclusions

To achieve near-total “greenness” of chemical processes, we need to focus

on every aspect of the chemical reaction.

Some of the challenges facing chemists in this regard could be summarized

as the following:
- employ solvents that also serve as catalysts,
- employ solvents that can be easily separated downstream,
- employ reagents that will be effective in catalytic concentrations,
- employ reagents that are recyclable,
- employ solvents and reagents that are biodegradable.

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Principle 6. Design for energy efficiency

Energy consumption should be minimized

environmental impact.
Synthetic methods should be conducted at the
ambient temperature and pressure

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Energy sources
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Most chemical processes use thermal sources of energy originating from
fossil (or nuclear) fuels.

U.S. (left) and world (right) sources of energy.

Percentages of total rounded to the nearest 1%

This dependency on fossil fuels has two major consequences:

(1) It is leading to rapidly diminishing reserves of this valuable non-
renewable resource.
(2) It is contributing to the increasing concentration of CO 2 in the
atmosphere.

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Devices for the conversion of energy from one form to another
(efficiencies in parentheses)
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The energy input to the process is non-specific, i.e. it is not directly targeted
at the chemical bond or even the molecules undergoing reaction.

Much of the energy is ‘wasted’ in heating up reactors, solvent and even the
general environment. For some processes alternative, more specific, forms of
energy, e.g. photochemical and microwave energy, may be beneficially
applied.

Whilst use of such alternative forms of energy is not new they are currently
being taken more seriously by manufacturing industries and hence can be
viewed as emerging technologies. Even with thermal sources of energy,
conservation measures can be applied to reduce cost and environmental
impact.

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Some measures for minimizing energy consumption

► Monitoring, control and maintenance. Many pieces of equipment operate

below design specification, and temperature control of many processes is far
from optimum. By use of modern computerized digital monitoring and control
systems, optimum system performance is more easily achieved. Regular
maintenance of equipment including replacement of filters on pumps and
regular lubrication can improve energy efficiency and extend equipment life.

► Loss prevention. Walking around many chemical factories will reveal

obvious sources of energy loss, probably the most noticeable being leaky
steam valves. Good housekeeping can do much to conserve energy.

► Waste heat recovery. Many processes, and whole factories, now employ
waste heat recovery, for example, hot flue gases pass through a heat
exchanger before being emitted, the resulting hot water being put to
beneficial use. Hot liquid streams from one process step are also used to
directly heat incoming streams for another.

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► Matching energy sources to requirements. Most householders realize that
heating a whole house to, say 200C, using electrical resistance heaters
(electric fires) is more costly and uses more energy that a modern gas central
heating system. The same principle applies to the process industries, for
example using high-pressure steam to heat a solution to 350C is highly
inefficient. Hence most industrial sites have a variety of energy sources to
meet specific process demands.

The use of techniques presented before, together with sophisticated analysis

programmes, coupled with improvements in the energy efficiency of
equipment and improved process chemistry, has resulted in the energy
consumption per tonne of product declining for the past 50 years.

Relative decline in energy used in chemicals

production (UK data) 38
 Photochemical reactions

Many photochemical reactions do, however, have quantum yields of several

thousand, implying that the photon is simply being used to initiate a chain
reaction. The current cost of generating photons (unless visible light can be
used) is generally such that, unless a reaction has a quantum yield far higher
than unity, it is unlikely to be commercially attractive unless there is no viable
alternative.

In practice quantum yields are not that easy to measure and it is more useful
to measure total energy consumption.

When a photon is absorbed it must transfer all its energy to the absorbing
molecule, the molecule being promoted to a higher energy state. For many
molecules the energy required for promotion from the electronic ground state
to the lowest excited state falls in the visible and UV regions of the
electromagnetic spectrum.

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 Advantages of and Challenges faced by photochemical processes

Green credentials:
► Photons are very clean reagents, leaving no residues. A photoinitiated
process therefore has potential advantages even when compared to
reactions initiated by the use of catalysts. Such processes may use fewer
raw materials compared to non-photochemical alternatives, e.g. comparison
of photo- and radical-initiated halogenation reactions.

► Since the energy is more directed, reaction temperatures are generally

low. This may give higher selectivities, by reducing by-product formation
from competing reactions.

► Some reaction pathways are more readily available via photochemical

processes, leading to products that would be difficult to make by other
routes.

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 Examples of photochemical reactions
The caprolactam syntheses
The chemistry involves a radical process resulting from the production of NO
and Cl radicals from NOCl by light of 535nm wavelength. The commercial
success of this process is partially due to the relatively low cost of producing
this 'visible region' light, using a low-pressure mercury lamp doped with
thallium iodide. The thallium iodide both increases the intensity of the required
wavelength and reduces the intensity of lower wavelengths, which initiate
polymer formation; hence fouling is reduced to acceptable levels.

Photochemical caprolactam synthesis

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The D3 vitamin syntheses

Photochemical electrocyclic ring opening followed by a thermal 1,7-hydride

shift.

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Some remarks:

► Photochemical reactions are most likely to be used in niche applications

for commercial and environmental reasons. Unless there is a major
breakthrough in reactor and lamp design, widespread use of this technology
is unlikely.

► Perhaps the best hope of producing high-intensity monochromatic sources

of radiation rests with lasers, but currently equipment costs are too high to
justify their use for commercial chemical production.

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 Chemistry using microwaves

Microwaves have wavelengths between 1mm and 1m and hence have similar
frequencies to radar and telecommunication devices.

So as not to cause interference with these systems the frequency of radiation

that can be emitted by household and industrial appliances is strictly
regulated, with most appliances operating at a fixed frequency of 2.45 GHz. To
some extent this reduces the flexibility of such equipment.

It is evident that whilst certain materials can be heated selectively, the energy
will soon be uniformly distributed throughout a homogeneous reaction
medium. Microwaves may be considered a more efficient source of heating
than conventional steam- or oil heated vessels since the energy is directly
imparted to the reaction medium rather than through the walls of a reaction
vessel.

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One of the reasons why there has been phenomenal growth in research in
microwave chemistry since the early 1990s is the realization that it can provide
a rapid method for screening reactions.

With a heating rate of 100C per second being achievable it is easy to see how
the overall reaction time can be considerably shortened. Although there are
examples of improved reaction selectivities and yields using microwave
heating, any specific microwave effects other than can be obtained by rapid
heating have not been conclusively proven, although it has been postulated
that microwave-induced reactions follow the most polar pathway possible.

Microwave assisted Hofmann elimination

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Water-bused microwave assisted reactions

Microwave assisted N-alkylation

and acylation reactions
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 Sonochemistry
Ultrasound refers to sound waves with frequencies higher than those
detectable by the human ear, i.e. around 18 kHz.

Some other uses of power ultrasound

The term sonochemistry is used to denote reactions initiated by ultrasound.

The range of reactions carried out under sonochemical conditions is large and
growing rapidly; in many cases some green benefits are obvious.

Typical reaction types assessed include:

- oxidation (can often be carried out more rapidly at lower temperatures),
- radical reactions (the radicals being generated under mild conditions),
- synthesis of nanopartides. 47
Example of sonochemical switching

Sonochemical Simmons Smith reaction

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 Electrochemical synthesis

Electrochemistry is widely used in industry:

- effluent treatment,
- corrosion prevention,
- electroplating,
- electrochemical synthesis.

Electrochemical synthesis is a well-established technology for major

processes such as aluminium and chlorine production; there is, however,
increased interest in the use of electrochemistry for clean synthesis of fine
chemicals.

The possible green benefits of using electrochemical synthesis include:

- often water-based processes,
- usually mild operating conditions (relatively energy efficient),
- atom efficient - replacement of reagents by electrons,
- novel chemistry possible.

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 Examples of electrochemical synthesis

The membrane cell for production of chlorine is the most recent of three
competing processes for chlorine production, the others being the mercury
and the diaphragm cell processes.

Schematic of an
electrochemical
membrane cell
for production of Cl2

The membrane is very selective, only allowing cations to pass; the NaOH is produced at
only 35% concentration, which is less than optimum.
Cell costs are lower than the mercury cell.
In Europe around 50% of chlorine is still produced using the mercury cell, although the
EU are trying to phase these out by 2010.
Since the late 1970s, however, mercury discharges have been reduced by some 95% and
now stand at 1.3 gHg/tCl2. In Japan the mercury process has been phased out, largely
because of intense public concern regarding mercury discharges following 50the
Minamata Bay incident in 1965.
Adiponitrile is produced at over 1 million t/year and, being used in the
manufacture of hexamethylene diamine and (to a small extent) adipic acid, it is
by far the highest-volume organic material that is produced electrochemically.
The mechanism involves electrolytic reduction of acrylonitrile followed by
protonation, further reduction, Michael addition and a final protonation step.

Electrochemical adiponitrile synthesis

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Synthesis of 3-bromothiophene provides an example of the obvious environmental
benefits of an electrochemical route compared to a conventional process.
Both routes start from 2,3,5-tribromothiophene, obtained via bromination of thiophene.

The conventional route uses

an excess of zinc and acetic
acid as the reducing agent,
producing a large waste
stream containing zinc
bromide and waste acid.

Competing routes to 3-bvomothiophene

In the electrochemical route the use
of a metal reducing agent is avoided
and no bromine is wasted since the
resulting bromide is oxidized to
bromine, for recovery, at the anode.
Additional bromide is required; this
is added to the electrolyte as
sodium bromide. In order to get
adequate solubility of the starting
materials dioxane is used as a
cosolvent.

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 Short conclusions
► Energy consumption, particularly for large-volume chemicals, has been
taken seriously by industry for many years.

►Through a combination of new processes, particularly catalytic ones,

improved engineering designs and ‘good housekeeping’, energy use
continues to fall.

► Unfortunately energy consumption is still not considered particularly

important by the average research chemist. The recent emergence of
technologies which input energy in an alternative forms (microwave and
ultrasound), together with renewed interest in photochemistry and
electrochemistry for green chemistry, will lead to selected future processes
being more energy efficient as well as cleaner.

► Ideally each research laboratory should be equipped with photochemical,

microwave, ultrasonic and electrochemical reactors as well as heating
mantles and oil baths; only then will these technologies become
mainstream.

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