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Green Solvents

By
Aditi Banerjee

Role of solvents
n

As reaction media: energy control, efficient mixing and


stirring

Used in extraction processes

Also used as coatings and for cleaning purposes

Need for alternative solvent


Minimise the environmental hazards
n Largest source of volatile organic
compounds (VOC) in atmosphere
n Global warming
n Toxicity
n Flammability
n

Effects on
human health

Damage to
respiratory system,
nervous system

Factors

Dose
Potency
Route of
exposure

Could lead to cancer,


dermatitis and death

(Routes of exposure: absorption, ingestion, inhalation etc.)

Green solvents
Source
n Sustainability of source
n Atom efficiency
n Energy processes
n Toxicity of by-products
n Reusability
n Product separation process
Just because the solvent is non-toxic it does not
make the process green
n

Product

Solute

Environment

Application
Solvent

Solvent

Recycle
Energy and efficiency
important

Toxicity or
neutralisation
important

Problems in solvent replacement


n

Solvents affect the rate of reaction

Alters chemo- regio- and stereo-selectivity


Reaction may not work at all!

Sustainable Solvent Development


expensive

hazardous to the
environment

hazardous to use

Solvent optimisation can give numerous benefits

Alternative solvents
No solvent solventless reactions
n Water
n Super critical fluids
n Ionic liquids
n

All have advantages and disadvantages which need to be


considered when assessing suitability for replacement

Solventless reactions
Simplest solution
n Fails on large scale Exothermic
reactions can be dangerous
n Problem in mixing especially in case of
solids
n Solvents still required for extraction,
separation and purification of products.
n

Use of water as the solvent


ADVANTAGES
n
n

Cheap, available and plentiful


Useful in biphasic processes in conjunction with other
solvents

DISADVANTAGES
n

Use is limited because of:


1.
2.

n
n

Low solubility of organic substrates


Compatibility with reagents

Clean up of aqueous waste difficult


Separation often energy intensive or long drying time.

Supercritical Fluids
Substance at a temperature and pressure
above its critical point
n Diffuse through solids like a gas dissolve
materials like a liquid
n Suitable substitute for organic solvents
n Carbon dioxide and water are the most
commonly used
n

Supercritical fluids are intermediate


between liquids and gases

Solid

Supercritical Fluid

Liquid

Gas

Critical point:31.1C and 74 bar pressure


Triple point:-56.3C and 5.1 bar

Ionic liquids
n

Consist of organic cation and inorganic anion

BF 4 N

1 . E th ylm e th ylim id a zo liu m


te tra flu o ro b o ra te , [e m im ][B F 4 ]

n
n
n

Me
Me

Z n 2 C l 5 -

N+
Me

OH

2 .C h o lin e ch lo rid e /Z in c ch lo rid e


io n ic liq u id

Great variety of structures possible


Very low vapour pressure attractive alternative to VOCs
Good solvents for a wide range of organic, inorganic and
polymeric compounds

Disadvantages of Ionic liquids


n

Expensive

Work-up processes and recycling involve


other solvents

Questionable toxicity

Ionic liquid used as reaction medium


n

Diels-Alder reactions

isoprene

n
n
n

but-3-en-2-one

Alkylation reactions
Hydroformylation reactions
Friedel Crafts reactions
Naphthalene

n
n
n

Pd-mediated C-C bond formation


Alkene polymerisation
Biotransformations

Conclusion
No process is GREEN
n There cannot possibly be an ultimate
green solvent. Hence we need to consider
the overall impact of any process on the
environment.
n We need to tailor a solvent as per the
application keeping in mind the
sustainability.
n

References
www.rsc.org
n www.pharmainfo.com
n www.supercriticalfluids.com
n www.wikipedia.com
n www.chem.leeds.ac.uk
n

Role of solvents
n

Coatings:

Cleaning

Paints, adhesives
1. Solvent usually removed by evaporation after application
leaving coating behind
2. Coating removal
E.g. Dry cleaning extensive use of perchloroethylene,
suspected of being carcinogenic, which also contaminates
groundwater supplies.

Extraction

E.g. Coffee decaffeination (benzene, CH2Cl2)

Use of solvents in reaction media


Used to bring reactants together at suitable
concentrations.
n Energy control
n

Endothermic

reactions require energy heat can


be supplied by heating solution
Exothermic reactions solvent acts as a heat sink
preventing runaway reactions. Heat can be
removed by allowing solvent to boil.
n

Efficient mixing and stirring

Use in solvent extraction


n
n
n

Very important part of reaction sequence need to consider


whole process NOT JUST REACTION ITSELF.
Often more solvent is used in work-up than as reaction
medium.
Compounds dissolved in one solvent shaken with water to
remove inorganic impurities, or other water soluble
contaminants. Generates aqueous waste as well as organic
waste, both of which will require disposal.
Solutes usually remain in the non-aqueous solvent, which is
then concentrated, and waste solvent discarded (often
incinerated generating CO2).

Need for an alternative solvent


n

n
n

Solvents define a major part of the environmental performance of a process.


The need for an alternative solvent arises from the need to minimize the
environmental hazards.
In the year 2000 the use of solvents was the largest source of volatile organic
compounds (VOC) in the atmosphere.
The major problem with the VOCs are:
Direct problems:
1.
Varying toxicity depending on nature of VOC, exposure method and
duration .E.g. DMF (teratogenic), CHCl3 (suspected to be carcinogenic)
2.
Flammability (fire hazards)
3.
Peroxide formation (usually ethers)
Indirect problems
1.
The use of Chlorofluorocarbons (CFCs) now phased out caused
Ozonedepletion.E.g.CF3Cl, lifetime in atmosphere 640 years
2.
In addition these solvents persist in the atmosphere and have a potential
of global warming.

Green solvents a solution


Thus we see that the current solvents that are being used pose a
potential threat to the environment hence we need to switch to
green solvents. Finding environmentally benign green-solvents is a
top priority of the organic chemist. Use of no-solvent, i.e. solventfree reactions is another solution, however, this may work for only
a few reactions as in general, a lack of reaction medium may lead
to overheating of the reaction mixture, yielding a mixture of byproducts.
So what are green solvents?

n
n
n
n
n

Just because the solvent is non-toxic it does not make the process
green. We also need to consider:
Energy (evaporation, pressurisation, stirring etc.)
Whether the solvent can be recycled and used again
Toxicity of any by-products that are formed
Atom efficiency of process
Product separation process that would be involved?

Solvent replacement
n
n

n
n
n
n
n

Solvent replacement is not a simple process. A number of factors are to be


considered.
The whole process has to be considered and not just one step i.e. the
solvent that would be used in the work-up and purification also have to be
considered and not just the solvent in the reaction media.
There are the various aspects of the solvent that need to be considered and
their importance is to be quantitatively determined.
Where does the solvent come from?
Is the source sustainable?
Where it will end up can its effects be neutralized?
How can its effects be neutralized?

The major problems in solvent


replacement
n
n

Solvents can be very difficult to replace.


As reaction media:
Solvents have a substantial effect on a reaction,
allowing a degree of control which will not be
possible in its absence
2. Can effect:
1.

n
n
n

Rates of reaction
Chemo-, regio- and stereoselectivity
Outcome of reaction may not work at all, or may
do something totally different!

Carbon dioxide as supercritical


fluid
n

Carbon dioxide is considered to be an


environmentally benign solvent because it is nontoxic
and nonflammable and isn't being created in the
process; what already exists is simply being used.
The carbon dioxide, in its supercritical state, is near
room temperature but is highly pressurized so that it
has a liquid-like consistency yet, like gas, expands to
fill a container.

Uses of supercriticalCO2
n
n
n
n
n

One of the biggest chemical reactions that is the production of


polythene is carried under supercritical condition.
Natural product like caffeine are extracted using supercritical
CO2.
Union Carbide developed a spray painting process using scCO2
that decreases VOC emission by 80%.
Thomas Swan & Co Ltd have built a SCF plant for continuous
synthesis with capacity of up to 1000 tonnes per year
There are a number of other uses scCO2.

Uses of ionic liquid


nSolvents for catalysis
nMetal deposition e.g. Al
nDesulphurisation of oil
nLubricants
nAnti-static agents

Why use sc fluids?


Increased mass transport
n Gases are totally miscible
n No surface tension
n Excellent for infusion and extraction
n Inert and non toxic
n Inexpensive fluids
n Environmentally compatible
n