de

delhi technological university

NARENDER SINGH
DTU/2K14/B7/1085

GREEN SOLVENTS
Green solvent or also known as bio-solvent is typically an alternative to the conventional solvents available
in the market. It is an innovative idea of reducing the environmental impact resulting from the use of
solvents in chemical production.
CHARACTERISTICS OF GREEN SOLVENTS
Green solvent has a lower environmental impact compared to other conventional petroleum-based solvents.
Besides, it has a host of advantages that gives it an added boost to edge out its rivals.
Completely biodegradable
Can be recycled
Non-corrosive

Non-carcinogenic
Non-ozone depleting
Attractive solvent properties

THE NEED FOR GREEN SOLVENTS

Play a major role in many areas of technology
Provide many opportunities for improvement of environmental aspects.
Represent a very large proportion of the volatile organic compounds (VOCs) released into the
atmosphere.
1,000 million spent on environmental technology, much of which is end of pipe equipment and
associated operating costs to clean up emissions and air.
THE VARIOUS GREEN SOLVENTS

No solvent solventless reactions

Super critical fluids
Water
Ionic liquids

NO SOLVENT- solventless reactions

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

EXAMPLE- polymerisation of propene (Catalyst is soluble in liquid propene)

MAIN DISADVANTAGES OF SOLVENT-FREE SYNTHESES:

 solvents are often still required during work-up (e.g. extraction)

poor heat transfer in the solid state (although this may be overcome using microwaves)

SUPERCRITICAL FLUIDS

Substance at a temperature and pressure above its critical point

Diffuse through solids like a gas dissolve materials like a liquid
Suitable substitute for organic solvents
Carbon dioxide and water are the most commonly used
Supercritical fluids are intermediate between liquids and gases

SUPERCRITICAL CO2
Similar advantages to water -Natural, cheap, plentiful (too much of it!)
Easily removed and recycled, and can be disposed of with no net increase in global CO2
No solvent effluent

ADVANTAGES
Non-toxic & cheaply available

DISADVANTAGES
High pressure equipment is expensive

Readily removed (and recyclable)

and potentially dangerous

Non-flammable

CO2 is a relatively poor solvent

Low viscosity (fast diffusion)

Reacts with strong nucleophiles (e.g.

Good solvent of gases (e.g. H2)

amines)
EXAMPLE Imine hydrogenation (20 times faster in SC-CO2 than CH2Cl2)
USES OF SUPERCRITICAL-CO2:
extraction of caffeine from coffee (traditional method uses CH2Cl2)
dry-cleaning (traditional method uses C2Cl4) & spray-painting

WATER AS A GREEN SOLVENT

One of the most obvious alternatives to VOCs.
Cheap, readily available, and plentiful
Clean up of aqueous waste difficult
Useful in biphasic processes in conjunction with other solvents

ADVANTAGES
Non-toxic
Cheap
Biorenewable

DISADVANTAGES
Removal requires distillation
energy intensive
Waste streams may be difficult to treat

 Non-flammable
Many reagents are water-sensitive
High specific heat capacity
Generally a poor solvent for organics
EXAMPLE -geraniol isomerisation - a source of fragrances without organic solvents.

IONIC LIQUIDS
Typically consist of organic cation (often ammonium or phosphonium salt) and inorganic anion
N

BF4-

Me

1. Ethylmethylimidazolium
tetrafluoroborate, [emim][BF4]

Me

Zn2Cl5-

N+

Me

OH

2.Choline chloride/Zinc chloride

ionic liquid

Usually only consider ILs which are liquid at room temperature

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

ADVANTAGES
Readily prepared

DISADVANTAGES
Non-biodegradable

Can act as catalysts

Concerns over toxicity

Tuneable viscosity (via anion)

Synthesis often requires haloalkanes

Stable at high temperature

Product isolation often requires distillation or

Highly solvating

extraction into an organic solvent

USES OF IONIC LIQUID

Solvents for catalysis
Metal deposition e.g. Al

Desulphurisation of oil
Lubricants & Anti-static agents

APPLICATIONS OF GREEN SOLVENTS

Replacing VOCs and Chlorinated solvents

New syntheses of ibuprofen and Zoloft.
Integrated circuit production & Getting the lead out of automobile paints.
Many new pesticides & Biodegradable polymers from renewable resources.