Alternative Solvents

Special Chemical Technologies: Renewable Raw Materials

Saba Amin
Nofal Habib
Daniel Higueras
Asad Imran
 CHARACTERISTICS OF SOLVENTS 2

Solvents are used in mass and heat process to

facilitate separations and purifications. Also, as
cleaning agents in adhesives and in coating.
They have harmful effects for human health like
eye irritation, headaches, allergic skin and even
cancer.

ALTERNATIVE SOLVENTS
Low toxicity.
Easy to recycle.
Inert and do not contaminate the product.
 LEGISLATION AND REGULATIONS 3

Group Characteristic Example

Trade area Legislation Human carcinogens and
Benzene, carbon
Registration Evaluation, Authorization of Class 1 environmental hazards. Should be
European Union tetrachloride.
Chemical Sustances (REACH) avoided.
Switzerland Swiss Chemicals Ordinance Non-genotoxic animal carcinogens. Hexane,
United States Toxic Substance Control Act (TSCA) Class 2 Possible causative agents of methanol,
irreversible toxicity. Their use is limited. toluene.
Canada Canadian Environmental Protection Act (CEPA)
Acetone,
Japan Chemical Substances Control law (CSCL) Class 3 No human health hazard
heptane, pentane.
No adequate toxicological data. Their Isooctane,
Class 4
use most be justified. petroleum ether.
Guide for industry called Q3C Impurities: Residual Solvents

List of solvents permitted in US for use

in the preparation of food ingredients. Solvent selection guide made by the company Pfizer
 SOLVENT-FREE CHEMISTRY 4

Many reactions are performed in gas phase.

Economic and environmentaly friendly.
The use of auxiliary substances (solvents or separation agents) should be made unnecessary whenever possible
Reaction may be solvent free but often the process as a whole does use solvents.

BIOMASS TRANSFORMATION
Pyrolisys (seaweed pyrolysis for bio-iol production) and mechanocatalysis (for depolymerizing
cellulose).

Transformation of glycerol into

Mechanocatalysis (for depolymerizing cellulose). glycerol carbonate.
 SOLVENT-FREE CHEMISTRY 5

INORGANIC AND MATERIALS SYNTHESIS

Supramolecular chemistry.
Coordination chemistry .
Formation of transition-metal clusters and polymers.
Preparation of inorganic molecules and nanoparticles.

Iodination of ortho-carboranes.

Preparation of graphitic carbon nanostructures

Solvent-free supramolecular self assembly of a using a microwave induced solid-state process
metallo-square.
 SOLVENT-FREE CHEMISTRY 6

ORGANIC SYNTHESIS
Thermochemical reactions: Oxidations, reductions, isomerization, additions, eliminations, substitutions, C-C
coupling, pinacol couplings, phenol couplings, oxidative couplings and polymerizations.

Photochemical reactions: Dimerization, polymerization, cyclisation, isomerization, decarboxylation and addition.

Some typical solvent-free photochemical

Some synthetic organic reactions that have employed reactions.
solvent-free conditions.
 WATER 7

Water is present abundantly.

Cheap as compare to other solvents.
Environment friendly.

Summary of Advantageous properties

of water as a solvent

a. Safety advantages (Non flammable +

Nontoxic)
b. Lost cost
c. Being polar, relatively easy to separate
from apolar solvents or products. It also
improves reactions

d. High dielectric constant and favors ionic

Microwave Assisted Reactions
reactions Microwave energy has been used for:
e. High thermal conductivity and high
specific heat capacity Free radical polymerization
Step-growth polymerizations
f. Renewable Living radical polymerization
g. Odorless and colorless
 WATER- 2nd Application
CARBON DIOXIDE FIXATION
Carbon dioxide is significantly soluble in water
and therefore water is a good medium for its
conversion.
Dissolution results in the formation of carbonic
acid.
It is essential to control the pH of aqueous-
carbon dioxide systems.
The mechanism of this process is shown below:
8
Metal catalysts like rhodium, ruthenium and iridium are used
for the study of aqueous solution for transformation of carbon
dioxide.
Most effective system of Iridium complex is shown in figure.
Catalytic activity of the complex and its solubility in aqueous
solution can be tuned by pH of solution.
Acidic Conditions: DHTP is protonated.
Basic Conditions: DHTP exists as oxyanion.
 SUPERCRITICAL 9
FLUIDS
Substances enter into SCFs phase when they are above their
Critical Pressures (Pc) and Critical Temperature (Tc).
Some substances have readily accessible critical points, for
instance, Tc for CO2 is 304 K and Pc is 72.8 atm, whereas other
substances have a high value of these conditions.

Advantageous Properties of SCFs

a. High solubility of any reacting gases

b. Rapid diffusion

c. Solvent is easily removed

d. Zero Surface tension

e. Recyclability

f. Zero Waste Production

g. Weakening of solvation around the reacting

species.
SUPERCRITICAL FLUIDS- 1st Application 10
Solubility in Supercritical CO2

Comparison of Advantages and

disadvantages of ScCO2 as solvent.

Schematic representation of solute-

solvent Clustering in an SCF
SUPERCRITICAL FLUIDS- 2st Application 11
Extraction

ScCO2 is widely used in Supercritical

Fluid Extraction (SFE).
This is preferred because it is chemically
pure, nontoxic, non flammable, nonpolar,
stable, colorless, odorless and tasteless.
Moreover, its separation is easy and highly
selective but after extraction, further
processing is required.
SCF can successfully be used to extract
valuable waxes and higher molecular
weight Sesqui-terpenes (C15H24) that are
not water soluble. It is also used to extract
valuable wax products from wheat straw.
Recently, SFE has been applied to
problems associated with renewable fuel
production for instance, it has been used
for algal lipid extraction for the sustainable
production of biodiesel and extraction of
fatty and resin acids from pine sawdust
which prevents auto-oxidation and allows
this fuel source to be stored safely without
the risk of spontaneous combustion.