GUJARAT TECHNOLOGICAL UNIVERSITY

Chandkheda, Ahmadabad
Affiliated

SHROFF S.R. ROTARY INSTITUTE OF CHEMICAL

TECHNOLOGY

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/ Shroff Family

Managed By Ankleshwar Rotary Education Society
Approved by AICTE, New Delhi, Govt. of Gujarat & GTU Affiliated

An open ended project Report on:-

“Application of SCFE Solvents”
Under the subject of Advanced Separation Technique
B. E. Semester – VI
(Chemical Engineering)
Academic year 2018-2019

Submitted By:-
Sr.No Name Roll No.
1 Ahir Haren 160990105001
2 Baraiya Ankit 160990105002
3 Chaddarwala Kartik 160990105003
4 Chauhan Vipul 160990105004

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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 CERTIFICATE
This is to certify that project work embodied in this prototype report
Entitled “Application of SCFE Solvents” was carried out by
AhirHaren(160990105001),BaraiyaAnkit(160990105002),Chaddarwa
la Kartik(160990105003),Chauhan Vipul(160990105004), studying at
Shroff S.R. Rotary Institute Of Chemical Technology code no. 099 for
partial fulfillment of the subject Advanced Separation Technique.This
project work has been carried out under my guidance and supervision and
it is up to my satisfaction.

Date:
Place:
Signature and name of supervisor:
Seal of institute

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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 Abstract

Supercritical fluids are very important in the modern chemical

technologies and have a very good potential to be used in various
fields. One of the main advantages of supercritical fluids is that they
are classified under green technology and are hence environmentally
friendly. They are majorly used in the chemical industries for
extraction purposes as they give excellent results due to their unique
properties. Other prominent applications are in the pharmaceutical
industry for micro ionisation and for analytical samples in
chromatography as well as dry cleaning, drying and impregnation.
Most commonly used supercritical fluid is carbon dioxide which is
popularly used in Decaffeination.

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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What does "supercritical" mean ?

Any substance is characterized by a critical point which is obtained at

specific conditions of pressure and temperature. When a compound is
subjected to a pressure and a temperature higher than its critical point,
the fluid is said to be "supercritical".

In the supercritical region, the fluid exhibits particular proporties and

has an intermediate behavior between that of a liquid and a gas. In
particular, supercrical fluids (SCFs) possess liquid-like densities, gas-
like viscosities and diffusities intermediate to that of a liquid and a
gas.

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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The fluid is said "supercritical" when it is heated obove its
crititcal temperature and compressed obove its cirical pressure.

What is supercritical CO2?

Carbon dioxide (CO2) is the most widely used supercritical fluid. This
is because CO2 is cheap, chemically inert, non-toxic, non-flammable
and readily available at high purities and at low costs. Besides, the
critical point of CO2 is easily accessible (critical temperature 31°C
and critical pressure 74 bar) allowing the fluid to be used at mild
conditions of temperatures (40-60°C) without leaving harmful organic
residues. Due to its interesting properties Supercritical CO 2 can be
described as a "green" solvent.

What is subcritical and supercritical water ?

The critical point of water is much higher than that of CO 2. However
its applications are very promising and some are in the process of
industrialization. Processes using subcritical and supercritical water
are called hydrothermal processes.

Water, in the subcritical phase (pressure:15 to 100 bar, temperature :

150 to 250°C) can solubilize hydrophobic compounds. Therefore,
subcritcal water (sometimes referred to as hot compressed water) can
be used for the extraction of plant materials (polyphenols, tannins,
terpenes ...). Oxidation in subcrtical water can also be carried out in
order to achieve efficient waste processing. In this case, the process is
called wet air oxidation (WAO).

In supercritical water ( pressure > 221 bar , temperature> 374°C )

organic compounds and gases become highly miscible and
precipitation of inorganic compounds occurs. Oxidation reactions in
supercrtiical water can also be performed. Applications include the

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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 treatment of harmful wastes and the synthesis of nanoparticles. These
processes are called supercritical water oxidation (SCWO).

Are there any other supercritical fluids ?

In addition to water and CO2 , compounds such as ethane, propane,
methanol, ethanol are also used in their supercritical phase for certain
applications (extraction, chemical reactions .. )

What's the point of using supercritical fluids ?

Depending on the fluid and equipment used, supercritical fluid
processes can :

 Raise technological barriers

 Optimize your manufacturing processes

 Provide a sustainable alternative to conventional production

methods

Supercritical fluids can be used to perform the following processes :

Atomization - Concentration - Crystallization - Enrichment -
Extraction - Impregnation - Cleaning - Drying - Polymerization -
Spraying - Purification - Strengthening - Separation - Sterilisation –
Solubilisation

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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Processes
Supercritical Processes
Supercritical fluids based processes include extraction, impregnation,
particle formation, formulation, sterilization, cleaning and chemical
reactions among others. In all cases, the supercritical fluid is used as
an alternative to traditional organic liquid solvents.The most widely
used super critical fluids are CO2
(Tc = 31°C, Pc = 74 bar) and water (Tc = 374°C, Pc = 221 bar) but
some processes (extraction, reactions) involove the use of
supercritical methanol, ethanol, propane, ethane mainly. Supercritical
CO2 processes are the most widely spread as these are exempt of the
operations of elimination of solvent residues, operations generally
needed when the solvent used is an organic compound.
Some examples of proceseses carried out under supercritical and
subcritical conditions are listed below:

Extraction

The principle of the extraction of solids using supercritical CO 2 relies

on the strong variation of the solvation power of CO 2 which occurs by
simple variation the operating conditions (temperature and pressure).
This allows to selectively extract molecules according to their
chemical nature. Very weakly polar, CO2 turns out to be an excellent
solvent of nonpolar or small polar molecules in supercritical
conditions. Once the desired compound is dissolved in supercritical
CO2, the pure extract can easily be obtained by simple
depressurization. This results in the separation of CO2, which
becomes gas again, from the extract, which is recovered in solid or
liquid form. In theory, any porous solid material (plants, plastics,
wood, can be treated by supercritical fluid extraction to recover
valuable compounds (oils, fragrances, pigments ...) or undesired

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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substances (pollutants, residual solvents).
Subcritical water extraction can also be carried out to extract
hydrophobic compounds (polyphenols, terpenes,tannins) from various
plant materials (fruits, wood, algae).
Chemical reactions
Conducting chemical reactions at supercritical conditions affords
opportunities to manipulate the reaction environment (solvent
properties) by increasing pressure to enhance the solubilities of
reactants and products, to eliminate interphase transport limitations
thus increasing reaction rates, and to integrate reaction and separation
unit operations. Supercritical conditions may be advantageous for
reactions involued in fuels processing, biomass conversion,
biocatalysis, homogeneous and heterogeneous catalysis,
environmental control, polymerization, materials synthesis and
chemical synthesis. Examples of chemical reactions carried out at an
industrial scale include hydrogenation, oxydation, esterification and
etherfication reactions among others.

Drying
Supercritical drying processes rely on the extraction of water and
other solvents using supercritical CO2. The absence of surface tension
allows the supercritical fluid to be removed without distortion. Such
processes are used to make aerogels but also for the lyophilization
(freeze-drying) of biological and food matrices and the dry-cleaning
of clothes (as a replacement for chlorinated solvenst) in an
environmentally-friendly way.

Cleaning
In the cleaning process, the use of supercritical CO2 with or without
the addition of specific surfactants avoids the use of solvents such as
trichloroethylene. For environmental reasons, this toxic solvent is
subject to many health and regulatory limitations, leaving the place to

Shroff S.R. Rotary Institute of Chemical Technology

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"green" solvents. Although only hydrocarbon solvents are nowadays
able to meet the market’s demand for alternative solutions to
chlorinated solvents, the use of CO2 under pressure or supercritical
CO2 appears as a particularly interesting industrial alternative to
chlorinated solvents. This process is industrialized for the dry-
cleaning of textiles, the cleaning of mechanical spare parts.

Chromatography
Supercritical Fluid Chromatography (SFC) is used for the analysis
and purification of low to moderate molecular weight, thermally labile
molecules and the the separation of chiral compounds. Principles are
similar to those of high performance liquid chromatography (HPLC),
however SFC typically utilizes carbon dioxide as the mobile phase.
Therefore the technique is more versatile, exhibits better resolution
and faster analysis times than conventional liquid chromatographic
methods.

Refrigeration
Supercritical CO2 can be used as a refrigerant in air-conditioning and
cooling system providing eco-friendly solutions in industrial and
domestic heat-pumps.

Applications

Supercritical Applications
Supercritical fluids based technologies are involved in a wide variety
of industrial applications which have shown significant progress in
recent years. Many industrial sectors are concerned including food,
cosmetics, pharmaceutics, materials, chemistry, energy and waste
treatment.The related supercrical fluid processes include extraction,
impregnation, formulation, sterilization, cleaning, energy and waste
treatment among others.

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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Some example of the industrial applications based on the utilzation of
supercrical fluids are listed below:

Food industry
The use of Supercritical CO2 as an extraction solvent for natural
products is the oldest and the most developed process on an industrial
scale, with applications especially in the food industry.

Decaffeination of coffee :This is the first example of the

industrialization of supercritcal fluids (Mawwell, USA).The
decaffeinated coffee produced presents a full aromatic profile (as a
result of the low temperatures used and the absence of organic
solvent). The extracted caffeine is, on the other side, sold to the
pharmaceutical and food industries. There is therefore very little
waste formed at the end of this process, making it economically and
environmentally sustainable
Cosmetic industry
Antioxidant such as polyphenols, carotenoids and tocopherols
(vitamin E), which are found in a wide variety of fruits and vegetables
(beta carotene in carrots, lycopene in tomato...) can be selectively
extracted using supercritical CO2. In addition, the textures of the
extracts obtained (thyme, rosemary, lavender, chamomile...) are free
from traces of organic solvents.

Pharmaceutical industry
Among the spectrum of the extracts obtained from plants, diterpenes
(antioxidants), triterpenes (phytosterols), or even the tetraterpenes
(carotenes) which may be of interest to the pharmaceutical sector, can
be easily extracted. Supercritical fluids may also be utilised for the
production of fine powders, in particular for the formulation of active
principles. Pierre Fabre laboratories (France) which have developped
the production of fine powders by supercritical CO2, were awarded

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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the Pierre Potier 2009 "Innovation in chemistry for sustainable
development" for its Formulplex ® process. This process uses
supercritcal fluids to increase the bioavailability of active principles.
Very recently, Critical Pharmaceuticles (United Kingdom) offers
biocompatible and biodegradable polymers (synthesized using
environment friendly supercritical CO2) for medical and
pharmaceutical applications.

Polymer and plastics industries

In the plastics industry, the diffusion of supercritical CO2 in polymers
is accompanied by a swelling of these materials and a change for their
physico-chemical properties. Supercritical CO2 is a good plasticizing
agent in particular because it reduces the glass transition temperature.
The resulting polymer properties are usually improved (resistance,
thermal stability, purity). Examples of applications iinclude the
impregnation of medical material, the purification of polymers from
residual solvents or monomers, the extrusion of elastomers, the
synthesis of polymers and composites

Chemical industry
Catalysis and biocatalysis of various organic compounds can be
efficiently carried out in supercritical CO2. Industrialization of the
process include the continuous catalytic hydrogenation of aromatic
compounds.

Wood industry
Superwood (Denmark) has industrialised the impregnation of wood
with fungicides dissolved Supercritical CO2 ensuring a lack of mould,
avoiding long baths and saving substantial amounts of fungicides.

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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Textile industry

Dyeing of textiles : The ecological and economical issues of

conventional dying of textile are met when Supercritical CO2 is used
as an alternative solvent. FeyeCon (Holland), which success in the
field of Ssupercritical CO2 dying (DyeCoos) is widely acknowledged,
has grown steadily

Tanning of leather : Based on the same idea, the tanning of skin into
leather by supercritical CO2, thus avoiding the use of large quantities
of aqueous solutions often difficult to treat. The chromium salts, even
found natural tannins, can impregnate a skin to heart in order to it turn
into leather.

Dry-cleaning : the process using supercritical CO 2 is industrialized in

the USA as an alternative to the chlorinated solvents used in the
conventional method. Existing pilot plants can also be found in
France and Germany.
Energy production
The very promising recent developments observed in the areas of
liquefaction and gasification of biomass (from agricultural wastes) in
subcritical and supercritical water opens up the way to novel energy
sources.
Waste treatment and valorization
Oxidation in supercritical water oxidation (SCWO) has been greatly
studied over the past 30 years particularly for the valorization and
treatment of waste. The oxidation of (biological and chemical)
refractory or hazardous waste in supercritical water is promising
because it allows a fast burning of substrates in a confined and
homogeneous environment where oxygen and organic compounds are

Shroff S.R. Rotary Institute of Chemical Technology

Principal Supporter & Sponsor-United Phosphorus Ltd (UPL)/Shroff Family Managed By Ankleshwar
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soluble. Less complex waste (such as sewage sludge and aqueous
effluent contaminated with high organic content) can also be treated
by wet air oxidation (WAO) also known as oxidation in subcritical
water. These processes also appear to be promising for the recovery of
metals which precipitate under hydrothermal conditions.The use of
supercritical CO2 for the extraction of valuable compounds from
various co-products and wastes of the agro-food and platics industries
are also very important

CONCLUSION:
By the study of Supercritical fluid extraction solvents and their
application We can say that SCFE solvents are very useful in many
ways as discussed above .The only problem with supercritical fluid
extraction is to achieve critical temp and pressure of that solvent

REFERENCE:

1. http://en.wikipedia.org/wiki/Supercritical_fluid
2. PROPERTIES of SCEF FLUIDS; IIT Bombay
3. Author: Michel PERRUT – SEPAREX, What is a Supercritical
Fluid,1999
4. Characteristics of Supercritical Fluids.html,15/01/15 19,45
5. Supercritical Fluid applications Supercritical Fluid
Extraction Phasex corporation.html
6. Supercritical Fluid Extraction (SCFE) Technologies from IIT
Bombay

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