07-02-2017

Pressurized Fluid Extractions

Factors affecting an Extraction Process

•The solubility of the substance to be separated in the
solvent

•The selectivity compared with other substances

•The diffusion in the case of solid raw materials

(capillary effects)

•The effort in removing the solvent after extraction

•Regulatory approval of the solvent within the

application range of the retrieved products

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Isolation of bioactive phytochemicals:

Conventional Methods:
• Maceration
• Percolation
• Steam distillation
• Hot continuous solvent extraction
(Soxhlet extraction)

Demerits of Conventional Techniques:

• They are highly time and energy consuming.

• A large volume of organic solvents is used in such methods

leading to health and ecological hazards.

• Complete removal of solvent from the end product is a

major issue in such methods.

• Selective extraction is not possible and this ends in various

undesirable co-extractives in the final products.

• Chances of thermal, photo and oxidative degradation of

sensitive compounds.

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The Need of The Hour: Design, develop and commercialize ‘green’

extraction technologies satisfying all current and foreseeable future
regulations concerning Safety, Health & Environment

Supercritical
Fluid
Extraction (SFE)

The Pressurized
Ultrasound
Potential Liquid
Assisted
Green Extraction Extraction
Extraction (UAE)
Brigade (PLE)

Microwave
Assisted
Extraction (MAE)

Supercritical Fluid
Extraction (SFE)
It is based on the fact that, near the
critical point of the solvent, its
properties change rapidly with only
slight variations of pressure.
Pc
SCFs have solvating powers similar
to liquid organic solvents, but with
Pressure

gas-like higher diffusivities, lower

viscosity, and lower surface
tension.

Tc
• It is a technique that employs a fluid
Temperature
phase having properties intermediate
between a gas and liquid, to effect the
solubilization of solutes in a matrix Phase Diagram of a Pure Substance
(Taylor, 1996).

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Fundamentals of SCF extraction

• Above the "critical point" it is impossible to liquefy a
gas irrespective of how high the pressure is applied.
However, the increase in pressure, changes density of
gaseous phase and approaches liquid like density.
This compressed gaseous phase is called "dense or
SCF (supercritical fluid)”.

• It has a high dissolving capacity, which can be varied

by changing process parameters (i.e. Temperature
and Pressure) ----------------- TUNABLE Solvents

Orders of Magnitude of Physical Properties of Solvents in

Different States (Klesper, 1980).

Property GAS SCF LIQUID

Density (g/cc) 10-3 0.3 1.0

Diffusivity (cm2/s) 10-1 10-3 5 x 10-6

Viscosity (g/cm.s) 10-4 10-4 10-2

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Physical properties of some common supercritical solvents (Klesper, 1980)

Fluid Normal Critical Constants

Boiling Pressure Temperature Density
Point (bar) (oC) (g/cc)
(oC)
Carbon Dioxide -78.5 73.8 31.1 0.468
Ethane -88.0 48.8 32.2 0.203
Ethylene -103.7 50.4 9.3 0.200
Propane -44.5 42.5 96.7 0.220
Propylene -47.7 46.2 91.9 0.230
Benzene 80.1 48.9 289.0 0.302
Toluene 110.0 41.1 318.6 0.290
Nitrous Oxide -89.0 71.0 36.5 0.457
Ammonia -33.4 112.8 132.5 0.240
Water 100.0 220.5 374.2 0.272
Chlorotrifluoromethane -81.4 39.2 28.9 0.580
Trichlorofluoromethane 23.7 44.1 196.6 0.554

CO2 – The most widely used SCF

• It has low critical parameters (Tc – 31.1 oC and Pc – 73.8 bar) making it
ideally suitable for thermolabile natural products.
• It is cheap and readily available at high purity.
• It is non-toxic and chemically inert.
• It is safe to handle owing to its non-flammable, non-explosive and non-
corrosive nature.
• It is odourless, tasteless and GRAS (Generally Recognized As Safe)
solvent.
• It has low latent heat of evaporation and its high volatility makes it easily
removable without leaving any residue in the final product.

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Video

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• CO2 fluid at temperatures below the critical value (31.1 oC)

and pressure above the vapour pressure is called the
subcritical or liquid CO2 whereas CO2 at temperatures above
31.1 oC and pressures above 73.8 bar is known as the
supercritical CO2.

• Subcritical (Liquid) CO2 is a selective extractant for essential

oils in the temperature range of 0 to 10 oC and pressures
between 50 and 80 bar while supercritical CO2 selectively
extracts oleoresins in the temperature range of 40 to 80 oC
and pressure range of 200 to 500 bar.

Liquid CO2 extraction

Very soluble Sparingly soluble Insoluble

Non-polar and
Non- Organic compounds <500MW Sugars, proteins
slightly polar molecules or with higher polarity Tannins, waxes,
<250 MW Chlorophyll,
amino acids and
Examples most pesticides

Terpenes,thiols Oleic acid, decanol, lipids <C18

esters, short chain
organic acids, alcohols
and ketones

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Supercritical CO2 extraction

Very soluble Sparingly soluble Insoluble

Non-polar and
Non- Chlorophyll, waxes Sugars, proteins
moderately polar molecules and carotenoids Tannins, amino
<500 MW acids and most
pesticides
Examples
Triterpenoids, alkaloids
lipids <C22

Limitations of CO2 as an SCF

• Its inability to extract polar compounds at typical working
conditions (80-600 bar). This limits the application of pure SC
CO2 to the extraction of only non-polar compounds.

• Addition of modifiers, entrainers or co-solvents is required for

extracting polar compounds.

• Commonly used modifiers include methanol, ethanol, propanol,

acetone, dichloromethane, dimethyl sulfoxide, chloroform,
carbon disulfide, water etc.

• They can either be introduced as mixed fluids in the pumping

system with the help of second pump or by injecting as liquid
onto the sample before beginning the extraction.

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TECHNICAL ASPECTS OF SUPERCRITICAL

FLUID EXTRACTION

1: CO2 cylinder, 2: compressor, 3: Heat exchanger, 4: Extractor, 5: Expansion

valve, 6: Gas-liquid separator, 7: Gas flow meter, 8: High pressure pump

Video

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• Advancement in the system

– Two or more separators to separate the extract in different
fractions of compositions

– Addition of co-solvents for polar compounds

– Multistage extraction for compounds showing different solubility at

different operating condition

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Features:
• Superior quality and yield of products from SCFE
– No loss of heat sensitive and volatile components, free of
residual solvent and microbial contaminants, Eco-friendly
process.
– The present international trend of increasingly stringent
regulations regarding residual organic solvents in processed
food product clearly indicates that the conventional solvent
extraction process may be phased out in the near future.
(Chlorinated solvents are banned from their use in food
processing)

• There is practically no effluent generation in SCFE.

• Residue after treatment

– No deterioration of cake/residue, unlike in solvent extraction
– Basic nature of the material is retained.

• Relatively higher investment. However…

– low solvent (CO2) cost, lower batch times, higher
concentration of active / desirable components in the
extract, no pollution control related costs etc.

• High operating pressure…A limiting factor…Safety concern

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• Process Governing parameters

• Temperature and Pressure

– The increase of temperature reduces the density

of SC-CO2 (for a fixed pressure) thus reducing the
solvent power of the supercritical solvent; but it
increases the vapor pressure of the compounds
to be extracted. Therefore, the tendency of these
compounds to pass in the fluid phase is
increased.

– The general rule is: the higher the pressure, the

larger is the solvent power and the smaller is the
extraction selectivity.

• Solubility
– Knowledge of the solubility of the compounds to be extracted and of the
undesired compounds.

• CO2 flow rate

– CO2 flow rate is a relevant parameter if the process is controlled by an
external mass transfer resistance.
– The amount of supercritical solvent feed to the extraction vessel
determines the extraction rate.

• Particle size
– Particle size plays a determining role in extraction processes controlled
by internal mass transfer resistances, since a smaller mean particle size
reduces the length of diffusion of the solvent.
– Smaller particle size, channeling inside the extraction bed.

• Process time
– Process time is interconnected with CO2 flow rate and particle size and
has to be properly optimized to maximize the yield of extraction process.
– Lower flow rate or smaller particle size are proportional to higher
residence time. This will give more chance to diffuse into solid interior,
leading to advanced extraction yield.

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SCFE application areas

• Extraction of botanicals
• Spice extraction
• Flavour and fragrance extraction
• Decaffeination of coffee and tea
• Deasphalting petroleum fractions
• Coal liquefaction
• Chemical separations and purification
• Polymer processing
• Microfine /nano particle formation for drug delivery /control
release applications
• Eco-friendly precision cleaning of electronic and optical
components
• Eco-friendly textile dyeing

Petroleum Refining
• Propane Deasphalting

– Refining lube oils using propane as a solvent

– At near critical conditions

– Single solvent can be used selectively to separate a lube

oil feedstock into paraffin wax, asphalt, heavy ends,
naphthenes, color bodies, and the desired product, a
purified light oil.

– Possible by changing the solvation power i.e. by altering

temperature and pressure
• Variation in temperature -42 oC to 100 oC
• Variation in pressure 22 bar to 46 bar

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• Solexol Process

– Separation and purification of vegetable and fish

oils using propane as a solvent

– To concentrate the polyunsaturated triglycerides

in vegetable oils

– To extract the vitamin-A values from fish oils

• ROSE Process

– Residuum Oil Supercritical Extraction (ROSE)

– Primary extraction at pressurized liquid conditions.

– Separation of fractions from critical to subcritical

conditions

– Butane as the solvent because…

• A higher solvent power for the heavy hydrocarbons
• Solubility can be altered by changing the temperature
• Effective solvent in dissolving the desired high molecular
weight components and precipitating the asphaltenes

– Sometimes Pentane is used for very heavy hydrocarbons

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Natural Products extraction using

SUPERCRITICAL FLUID

Mass Transfer Mechanism in Solid-Liquid Leaching

• Transfer of solvent into the solid particle through its porous structure.
• Dissolution of solute from the solid into the solvent within the particle.
• Diffusion of the dissolved solute from within the particle to the particle
surface through its porous structure.
• Transfer of solute from the particle surface into the bulk solvent
surrounding the particle.

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Pressurized Liquid Extraction (PLE):

• A solid-liquid extraction process

performed at elevated temperatures,
usually upto 200 oC and at pressures
between 35 and 200 bar (500-3000
psi).

• Also known as Pressurized Solvent

Extraction (PSE), Pressurized Fluid
Extraction (PFE) or Accelerated
Solvent Extraction (ASE, Dionex
Trade Name).

• PLE uses common organic solvents

as extractants which remain in liquid Operating Principle of PLE
state even at elevated temperatures
owing to the applied high pressure.

• Reduce Solvent Costs

Pressurized liquid extraction uses as little as 15 mL of solvent compared to
more than 500 mL of solvent required to perform Soxhlet extractions.

• Reduce Solvent Waste

The PLE system reduces solvent waste by using solvents more efficiently.

• Increase Productivity
The entire extraction and cleanup may be performed in less than 30
minutes. Traditional methods can take 10 to 16 hours.

• Reduce Operating Costs

Rapid extraction and clean-up, along with reduced solvent use and waste,
reduces operating costs by as much as 70 percent.

• Five to 250 mL Extraction Cell Sizes

The PLE™ system offers 5-250 mL low cost stainless steel extraction cells
with Teflon endcap filtration. This wide range of extraction cell volumes
allows the use of the same unit for all sample sizes, even in the same run.

• Temperature- and pressure-tunable solvating power of the extraction

solvent

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Applied Separations Fast PSE System

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Physicochemical Considerations in PLE

• disruption of analyte-matrix interactions i.e. van der Waals

forces and hydrogen bonds
• improved mass transfer due to enhanced diffusivities of
analytes
• better penetration of the solvent into the matrix pores
owing to elevated pressure
• reduced viscosity and surface tension of the solvent at
elevated temperatures
• water miscibility at elevated temperatures

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PLE Application Areas:

Recently PLE has found applications in the extraction of:

• Chemical constituents from plants and herbal materials

• Agrochemicals and other pollutants
• Pharmaceuticals
• Biologicals
• Foodstuffs

Schematic diagram of High Pressure Soxhlet Apparatus

1-High pressure valve, 2-Pressure gauge, 3-Sapphire window, 4-Cooling finger, 5-Cylinder,
6-Glass extractor with thimble, 7-Glass vessel serving as reservoir, 8-Water bath

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