Supercritical Fluid

Chromatography in
Food Industry
Sairaj(102116044)
Kavya(102116017)
Maheswari(102116020)
Preethi(102116032)
What is a Supercritical Fluid?

At a certain temperature and pressure

condition (critical condition), liquid and
vapor phases of a substance become
indistinguishable. A substance whose
temperature and pressure are higher
than its critical point is known as
supercritical fluid (SCF).
Physical and thermal properties of SCFs:
(i) Liquid like densities

(ii) Reduction in surface tension

(iii) Gas like viscosity

(iv) Gas like compressibility properties

(v) Diffusivities higher than liquids

Commonly used supercritical (SC) solvents:
CO2 is widely used as a supercritical solvent. Why??

(i) Low critical pressure (74 atm) and low critical temperature (31.1C)
● Carbon dioxide,
● Nitrous oxide, (ii) Relatively non-toxic
● Ethylene,
● Propylene, (iii) Non-flammable
● Propane,
● N-heptane, (iv) Readily Available
● Ethanol and
(v) Low cost
● Ammonia
(vi) Easily removable from extract

(vii) It has polarity like liquid pentane at supercritical conditions and thus,
best suited for lipophilic compounds.
Height Equivalent to Theoretical Plate
(HETP)

(i)Complete Equilibration of analyte between the stationary and mobile phase occurs within each
Theoretical Plate.

(ii)Greater separation occurs with- greater number of Theoretical Plates as Plate Height becomes
smaller.

N=L/H
Why deploy SFC?
The van Deemter (Knox) equation describes the
kinetic performance of a chromatographic
column. In its simplest form, this equation
comprises three terms, each describing a
different form of diffusion
(A) eddy diffusion, (B) longitudinal diffusion, and
(C) mass transfer
Eddy diffusion, the A term, is caused by a
turbulence in the solute flow path and is mainly
unaffected by flow rate.
Longitudinal diffusion, the B, or difference, term,
is the movement of an analyte molecule
outward from the center to the edges of its
band. Higher column velocities will limit this
outward distribution.
Mass transfer, the C term, is the movement of
analyte, or transfer of its mass, between the
mobile and stationary phases. Through this type
of diffusion, increased flows have been
observed to widen analyte bands, or lower peak
efficiencies.
Instrumentation of SFC

The SFC technology could only practically be used after 1980s after the
commercial system was introduced by Hewlette Packard.

It consisted of capillary column, oven, pure CO2 as mobile phase, pumps for
maintaining the pressure density programming, Fixed restrictors to maintain the
pressure, Flame ionization Photometry as detector.

Limitation: Long retention time

Low efficiency
Components of SFC

The main components of the modern SFC system are:

1. Solvent delivery system

2. Injectors
3. Thermostated Column
4. Back Pressure Device
5. Detector
6. Data Handling System
Supercritical Fluid Chromatography
Instrument
Solvent Delivery System

Responsible for the transport of solvent through the injector and further into the
SFC column.

Precise control of mobile phase flow rate is maintained by the system.

Maintains the desired pressure of the system.

Components: CO2, Liquid modifier pump, BPR

Pumps and Oven

Here mainly control flow is necessary so syringe pumps are used for capillary
SFC for consistent pressure.

For packed column, easier blending of mobile phase or introduction of modifier

fluids is necessary. Thus reciprocating pumps are used.

Conventional Gas Chromatography and Liquid Chromatography ovens are used.

Injectors

In capillary SFC, small sample should be injected into the column so

pneumatically driven valves are used. For packed SFC, a typical injection valve is
used.
Detectors in SFC

Classification: i) analyze solutes in mobile phase

ii) analyze solutes in stationary phase

Refractive index detector: change of RI of eluent w.r.t mobile phase

UV-Vis Detector: allows selection of operating wavelength

Better sensitivity than RI detector

Other Detectors in SFC

Electrical Conductivity Detector

Electrochemical Detector

Fluorescence Detector

FID, ECD, TCD

Mass Spectrometer
Stationary Phase in SFC

Neutral compound

Source of friction

Example: Silica
Stationary Phase in SFC continued…..

Open Tubular & Packed Columns

Similar to HPLC columns

Open Tubular - most preferred

Dimensions: Length = 10-20 meters

Thickness of Coating = <1µm

Polar SP’s

Relative retention of sample solutes based only on the bonded phase

Polar SP’s continued…..
Chiral Molecules

Cellulose type SP or some other chiral SP

Molecules with matching chirality stick to the column

Non-sticking enantiomer elutes first

SP’s in Food Industry

Examples: Bare silica for PPL(Phospholipids) & Carbohydrates separation.

Pressure drops across the column (especially with smaller particle size) and the
cost of specialized stationary phases seem to be the practical and economic
issues limiting industrial uptake of SFC.
SP’s in Food Industry continued…..
 Applications of SCF in Food Industry

Supercritical fluid extraction provides a distinct advantage not only in the

replacement but also extracts oils that are lower in iron and free fatty acid.

To satisfy the consumer's need for 'lighter' foods, developmental work on

supercritical extraction of oils from potato chips and other snack foods are been
carried out.

In addition, supercritical carbon dioxide has also been used to extract lilac,
essential oils, black pepper, nutmeg, vanilla, basil, ginger, chamomile, and
cholesterol.
Some Special Applications of SCF extraction:

1. Removal of fat from foods

2. Extraction of vitamin E from natural resources

3. Removal of alcohol from wine and beer

4. Extraction of pesticides

5. Extraction of polyaromatic hydrocarbon, polychloro benzene

Why CO2 is widely used in Food Industry?
Carbon dioxide is the most common supercritical fluid in the food industry.

Due to the non-toxicity and low critical temperature, it can be used to extract
thermally sensitive food components and the product is not contaminated with
residual solvent.

The extracts color, composition, odor, texture are controllable and extraction by
supercritical fluid carbon dioxide retains the aroma of the product.

Supercritical carbon dioxide extraction is used as a replacement for hexane in

extracting soybean-oil and has been tested for extraction from corn, sunflower
and peanuts.
Decaffeination of Coffee Beans

Supercritical carbon dioxide decaffeination, is very similar to the direct solvent

methods, except that in this case the solvent is carbon dioxide.

High-pressure vessels (operating at roughly 250 to 300 times atmospheric

pressure) are employed to circulate the carbon dioxide through a bed of
premoistened, green coffee beans.

At such pressures, carbon dioxide takes on unique, 'supercritical' properties that

enhance its usefulness as a solvent. The caffeine-rich carbon dioxide exiting the
extraction vessel is either channeled through a bed of activated charcoal or
through a water 'bath' tower to absorb the caffeine.
The carbon dioxide is then recirculated back to the extraction vessel.

Supercritical carbon dioxide decaffeination is capital-cost intensive, but it offers

very good yields. It typically can extract 96 to 98 percent of the caffeine originally
present in the beans.
Thank You