SUPER CRITICAL FLUID EXTRACTION

SCFE
UNIT-IV
Transition of CO2
 Contents
• Introduction to SCFE
• Supercritical Fluids
• Properties of solvent in extraction processes
• Physical properties of gases, liquids and SCFs
• Summary of properties of SCF
• Phase Diagram
• Phase Diagram for CO2
• Principles of SCFE
• SCFE Unit
• Process description
• Advantages and disadvantages of using CO2 in SCFE
• Applications of SCFE
• Decaffeination of Coffee beans
• Separation of ethanol-water by Pressure reduction
 P-T diagram (Triple point and Critical point)

Deposition is the transition of a substance directly from the gas to the

solid state on cooling, without passing through the liquid state.
P-T diagram simplified
 PT diagram for CO2

1 bar=0.9869 atm
 Critical temperature, critical pressure
• Critical temperature (Tc) of a substance is defined as the temperature
above which a distinct liquid phase cannot exist regardless of
pressure.

• The vapor pressure of the substance at its critical temperature is

called critical pressure. Pc
Or
Defined as the pressure to liquefy a gas at its critical temperature.

A substance above and close to its critical temperature and pressure

will exist as a supercritical fluid.
 Introduction to SCFE
• Extracts from agro-products viz. spices, herbs, aromatic plants,
medicinal plants etc.
• End uses: In cosmetics, flavors, medicines, perfumes, toiletries etc.

• Traditional solvent extraction can be applied, but for some major

limitations.
• Limitations are: lower efficiency, lower purity, long processing times
etc.
• To overcome these limitations, SCFE is developed.

Note: Large number of commercial plants were built in early 1980s, starting with
decaffeination of coffee beans using CO2.
• HAG AG, Bremen Germany; Maxwell House U.S (Division of General Foods Corp).
• Several hops extraction plants in Germany, US, UK and Australia.
• More than 1800 patents filed worldwide for SCFE technology.
 SCFE
• Supercritical fluid extraction
The process of separating one component (the extract) from another (the
matrix) using supercritical fluids as extracting solvents.

• Motivation for SCFE processes was to eliminate residual solvents in products.

E.g. Methylene chloride

• Traditional extractions viz. edible oil from vegetable sources, usually n-hexane is used.

• Traces of hexane, found in the product.

• Traces of hexane: Carcinogenic

• Food grade hexane: Approved by the FDA (Food and Drug Administration, U.S.)
 Super critical fluids (SCFs)
• Substances (fluids) with properties that fall between a normal gas
and a liquid.

• The changes done in pressure values will change the properties of

SCFs continuously from more gas-like to more liquid-like.

• Potential super critical extracting solvents are:

CO2, N2O, SO2, C2H6, C3H8, C4H10, water, xenon, ammonia,
chlorodifluromethane, methanol and ethylene.

• Of all, CO2 is widely used.

• Non toxic, non hazardous in nature.
• Critical temperature Tc = 31 ̊C and critical pressure Pc = 72 to 74 Bar
What is a supercritical fluid?
• A substance that exists above its critical temperature and pressure
and can effuse-through like a gas and dissolve materials like a liquid.

• The properties of a fluid can be changed by changing its pressure and

temperature.

Effusion occurs when a gas passes through an opening that is smaller than the
mean free path of the particles.
 Properties of solvent in extraction processes
• Transport properties and thermo physical properties.
• Density, viscosity, diffusivity etc. (Transport)
• Heat capacity and latent heat of vaporization etc. (Thermo physical)

Liquids have high solvating power; gases have high

penetration ability.

• SCFs combine high solvating power of liquids along with low viscosity
and high penetration ability of gases.

• Viscosity, density and diffusivity lie intermediate between gases and

liquids.

 Viscosity of SCFs usually low and diffusivity high.

 Physical properties of gases, liquids and SCFs
Property Gases (STP) SCFs Liquids

Density (gm/cc) (0.6 – 2.0) 10˄-3 0.2 – 0.5 0.6 – 2.0

Viscosity (1.0 – 3.0) 10˄-4 (1.0 – 3.0) 10˄-4 (0.2 – 3.0) 10˄-2
(gm/cm-s)

Diffusivity (1.0 – 4.0) 10˄-1 10˄-3 – 10˄-4 (0.2 – 2.0) 10˄-5

(cm2/s)
• SCFs have low viscosity and high diffusivity.

• Diffuse more rapidly into a sample and penetrate into it.

• Solvent strength of SCF is controlled by the pressure on the fluid.

• Increase in pressure increases density and later solvent strength.

• Near the critical point, small changes in pressure create large changes in the density of
SCF.

• Latent heat of vaporization (kJ/kg) of solvent decreases rapidly in the

SCF region and is zero at critical point, as there is no phase change.
(Low latent heat of vaporization helps in volatilization)

• The heat capacity (J/kg ̊K) of SCF is many times greater than that of a
normal liquid.
(High heat capacity helps in processing, energy conservation etc.)
 Summary of properties of SCF

• Liquid-like densities (100-1000 times greater than gases).

• Good solvating power.

• Low viscosity than liquid (10-100 times less than a liquid).

• Gaseous-like compressibility.

• Diffusion properties are higher than liquids.

• High penetrating power.

 Phase Diagram
• With the use of a phase diagram, importance of physical properties
particularly density of SCF as a function of temperature is well
understood.

• CO2 as a SCF

• Density variations with both temperature and pressure for CO2 .

• Two regions shown.

1. TER, Total Extraction Region (0.6 to 0.9 g/cc)

2. FR, Fractionation Region (0.2 to 0.6 g/cc)
 Phase Diagram for CO2

600
1.1 1.0

TER (0.6-0.9)
400
Solid
Liquid
Pressure
Bar 200
FR (0.2- 0.6)

0.2
Pc

Gas 0.1
0
0 -50 0 Tc 50 100
Temperature ̊C
 Principle of SCFE
• The principle involved depends on the solvent power.
• Solvent power is the ability of a solvent to extract a particular component in a
mixture of SCF.

• The solvent power is highly dependent on the density of SCF, which in

turn depends on the pressure and temperature.

• The close proximity of the molecules in a liquid phase (large density) imparts
solvent power as the intermolecular forces allow the solvent molecules to
surround the solute molecule and hold it in the solution.

• Therefore, there is a direct relation between the density and the

solvent power.

 In general, the solvent power of a SCF increases with increasing density at

constant temperature, and at a constant density, it increases with increasing
temperature
• CO2, as a solvent, the solvent power also depends on the similarity of
physical and chemical properties of both the solute and the solvent, and
close similarity resulting in high solubility.

• As the solvent power of CO2 increases, the percentage solubility of a

solute increases, the range of extractable solutes also increases,
hence at high solvent power, selectivity is low.

• On the other hand, at low solvent power, CO2 exhibits high selectivity
in dissolving solutes.

 Thus, SC CO2 offers the possibility of tailoring the extracting

conditions to optimize the recovery and purification of the desired
solute components from a mixture.
 Co-solvents/Modifiers

• The solubility of a solute in SC CO2 may be enhanced by the addition

of a co-solvent or entrainer or modifiers or moderators such as
alcohols and acetone. Use of surfactants a recent update.

• The addition of a co-solvent modifies the thermodynamic affinity

between the solute and the extractant (solvent) favorably.

• 1 to 10% ethanol or methanol can be used as co-solvents.

• Benzoic acid in phenanthrene extraction.

• Many non volatile polar substances cannot be dissolved at moderate temperature

in non polar fluids such as CO2
 SCFE Unit (Courtesy: pilot plant @ IIT Powai; Bombay, Nov. 2011)
Typical SCFE unit (simplified)
Compressor
Extract rich CO2 Extract free
(100-500 Bar)
solvent CO2

Valve

Reduced
Feed Pressure
High
Extractor Pressure and Temp
Separator Still

CO2

Raffinate Extract
 Process description
• Potentially applied for both L-L and L-S extraction.
• LLE, aqueous feed pumped into extraction unit.
• Contacted with a SCF at high pressures.
• Extract phase, brought to a lower pressure in a separator still.
• Separation and recovery of product from solvent.
• Solvent recompressed and recycled.

• In SLE, the SC solvent is pumped through a bed of solids to leach out

the solute.
• Extract phase pumped to a separator still at lower pressures to
precipitate out the solid product.
• The solute-lean fluid is compressed and recycled.
 Advantages of using CO2 in SCFE
• Offers precise control- selective extraction of the desired component from a
complete mixture.

• Economically viable and safe. (requirements of large amounts of solvents,

eliminated)

• Recovery rates are higher.

• CO2 as a SCF is non-contaminating.

• CO2- safe (non toxic to almost all bio products)

• Moderate critical pressure (73.8 bar).

• Low critical temperature (31.1°C).

• Reasonably good extractant for moderately poor species, e.g. PAHs and PCBs.
(Poly alicyclic Hydrocarbons and Poly chlorinated biphenyl)
 Advantages contd….
• Transport properties of SCFs- facilitate better extraction/separation.

• SCFs usually have low LHV (kJ/kg)- facilitates separation from products with a
minimum expense of energy. (353.4 kJ/mol @T.P)
(179.5 kJ/mol @15 ̊C)
• HTCs are greater during product recovery, it is due to high heat capacity of SCFs.
(0.849 J/mol K)

• As CO2 has low CP values, it can be used for extraction of heat labile materials, e.g.
aroma, flavors etc.

• Solids, semisolids/liquids of varied chemical nature can also be handled.

 Disadvantages
• The main disadvantage of CO2 is its non-polar nature. (it has no
permanent dipole moment)
Non- Polar Molecules: A molecule which does not have the charges present at the end and
cancel out each other are the non- polar molecules.
In a solution, a polar molecule cannot be mixed with the non-polar molecule.
Since carbon and oxygen have different electro negativities, electrons aren't shared
equally between them. There is no net molecule dipole moment since the two bond dipole
moments cancel out.
Thus, carbon dioxide is a non-polar gas.

• The solubility of solid solutes is low in non-polar solvents

• High level of automation and operator skills

• Expensive
 Applications of SCFE
• Food Industries:
Extraction of bitter flavor from hops. Hops are dried flowers of hop plants. Has
non-volatile soft resins consisting of α-acids that are desirable and β- acids
imparting bitter taste.

Decaffeination of coffee beans.

Caffeine is an alkaloid compound, stimulant of central nervous system, CNS
Increases breathing rate, increases mental alertness and physical energy.
Caffeine molecular formula is C8H10N4O2
Single coffee bean – 6mg of caffeine.
Variety: Coffee arabica – 12mg of caffeine/gram
Coffee robusta – 22 mg of caffeine/gram
Excelsa - 0.86 to 1.13g per 100g
Liberica - 1.23g of caffeine for every
100g of beans
Extraction of
flavors from fruits,
oils from black pepper, almond, lilac etc.
β-carotene from plant materials
edible oils
non edible oils; rape seed oil
mono glycerides from vegetable oils- emulsifiers
nicotine from tobacco
cholesterol from fat and eggs.

Extracts of orange, apple, nutmeg, vanilla, paprika, rosemary, chamomile and

ground chillies, ginger, basil etc.
• Pharmaceutical Industries:
Vitamin E from soybean oil
Separation of acetone from antibiotics
Niacinamide

• Petroleum Industries:
Fractionation of residuum oil and petroleum deasphalting
Polymer fractionation
Extraction of butanol from isobutene
Using ROSE (Residuum Oil Super critical Extraction) process for separation of heavy
components from crude oil
• Environmental applications:
The most eco friendly solvents such as CO2 and water are least expensive.
CO2 is a leading replacement for organic solvents to reduce the organic waste and
volatile organic emissions.

Also used for extraction of organics like alcohols, ketones, carboxylic acids, esters
from aqueous media.

Recently, applied for hydrothermal oxidation of organic wastes in water which is a

reactive separation.
 Decaffeination of Coffee beans
• Caffeine is an alkaloid compound, stimulant of central nervous
system CNS.

• Increases breathing rate, increases mental alertness and physical

energy.

• Caffeine molecular formula is C8H10N4O2

Single coffee bean – 6mg of caffeine.
Variety: Coffee arabica – 12mg of caffeine/gram
Coffee robusta – 22 mg of caffeine/gram
Excelsa with caffeine content of 0.86 to 1.13g per 100g
Liberica with caffeine content of 1.23g of caffeine for every
100g of beans
• In this process, use of water saturated with carbon dioxide as a
solvent, the caffeine content of coffee beans can be reduced from
3.0% to 0.2%.
• Removal of caffeine is necessary for the following reasons. As we know caffeine is
an alkaloid present in coffee, chocolate, tea, and many cola drink. The amount of
caffeine in these beverages varies from 110-150mg in 180ml of coffee, from 2-5mg
in decaffeinated coffee and from 20-46mg in 150ml of tea while 30-60mg in 360ml
of cola drinks. Excessive caffeine ingestion usually more than 250mg, following side
effects are experienced; restlessness, nervousness, excitement, insomnia, flushed
face, gastrointestinal disturbance, muscle twitching, diuresis, rambling flow of
thought and speech, tachycardia or arrhythmia, periods of inexhaustibility and
psychomotor agitation all these are said to be caffeine intoxication.
(Taber’s Cyclopedia Medical Dictionary; 18th edition, F.A.Davis
Company, USA 1997)
 Kraft process
• Kraft process
Make-up CO2
Green wet coffee beans Caffeine-lean
CO2
Fresh water

R.O
1 Caffeine- 3
rich 2
carbon
dioxide

CO2
4
Decaffeinated green coffee
Caffeine-rich water
1: Coffee Extraction column. 2: Water absorption column.
3: Conc. caffeine and water. 4: Caffeine crystals from crystallizer.
 Process description
• The feed comprising of moist and mashed coffee beans enter from
the top of the coffee extractor.

• Carbon dioxide is passed through the bottom.

• The countercurrent flow is preferred over other configuration as it

provides a better contact and the equilibrium attainment.

• The decaffeinated green coffee beans are removed from the bottom
of the extractor later sent to the roasting tower to produce coffee.

• While caffeine-rich carbon dioxide is withdrawn as a product from

the first column.
• Caffeine-rich carbon dioxide stream now treated with water.

• Fresh water is added from the top of the tower through spray device.

• From the top of the water column, the caffeine-lean CO2 is recycled
to the first column along with make-up CO2.

• Downstream end of the second column which is caffeine-rich, water

is fed to the reverse osmosis (RO) plant to treat the used water.

• Reused for the absorption of CO2 and simultaneously concentrate the

amount of caffeine in the product stream by membrane separations.

• Product stream from the RO plant is concentrated caffeine and to

some extent water.

• Later sent to a crystallizer giving purer crystals of caffeine.

Note:
In commercial practice the dimensions of an extraction vessel are:
diameter is approximately 7ft. and the height is usually 70ft.

• Caffeine crystals image

 Separation of ethanol-water by Pressure reduction
• Use of SCF CO2

Pressure reduction
CO2- EtOH & valve
traces of H2O
Ethanol-water LP
feed 2
CO2
HP

1
Ethanol

CO2 recycle
3
Raffinate; Water
1: Extraction column. 2: Separator. 3: Compressor.
• Ethanol-water mixture, a feed is pumped as a liquid to the pressure
of the extraction column (1) which is at a high pressure (HP).

• It is contacted with SCF CO2. This super critical CO2 has a tendency to
dissolve in water as well in ethanol.

• The raffinate which is enriched with water comes at the bottom while
the extract containing most of the CO2, ethanol and traces of water is
collected from the top.

• Later sent through the pressure reduction valve (PRV) to get the
reduced pressure.
• Within the PRV, expansion takes place at a lower pressure.

• Downstream end of the PRV is a flash drum held at the reduced or

low pressure (LP).
• The mixture of EtOH-CO2 is flashed to get the ethanol separated.

• Later CO2 recycled through the compressor.

• This is because, by then, the solvent has lost sufficient pressure, to

regain the pressure, the same as the column pressure it is sent
through the compressor.
• It is to be noted that unless the pressure is greatly reduced across the
valve, resulting in large compression costs, little of Et-OH is
condensed.

Note:
Ethanol-water can also be separated by using azeotropic distillation but due to the
energy crisis some where in 1970s, the energy efficient processes were tried and
commercialized.
This is one of them.
Due the unlimited capacity of CO2 to dissolve ethanol and water, today
pervaporation processes are also employed.