Supercritical Fluid

Extraction
Supercritical Fluid Extraction
Critical Condition: 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)
Supercritical-fluid Extraction
In 1879, Hannay and Hogarth reported that solid potassium iodide could be
dissolved in ethanol, as a dense gas, at supercritical conditions of T > Tc = 516K
and P > PC = 65 atm
The iodide could then be precipitated from the ethanol by reducing the
pressure.
This process was later referred to as supercritical-fluid extraction, supercritical-
gas extraction, supercritical extraction (SCE), dense- gas extraction, or
destraction (a combination of distillation and extraction)
SCF
Physical and thermal properties of SCFs are in between pure liquid and gas.
Changes in properties are for a SCF
(i) Liquid like densities
(ii) Reduction in surface tension
(iii) Gas like viscosity
(iv) Gas like compressibility properties
(v) Diffusivities higher than liquids
Supercritical (SC) solvents
Some commonly used supercritical solvents are carbon dioxide, nitrous oxide, ethylene,
propylene, propane, n-heptane, ethanol and ammonia.
Among these, CO2 is widely used as a supercritical solvent
Why CO2 is a supercritical fluid (SCF)?
(i) Low critical pressure (74 atm) and low critical temperature (320 C)
(ii) Relatively non-toxic
(iii) Non-flammable
(iv) Available as high purity
(v) Low cost
(vi) Easily removable from extract
(vii) It has polarity like liquid pentane at supercritical conditions and thus, best suited for
lyophilic compounds.

Drawback: It cannot extract polar solutes.

Nitrous Oxide
It is good for removal or solubilize polar solutes, as it has a permanent dipole moment.
N2O is better than CO2 for extraction of polychlorinated dibenzo-dioxines from fly ash.
Disadvantage: It is highly explosive
H 2O
Disadvantage:
(i) High Pc and Tc (Tc > 3740 C, Pc > 221 bar)
(ii) At these conditions, H2O is corrosive.
Important parameters for SCF extraction
Threshold pressure: Pressure at which miscibility of solute starts.

Typical solubility curve of a material at a particular temperature

(ii) Pressure at which solute reaches its maximum solubility.
(iii) Knowledge of physical properties of solutes (particularly, melting points).

Solutes are dissolved better in liquid state.

Co-solvents or Modifiers
Co-solvents are added to modify the polarity of the SCF, so that the power of
SCF to solvate polar solutes increases.
Ex: CO2 should be mixed with 1-10% of methanol to solubilize more polar
solutes.
Advantages of SCF extraction
(i) Simple expansion of SCF leads to lowering in solubility capacity of it. Thus,
dissolved solutes are separated.
(ii) They have liquid like density but superior mass transfer behaviour
compared to liquids due to high diffusivity and low surface tension so that they
can penetrate into the porous structure of solid matrix to release the solute.
Mechanism
There exists four mechanisms for solubilization of solutes in SCF:
(i) If there is no interaction between solute and solid phase, the process is dissolution of solute
in suitable solvent.
(ii) If there is interaction between solute and solid, extraction is desorption. Adsorption
isotherm of solute on the solid in presence of solvent determines the equilibrium.
(iii) Swelling of solid phase by the solvent accompanied by extraction of entrapped solutes
through the first two mechanisms.
(iv) Reactive extraction.
Insoluble solutes react with solvent and products are soluble and hence extractable. For
example, lignin extraction from cellulose.
Thermodynamic Parameters
Temperature
Pressure
Adsorption equilibrium constant
Solubility of solute in solvent
Basic Techniques in SCF technology:
RESS (Rapid expansion of supercritical solutions):
RESS
A supercritical solvent saturated with a solute is allowed to expand rapidly,
leading to precipitation of solute.
Rapid expansion is achieved by allowing it to pass through a nozzle at supersonic
speed.
Supercritical fluid (SF) is pumped through a pre heater into the vessel containing
solid solute and the resultant solution is sent into a precipitation chamber by
expansion through capillary or laser drilled nozzle.
At precipitation chamber, pressure is much lower and solute solubility in SF is
quite low and solute precipitates out of it.
RESS
Size distribution and morphology of precipitated material is a function of pre-
expansion concentration and its conditions.
Pre-expansion concentration in term depends on SF, nature of solute, addition of
co-solvent, operating pressure and temperature.
Particle size is smaller and distribution is narrower if pre-expansion
concentration is higher.
When CO2 is used as a solvent, it must be recovered and recycled.
Three schemes discussed by McHugh and Krukonis
In the first scheme, for the separation of ethanol and water, the ethanol-water feed is
pumped as a liquid to the pressure of the extraction column, where it is contacted with
supercritical carbon dioxide.
The raffinate leaving the extractor at the bottom is enriched with respect to water and
can be sent to another part of the plant for further processing.
The extract stream, which leaves from the top of the extractor and contains most of
the carbon dioxide, some ethanol, and a smaller amount of water, is expanded across a
valve to a lower pressure.
First Scheme
In a flash drum downstream of the valve, ethanol-water condensate is collected and the C02-
rich gas is recycled through a gas compressor back to the extractor.
However, unless the pressure is greatly reduced across the valve, resulting in large compression
costs, little of the ethanol is condensed.
Second scheme
A second C02 recovery scheme by de Filippi and Vivian
The flash drum is re- placed by a high-pressure distillation column, which
operates at a pressure just below the pressure of the extraction column to
produce a C02-rich distillate and an ethanol-rich bottoms.
The distillate is compressed and recycled through the reboiler and back to the
extractor.
Both the raffinate and the distillate are flashed to recover dissolved C02.
This scheme, although more complicated than the first, is more versatile.
A third C02 recovery scheme by Katz et al. for the decaffeination of coffee.
In the extractor, green, wet coffee beans are mixed with supercritical C02 to extract
caffeine.
The extract is sent to a second extraction column, where the caffeine is extracted with
water. The CO2-rich raffinate from this column is recycled through a compressor back to
the first extraction column, from which the decaffeinated coffee leaves from the bottom
and is sent to a roasting tower.
The caffeine- rich water leaving the second column is sent to a reverse- osmosis unit,
where the water is purified and recycled through a pump to the water column.
All three separation steps operate at high pressure. The concentrated caffeine-water
mixture leaving the osmosis unit is sent to a crystallizer to produce caffeine crystals
 Comparision of the properties of Supercritical
Fluid,Gas and Liquid

1) Edit Székely. "What is a supercritical fluid?". Budapest University of Technology and Economics.
2) 2) "Supercritical Fluid Extraction, Density Considerations".
Different SCF Critical Conditions and Applications
 Comparision with organic solvents

[1] Giovani L. Zabot,Decaffeination using supercritical carbon dioxide ,Green Sustainable Process for Chemical and Environmental Engineering and Science 2016, Elsevier Inc.(page-257)
[2] D-Pyo,JisunYoo & Jeonghee Surh(2009),Comparison of Supercritical Fluid Extraction and Solvent Extraction of Isoflavones from Soybeans, Journal of Liquid Chromatography & Related
Technologies
Decaffeination by batch process
Semi continuous
Continuous
 Super Critical Extraction by SC-CO2

Shuchen B.Thakore,Bharat I. Bhatt,Introduction to Process Engineering and Design Tata McGraw-Hill Publishing Company Limited,page-369
 Advantages and Disadvantages of SCE over
Extraction operation with conventional Solvents
ADVANTAGES DISADVANTAGES
• Required high capital investment for
• Consumes less energy compared to Design high pressure equipment.
conventional extraction. • Very few supplier of SCFE
• No distillation required. 100% recovery of
technology.
solvent
• Due to low Distribution Coefficient ,
• 100% pure product. No contamination of
solvent Large amount of CO2 required.
• Highly Selective to Extract. Low viscosity • Thermodynamics of SCF system is
and High diffusivity. No mass transfer not fully understood. So limited
Resistance. knowledge of Design Data.
• Not Toxic, Corrosive and inflammable.
• No Bad effect on Environment

Shuchen B.Thakore,Bharat I. Bhatt,Introduction to Process Engineering and Design Tata McGraw-Hill Publishing Company Limited,page-366
Example
Naphthalene extraction process
Naphthalene extraction
A naphthalene-chalk dust mixture is fed to the extraction vessel.
Assume, extraction condition is 300 bar and 55 C. At this condition CO2 SCF
contains naphthalene dissolved at 15 wt%.
Then it is expanded to 90 bar through pressure reduction valve (assuming
isenthalpic expansion)
After expansion its temperature is 36 C at 90 bar.
Solubility of naphthalene is 2.5%. So, it falls out of solution.
Precipitated naphthalene is collected and CO2 is compressed to 55 C and 300 bar
and recycled to extractor.
Solubility diagram of naphthalene under
supercritical condition
Mollier Diagram:
(1) at 55 C, pressure is 300 bar
(2)at 36 C, 90 bar (after expansion)
(3)at 72 C, 300 bar (after compression)
Energy required to compress from 90 to 300 bar is, (152-145) = 7 Kcal/kg
(12.6 BTU/lb)
Then it is cooled to 55 C
(4) at 72 C, 300 bar to 55 C, 300 bar
Decrease in solubility is 15 to 2.5 wt%
1 kg CO2 contains = 0.15 kg Naphthalene
After extraction
1 kg CO2 contains = 0.025 kg Naphthalene
Extracted naphthalene = 0.15 - 0.025= 0.125 kg
0.125 kg naphthalene extracted for 1 kg CO2
So, for 1 kg naphthalene extraction
1000/125 = 8 kg CO2
8 kg CO2 required to recycle for extraction of 1 kg naphthalene.
Energy required for compression from 90 to 300 bar is =7 kcal/kg × 8 = 56 kcal
for extraction of 1 kg naphthalene
Special Applications of supercritical
fluid 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
 Super Critical Water Oxidation for Sludge
Destruction(SCWO) NOT FOR EXAM

• Two methods for complete distrction of toxic Sluge from

industires : 1. Incineration
2. Super Critical Water Oxidation.
• Incinertion has problem such as high cost and public
resentment.
• Supercritical Water: Tc=374 oC and Pc=22.1 MPa
• SCW provide enhanced solubility of Organic reactant.
• Oxident : Aqueous Hydrogen Peroxide Solution
• low Concetrated Sluge treatment.

[1] Yanhui Li and Shuzhong Wang(2019),Supercritical Water Oxidation for Environmentally Friendly Treatment of Organic Wastes.
[2] Veriyansyah, Bambang, Kim Jae duck(2006), Supercritical water oxidation for the destruction of toxic organic wastewaters.
 Super Critical Water Oxidation for Sludge
Destruction(SCWO) NOT FOR EXAM

DEMERITS:
• This method is not economically useful for waste containing more than 1% organic.
• The main drawbacks are the high operating pressure.

Anders Gidner and Lars Stenmark,SUPERCRITICAL WATER OXIDATION OF SEWAGE SLUDGE – STATE OF THE ART
Chematur Engineering AB.Box 430, 691 27 Karlskoga, Sweden.
 Super Critical Water Nuclear Reactor NOT FOR
EXAM
Conventional two type of Nuclear Reactor
1. Boiling water reactor-BWR
2. Pressurized water reactor-PWR
• Issues : Poor heat recovery
High construction cost

• To Overcome this 4th Generation

Super Critical Water Reactor(SCWR)
• SCW use as coolent.
• Significantaly increase thermal efficiency up to 40-45%
• Eliminate steam dryers,steam separators, re-circulation
pumps and steam generators
• A higher power density, generating more power for the
same size of reactor
1) R.B. Duffey and I.l.Pioro(2015), Super Critical Water Cooled Nuclear reactors: review and status,Atomic Energy of Canada limited,
Encyclopedia of life Support Systems.
2) The US DOE(Roadmap) Generation IV Nuclear Energy Systems Report(2001).
 SUMMARY

Super Critical fluids are the stepping stone to a modern technology.

This is considered as Green Engineering. It is Environment Friendly and gives better

results than conventional technology in chemical industries.

Following are the advance researches carried out in this Area:

1. Use of SC-CO2 for Drying Operation.

2. Use of SC-Methanol to produce Bio-Diesel by transesterification reaction.

3. Use of SC-CO2 for hydrogenation reaction in petrochemical industries.

4. Use of SC-Ammonia to increase Bio-ethanol conversion from Biomass matter.