NPTEL Novel Separation Processes

Module : 10 Supercritical Fluid Extraction

Dr. Sirshendu De
Professor, Department of Chemical Engineering Indian Institute of Technology, Kharagpur e-mail: sde@che.iitkgp.ernet.in

Keywords:
Separation processes, membranes, electric field assisted separation, liquid membrane, cloud point extraction, electrophoretic separation, supercritical fluid extraction

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NPTEL Novel Separation Processes

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). Fig. 10.1 shows typical pressure temperature history of a substance.

Liquid Pressure Solid

Supercritical regime

Vapour

Temperature Fig. 10.1: Typical pressure temperature history of a substance Physical and thermal properties of SCFs are in between pure liquid and gas. Changes in properties are for a SCF are as follows: (i) (ii) (iii) (iv) (v) Liquid like densities Reduction in surface tension Gas like viscosity Gas like compressibility properties Diffusivities higher than liquids

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NPTEL Novel Separation Processes

Commonly used supercritical (SC) solvents:

Some commonly used supercritical solvents are carbon di oxide, nitrous oxide, ethylene, propylene, propane, n-heptane, ethanol and ammonia. Among these, CO2 is widely used as a supercritical solvent. Substance Tc (0K) Pc (atm) Density (g/cc) CO2 Ethane Ethanol Propane 304.2 305.5 516.6 370.3 73 48.2 63.0 42.0 0.47 0.20 0.28 0.22

Why CO2 is a supercritical fluid (SCF)?

Following properties of CO2 make it qualified to be an SCF. (i) (ii) (iii) (iv) (v) (vi) (vii) Low critical pressure (74 atm) and low critical temperature (320C) Relatively non-toxic Non-flammable Available as high purity Low cost Easily removable from extract It has polarity like liquid pentane at supercritical conditions and thus, best suited for liophilic compounds.

Drawback: It cannot extract polar solutes.

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NPTEL Novel Separation Processes

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 dibenzodioxines from fly ash. Disadvantage: It is highly explosive

H2O:
Disadvantage: (i) (ii) High Pc and Tc (Tc > 3740C, Pc > 221 bar) At these conditions, H2O is corrosive.

Important parameters for SCF extraction:

(i) Threshold pressure: Pressure at which miscibility of solute starts. Fig. 10.2 shows typical solubility curve of a material at a particular temperature.

Solubility (g/l)

T = 450C for CO2 Threshold Pressure

Pressure Fig. 10.2: Typical solubility curve of a material at a particular temperature. (ii) (iii) Pressure at which solute reaches its maximum solubility. Knowledge of physical properties of solutes (particularly, melting points). Solutes are dissolved better in liquid state.

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NPTEL Novel Separation Processes

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 of solubilization of solutes from solid materials:

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.

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NPTEL Novel Separation Processes

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 and solubility of solute in solvent are the major thermodynamic properties in this regard.

Basic Techniques in SCF technology:

1. RESS (Rapid expansion of supercritical solutions): A typical flow chart of a supercritical fluid extraction process is outlined in Fig. 10.3. 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.
Pressure regulator

Fluid Reservoir

Preheater

Pump Valv

Heating region Collection surface Collection chamber Expansion nozzle

Fig. 10.3: A typical flow sheet of a SCF process

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NPTEL Novel Separation Processes

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. 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. Example: Naphthalene extraction process A typical naphthalene extractor is shown in Fig. 10.4.

Pressure reduction valve

Extraction Vessel

Separator

Compressor

Fig. 10.4: A typical naphthalene extractor

The solubility diagram of naphthalene is shown in Fig. 10.5.

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NPTEL Novel Separation Processes

15% 15 300 bar

Concentration of naphthalene 1.0 (wt%) log scale 70 bar 20 30 40

0

120 bar

90 bar

Temperature ( C)

Fig. 10.5: Solubility diagram of naphthalene under supercritical condition

A naphthalene-chalk dust mixture is fed to the extraction vessel. Assume, extraction condition is 300 bar and 550C. 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 360C at 90 bar. Solubility of naphthalene is 2.5%. So, it falls out of solution. Precipitated naphthalene is collected and CO2 is compressed to 550C and 300 bar and recycled to extractor.

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NPTEL Novel Separation Processes

Mollier Diagram:

P = 600 bar
800C 720C

Enthalpy (Kcal/Kg) 155 152 145 135

2 1

300 bar

200 bar 90 bar

Temperature

600C 550C 400C 360C 200C

0.6

0.7

0.8

0.9

1.0

(1) 550C, 300 bar (2) 360C, 90 bar (after expansion) (3) 720C, 300 bar (after compression) Energy required to compress from 90 to 300 bar is,

(152 145) = 7 Kcal/kg

Then it is cooled to 550C

(12.6 BTU/lb)

(4) 720C, 300 bar to 550C, 300 bar Decrease in solubility is 15 to 2.5 wt%
1 lb CO2 contains 0.15 lb Naphthalene

After extraction
1 lb CO2 contains 0.025 lb Naphthalene

Extracted naphthalene = 0.15 0.025 = 0.125 lb

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NPTEL Novel Separation Processes

0.125 lb naphthalene extracted for 1lb CO2

So,

0.125 lb naphthalene extracted for =

1000 = 8 lb CO 2 125

So, we require 8 lb CO2 to recycle for extraction of 1 lb naphthalene. Energy required for compression from 90 to 300 bar is = 12.6 8 BTU

= 100.8 BTU for extraction of 1 lb naphthalene

Some 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

References:
1. K. A. Abbas, A. Mohamed, A. S. Abdulamir, and H. A. Abas, A Review on Supercritical Fluid Extraction as New Analytical Method, American Journal of Biochemistry and Biotechnology, 4 (4) (2008) 345-353. 2. M. Zougagh, M. Valcarcel and A. Rios, Supercritical Fluid Extraction: A Critical Review of its Analytical Usefulness, Trends in Analytical Chemistry, 25 (2004) 399-405. 3. I. J. Barnabas and J. R. Dean, Supercritical Fluid Extraction of Analytes from Environmental Samples, Analyst, 119 (1994) 2381-2394.

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NPTEL Novel Separation Processes

4. K. K Darani and E. V. Farahani, Application of supercritical fluid extraction in biotechnology, Critical Reviews in Biotechnology, 25 (2005) 231-242. 5. S. M. Pourmortazavi and S. S. Hajimirsadeghi, Supercritical fluid extraction in plant essential and volatile oil a, Journal of Chromatography A, 1163 (2007) 1-24.

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