2 Supercritical Fluid Extraction

2.1 Introduction

Solvent extraction is one of the oldest methods of separation known and certainly dates to prehistory.
The science of solvent extraction has evolved accordingly over a long period of time and much
progress has been made in the understanding of solvation and the properties of liquid mixtures used
in extraction processes. The associated literature on phase behaviour is certainly extensive and,
although representation of highly non-ideal mixtures is still problematic, many theoretical models
have been successfully developed. Extensive databanks of pure component properties have grown to
support such models to predict solvent performance in process applications. Today, even with the
introduction of new separation technologies, solvent extraction remains one of the most widespread
techniques operating on an industrial scale.

Hannay and Hogarth’s (1879) early observations of the dissolution of solutes in supercritical fluid
(SCF) media introduced the possibility of a new solvent medium. However, it is only in recent years
(since 1960) that commercial process applications of supercritical fluid extraction have been
extensively examined.

In the last decade many advances have been made in researching SCF extraction both in terms of
fundamental aspects and commercial applications. The high degree of selectivity and control over
solubilities afforded by pressure (and temperature) variation has led to the introduction of many
novel SCF extraction and fractionation processes. Of all possible gases, the benign properties (non-
toxic, non-flammable) and accessible critical temperature of CO2 have ensured its predominance as a
safe SCF solvent for the food industry.

Supercritical Fluid Extraction (SFE) is the process of separating one component (the extractant) from
another (the matrix) using supercritical fluids as the extracting solvent. Extraction is usually from a
solid matrix but can also be from liquids.

2.2 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). Fig. 2.1 shows typical pressure –
temperature history of a substance.

Above its critical values, a compound’s liquid-vapor phase boundary no longer exists, and its fluid
properties can be tuned by adjusting the pressure or temperature. Although supercritical fluid has

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liquid-like density, it exhibits gas-like diffusivity, surface tension and viscosity. Its gas-like viscosity
results in high mass transfer. Its low surface tension and viscosity lead to greater penetration into
porous solids. Because of its liquid-like density, a supercritical fluid’s solvent strength is comparable
to that of a liquid.

Fig. 2.1: Typical pressure – temperature history of a substance

Physical State Density (g/ml) Viscosity (g/cm-s) Diffusivity (cm2/s

Gas 10-3 10-4 10-1

Liquid 1 10-2 10-6

Supercritical Fluid 0.2-0.9 10-4 10-3

2.3 COMMONLY USED SUPERCRITICAL (SC) SOLVENTS

Physical and thermal properties of SCFs are in between pure liquid and gas. Changes in properties
are for a SCF are as follows:

(i) Liquid like densities

(ii) Reduction in surface tension
(iii) Gas like viscosity
(iv) Gas like compressibility properties
(v) Diffusivities higher than liquids

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.

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 Substance Tc (°C/K) Pc (atm) Density (g/cc)

CO2 31.05/304.2 73 0.47

Ethane 32.35/305.5 48.2 0.20

Ethanol 243.45/516.6 63.0 0.28

Propane 97.15/370.3 42.0 0.22

2.3 WHY CO2 IS AN IDEAL SUPERCRITICAL FLUID (SCF)?

Following properties of CO2 make it qualified to be an SCF.

1) Low critical pressure (74 atm) and low critical temperature (32°C)
2) GRAS and non-toxic
3) Non-flammable
4) Available as high purity
5) Low cost
6) Easily removable from extract
7) It has polarity like liquid pentane at supercritical conditions and thus, best suited for liophilic
compounds.

Drawback: It cannot extract polar solutes.

Many reactions, extractions, separations and other operations in the food process industries involve
the use of organic solvents. In addition to handling and disposal issues, organic solvents can pose
several health risks and environmental concerns, such as atmospheric and land toxicity. In many
cases, conventional organic solvents are regulated as volatile organic compounds (VOCs). In
addition, certain organic solvents are under restriction due to their ozone-layer-depletion potential.

Supercritical carbon dioxide is an attractive alternative in place of traditional organic solvents. CO2 is
not considered a VOC. Although CO2 is a greenhouse gas, if it is withdrawn from the environment,
used in a process, and then returned to the environment, it does not contribute to the greenhouse
effect.

Nitrous Oxide

It is good for removal or solubilize polar solutes, as it has a permanent dipole moment. N 2O is better
than CO2 for extraction of polychlorinated dibenzodioxines from fly ash.

Disadvantage: It is highly explosive

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Water (H2O)

Disadvantage:

1) High Pc and Tc (Tc > 374°C, Pc > 221 bar)

2) At these conditions, H2O is corrosive.

2.4 IMPORTANT PARAMETERS FOR SCF EXTRACTION

1. Threshold pressure: Pressure at which miscibility of solute starts. Fig. 2.2 shows typical
solubility curve of a material at a specific temperature.

2. Pressure at which solute reaches its maximum solubility.

3. Knowledge of physical properties of solutes (particularly, melting points). Solutes are dissolved
better in liquid state.

Fig. 2.2: Typical solubility curve of a material at a specific temperature.

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.

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2.5 NEED OF SCF EXTRACTION

Currently, the widest application of supercritical CO2 is in extraction in food processing industry for
products like decaffeination of coffee, extraction of hops during the brewing process. The increasing
need of SCF extraction is because of following reasons:

1) An increasing public awareness of the health, environment and safety hazards associated with
the use of organic solvents in food processing.
2) Possible solvent contamination of the final products.
3) High cost of organic solvents
4) Stringent environmental regulations
5) New requirements of the medical and food industries for ultra-pure and high added value
products.

Conventional processes for extracting various components from food products have limitations
regarding the solvent toxicity, flammability and wastefulness. Prior to the use of supercritical CO2,
several different solvents including methylene chloride, ethyl acetate, methyl acetate,
methylethylketone and trichloroethane have been used for decaffeination.

2.6 CLASSIFICATION OF SCF EXTRACTION METHODS

1) Single stage supercritical fluid extraction

2) Counter current multistage processing
3) Preparative chromatographic separation

2.6.1 Single Stage SCF Extraction

It consists of 2 process steps, extraction and separation of extract from solvent. In the extraction, the
SCF flows through a fixed bed of solid particles and dissolves the extractable components of the
solid. The loaded solvent is removed from the extractor and fed to the precipitator. The solid material
will be depleted from the extractable material in the direction of flow. Example: Extraction of Oil
from rapeseeds.

Process Description for Lab-Scale Plants

The Carbon dioxide gas from the cylinder is first liquefied & then pressurized above the critical
pressure of CO2 (73.8 bar) to the required pressure necessary for extraction. This high-pressure liquid
CO2 is then heated above the critical temperature of CO2 (31 °C) to the required temperature.
CO2 which is now in supercritical phase (SCCO2) enters the extractor where the raw material is fed
in powder form & the extraction is achieved on the basis of solubility. The compounds dissolved in
SCCO2 finally come to the separator at atmospheric pressure & get precipitated. CO2 leaving the
separator is then measured by passing it through a CO gas flow meter.

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 Fig. 2.3: Flow Scheme of Single Stage Processing with Supercritical Fluids

Process Description for Commercial Scale Plant

The raw material in powder form is fed to the extractor. The liquid carbon dioxide from the CO2 tank
is precooled by passing it through the precooler. This precooled liquid carbon dioxide is then
pressurized by means of a positive displacement plunger pump to a pressure above the critical
pressure of CO2 (i.e. 73.8 bar). High pressure liquid CO2 is then heated above the critical temperature
of CO2 (i.e. 31 °C) by passing it through preheater. CO2 which is now in the supercritical state enters
the extractor in which the raw material is loaded. The SCCO2 dissolves substances on the basis of
solubility, depending on operating conditions. The SCCO2 with soluble extracts enters the separators
where the pressure & temperature are reduced sequentially so that solubility decreases & extract
precipitates in the separators. Finally, the clean CO2 without any traces is recycled back to the
CO2 tank via condenser.

2.6.2 Counter-Current Multi-Stage Processing

Multi-stage counter-current contacting is the most effective mode. It reduces the amount of solvent
and makes possible continuous production of extract, enables higher extract concentrations in the
solvent and lower residual concentrations in the raffinate. Real counter-current contact is not easily
established for solids, since special effort is necessary for moving the solid, with increased
difficulties at elevated pressure. Process equipment consists of the separation column where gaseous
and liquid phases are contacted counter- currently. A separator at the top for separating solvent and
extract, devices for feeding reflux to the column, for recovering top product(extract). Devices for
delivering feed to the column, for recovering product at the lower end of the column (raffinate), and
for recycling the solvent. Example: Separation of alcohol and water, fractionation of citrus oils.

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 Fig. 2.4: Flowsheet for Countercurrent Extraction of Ethanol With SC-CO2

2.6.3 Supercritical Fluid Chromatography

SFC is utilized as an analytical technique rather than a processing tool. It has been used in the food
and pharmaceuticals industries at the quality control level, where heat-labile non-volatile components
need to be quantitated. In chromatographic separation, the supercritical solvent is used as mobile
phase. Replacing LC methods by SFC decreases analysis time, increases sample throughput and
decreases liquid waste. Example: Separation of phytol isomers, purify pharmaceuticals (Vitamin D).

2.7 ADVANTAGES OF SCF EXTRACTION

SFE is used on a large scale for the extraction of some food grade and essential oils and has several
advantages over conventional extraction processes:

• Extract with delicacy & freshness close to natural

• High potency of active components
• Longer shelf life extracts
• Eco-friendly & green technology with no residual solvent & effluents

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 • High flexibility of process conditions
• Simultaneous fractionation of extracts
• High yields compared to solvent extracted products
• Low batch times for extraction
• Recycling of CO2
• Low operating cost

2.8 APPLICATIONS OF SCF EXTRACTION IN FOOD PROCESSING

There has been a great deal of interest in supercritical CO2 extraction beyond caffeine extraction,
particularly in the preparation of high value food processing products, such as flavors and fragrances,
food supplements and nutraceuticals.

1) Enrichment of Vitamin E from natural sources

2) Encapsulation of liquids for engineering solid products
3) Lycopene extraction from processed tomatoes
4) Extraction of anti-oxidants from pepper
5) De-fatted french fries/meat
6) Removal of pesticides
7) Extraction of essential oils and aroma materials from spices
8) Production of active ingredients from herbal plants for pharma industry

2.8.1 Processing of Natural Fats and Oils by SFE

A wide range of other applications for supercritical CO2 has been investigated and represented in
table below:

Mixture Solvent Extraction Separation

Oil from oil seeds CO2, ethane 40°C, 220 bar 40°C, 20 bar

Refining of oils Propane 130°C, 150 bar 40°C, 7.4 bar

Free fatty acids 100-110°C,

Ethylene 125-130°C, 100 bar
removal 100 bar

Acid removal, 70-80°C,

CO2, propane 110-125°C, 135 bar
deodorization 135 bar

Fractionation of cod 55-90°C,

Ethane Decrease in pressure
liver oil 100-160 bar

Increase in temperature,
Fat from milk Ethylene, CO2 20°C, 200 bar
65 bar

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2.8.2 Extraction of Active Substances from Plant Material

Mixture Solvent Extraction Separation

40-90°C,
Caffeine from coffee CO2 Absorption in water,
160-220 bar

60-95°C, Absorption in
Caffeine from water CO2
250 bar water

35-80°C,
Humulones from hops CO2 Decrease in pressure
80-300 bar

35-80°C,
Oleoresins from spices CO2 Decrease in pressure
80-300 bar

35-100°C, Decrease in pressure,

Nicotine from tobacco CO2, Ar, SF6
80-300 bar Adsorption

2.9 Commercial Scale Supercritical CO2 Plants

Large-scale commercial plants using supercritical CO2 extraction are found in the food industries and
involved in processing of following products.

PROCESS MANUFACTURER

Tea/Coffee decaffeination General Foods, Café HAG, SKW Trostberg

Natural pesticides Agropharm

United beweries ltd, Botanix, Hops Extraction

Hops extraction
Corporation of America

Spices/ Flavors/ Aromas/ colors/ Natural

Synthite, Fermenich, Sensient, Newly Weds Foods Inc.
products

Nicotine extraction Philip Morris

Processing materials with supercritical fluids is a proven and industrially applied technology.
Processing costs can be very competitive to other processes, but sometimes supercritical processes
are unique in their ability to produce solvent free products. Many food processing industries are
recognizing SFE with CO2 as a promising green technology in extraction of food products.

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