Supercritical Fluid Extraction (S.F.E.

)
1. Definition
SFE : Supercritical Fluid Extraction of solids, generally operated in batch mode on
milled materials (or pellets, granulates,), with carbon dioxide as solvent, possibly added with
a co-solvent (ethanol most often) to increase its polarity. The equipment is composed of one or
several extractors consisting in high pressure autoclave(s) with fast-opening systems in which the
material to be treated is set inside a basket easy to put in and to remove, and a separation
section where extract and fluid are separated prior to fluid recycle through condensation and
liquid pumping. As it is operated in batch and requires manpower to change the solid material at
each cycle of extraction, this process generally leads to significant costs, often higher than those
obtained in classical organic solvent extractions. However, it is to be noticed that no organic
residue is found both in extract and solid residue and no thermal degradation appears, what
results in very high quality products.
A supercritical fluid is any substance at a temperature and pressure above its critical point, where
distinct liquid and gas phases do not exist. It can effuse through solids like a gas, and dissolve
materials like a liquid. In addition, close to the critical point, small changes in pressure or
temperature result in large changes in density, allowing many properties of a supercritical fluid to
be "fine-tuned". Supercritical fluids are suitable as a substitute for organic solvents in a range of
industrial and laboratory processes. Carbon dioxide and water are the most commonly used
supercritical fluids, being used for decaffeination and power generation, respectively.
Extraction can be defined as the removal of soluble material from an insoluble
residue, either liquid or solid, by treatment with a liquid solvent. It is therefore, a solution
process and depends on the mass transfer phenomena. The controlling factor in the rate of
extraction is normally the rate of diffusion of the solute through the liquid boundary layer at
the interface.Extraction involves the separation of medicinally active portions of plant or animal
tissue from the inactive or inert components using selective solvents in standard extraction
procedures. The products so obtained from plants are relatively impure liquids, semisolids or
powders intended only for oral or external use. So extraction continues to be of considerable interest
in order to obtain improved yields of drug derived from plant and animal sources.

Solvent extraction
Solvent extraction also known as liquid-liquid extraction and partitioning, is a
method to separate compounds based on their relative solubilities in two different
immiscible liquids, usually water and an organic solvent. It is an extraction of a substance
from one liquid phase into another liquid phase. It is a basic technique in chemical
laboratories, where it is performed using a separatory funnel. In other words, this is the
separation of a substance from a mixture by preferentially dissolving that substance in a
suitable solvent. Solvent extraction may be made use analytically for concentrating or
rejecting a particular substance, or for the separation of mixtures. This process usually
separates a soluble compound from an insoluble compound. Solvent extraction is used in
nuclear processing, ore processing, production of fine organic compounds, processing of
perfumes and other industries. Thus, although the method can be used for extraction and
preconcentration of a wide range of non volatile or semi volatile species from water using
only routine laboratory equipments, its use is decreasing in most situations because solvents
of the required purity tend to be expensive, and can also cause problems with proper

disposal after use.

2. Process description and variants
Except for decaffeination of green coffee beans operated at very large scale according to a
semi-continuous process, all SFE processes are operated on batch mode as the raw material,
generally in form of a powder obtained by milling or pellets by granulation, has to be loaded
in the extractors and the spent material unloaded at atmospheric pressure. This is a very strong
limitation as it induces both investment costs (autoclave closing/opening systems) and
operating expenses (manpower, fluid losses, ). But until now, no satisfactory solution has
been proposed to fill and remove the material from a high-pressure autoclave. In most
equipment, the raw material is not loaded directly in the extractor, but in a basket consisting
in a cylinder closed by filters through which the fluid will flow in and out. Few very large
extractors, like for hop processing, are directly loaded with the material, the spent material
being removed by aspiration with a vacuum cleaner.
On the other hand, it is important to note that, at the difference with lab or pilot-scale
equipments, industrial-scale SFE units always comprise several extractors for several reasons
:
Increase of productivity as the plant can work during the time needed for
unloading/loading one extractor ;
Decrease of the fluid losses as it is possible to depressurize one extractor (at the end of
the extraction) into another one (just loaded with raw material) ;
Increase productivity by reducing the total extraction time when operating a simulated
counter-current between the fluid and the material : In many cases where extraction is
limited by extract solubility at first and later by extract diffusion (see below at 4.6),
it is preferable to use the fluid until saturation, meaning that the fluid leaving the last
extractor in the sequence shall be saturated in extract ; it is easy to understand that the
quantity of fluid required to perform a given production of extract is minimal when the
fluid exits the extraction zone saturated in extract.
This requires several extractors in series that, for ease of comprehension, we will number at 4
and called A, B, C, and D.
Suppose D is at the end of the extraction cycle and in the phase of unloading the spent
material and loading the raw material ; during this period of time, extraction is performed on
extractors A, B, C, C being in last third period of extraction, B in the second one and A in the
first one ; fluid saturation can be easily obtained if the fresh fluid is firstly sent to autoclave
C (lean), and then to extractor B (medium) and finally to autoclave A (rich). After an
extraction time t equal to one third of the total extraction time, the material in extractor C is to
be unloaded meanwhile extractor D is ready for extraction. Then, the fresh fluid is sent to
extractor B (lean), then to extractor A (medium) and finally to extractor D (rich). And again
after the same period of time t, extractor B is unloaded meanwhile the fluid is sent to extractor
A (lean), then to extractor D (medium), and finally to extractor C (rich). And so on.
Optimization of the extraction cycle shall also deal with fluid management to avoid costly
venting to atmosphere. In most industrial SFE units, the fluid (generally carbon dioxide) is
pressurized in liquid phase by a pump and recycled by gas condensation (see flow sheet
below). As the performance of cooling machines is very dependent on the temperature

required for the cooling fluid, the condensation temperature is chosen around 8 to 10C
corresponding to a vapor pressure about 45 bar for CO2. This means that, when depressurizing
the extractor for unloading/loading operation, the fluid can be recycled only when its pressure
remains over 45 bar ; then, it is generally vented to atmosphere as, for economic reasons, only
very large-scale plants can be designed with a fluid recompression system permitting to
recycle the fluid at a much lower pressure. According to our experience, the best fluid
management consists in the following sequence of operations when extractor C is to be
unloaded and extractor D is ready for extraction : The fluid pump is stopped, extractor D is
slowly pressurized up with recycle gas at 45 bar and then equilibrated with extractor C. After
equilibration, extractor C is depressurized to 45 bar, the fluid pump is re-started and
extraction performed. Then, extractor C is depressurized to atmosphere by venting the fluid,
prior to unloading/loading operation. This leads to minimal losses as only compressed gas (45
bar, ~25C) is vented.
Optimization of the extraction cycle requires to manage the time duration of each operation.
It is easy to understand that the loading/unloading operation should be shorter than the time of
extraction between commuting the circuit (one third of the total extraction time in the
precedent example). In fact, depressurizing and pressurizing extractors cannot be done
brutally as this may cause damages to the equipment and/or the processed material :
deformation of the baskets containing the material, agglomeration of the material and
consequently bad contact with the fluid (channeling), dry ice formation during
depressurization with total plugging of lines and or basket. SEPAREX and HITEX developed
a proprietary process for reducing the final depressurization time without formation of dry ice
: Carbon dioxide is vented to atmosphere until its pressure reaches 10 bar or so ; at that
moment, compressed nitrogen (or air) is pumped and the gaseous mixture is vented with an
increasing concentration in nitrogen (or air) without temperature decrease due to the JouleThomson depressurization of CO2.
It is very important that all these operations are automated through a reliable control system,
both for safety and economic reasons.

Advantages
Environmental improvement and reduced product contamination
SFE is an alternative to liquid extraction using solvents such as hexane or
dichloromethane. There will always be some residual solvent left in the extract and matrix,
and there is always some level of environmental contamination from their use. In contrast,
carbon dioxide is easy to remove simply by reducing the pressure, leaving almost no trace,
and it is also environmentally benign. The use of SFE with CO 2 is approved by the Soil
Association for organic products. The CO2 used is largely a by-product of industrial
processes or brewing, and its use in SFE does not cause any extra emissions.
Selectivity
The solvent strength of a supercritical fluid can be varied by change in the pressure
and a lesser extent in the temperature.
For example, volatile oils can be extracted from a plant with low pressures (100 bar),
whereas liquid extraction would also remove lipids. Lipids can be removed using pure CO 2
at higher pressures, and then phospholipids can be removed by adding ethanol to the solvent. 742 G.
N. Sapkale et al.: Supercritical Fluid.

Speed
It is a fast process and completed in 10 to 60 minutes. It is a diffusion-based process,
with the solvent required to diffuse into the matrix, and the extracted material to diffuse out
of the matrix into the solvent. Diffusivities are much faster in supercritical fluids than in
liquids, and therefore extraction can occur faster. Also, there is no surface tension and
viscosities are much lower than in liquids, so the solvent can penetrate into small pores
within the matrix inaccessible to liquids.
Purity
A supercritical fluid can be separated from analyte by simply releasing pressure.
Supercritical fluids are cheap, inert and nontoxic. Thus, they are readily disposed off
after an extraction is completed by allowing them to evaporate into the atmosphere.
Recovery
Recovery of analytes becomes simple.