Supercritical Fluid Extraction (S.F.E.

)
Author : Dr. M. PERRUT

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.

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.

EXTRACTOR
S

SEPARATOR
S

Condenso
r

EXTRACT
CO2
reservoi
r
Heater

CO2
pump

Co-solvent
pump

Supercritical Fluid Extraction flow sheet

General view of a large-scale SFE plant at ESSENCES Srl (Italy)

Control system and view of a large-scale SFE plant