Supercritical carbon dioxide extraction of rape seed oil

Alberto Bueno, Martha Taboada, Pablo Santiago Flores

Introduction
Supercritical fluid extraction (SFE), specially performed with CO2, is a
promising field in the separation of oils and other liquid hydrocarbons
from plant materials. Although SFE is similar to a conventional solvent
extraction, the use of liquids above the critical point as solvent offers the
following attributes: relatively nonvolatile hydrophobic materials can be
dissolved by supercritical fluids, properties can vary by means of
pressure and temperature changes, and final separation of the extracted
substances from the supercritical fluid is performed by altering the
pressure and/or temperature of the fluid. After the separation, the
products extracted become quasi-solid at room temperature after the
removal of the solvent. The efficiency of the SFE depends on
temperature, pressure, contact time, diffusion and solubility of the oil in
the solvent. Supercritical CO2 is commonly used as extracting solvent
since it is nontoxic and allows supercritical operation at relatively low
pressures and near room temperature, the selectivity can also be
adjusted from gas-like to liquid like.

Materials and methods

In the practical course oil was extracted from dry grape seeds by using
supercritical CO2. The equipment used for the experimental extraction is
located in the Technikum at the TUHH. CO2 was first condensed in order
to be pumped and pressurized in liquid state at room temperature. Then,
temperature was increased to 50C and pressure was adjusted to 300
bar. CO2 in super critical stage crossed the extraction column to be in
contact with the dry grape seeds and extraction took place. CO 2 carrying
extracted oil was expanded first to 50 Bar and then to atmospheric
pressure and samples were taken after several intervals. Grape seed oil
remained in the samples in quasi-solid stated whilst exhausted CO 2
volatilized in gaseous state.

Results and discussion

Total extraction curve
In figure 1, the total extraction curve is plotted. From this figure it is
possible to conclude that during the time of the experiment it was not
reach the state of internal mass transfer resistance. This means that the
extract available in the area near the surface or over the surface was not
depleted. To deplete completely this extract with the same operation

conditions it is necessary to increase the extraction time. It is worth to

mention that the yield was calculated with the initial rape seed mass
introduced in the extractor. The total extraction curve is really important
for the optimization of the extraction process, the optimal extraction
time can be determined from here. This time is somewhere in between
the end of the constant mass transfer rate and the beginning of the
internal mass transfer resistance stage. As soon as the extract in the
neighborhood of the surface is depleted the transport phenomena
depends heavily on diffusion and the extract mass remaining inside the
particle does not justify the time consumed for extracting it.
Figure 1: Total extraction curve
0.25

0.2

0.15

Yield (%)
0.1

0.05

20

40

60

80

100

120

Time (min)

Mass transfer coefficient

Integrating equation 1 it is possible to determine the mass transport
coefficient .
Eq. 1
The integrated form of Eq. 1 is depicted in Eq. 2.
Eq. 2
The only unknown variable in equation 2 is the mass transfer coefficient
since we know the solubility of our product in CO 2 at a given density. As
a result the mass transfer coefficient results is: =5,51 X 10-6 m/h. Which is
in the range of industrial processes. For increasing this coefficient it is possible

to increase the scCO2 flow with the disadvantage of increasing the pressure
drop along the fixed bed and later the fluidization of the bed.

Mass balance
The mass balanced of the extract was obtained using Eq.3. Which is the
difference of the initial loaded substrate mass and the final mass of the
depleted substrate.

Oil Extracted [g] = Intial Rape Seed Mass [g]- Final Rape
Seed Mass [g]

Eq. 3

In table 1, the results of the Oil extracted and Oil collected are shown.
Oil Extracted
48.1
[g]
2
Oil Collected
39.8
[g]
8
Table 1: Mass balance results
The difference between the two values can be due to extracted
accumulated inside the equipment and also due to the extract/CO 2
equilibrium inside the separator.

Conclusions
It is possible to extract oils from seeds using a scCO 2 process. Using the total
extraction curve it is possible to determine the ideal extraction time for the
process. Increasing the superficial velocities of the scCO 2 increases the mass
transport coefficient up to certain extent when the fixed bed starts to deform
and finally fluidized. With the pressure of extraction (density of scCO 2) is
possibly to adjust the extraction due to the different solvent power of the
supercritical fluid. The design of the equipment is very important to avoid
entrapped residues inside the equipment.