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A CONTINUOUS COUNTERCURRENT SUPERCRITICAL FLUID FRACTIONATION

PROCESS APPLICATED TO OIL BORAGE

Conference Paper · April 2010

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 II Iberoamerican Conference on Supercritical Fluids
PROSCIBA 2010

A CONTINUOUS COUNTERCURRENT
SUPERCRITICAL FLUID FRACTIONATION PROCESS
APPLICATED TO OIL BORAGE
P. Blanco1, C. Mantell1, M. Rodríguez1, E. Martínez de la Ossa1 and A. de Haro2
1
Department of Chemical Engineeringand Food Technology
(Faculty of Science, University of Cádiz)
Box 40, 11510 Puerto Real, Cádiz – Spain
2Department of Vegetable Genetic Improvement

(Institute of Sustainable Agriculture, CSIC)

14080 Córdoba - Spain
E-mail: pilar.blanco@uca.es

Abstract. An analysis of the application of a continuous countercurrent

supercritical carbon dioxide fractionation process from oil borage has been
carried out. The influence of pressure and temperature about fatty acids content
in borage oil was investigated. Twelve assays were done in the pilot plant; the
operation conditions process were 35ºC, 55ºC and 75ºC of temperature and
100, 200, 300 and 400 bar of pressure. The feed flow-rate was 3 g/min and
CO2 flow-rate was 20 g/min. The experimental results obtained indicate that
fatty acid concentration increases in the extract at low pressures and high
temperatures, occurring the opposite in the raffinate.

Keywords: borage, supercritical carbon dioxide, extraction, continuous countercurrent

processing.
1. Introduction
Borage (Borago officinalis) is a plant originated in the Mediterranean region, but is now
cultivated worldwide, with 95% of the world’s crop grown in the United Kingdom, The
Netherlands, Canada, New Zealand and Poland (Kapoor, R. and Nair, H., 2005). Borage
seed contains 30% of oil, of which 24% is γ-linolenic acid (GLA) and 34–38% is linolenic
acid (LA). The oil obtained from the seeds presents one of the highest amounts of GLA (n-
6) and other n-6 essential fatty acids (Kotnik, P. et all, 2006). GLA is the first intermediate
formed during the conversion of LA to prostaglandins, very important to be present in many
reactions in the human body. This omega-6 acid has anti-inflammatory, antithrombotic and
anti-carcinogenic properties. Also, it has been used for treating arthritis, certain skin
problems (i.e., atopic eczema), reproductive disorders, including breast pain and
premenstrual syndrome, cardiovascular diseases and neurological problems related to
diabetes (Kotnik, P. et all, 2006; Molero-Gómez and Martínez de la Ossa, 2002; Horrobin,
D.F., 1992).
The most important objetive of our work is the concentration of γ-linolenic acid from
borage seed oil. For that, we are doing different assays using supercritical fluid technology,
specifically, supercritical fluid extraction with carbon dioxide. Extraction with carbon
dioxide under supercritical conditions constitutes an emerging technology in terms of
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environmental impact. The advantages in using carbon dioxide include its lack of toxicity,
chemical inertness, low cost and ready availability. Furthermore, the use of carbon dioxide
is also beneficial in adding quality to the products obtained since this technique does not
give rise to excessive heating, which usually has a negative effect on thermolabile
compounds. SFE uses CO2 instead of organic solvent and CO2 has unusual properties such
as high compressibility, liquid-like density, high diffusivity, low viscosity and low surface
tension. A continuous countercurrent supercritical carbon dioxide fractionation column goes
to be used to do the experiments. The results of these ones will depend on the solubility of
the interest substances of the oil in the supercritical CO2. In general, the economic
feasibility of industrial operations is higher for continuous processes when compared to
batch or semicontinuous processes. Also, countercurrent operations tend to be more
efficient due to the larger driving force for mass transfer between solvent and solute
(Dunford, N.T. et all, 2003).
2. Materials and Methods
Samples and chemicals. Refined borage oil (from Apsara Vital, Barcelona, Spain) was
used as feed material for this study. The supercritical extraction process was carried out
with carbon dioxide (99.995% purity) from Carburos Metálicos.
Acidity index of feed oil and of extract and raffinate fractions was analyzed, according
to UNE-55011. For that, the following reagents were utilized:

Table 1. Reagents
Reagent Purity Company
Ethanol PA Panreac
Toluene PA Panreac
Potassium Hydroxide 0,1 PA Panreac
mol/l (0,1N) ethanolic SV
Phenolphthalein solution PA Panreac

Supercritical fluid fractionation column. A supercritical fluid fractionation

equipment, that consists of a stainless steel column (Thar Technology, Pittsburgh, PA,
USA), was used for the fractionation experiments. A schematic of this pilot plant is shown
in Fig. 1.
There are four independently controlled temperature zones in the column; each zone
was heated to the desired temperature using two heaters wrapped around the column and
powered through solid state relays. The temperature of each individual zone was
maintained with PID (Proportional-Integral-Derivative) controllers. Internal zone
temperatures are monitored with a digital indicator. There are six temperature sensors
along de column and a manometer connected to the body of the column to check pressure
in the system.
The pilot scale fractionation column’s internal dimensions are 2.8 m long and 2 cm
diameter providing a total column volume of 1765 mL. The column is packed with stainless
steel packing material (Propak perforated flakes). There are three lateral inputs: one at the
bottom, for solvent addition (supercritical CO2), one in the middle and one at the top, for
the feed (borage oil). Also, there are two outputs, one at the top (extract exit) and one at the
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bottom (raffinate removal exit). The lower section of the column, below the CO2 inlet, (30
cm of length) is used as a raffinate reservoir. In addition, there is a heat exchanger that
allows controlling automatically the solvent temperature.
Carbon dioxide and feed are introduced into the column using two double piston liquid
pumps (Model P50, Thar Technology, Pittsburgh, PA, USA). For that, it is necessary to
condense carbon dioxide before inputting the pump with a bath that cools carbon dioxide
below 5 ºC. On the other hand, for going down oil viscosity, the oil storage container is
thermostatized with an electric heater that allows oil to maintenance at 60ºC temperature
approximately.

T T SALIDA
P BPR1
DE CO2

Bomba MV-2
P50 MV-4 BPR2

Separador
Aceite

P P

T S1

Controlador
Baño MV-3
Criotermostato
EXTRACTO

T HE2 T

Caudalímetro

Bomba P
P50

CO2

MX-1 T

HE1 REFINADO

Fig. 1. Scheme of countercurrent supercritical fluid fractionation column.

The extract is collected in the cyclonic separator S1, which consists in a stainless steel
container of 500 mL capacity that store the obtained extracts. Temperature and pressure of
the separator are monitorized by a manometer and a temperature sensor connected by the
plant control system. Pressure conditions are controlled by a back pressure regulator at the
end of the column.
The pilot plant is automated by a control system connected to a computer with the
software ICM (Thar Tech. Pittsburg, PA. USA). The program allows carrying out
countercurrent extractions at constant pressure and temperature.
2. Column Fractionation Operation
Fractionation experiments were carried out in a continuous countercurrent mode of
operation. Initially the column was filled with CO2 and allowed to equilibrate at the desired
temperature and pressure. Then, continuous flow of oil and CO2 began and extract
collection was initiated. Carbon dioxide was allowed to enter the system from the bottom of
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the column, right above the raffinate collection section. In this particular study, oil was
delivered into the system from the top of the column to allow countercurrent contact of
supercritical CO2 with the feed material. The solute dissolved in the supercritical CO2
circulated upwards in the column and the resultant extract was collected from the top of the
column in the separator. The oil components, which were not solubilized significantly in
supercritical CO2 accumulated in the raffinate reservoir at the bottom of the column. The
raffinate reservoir was drained in 20-min intervals to avoid overflow of the raffinate fraction
into the fractionation section of the column.
The fractionation experiments were carried out under isobaric and isothermal conditions.
Twelve assays were carried out, with the following conditions:

Table 2. Operation conditions

No Assay Temperature (ºC) Pressure (bar)
1 35 100
2 35 200
3 35 300
4 35 400
5 55 100
6 55 200
7 55 300
8 55 400
9 75 100
10 75 200
11 75 300
12 75 400

Carbon dioxide and oil flow rates were 20 g/min and 3 g/min, respectively. After the
completion of the experiment the column was depressurized and residual oil drained off at
the end of each run. Operation time of each assay was 3-4 hours.
3. Results and Discussion
Flow-rates of extract and raffinate were measured to verify mass balance. Depending on
the oil solubility in supercritical CO2, flow rates of extract and raffinate will be higher or
lower, but the sum should be the flow-rate feed. In the figure 2, the tendency of flow rates in
each operation condition can be observed: extract flow-rate increases when pressure
increases and temperature decreases.
In addition, analyses about free fatty acids concentration in extract and raffinate flows
were carried out. Free fatty acids content is expressed by means of the acidity index,
calculated according to conventional method. Acidity index is the mass, in mg, of potassium
hydroxide that is necessary to neutralize free fatty acids present in 1 g of sample. It is usual
to represent such as percentage of oleic acid, that it is the most abundant fatty acid. If we
observed the figure 3, we can see that, at constant temperature, if pressure increases, free
fatty acid concentration decreases in the extract, whereas it increases in the raffinate. In the
other hand, at constant pressure, if temperature increases, free fatty acid concentration
increases too, whereas it decrease decreases in the raffinate. We should notice variations are
not very significant in general, because oil feed is refined and its acidity index is very low.
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4,5

4,0

3,5

3,0
Flow rate (g/min)

Extract 35ºC
2,5 Raffinate 35ºC
Extract 55ºC
2,0 Raffinate 55ºC
Extract 75ºC
1,5
Raffinate 75ºC
1,0

0,5

0,0
100 200 300 400
Pressure (bar)

Fig. 2. Flow rates of extracts and raffinates.

6,0

5,5

5,0

4,5

4,0
Acidity Index (%)

Extract 35ºC
3,5
Raffinate 35ºC
3,0 Extract 55ºC
2,5 Raffinate 55ºC
Extract 75ºC
2,0
Raffinate 75ºC
1,5

1,0
Inicial Acidity
0,5

0,0
100 200 300 400
Pressure (bar)

Fig. 3. Acidity index of extracts and raffinates.

Finally, we represented the acidity index respect to supercritical carbon dioxide density.
If we observe the figure 4, we can see that the highest variations of acidity index in the
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extract are produced when supercritical CO2 density is between 600-1000 Kg/m3. Variations
in the raffinate are low because the initial acidity index was very low.

6
5,5
5
4,5
4
Acidity Index (%)

3,5
Extract Acidity
3
Raffinate Acidity
2,5
2
1,5
1
0,5
0
100 200 300 400 500 600 700 800 900 1000 1100
Density CO2 (Kg/m 3)

Fig. 4. Relation between acidity index of extracts and raffinates and supercritical CO2 density.

3. Conclusions
This study demonstrates that a continuous countercurrent SFF column fractionation
process carried out at low pressure and high temperature can be utilized to enrich free fatty
acids in the extract and to decrease them in the raffinate, i.e., we are carrying out the
deacidification of refined borage oil. The described supercritical fluid fractionation
technique is relatively simple to execute and environmentally benign through the use of
supercritical CO2, yielding an end product with no chemical residues.
Acknowledgments
The authors thank the Junta de Andalucía for financial support (Project PAI07-AGR-
2759), which enabled this work to be carried out.
References
Dunford, N.T. et all. A continuous countercurrent supercritical fluid deacidification process for
phytosterol ester fortification in rice bran oil. Food Research International 36 (2003) 175–
181.USA.
Horrobin, D.F., Nutritional and medical importance of gamma-linolenic acid. Prog. Lipid Res. Vol.
31, No.2, pp. 163-194. Nova Scotia, Canada.
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Kapoor, R., Nair, H. (2005). Gamma linolenic acid oils. Bailey’s Industrial Oil Fat Products. Edible
Oil and Fat Products: Specialty Oil and Oil Products. Vol. 3. 6th Edn. Ed. F. Shahidi, John Wiley
& Sons, pp. 67–120, New York (USA).
Kotnik, P. et all. Kinetics of supercritical carbon dioxide extraction of borage and evening primrose
seed oil. Eur J Lipid Sci Technol. 2006, 108, 569–576. Maribor, Slovenia.
Molero-Gómez, A., Martínez de la Ossa, E. Quality of borage seed oil extracted by liquid and
supercritical carbon dioxide. Chem Eng J. 2002, 88, 103–109. Cádiz, Spain.

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