Journal of Supercritical Fluids 17 (2000) 177 186

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Extraction of coriander seed oil by CO2 and propane at

super- and subcritical conditions
V. Illes a, H.G. Daood b,*, S. Perneczki c, L. Szokonya a, M. Then d
a
Department of Chemical Engineering, Uni6ersity of Veszprem, Veszprem, Hungary
b
Central Food Research Institute, Budapest, Hungary
c
National Judicial and Toxicological Institute, Budapest, Hungary
d
Institute of Pharmacognosy, Semmelweis Uni6ersity of Medicine, Budapest, Hungary

Received 22 July 1999; received in revised form 17 November 1999; accepted 17 November 1999

Abstract

Oil extraction from coriander seed was studied with carbon dioxide and propane as solvents, under sub- and
supercritical conditions. The ratio of solvent to seed (g/g) required to achieve a complete oil extraction was between
20 and 40 using CO2 at pressures of 200 and 300 bar and temperature of 35C. A complete oil recovery could be
attained with propane or propane-rich solvents at 25C and 50, 80 and 100 bar. The ratio of solvent to seed needed
to approach maximum extraction was varied between 1.3 and 2.5. The solvating power of propane and propane-con-
taining solvents was proved to be much higher than that of CO2. The fractions trapped in the initial period of
extraction with CO2 were rich in essential oils. It was stated that the content and composition of essential oils in the
extracts can be influenced by modifying the solvent composition and changing the extraction conditions, which had
negligible effect on the fatty acid composition of the recovered oils. The changes in the tocopherol content of the
extracts as a function of supercritical fluid extraction (SFE) conditions are also investigated in the present work.
2000 Elsevier Science B.V. All rights reserved.

Keywords: Supercritical extraction; Coriander seed; Essential oils; Fatty acids; Tocopherols

1. Introduction 2% of essential oils can be recovered from the

Coriander seeds (Coriandrum satium L.) are
widely used as a seasoning agent in liqueurs, teas,
meat products and pickles. The coriander seed
contains essential oils, triglycerides, sugars,
proteins and vitamin C. By distillation only 0.5
* Corresponding author. Present address: Herman Otto u.
15, 1022 Budapest, Hungary. Fax: + 36-1-2129853.
coriander seed, which contains mainly a-linalool
[1].
Steam distillation has traditionally been applied
for essential oils recovery from plant materials.
One of the disadvantages of the hydro-distillation
methods is that essential oils undergo chemical
alterations and the heat-sensitive compounds can
easily be destroyed. Therefore, the quality of the
essential oil extracts is extremely impaired.

0896-8446/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 8 9 6 - 8 4 4 6 ( 9 9 ) 0 0 0 4 9 - 2
178 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186

The other method applied for oil recovery Germany) pumped the liquid solvent through a
from plant materials uses organic solvent extrac- buffer vessel into the thermostated extraction
tion, which has limitations with regard to the column. The pressure of the solvent was con-
loss of valuable volatiles during vacuum evapo- trolled with a backpressure valve. The solute-
ration of solvent, and difficulty in obtaining sol- rich compressed gas was expanded through a
vent free extracts [2,3]. These disadvantages can heated needle valve to atmospheric pressure.
be avoided if the extraction is carried out by The extract was trapped in a cooled vessel and
compressed gases. Over the last 15 20 years in the amount of solvent gas also measured. More
the food, cosmetic and pharmaceutical indus- details on apparatus and method have been re-
tries, extraction of some materials using com- ported previously [11].
pressed gases has been investigated [4 9]. The fatty acid and essential oil composition of
Carbon dioxide alone or with solubility the extracts was analyzed by gas chromatogra-
modifiers has been widely used as solvent in the phy (GC). Before analysis the glycerin-esters of
supercritical fluid extraction (SFE) of plant ma- triglyceride were converted into methyl-esters ac-
terials. Ethane, propane, ethylene, dinitrogen ox- cording to the Hungarian Standard methods:
ide etc. have also been recommended as solvents
No-19929-86 and No-195228-86. The conditions
under sub- or supercritical conditions for SFE
for the GC analysis were as follows:
[8,10,11].
Extraction of coriander seed has been carried
Sample: Essential oil Triglyceride
out by CO2 at near supercritical condition
Column: 3% OV-17 10% GPBE
[12,13]. The extract, by such a process, was es-
Chromosorb 2300
sential oil. To achieve total oil extraction, other
WAW Chromosorb
types of solvents at higher pressure are needed.
WA
In the present work extraction of coriander
Temperature: 50200C 160C
seed, by CO2 and propane under sub- and su-
N2: 1.5105 Pa 1.5105 Pa
percritical conditions was studied with special
O2: 50 ml/min 50 ml/min
focus on the effect of different parameters on
H2: 50 ml/min 50 ml/min
the yield, essential oil content and fatty acid
Injected vol- 5 ml 5 ml
composition of oils.
ume:

The different fatty acids and essential oils

2. Materials and methods
Technical grade carbon dioxide and propane
(of 99.95% purity) were purchased from Messer
Griesheim Hungaria (Budapest, Hungary). The
commercial quality coriander seeds were ground
so as to pass through a 20-mesh sieve before the
extraction. Standard fatty acids (methyl esters),
tocopherols, linalool, geranyl acetate and linalyl
acetate were purchased from Sigma (St Louis,
MO).
The extraction experiments were performed in
a high-pressure, flow-up apparatus, in which oil
solubilization by the different solvents takes
place in adynamic mode. A model EL-1 mem-
brane pump (from LEWA Herbertott, Leonberg,
were identified by injection of standard solu-
tions, which were also used for quantitative
determinations.
For the determination of tocopherols, the
high-performance liquid chromatographic
(HPLC) method, which has been validated for
plant oils by Speek and his co-workers [14] was
used. After saponification, the tocopherols were
separated on Si-100-S normal-phase column
(from BST, Budapest) and fluorometrically de-
tected (Shimadzu Model RF-353 HPLC Detec-
tor) at 290- and 320-nm excitation and emission
wavelengths, respectively. Identification and
qualitative determination of tocopherols was
based on comparison of retention times with
those of standard solutions.
 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
3. Results and discussion
The extraction was carried out with CO2 super-
critical conditions (35C, and 100 350 bar) and
subcritical conditions (25C and 100 bar), while
subcritical conditions were applied for extraction
with propane or propane-containing solvent.
Fig. 1. Effect of pressure on the extraction of oil from corian-
der seeds as a function of the solvent/seed ratio using SF-CO2.
Fig. 2. Effect of extraction pressure on the amount of oil (gE)
dissolved in 100 g of SC-CO2 at 35C.
179
The gas volume at the absolute temperature 273
K and 1 bar was calculated using the Peng-
Robinson equation of state [15]. After normaliza-
tion of gas volume, the mass of gas and
gas-mixture could then be determined.
3.1. Extraction by CO2
The relationship between solvent use and
amount of extract obtained from 100 g coriander
seed at different temperatures and pressures is
shown in Fig. 1. Complete extraction could be
achieved at 35C and 200 and 300 bar in 2.0 and
1.5 h, respectively. The extract consist of, besides
essential oils, triglycerides (glycerol esters of fatty
acids) and waxes. Under subcritical conditions
(25C and 100 bar) the oil solvating capacity of
SF-CO2 was substantially decreased so that a
complete extraction could be achieved in  6 h.
At 100 bar and 35C the solvating power of
SF-CO2 was so low that 100 g of the solvent
solubilized only 0.03 g of oil (Fig. 2).
The first fraction of subcritical extraction with
CO2 (at 15% extraction degree) was composed
mainly of essential oils. As the pressure was raised
to 200 bar the yield of the non-volatile oils was
markedly increased with observable reduction in
the solubility of essential oils. The oil solubility
increased to 1.08 g/100 g CO2 when the extraction
was performed at 350 bar. The maximum amount
extracted from 100 g coriander seed was 15.3 g at
200 bar and 16.4 g at 300 bar when the tempera-
ture was 35C.
3.2. Extraction with propane
The results of propane extraction at 25C, and
50 and 80 bar are shown in Fig. 3. After a steep
increase, the extraction curve reached a plateau
giving the maximum oil yield. The oil solubility in
propane was so high that a ratio of solvent/seed
of 1.5 was all that required for the implementa-
tion of complete extraction of oil. The maximal
amount of oil extracted from 100 g seed ranged
between 15.4 g and 16.9 g. These values were
similar to those approached using supercritical
CO2 or propane rich solvent mixture. Because the
solvent is not capable of penetrating into the inner
180 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
Fig. 3. Supercritical propane extraction of coriander seed oil as
a function of the solvent/solid ratio at different pressures.
Fig. 4. Extraction of oil from coriander seeds by CO2,
propane-CO2 and propane at different super- and subcritical
conditions.
layers of the ground seeds, it cannot totally sol-
vate the oil. Thus, the quantity of the solubi-
lized oil decreased with the progress of
extraction process. The estimated time to com-
plete the extraction with subcritical propane is
50 70 min.
3.3. Comparison between CO2 and propane
extraction
Fig. 4 illustrates the influence of extraction
conditions on oil recovery using propane and CO2
solvents. Very steep increase in oil solubility in
propane was observed as a function of the solvent
used. In the case of SC-CO2 (supercritical carbon
dioxide) the extraction curves indicated a more
limited removal of the oil.
The ratio of solvent/solid required for complete
extraction of coriander seed oil by SC-CO2 was 40
and 20 when a pressure of 200 and 300 bar was
applied, respectively, at 35C. This ratio decreased
to 2.6 using a mixture of 2:1 propane-CO2. In case
of pure propane, under subcritical conditions, a
ratio of 1.3 and 1.5 was needed for the implemen-
tation of complete extraction at 80 and 50 bar,
respectively. Such experimental data agree with
those published earlier [811], which concern ex-
traction capacity of propane-rich solvents. Ac-
cordingly, small proportions of propane-rich CO2
are needed to achieve complete recovery of oils
from plant materials. From the economic point of
view it is of great interest that the ratio of
propane/seed is several times lower than the ratio
of CO2/seeds, thus, the use of propane can sub-
stantially reduce the cost of extraction technology.
Fig. 5. Extraction of essential oil from coriander seeds as a
function of oil output using different solvents at different
conditions.
 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
Fig. 6. Gas chromatography profiles of essential oils from
coriander seeds at different extraction degrees. For explana-
tion of 2/A, B, C see Table 1.1, D-linalool; 2, geranyl acetate;
3, linalyl acetate.
Fig. 7. Change in the essential oil content (%) as a function of
extraction degree (%) using CO2, propane-CO2 and propane at
different super- and subcritical conditions.
3.4. E6aluation of the quality of extracts
Table 1 summarizes the data on essential oil
composition and content of coriander oils recov-
ered under different conditions, while Fig. 5 illus-
trates the change in the essential oil content of the
181
extracts as a function of increased output of oil.
With SC-CO2, irrespective of pressure and tem-
perature, the essential oil content of the extract
rapidly decreased in accord with the increased
quantity of the recovered oil. The oil obtained
with 1015% yield contained 7080% of the total
essential oils. At 30% extraction, the essential oil
content decreased to 38%, further on it fluctu-
ated between 1 and 2%. This means that essential
oils are first solubilized by SC-CO2 and their
extraction is practically completed by the time
that 30% of the oil is recovered. The essential oil
composition of coriander oil obtained at three
different times of extraction is shown in Fig. 6.
When the extraction was performed with
propane or propane-rich solvent, oil solubility
was so high that 35% of the total oil was recov-
ered in less than 10 min. At this degree of extrac-
tion, the oil contained 515% of the total
essential oils. With 5560% extraction degree, the
concentration of essential oils increased to 20
85% and then gradually decreased to 10%. The
difference between SC-CO2- and subcritical
propane-extracted oils in their essential oil con-
tent can be explained by the fact that the oil
solubilization rate of SC-CO2 is constant and
much lower than that of propane. The later re-
moves volatile and non-volatile fractions from the
seeds within a short time giving no possibility for
fractionation. Fractionation of coriander oil into
volatile and non-volatile oils is possible with SC-
CO2 particularly at subcritical conditions (25C
and 100 bar). From these results it can be con-
cluded that subcritical propane is more powerful
than SC-CO2 in solvating of oils, but due to its
high extraction rate the separation of essential oils
is practically not possible under the given
conditions.
Fig. 7 shows the extraction curves of two main
components of essential oil fraction, using three
different solvents at different conditions. The
slope of the SC-CO2 extraction curve of D-linalool
is similar to that found for the total essential oils
(as shown in Fig. 5). The concentration decreased
rapidly from 70% to 45% of the total when the
oil yield approached 35% and to 01% with
longer extraction time. In case of propane or
propane-containing solvent mixture, the concen-
 182
Table 1
Content of the major volatile compounds in coriander oils extracted by CO2, propane and CO2+propane super- and subcritical conditionsa

Runs Extraction parameters Essential oil content, % Volatiles, %

P (bar) T (C) Solvent Extraction degree, % D-Linalool Geranyl acetate Linalyl acetate

1
A 250 35 CO2 15.3 80.0 70.0 7 0.3
2
A 250 35 CO2 11.9 70.0 70.0 7 0.1
B 21.7 10.0 49.0 7 0.3

V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186

C 30.7 5.0 Traces Traces Traces
D 45.8 1.0 Traces Traces Traces
3
A 300 35 CO2 18.3 20.0 70.0 0.2 0.1
B 31.4 10.0 12.0 10.0 9.0
4
A 300 35 CO2 15.4 45.0 70.0 0.2 0.1
B 27.1 5.0 22.0 1.1 0.4
C 31.9 2.0 14.0 1.7 0.6
5
A 300 35 CO2 22.6 25.0 66.0 6.5 Traces
BE 83.1 2.0 Traces Traces Traces
6
A 200 35 CO2 15.9 25.0 59.0 7.2 Traces
BC 35.8 2.5 Traces Traces Traces
7
AK 100 25 CO2 15.2 35.0 69.1 2.9 3.1
LN 33.3 Traces 0.1 Traces Traces
8
AD 100 28 C3H8+CO2 100.0 20.0 61.0 10.0 Traces
9
A 80 28 C3H8+CO2 59.2 30.0 74.0 2.0 Traces
BD 100.0 20.0 54.0 6.0 Traces
10
A 100 25 C3H8+CO2 37.7 10.0 71.0 3.6 2.5
BH 99.6 1.0 60.1 Traces Traces
 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
Table 1 (Continued)

Runs Extraction parameters Essential oil content, % Volatiles, %

P (bar) T (C) Solvent Extraction degree, % D-Linalool Geranyl acetate Linalyl acetate

11
A 80 25 C3H8+CO2 34.8 5.0 60.3 5.4 Trace
s
BG 99.8 8.0 63.0 0.5 0.3
12
A 50 25 C3H8+CO2 38.5 15.0 64.0 3.0 Trace
s
BH 100.0 10.0 64.0 0.3 0.3

a
A, B, C represent the samples taken in each extraction run under the given conditions. In propane+CO2 solvent a ratio of 2:1 was used.

183
184 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
tration of D-linalool fluctuated between 60 and
70% in the oils recovered at extraction degree of
35 100%. With regard to geranyl-acetate (irre-
spective of solvent type and extraction condi-
tions) its concentration in the extracts was
5% at any extraction degree.
Tocopherol content and fatty acid composi-
tion are the other important quality attributes of
coriander oil. The effect of extraction conditions
on these moieties is given in Table 2, while Fig.
8 describes the relationship between extraction
degree (yield %) and content of the major fatty
acids in the oil. Extraction with CO2 at super-
critical conditions yielded oils containing the
lowest levels of a- and b +g-tocopherols (under
the given conditions the behavior of d-toco-
pherol was not understood). It is of interest that
application of CO2 at subcritical conditions
(100 200 bar and 25C) resulted in an increased
concentration of a-tocopherol (the main compo-
nent of vitamin E) in the oil. The average con-
centration of a-tocopherol increased from 2.4
mg/g in SC-CO2-extracted oils to 5.2 mg/g in
oils recovered by CO2 at mild conditions. A
similar trend was observed with the b +g-toco-
pherols.
The combined use of CO2 and propane under
subcritical extraction conditions (80 100 bar
Fig. 8. Change in fatty acid content (%) as a function of
extraction degree (%) using CO2, propane-CO2 and propane at
different super- and subcritical conditions.
and 2528C) was efficient in solvating the to-
copherols with the exception of d-tocopherol.
The solvent efficiency increased substantially
when the temperature was adjusted to 25C, in-
dicating that subcritical conditions suit extrac-
tion of tocopherol from the coriander seeds.
This was also found for application of propane
at subcritical conditions, which gave similar re-
sults to those obtained with CO2 + propane at
100 bar and 25C.
The changes in extraction conditions and sol-
vent type had a slight effect on fatty acid con-
tent and composition of the extracts (Table 2
and Fig. 8). Increasing the extraction degree up
to 40% caused stearic acid to decrease, and later
during the extraction, its concentration fluctu-
ated between 1 and 2%. Though unlikely, oleic
acid (C18:1) tended to increase from 65 to 79%
when the oil yield was increased to 40%, but at
higher extraction degree its concentration re-
mained unchanged. The concentration of the es-
sential fatty acid (linoleic, C18:2) was only
slightly affected by the extraction conditions and
increased degree of extraction.
4. Conclusion
According to the results of the present
study, an oil with high biological and commer-
cial value can be produced with compressed
gases at super- or subcritical conditions. The
changes in the extraction conditions and/or
modification of solvent composition can sub-
stantially influence the essential oil and toco-
pherol content of coriander seed oil. Fatty acid
composition of the extracts was hardly affected
by the changes in the extraction conditions.
While supercritical conditions are essentially re-
quired for the complete extraction of essential
oils, mild subcritical conditions with CO2,
CO2 + propane and propane are sufficient to ex-
tract tocopherols and triglycerides from corian-
der seeds. The ratio of solvent/seeds needed for
the implementation of complete extraction of oil
was 2040 and 1.52.5, for CO2 and propane,
respectively.
Table 2
Tocopherol and fatty acid content of coriander extracted by CO2, propane and CO2+propane at super- and subcritical conditionsa

Measurement Extraction parameters Tocopherol content, mg/g oil Fatty acid content, %
signals

P (bar) T (C) Solvent Extraction degree, % a-Tocopherol b+g-Tocopherol d-Tocopherol C16:0 C18:1 C18:1 C18:2

2
A 250 35 CO2 15.3 2.4 3.9 1.4 5.0 5.0 67.0 17.0
4
A 300 35 CO2 15.4 4.0 5.0 68.0 14.0

V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186

5
A 300 35 CO2 22.6 5.6 0.8 70.3 20.1
BE 83.1 8.0 11.3 3.6 4.2 0.8 69.1 18.1
6
A 200 35 CO2 15.9 2.1 0.4 65.3 19.3
B, C 35.8 2.1 4.1 0.8 3.6 0.9 77.8 16.9
7
AK 100 25 CO2 15.2 6.2 10.9 2.2 5.0 Trace 76.5 17.7
LN 33.3 4.2 7.2 3.2 3.9 Trace 77.1 18.3
8
AD 100 28 C 3H 8 100.0 5.6 6.7 1.8 3.0 2.0 70.0 15.0
+ CO2
9
BD 80 28 C3H8 100.0 3.0 2.0 70.0 16.0
+ CO2
10
A 100 25 C 3H 8 37.7 3.7 Trace 80.1 15.9
+ CO2
BH 99.6 7.4 12.4 1.3 3.3 Trace 79.7 16.4
11
A 80 25 C 3H 8 34.8 3.4 0.7 79.2 16.1
+ CO2
BG 99.8 6.0 12.6 2.2 3.7 0.7 78.1 16.7
12
A 50 25 C3H8 38.5 4.5 0.7 77.1 16.5
+CO2
BH 100.0 7.4 12.4 5.7 0.7 77.1 16.2

185
a
A, B, C represent the samples taken in each extraction run under given conditions.
186 V. Illes et al. / J. of Supercritical Fluids 17 (2000) 177186
Acknowledgements
This research work was financed by the Hun-
garian Scientific Research Fund (OTKA) under
grant numbers T 4031 and T 15775. The financial
support of the Hungarian Ministry of Agriculture
(FM) to the research work being carried out in
the Central Food Research Institute on supercriti-
cal extraction is also acknowledged.
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