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ABSTRACT: Extraction of poppy seed oil with supercritical carbon dioxide (SC-CO2) was performed and the effect
of extraction conditions on oil solubility and yield as well as oil composition was evaluated. Within the tempera-
Food Chemistry and Toxicology
ture (50 to 70 °C) and pressure (21 to 55 MPa) ranges studied, 55 MPa/70 °C gave the highest oil solubility (24.1
mg oil/g CO2) and oil yield (38.7 g oil/100g seed). Fatty acid composition of the oil obtained with SC-CO2 at 55
MPa/70 °C was similar to that of petroleum ether-extracted oil (p > 0.05) with linoleic acid making up 69.0 to
73.7% of fatty acids. Tocol content of the SC-CO2-extracted oils varied from 22.37 to 33.35 mg/100 g oil, which
was higher than that of petroleum ether-extracted oil (15.28 mg/100 g oil). Poppy seed oil may have potential in
the rapidly growing specialty oil market.
Keywords: extraction, fatty acid, poppy seed oil, supercritical CO2, tocol
422 JOURNAL OF FOOD SCIENCE—Vol. 68, Nr. 2, 2003 © 2003 Institute of Food Technologists
Further reproduction prohibited without permission
Extraction of poppy seed oil. . .
HD5112, Stamford, Conn., U.S.A.) for 5 s. Moisture content was de- to methylate the samples. Tubes were capped tightly and placed in
termined according to the AOCS Method Ca 2c-54 (AOCS 1989). Oil a water bath at 90 °C for 45 min. After cooling to room temperature,
content was determined by Soxhlet extraction using petroleum 10 mL hexane and 5 mL water were added, the contents were
ether (40 to 60 °C) for 5 h, followed by solvent removal under vac- mixed well and allowed to phase separate. The top hexane layer
uum at 40 °C. was transferred into a 1.5-mL vial and the final concentration of
total lipids was adjusted to 0.2 to 0.3 mg/mL hexane. The fatty acid
SC-CO2 extraction methyl esters (FAMEs) were analyzed by gas chromatography (Vari-
The laboratory-scale supercritical fluid extraction system (New- an 3600 GC, Mississauga, Ont., Canada) equipped with an au-
port Scientific Inc., Jessup, Md., U.S.A.) used for this study is shown tosampler (Model 8200; Varian) and flame ionization detector; and
in Figure 1. Carbon dioxide (99.95% purity, Praxair, Edmonton, data were processed by a computer using Class VP data processor
Alb., Canada) was compressed to the desired pressure by a dia- (Shimadzu Corp., Columbia, Md., U.S.A.). Helium was used as the
phragm compressor. The extraction vessel (300 mL) was heated by carrier gas. The FAMEs were separated on a fused silica capillary
a heating jacket and temperature was controlled by a thermostat (± column (50 m × 0.32 mm, BPx-70, SGE Column, Pty Ltd., Victoria,
Multiple comparison of the means was performed by the least sig- Table 1—Poppy seed oil solubility, yield, and recovery ob-
nificant difference (LSD) test at ␣ = 0.05 level. tained with SC-CO2 under different conditions at 1 L/min
CO2 flow rate
Results and Discussion Pressure CO2 Solubility Oil Recovery
Temp. density (mg oil/ amount 1 Oil
M OISTURE CONTENT OF POPPY SEED WAS 5.3% (W/W). OIL CONTENT (MPa) (% of
of poppy seed was found to be 49.5% (w/w, dry matter basis) (%) (°C) (g/mL) g CO2) (g) yield 2 total oil)
as determined by Soxhlet extraction using petroleum ether for 5 h. 21 50 0.79 5.2b 1.15b 24.3b 49.1b
This result is in agreement with previously reported data (Nergiz 35 50 0.90 12.0c 1.31c 27.7c 55.9c
55 50 0.98 20.9d 1.64c 34.5c 69.8c
and Otles 1994; Singh and others 1998).
21 70 0.67 3.9a 0.75a 15.8a 31.9a
35 70 0.83 9.2c 1.61c 33.9c 68.5c
SC-CO2 extraction 55 70 0.93 24.1d 1.84c 38.7c 78.3c
Figure 2 shows SC-CO2 extraction curves for oil removal by SC- 1 Amount of oil extracted after 4 h
2 Oil yield obtained after 4 h (g oil/100 g seed, dry matter basis)
CO2 at 50 °C, 1 L/min CO2 flow rate and at the various pressures a-d Means in a column followed by different letters are significantly different
Food Chemistry and Toxicology
studied. At such low flow rates, the slope of the initial linear portion ( p < 0.05).
corresponds to the solubility of poppy seed oil in SC-CO2. Then
there is a transition region in which the rate of oil removal diminish-
es, followed by an asymptotic approach as the final amount of the
oil is removed from the seed. The solubility of poppy seed oil in SC- Similar solubility behavior has been reported for other vegeta-
CO2 was determined from the initial linear portion for each condi- ble and seed oils. The solubility of poppy seed oil, 12.0 mg/g CO2 at
tion at 1 L/min of flow rate. 50 °C/35 MPa, was similar to that of other vegetable oils with a sim-
The solubility of poppy oil, as expected, increased (p < 0.05) with ilar fatty acid composition (rich in linoleic and oleic acids) reported
pressure at both temperatures investigated, due to an increase in previously. For example, corn and soybean oil solubilities were both
CO2 density (Table 1). The results showed that the solubility varied reported as 12 mg/g CO2 at 35 MPa and 50 °C (Friedrich and List
from 5.2 to 20.9 mg/g CO2 at 50 °C and 3.9 to 24.1 mg/g CO2 at 70 °C, 1982; Christianson and others 1984). On the other hand, Christian-
within the pressure range of 21 to 55 MPa. son and others (1982) determined the solubility of maize (corn) oil
Although the solubility increased slightly with temperature at in SC-CO2 at 50 °C/55 MPa as 27 mg/g CO2.
higher pressures (35 MPa and 55 MPa), this increase was not statis- The amount of oil extracted, oil yield, and recovery from poppy
tically significant (p > 0.05). However, at the pressure of 21 MPa seed after 4 h under different conditions are shown in Table 1. The
solubility decreased significantly (p < 0.05) with temperature. Such maximum yield (g oil extracted/100 g seed) of oil obtained from
cross-over behavior of solubility isotherms has been reported pre- poppy seed by SC-CO2 was 38.7% (dry matter basis), which was
viously (Fattori and others 1988; Temelli and others 1995). This is 78.3% of the total available oil (determined by Soxhlet extraction),
due to the fact that an increase in temperature at constant pressure at 70 °C/55 MPa and a flow rate of 1 L/min for 4 h extraction time.
leads to a drop in CO2 density as well as an increase in the vapor Oil yield increased with pressure from 24.3% to 34.5% and 15.8% to
pressure of solutes. The drop in CO2 density is substantial at pres- 38.7% at 50 °C and 70 °C, respectively. The oil recovery can be fur-
sures near the critical point, resulting in a drop in solubility. How- ther enhanced by increasing the extraction time and the solvent-
ever, at higher pressures the drop in CO2 density due to a similar to-feed ratio.
temperature increase is small, which is overcome by the vapor pres- The effect of CO2 flow rate on the poppy oil extraction was inves-
sure increase and the net effect is a solubility increase. tigated at 50 °C and 35 MPa. As expected, the higher flow rate (3 L/
min) yielded a higher amount of oil for the same amount of CO2
consumed. A significant increase was observed in the extraction
time by approximately 5-fold and 10-fold to achieve 50% and 70%
oil recovery, respectively, with a decrease in the CO2 flow rate from
3 L/min to 1 L/min. Extraction time for 50% oil recovery (requiring
240 g CO2) was 120 min at CO2 flow rate of 1 L/min, but was reduced
to 25 min at 3 L/min flow rate (Table 2).
Extract composition
Table 3 presents the fatty acid composition of SC-CO2- and pe-
troleum ether-extracted oils. Poppy seed oil obtained by SC-CO2
under different conditions and Soxhlet extraction contained
mainly palmitic (8.9 to 9.3%), stearic (2.1 to 2.2%), oleic (13.1 to
16.9%), linoleic (69.0 to 73.7%), and linolenic (0.7 to 1.2%) acids.
These results were in agreement with previous reports (Sengupta
and Mazumder 1976; Nergiz and Otles 1994; Singh and others
1998).
There was no significant difference (p > 0.05) in the fatty acid
composition of the oils obtained at 50 °C/35 MPa and 50 °C/55 MPa,
as well as those obtained at 70 °C/35 MPa, 55 MPa, and Soxhlet ex-
traction. However, there was a significant difference (p < 0.05) for all
fatty acids, except C18:0, between the oils obtained at 50 °C and
those obtained with SC-CO2 at 70 °C and solvent extraction. Oleic
Figure 2—Effect of CO2 pressure on the amount of oil ex-
tracted from poppy seeds using supercritical CO2 at 50 °C acid content decreased with temperature, whereas linoleic acid
and 1 L/min CO2 flow rate content increased. Fatty acid compositions of the oils obtained by
SC-CO2 and solvent extraction vary in the literature. More palmitic, Table 2—Effect of CO2 flow rate on the recovery of poppy
oleic, linoleic, and linolenic acids were reported in hexane-derived seed oil (% of available oil) at 50 oC/35 MPa
oil than in CO2-extracted rice bran oil, whereas the SC-CO2-extracted CO2 50% oil recovery 70% oil recovery
oil contained a higher proportion of long-chain fatty acids C20 to C34 flow Average CO 2 Average Average CO 2 Average
(Garcia and others 1996). Temelli and others (1995) reported that rate consumption time consumption time
eicosapentaenoic (EPA, C20:5) and docosahexaenoic acids (DHA, (L/min) (g) (min) (g) (min)
C22:6) in SC-CO2-extracted Atlantic mackerel (Scomber scombrus) 1 240 120 800* 420*
oil increased with extraction pressure at all temperatures, and EPA 3 200 25 290 40
content of the oil obtained with SC-CO2 was higher than that of *Calculated based on extrapolation of the extraction curve
hexane-extracted oil, while DHA content was similar in both oils.
Cheung and others (1998) found that PUFA content of SC-CO2-
extracted seaweed oil increased with pressure and solvent density;
and it was higher in the oil obtained with SC-CO2 at all extraction
content of the soybean oil obtained by SC-CO2 at 50 °C increased 50 °C/35 MPa 19.3 3.4 — 1.0 18.1 0.6 0.6 23.8
with pressure from 13 to 26 g/kg at 35 MPa and 55 MPa, respectively 50 °C/55 MPa 25.9 5.2 0.7 0.8 25.3 0.8 0.6 33.4
70 °C/35 MPa 23.4 4.9 — 0.7 24.4 0.7 0.7 31.4
(Friedrich and List 1982). A higher level of FFA was reported in the 70 °C/55 MPa 22.8 4.0 0.5 0.9 21.6 0.9 0.6 28.5
CO2-extracted cottonseed oil (1.3 to 1.7%) than in the hexane-de- Soxhlet 18.6 — — — 14.2 0.5 0.6 15.3
rived oil (1.15 %) (List and others 1984). 1 T: Tocopherols; T3: Tocotrienols
Minor components in seed oils, such as tocols (tocopherol and
tocotrienol) along with fatty acid composition, are also receiving
increasing attention due to their nutritional and antioxidant prop-
erties. Poppy seed oil contained ␣-, -, ␥-, and ␦-tocopherol as Conclusions
well as ␥-tocotrienol. Tocol content of the poppy oil extracted with
SC-CO2 increased with pressure at 50 °C, whereas it decreased at
70 °C. The total tocol content of the SC-CO2-extracted oils (23.8 to
A MONG THE CONDITIONS STUDIED FOR SC-CO2 EXTRACTION OF POPPY
seed oil 50 °C and 70 °C at 55 MPa gave the highest solubility.
The SC-CO2-extracted oil recovery obtained after 4 h at 70 °C/55
33.4 mg/100 g oil) was almost double that of petroleum ether-ex- MPa was 78.3% of the total available oil. The fatty acid composition
tracted oil (15.3 mg/100 g oil) (Table 4). It is well established that of the oil extracted with SC-CO2 was comparable to that obtained by
the phospholipid and glycolipid contents of the solvent-extracted solvent extraction, however, tocol content was higher in the oils
oils are higher than those of SC-CO2-extracted oils since these obtained with SC-CO2. Therefore, poppy seed oil obtained with SC-
compounds are sparingly soluble in SC-CO2. Therefore, the rela- CO2 may have potential for use as specialty oil in various product
tive concentration of tocols is expected to be lower in the solvent- applications.
extracted oils. However, there is variability in the literature when
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