Separation and Purification Technology 19 (2000) 113 120

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Simple fractionation through the supercritical carbon

dioxide extraction of palm kernel oil
M.N. Hassan a, N.N. Ab. Rahman b, M.H. Ibrahim c, A.K Mohd. Omar c,*
a
Uni6ersiti Teknologi MARA, Arau, 02600 Perlis, Malaysia
b
School of Distant Education, Uni6ersiti Sains Malaysia, Minden, 11800 Penang, Malaysia
c
School of Industrial Technology, Uni6ersiti Sains Malaysia, Minden, 11800 Penang, Malaysia

Received 16 November 1999; accepted 23 November 1999

Abstract

Supercritical carbon dioxide (SC-CO2) in the pressure range 20.7 48.3 MPa (3000 7000 psi) and temperatures
between 40 and 80C was used as a solvent in the extraction of palm kernel oil (PKO). At 20.7 and 27.6 MPa, the
solubility of PKO in SC-CO2 decreased with temperature. However, at higher pressures of 34.5, 41.4 and 48.3 MPa,
the solubility increased with temperature. The composition of the oil extracted varied with time. Earlier fractions were
rich in short-chain triglicerides, while the later fractions were rich in longer chain triglicerides and unsaturated
triglicerides. However, at higher pressures, the fractionation effect diminished and the oil could be considered as a
single component. At 48.3 MPa and 80C, the solubility of PKO in SC-CO2 of about 20% was relatively high
compared with that of soybean oil of about 3%. 2000 Elsevier Science B.V. All rights reserved.

Keywords: Palm kernel oil; Supercritical carbon dioxide; Extraction; Solubility; Fractionation

1. Introduction (15.6%) and oleic acids, C18:1 (15.1%) [13]. The

Palm kernel is a by-product of the palm oil
industry. It constitutes about 45% of the palm nut
of the palm oil Elaeis guineensis. On a wet basis,
the kernel contains about 47 50% oil. Although it
lies within the palm nut, palm kernel oil and palm
oil differ greatly in their characteristics and prop-
erties. Palm kernel oil is rich in lauric acid, C12
(48.3%). Other major fatty acids are myristic, C14
* Corresponding author. Tel.: +6-4-6577888; fax: + 6-4-
6573678.
E-mail address: akmomar@usm.my (A.K.M. Omar)
oil is conventionally extracted using screw press
with 4043% (g oil/100 g kernel) yield or hexane
extracted with 44.546.5% yield [4]. In 1998,
Malaysia produced about 2.4 million metric ton-
nes of palm kernel, of which about 1.1 million
metric tonnes of crude palm kernel oil was ex-
tracted [5].
Palm kernel oil (PKO) is regarded as a high-
quality oil for food use. It is a valuable compo-
nent of margarine formulation, giving rapid melt
down in the mouth characteristics. Its high solid
content at 1520C, together with rapid melt
down, makes it particularly useful in confec-

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114 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120
tionery products. It is commercially fractionated
into liquid olein and solid stearin, the latter being
a premium product. Fractionation increases the
lauric (C12) and myristic (C14) acid concentration
in the resulting stearins, and leads to a corre-
sponding fall in the levels of short-chain (C6
C10) and unsaturated (C18:1 and C18:2) fatty
acids. Normally, 20 40% stearin is produced. In
these ways, a large number of fats become avail-
able suitable for toffees, chocolate type coatings,
wafer filling, biscuit sprays, ice cream filled milk
products and filling creams. Palm kernel stearins
are called cocoa butter substitute and are mainly
used as total replacement for cocoa butter in
special recipes [1,6].
Supercritical fluid extractions of oilseeds have
been thoroughly studied by many researchers [7
9]. At 48.3 MPa and 80C, the solubility of soy-
bean and cottonseed oil in supercritical carbon
dioxide (SC-CO2) is about 3%, and rises dramati-
cally at pressures and temperatures above 55.7
MPa and 60C, respectively. Soybean triglycerides
become infinitely miscible with SC-CO2 at 81.1
MPa and 70C [7]. SC-CO2 is the most common
gas used as a solvent. It is non-toxic, non-
flammable, easily available and relatively cheap. It
has a moderate critical pressure of 7.38 MPa and
Fig. 1. Schematic diagram of supercritical fluid extraction of palm kernel oil.
critical temperature of 31.1C, which are both
easily achieved [1013].
The fractionation effect of supercritical extrac-
tion of seed oil is caused by a large disproportion
in solubilities of triglycerides in SC-CO2. Triglice-
rides with short chains and low polarity fatty
acids are more soluble in SC-CO2 and can be
easily removed from extracting materials. Gener-
ally, the solubility of triglicerides depends upon
the density of CO2, which can be manipulated
through the variation of pressure. Hence, with the
use of multiple separators, the pressure drops
from the extractor to the multiple separators can
be reduced gradually by adjusting the individual
back-pressure regulator of each separator [14].
Snyder et al. [15] found that fractionation of
soybean oil in SC-CO2 extraction at 8000 psi and
50C only occurred in the last 1015% of the oil
extracted in which the composition of fatty acid in
triglycerides varied.
In this study, carbon dioxide was used as a
solvent in the extraction of palm kernel oil at a
pressure range of 20.748.3 MPa and tempera-
tures between 40 to 80C. Fractionation of PKO
into various fractions were effected by collecting
the extracted oil at various time or volume
intervals.
 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120
Fig. 2. Photograph of full-fat ground palm kernel.
2. Experimental
The set-up for the extraction process is shown
in Fig. 1. It consists of a pump (American Lewa,
Holistic, Massachusetts, USA) with a maximum
capacity of 69.0 MPa (10 000 psi), an oven (C.C.S
Instrument System), a chiller (Yin Deer, B/L-730)
and a 50 cm3 extraction cell (Keystone), with 13
mm diameter and 320 mm height, and a wet gas
meter (WNK-1A; Sinagawa Corp., Tokyo,
Japan).
Carbon dioxide gas (Malaysian Oxygen,
Penang, Malaysia) from a gas cylinder was
liquefied to a temperature below 5C and
pumped into the heated extraction cell loaded
with about 18.5 g ground palm kernel, 92% of
which passed through a sieve with a 2 mm open-
ing. Static extraction was performed for 5 min
before the pump was opened to stabilize the tem-
perature and another 5 min after the set pressure
was reached before the exit valve was opened. The
oil receiver was replaced when about 20% of the
total oil content in the palm kernel matrices were
extracted. Separation of the oil from the CO2 was
effected by expanding the extract at atmospheric
115
pressure and temperature. The volume of CO2
passed through the extraction cell was recorded at
atmospheric pressure and temperature immedi-
ately before the analyte receiver was replaced
using the wet gas meter.
Solubility of PKO in SC-CO2 was calculated
based on the 40% (40g oil/100 g palm kernel) of
oil extracted from the kernel (actual oil content,
50.09 1.3%). Fatty acid (as fatty acid methyl
ester) compositions of PKO were analyzed ac-
cording to Palm Oil Research Institute of
Malaysia (PORIM) methods [16]. A gas chro-
matograph (Hitachi, G-3000) with flame ioniza-
tion detector and a chromato-integrator (Hitachi
D-2500), together with a 30 m0.25 mm 0.25
mm TC-Wax capillary column (GL Sciences Inc.,
Tokyo, Japan) at an isothermal temperature of
190C with nitrogen as a carrier gas, were used.
3. Results and discussion
Figs. 2 and 3 show pictures of the ground palm
kernel and the scanning electron micrograph of
the oil cells after being extracted with SC-CO2,
116 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120

Fig. 3. Scanning electron micrograph of the oil cells of SC-CO2 extracted ground palm kernel.

Fig. 4. Solubility of palm kernel oil in SC-CO2 (80% yield) as a function of temperature at various pressures.
 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120 117

Fig. 5. Solubility of palm kernel oil in SC-CO2 (80% yield) as a function of pressure at various temperatures.

respectively. Figs. 4 and 5 show that at 27.6 MPa, respectively. At 34.5 MPa, the intensity of yellowish
the solubility of PKO decreases with an increase in colour increases with time or fraction collected,
temperature. At higher pressures of 34.5, 41.4 and while at 48.3 MPa, the intensity of yellowish colour
48.3 MPa, the solubility increases with tempera-
ture. At 48.3 MPa, the solubility of PKO in SC-CO2
almost tripled from about 7 to 20% as the temper-
ature was increased from 40 to 80C. At lower
pressures, the solvent strength of SC-CO2 is much
affected by the changes in density. However, at
higher pressures, the change in density with temper-
ature is less significant compared with the changes
caused by the increase in vapour pressure of the oil.
Physical observation showed that the colour of
the extracted oil was lighter than the oil extracted
from Soxhlet extraction using hexane as a solvent.
The colour of the extracted oil also varied with
extraction pressure and temperature. At room
temperature (ca. 25C), the oil collected at 20.7
MPa (3000 psi) and 40C were crystalline white in
colour as shown in Fig. 6. Figs. 7 and 8 show the
photographs of the PKO fractions collected at 34.5 Fig. 6. Photograph of palm kernel oil fractions extracted at
MPa (5000 psi) and 48.3 MPa (7000 psi) at 70C, 20.7 MPa (3000 psi) and 40C.
118 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120

Fig. 7. Photograph of palm kernel oil fractions extracted at 34.5 MPa (5000 psi) and 70C.
Fig. 8. Photograph of palm kernel oil fractions extracted at 48.3 MPa (7000 psi) and 70C.

does not change much with time. Fig. 9 shows the
variation of fatty acid composition of each frac-
tion of PKO collected in the extraction at 34.5
MPa (5000 psi) and 70C. It is apparent that the
percentage of C8, C10 and C12 fatty acids de-
creased with time, while the percentage of C16,
C18:0, C18:1 and C18:2 fatty acids increased with
time. The percentage of C14 fatty acid remained
unchanged at about 16.2%. The variation of oil
composition, and hence the characteristics such as
 M.N. Hassan et al. / Separation/Purification Technology 19 (2000) 113120
Fig. 9. Fatty acid composition of the fractions of palm kernel oil extracted at 34.5 MPa and 70C.
slip melting point and solid fat content, would
enable each fraction to be used for different end
products, such as in margarine formulation and as
a cocoa butter substitute. At a higher pressure of
48.3 MPa and 80C, the colour and composition
of each fraction did not change significantly, indi-
cating low selectivity of SC-CO2; however, the
rate of extraction and solubility of PKO in SC-
CO2 were higher. The fraction of PKO, however,
could be achieved by multiple reduction of pres-
sure of the extracted oil.
4. Conclusions
The prospect of applying supercritical technol-
ogy in the extraction of palm kernel oil is better
compared with the non-lauric based oil such as
soybean, palm oil and cotton seed oils. The
triglicerides of PKO are of shorter chains and
thus easily soluble in SC-CO2 compared with
non-lauric oils. At 48.3 MPa and 80C, the PKO
solubility in SC-CO2 is about 20% compared with
about 3% for soybean oil at the same pressure
and temperature. Oil of various characteristics
could be produced through a simple fractionation
process, i.e. just by collecting the oil at various
119
time or mass intervals. At higher pressures, the
fractionation effect or selectivity of the solvent
diminished and the oil composition does not
change with time. A better and efficient extraction
and fractionation process is expected if the system
is operated at higher pressures together with mul-
tiple pressure reduction collectors.
Acknowledgements
This work was supported by the Research and
Development grant No. 190/9609/2402 from the
Malaysian Government.
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