336 DOI 10.1002/ejlt.200600309 Eur. J. Lipid Sci. Technol.

109 (2007) 336349

Marc Kellens Palm oil fractionation

Vronique Gibon
Marc Hendrix
Wim De Greyt Modification techniques like fractionation, interesterification (chemical or enzymatic)
and hydrogenation allow proposing a large range of new fatty products. At a time when
De Smet Technologies trans fatty acids are questioned, fractionation of fats and oils catches more and more
and Services, interest; in this context, dry fractionation is by far the simplest and cheapest fractional
Zaventem, Belgium crystallization technique (no chemicals, no effluent and no losses). The oil processing
industry uses dry fractionation to extend the application of a whole variety of fatty
matters as well as to replace, fully or partially, the chemical modifications. Due to the
continuous developments of the dry fractionation process, a whole variety of products
normally produced by solvent fractionation can now be obtained with a high degree of
selectivity with dry fractionation. As the crystallization operates in the bulk, viscosity
problems limit the degree of crystallization in one single step, and multi-step opera-
tions are currently used, giving rise to a wide range of fractions suitable for different
applications. The secret is to combine proper crystal development with highly efficient
separation by using membrane press filters allowing squeezing out the stearin cake for
as much liquid occlusion (olein) as possible. The original booming of the dry fraction-
ation process has helped mostly palm oil to conquer a strong position on the com-
modity market in one single stage; today, palm oil is without doubt the most widely
fractionated oil. New demands for special cuts drifted the industry towards a more
sophisticated approach: high-iodine value super and top oleins, palm red fractions
(high carotene and tocopherol/tocotrienol contents) or solvent-free cocoa butter
equivalents (palm mid fractions) are certainly what the future has in store.

Keywords: Fractional crystallization, dry fractionation, specialty fats, membrane filter

press.

1 Introduction the nutritional quality of oils. The issue whether trans

Most of the natural oils and fats have only a limited appli-
cation in their original forms, as a consequence of their
specific chemical composition. To extend their use in fat-
based food products, oils therefore often undergo a
chemical or physical modification. The best known mod-
ification processes applied today in the edible oil industry
Review Article
fatty acids, which are produced during hydrogenation,
have a negative impact on health forces producers today
to seek a strong reduction in the trans isomer content of
fats. New technologies are developed or existing pro-
cesses are modified in order to respond to the new quality
standards. More and more attention is also paid to the
benefits of a combined use of the different modification

are hydrogenation, interesterification (chemical or enzy-
matic) and fractionation. The main purpose of these pro-
cesses is to change the physicochemical properties of
the oil or fat, by reducing the degree of unsaturation of the
acyl groups (hydrogenation), by redistributing the fatty
acids chains (interesterification) or by a physical separa-
tion of the triacylglycerols (TAG) through selective crys-
tallization and filtration (fractionation) [1, 2].
At present, quite a number of questions arise with respect
to the effect of the chemical modification processes on
Correspondence: Vronique Gibon, De Smet Technologies and
Services, Da Vincilaan, 2 Bus G1, 1935 Zaventem, Belgium.
Phone: 132 2 716 1111, Fax: 132 2 716 1109, e-mail: giv@des-
metgroup.com
processes to achieve the stated goals.
Hydrogenation and interesterification (chemical and
enzymatic) are strictly based on an irreversible chemical
change in the composition of the fatty matter, whereas in
fractionation the composition is modified by a selective
physical separation of the different component groups.
Due to the contaminative effect of the catalysts used, as
well as to the side reactions which cannot be fully
excluded, the chemical modification processes always
require a refining step in order to make the modified oil
edible again. Fractionation is a fully reversible modification
process; it is basically a thermo-mechanical separation
process in which a multi-component mixture is physically
separated into two or more fractions with distinct physical
and chemical properties. The separation can be based on

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Eur. J. Lipid Sci. Technol. 109 (2007) 336349
differences in solidification, solubility, or volatility of the
different compounds: fractional crystallization, fractional
distillation, short-path distillation, supercritical extraction,
liquid-liquid extraction, adsorption, complexation, mem-
brane separation, etc. are the main techniques practiced.
Today, the oil processing industry more and more uses
fractionation to extend the application of a whole variety
of fatty matters as well as to replace, fully or partially, the
chemical modification processes.
2 Fractional crystallization
Hippolyte Mge Mouris (18171880) is most probably
the pioneer in fractionation with his famous patent con-
cerning margarine: Application for a patent of fifteen
years for production of certain fats of animal origin,
accepted on October 20th 1869 in Paris (patent number
86480). On the other hand, Holde et al. reported in 1901
that olive oil, when cooled in an ether solution to 40 7C,
produced small quantities of solid TAG (principally oleo-
dipalmitin) [3]. This publication is the first report of the use
of low-temperature fractional crystallization for the
separation of TAG.
Fractional crystallization refers to a separation process in
which the fatty material is crystallized, after which the
liquid phase is separated from the solid. It is based on
differences in solubility of the solid TAG in the liquid
phase, depending on their molecular weight and degree
of unsaturation; this is a consequence of the ability of fats
to produce crystals [4]. On an industrial scale, crystals
can be obtained according to three main technologies:
detergent fractionation, solvent fractionation and dry
fractionation. In 1905, Lanza patented the addition of a
detergent to wet the crystals, which are consequently
transferred to the aqueous phase: the mixture is then
easily separated by centrifugation. One form of this pro-
cess is known as Lipofrac concept. In solvent fractiona-
tion, the fat is dissolved in acetone or hexane and the
diluted solution is cooled to initiate the crystallization of
the highest-melting TAG. Crystals are consequently
separated by filtration and the fractions are recovered by
solvent evaporation. Dry fractionation is the simplest and
cheapest fractional crystallization process, qualified as
natural or green technology (no effluent, no chemi- cocoa butter (CB) replacement fats.
cals, no losses). In contrast to detergent or solvent frac-
tionation, dry fractionation does not require any additional
substance. It simply consists in a controlled crystallization
of the melted oil, conducted according to a specific cool-
ing program followed by separation of the solid from the
liquid fraction. Due to the continuous developments of the
dry fractionation process, a whole variety of fractions
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Dry fractionation of palm oil 337
normally produced by solvent or detergent fractionation
can now be obtained with a high degree of selectivity with
dry fractionation (multistage).
3 Detergent and solvent fractionation
Detergent fractionation was developed to improve the
separation of the crystallized phase from the remaining
liquid by adding an aqueous detergent solution to the
crystallized oil. The wetting agent, usually sodium lauryl
sulfate, in combination with an electrolyte, usually mag-
nesium sulfate, allows the crystals to be easily suspended
in the aqueous phase. Separation of the water phase from
the remaining liquid oil is performed by means of a cen-
trifuge. The water phase is subsequently heated and the
melted stearin is recovered in a second centrifugation
step. After separation, the olein and stearin fractions are
washed and dried in order to remove traces of detergent.
Today, the technique has lost its interest due to the high
costs and contamination of the end-products with the
detergent.
In solvent fractionation, crystallization is performed in
dilute solutions, thereby reducing viscosity. Mainly ace-
tone or hexane is used as a solvent. The process is char-
acterized by a short crystallization time and easy filter-
ability. The main advantage of solvent fractionation is the
high separation efficiency and hence improved yield and
higher purity of the finished products. The major reason
for this can be explained quite simply by the fact that with
any type of separation technique, it is not possible to
remove all liquid from the solid portion. Part of the liquid
will always remain entrapped within the solid phase. The
amount of liquid is strongly dependent on the origin of the
fatty matter as well as on the crystallization conditions
and the separation technique applied. In a dilute solution,
as is the case in solvent fractionation, this liquid portion
consists of a considerable quantity of solvent that hinders
oil occlusion. After separation, the solvent is evaporated,
leaving behind a much lower quantity of liquid oil in the
solid phase.
Due to the high production costs and capital investments,
as well as the possible fire hazards, solvent fractionation
is becoming less interesting. Today, most of the plants still
in operation produce specialty fats as, for example,
4 Dry fractionation
In dry fractionation, crystallization operates in the bulk
and for this reason viscosity problems limit the degree
of crystallization of the fat. Multi-step operations
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338 M. Kellens et al.
are therefore used, with the advantage of producing
a wide range of fractions suitable for different ap-
plications.
The process consists in two steps: the crystallization
stage which produces solid crystals in a liquid matrix and
the separation stage where the liquid phase (olein) is
separated from the crystals (stearin).
4.1 Crystallization
4.1.1 Polymorphism
In the solid state, TAG are packed together side by side in
separate layers in a head-to-tail arrangement [5]. Different
packing modes are possible, in pairs of two, three or more
fatty acid chain lengths. There are generally three crys-
talline states in which an oil or fat can solidify. According
to the thermal conditions, TAG tend to pack together in a
hexagonal structure (a crystal form), an orthorhombic
(b form), or a triclinic form (b form). The stability increases
from a to b to the b crystal form. Furthermore, the rate of
crystallization of the a form is greater than that of the
b form, which in turn is greater than that of the b poly-
morph. Different thermal conditions are needed to induce
crystallization of the different polymorphic forms. In high
supercooling conditions, a crystallization occurs, yielding
a dense mass of very small crystals. The b form, on the
other hand, is more difficult to obtain and only appears in
some exceptional cases, as for example in CB. The
b crystal texture does not always allow easy separation
and should therefore be avoided in most cases.
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Eur. J. Lipid Sci. Technol. 109 (2007) 336349
In order to achieve good separation, the crystals should
be firm and of uniform spherical size, which is a condition
found when they are mainly in the b form.
The physical properties of the polymorphic forms are as
follows, with b always in midrange: melting point, melting
enthalpy, stability, selectivity, and activation energy are all
low for a and high for b; the nucleation rate, crystallization
rate, miscibility in solid state, and TAG compatibility are all
high for a and low for b.
4.1.2 Intersolubility
Depending on the chemical composition and the crystal
structure (polymorph), TAG may form different kinds of
solid solutions. In consequence, the efficiency of frac-
tional crystallization is not only dependent on the effi-
ciency of separation but is limited by the phase behavior
of TAG in the solid state.
Because of closely linked structural properties, TAG can
produce co-crystals by intersolubility; they most frequently
show solid solutions, monotectic interactions, eutectic
systems, molecular compounds, etc. Binary systems of
pure components have been extensively studied [611].
The case of edible oils and fats is more complex: they are
made of numerous TAG that have very similar chemical
structures but variable chain lengths, degrees of unsatura-
tion and positional isomers. Depending on their chemical
structure or polymorphic form, some TAG will be very sol-
uble when mixed and form solid solutions; others will crys-
tallize separately, being immiscible in the solid state and
giving rise to eutectic or monotectic interactions (Fig. 1) [4].
Fig. 1. Binary phase diagrams (temperature-
composition) of PPP/PStP and PPP/POO
(established based on powder X-ray diffraction
and DSC data) [4]. Binary phase diagrams have
been established by mixing and melting pure
TAG. The samples were afterwards quenched at
40 7C and heated at a constant rate (5 7C/min):
transition (squares) and melting (circles) peaks
are detected by DSC. Powder X-ray diffraction
is used under similar thermal conditions to
determine the polymorphic behavior.
P: palmitic fatty acid. O: oleic fatty acid. St:
stearic fatty acid.
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Eur. J. Lipid Sci. Technol. 109 (2007) 336349
In practice, the phase behavior of a fat blend in the solid
state is considerably influenced by the crystallization
conditions. Crystallization does not start once the liqui-
dus temperature is reached as a consequence of the
existing activation free energy of crystallization. Crystal-
lization normally takes place at a lower temperature, i.e.
the process needs a certain degree of supercooling to
start. This activation free energy of crystallization is the
highest for b, intermediate for b and the lowest for a. The
crystallization behavior is a function of the intersolubility
of the different components in the solid state under the
given conditions of cooling. These conditions normally do
not conform to the rule of true thermodynamic equilibrium
but are mainly kinetically dependent.
4.1.3 Crystallization
Crystallization consists of successive stages: super-
cooling of the melt, nucleation, and crystal growth; crys-
tals normally do not remain single but tend to agglomer-
ate. The key point in fractionation consists in controlling
the selectivity of crystallization and separation. This
selectivity is limited by the degree of compatibility of the
different TAG in the solid state, which in turn is a function
of the crystal form and of the composition. How far this
selectivity is affected by the cooling conditions depends
not only on the overall cooling rate but also on the prac-
tical limitations imposed by the unit process itself. The
heat transfer characteristics of the crystallizer vessel as
well as the efficiency of the separation technique largely
determine the quality of the obtained fractions. Several
cooling modes are possible (Fig. 2) [12]. The oil cooling
curve can be based on a fixed water cooling profile; in this
case, the temperature of the oil will depend on the tem-
perature of the water. Another design is based on the DT
principle; here, the temperature of the water is regulated
by the temperature of the oil itself. The differences in the
cooling schemes result in technological variations essen-
tially expressed in the geometry of the cooling surfaces
and in the agitation design (Fig. 3) [4].
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Dry fractionation of palm oil 339
Normally, prior to crystallization, the oil is fully melted in
order to destroy the crystals present in the oil phase (to
erase the thermal memory). Thereafter, the oil is cooled
in a controlled manner according to a given cooling
profile that is a function of the feedstock and of the
required fractions. Nucleation occurs when the temper-
ature of the melt is much lower than the thermodynamic
equilibrium temperature, i.e. when the melt becomes
supercooled.
Three types of nucleation phenomena can occur. Homo-
geneous nucleation takes place in the bulk of the mother
phase. Heterogeneous nucleation refers to formation of
nuclei on foreign substances. Secondary nucleation
appears when tiny crystallites are removed from the sur-
face of existing crystals, which in turn act as new nuclei.
In many real systems, heterogeneous nucleation occurs
before homogeneous nucleation. It takes place at solid
particles for which the new phase has some chemical or
physical affinity, such as dust particles, walls of crystal-
lizers, or foreign material.
Once the nuclei are formed, they grow further. The rate at
which they further develop depends not only on external
factors (degree of supercooling, presence of inhibitors,
etc.) but also on internal factors (polymorphic form, crys-
tal morphology, crystal defects, etc.). The growth rate is
proportional to supercooling and inversely proportional to
viscosity. The higher the viscosity, the more difficult is the
exchange of material between the bulk phase and the
crystal surface and the slower will be the crystal growth.
Therefore, in order to allow a continuous and uniform
crystallization, the fatty matter needs to be kept homo-
geneous. This requires an intense but non-destructive
agitation.
During cooling and subsequent crystallization, the vis-
cosity increases (Fig. 4). Viscosity is not only a result of
increasing amounts of solids present in the liquid, but is
also influenced by the crystal size distribution as well as
the interactions between the different crystals.
Fig. 2. Schematic representation of (a) an oil
temperature-related profile and (b) an independ-
ent water cooling profile, during the crystallization
step of a dry fractionation operation [12].
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340 M. Kellens et al.
Fig. 3. Different crystallization equipments: (a) propeller
agitation, (b) concentric jackets and sweeping surface
agitation, and (c) stirring cooling surfaces.
Due to attractive interactions between the crystals, they
tend to form agglomerates. The very large crystals that
can be observed during crystallization are often com-
posed of different small crystals held together by weak
bonds. Agglomeration, however, can lead to lower
separation efficiency due to a higher entrainment of liquid
inside the clusters.
The crystal morphology is determined by internal as well
as external conditions. The overall crystallization kinetics
depends on the rate of formation of nuclei as well as on
the rate at which the nuclei will grow. The size and shape
of the ultimate crystals depend on the relationship be-
tween these two factors. Normally, slow cooling results in
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 109 (2007) 336349
large crystals, whereas fast cooling gives smaller crystals.
The optimal crystal size is largely determined by the
separation technique, more specially the fineness of the
filter belt or filter cloth. More important than the size,
however, is the uniformity in crystal size and shape as well
as the resistance against mechanical stress. To reach this
state, controlled nucleation and selective crystallization
are required.
4.2 Separation
The goal of the separation is to produce a solid (stearin)
and a liquid (olein) phase, each having its proper physi-
cochemical characteristics and its particular applications.
At the end of the crystallization process, TAG are distrib-
uted in three locations: (1) as solids in the form of co-
crystals, (2) as liquids (non-crystallized oil), and (3) as
liquids physically trapped on the surface of the crystals.
Based on this, different separation equipments are avail-
able, depending on the efficiency of the separation
required: (1) vacuum filters (rotary drum or belt filters),
(2) press filters (membrane or hydraulic), and (3) cen-
trifuges (nozzle centrifuge [13], centrifugal filter [14] and
centrifugal decanter [15]) (Fig. 5).
Two types of vacuum filters are in use: the rotary drums
and the belt filters, which both operate in two stages.
The first stage consists in the separation of the crystals
from the mother oil, and the second stage permits a
drying of the cake by sucking under vacuum in order to
reduce the entrained liquid oil. Such filters are still in
operation in fractionation plants when the market favors
soft stearins.
Fig. 4. Effect of cooling on SFC formation
(followed by pulsed NMR) and viscosity
increase during fractional crystallization of
palm oil (fixed water cooling profile).
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Eur. J. Lipid Sci. Technol. 109 (2007) 336349 Dry fractionation of palm oil 341

Fig. 5. Separation technolo-

gies: (a) rotary drum, (b) Flor-
entine belt filter, (c) membrane
press filter, (d) nozzle centrifuge,
(e) centrifugal filter, and (f) cen-
trifuge decanter.

Nowadays, many users of fractionation plants favor the the higher percentage of liquid it yields, by applying a
automatic press filter, fitted with airtight membranes. Al- pressure to the cake during each filtration cycle. The
though it does not have the benefit of the continuous result is to expel more of the liquid physically trapped on
operation of vacuum filters, its advantage lies mainly in the crystals.

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342 M. Kellens et al.
A membrane press filter consists of a series of filter
chamber plates that are kept together by means of a
hydraulic cylinder. The available filter surface is much
larger compared to a vacuum filter, allowing a much faster
and more uniform filtration. The stearin crystals, after
being concentrated upon filling the filter chambers, are
additionally squeezed together by means of the inflatable
membrane, which results in better removal of the
entrained liquid phase and a higher yield of olein. Due to
the higher differential pressures applied, separation is less
sensitive to changes in crystal structure. Membrane press
filtration is a semi-continuous process that can be divided
into two sequences: filtration and squeezing (Fig. 6). On
filling the filter, the slurry is pressed into the filter cham-
bers, which allows a large part of the free olein to be
separated from the slurry. In the second step, the con-
centrated crystals are mechanically squeezed between
the filter cloths by inflating the membranes, in order to
squeeze out part of the olein that is entrapped inside the
solid mass. Thereafter, the filter is opened and the cakes
are discharged by gravitation.
The use of centrifuges to separate the different fractions
is based on the difference in density between the liquid
and the solid phases. The density of the solid fraction is
dependent on both the crystal size as well as on the
crystal habit and increases from a to b and further to the
b form, as a result of the closer packing mode of the
molecules in the crystal lattices. The density difference
between stearin and olein fractions (about 100 kg/m3) is
furthermore determined by the amount of liquid entrained
inside the crystal mass. A new type of separator (nozzle
centrifuge) has been developed and launched for the
separation of fat crystals in a centrifugal field by density
difference between olein and stearin without additives
[13]. Another type of centrifuge, a conical sieve centrifuge
Fig. 6. Filtration sequences in a membrane press filter: (a) filling, (b) squeezing, and (c) discharge.
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 109 (2007) 336349
fitted with a tightly fitting, co-rotating worm, has also been
investigated [14]. Recent development work in centrifuge
decantation [15] has shown that it is possible to easily
separate a stearin from an olein as the sedimentation rate
depends on the crystal size, the crystal shape, the density
difference between olein and stearin and the viscosity of
the olein.
In Fig. 7, a typical diagram of a dry fractionation system
including separation on a membrane press filter is pre-
sented.
5 Dry fractionation of palm oil
Palm oil is by far the most important fractionated oil.
There are industrial fractionation installations in operation
that process up to 2000 tons of palm oil per day. Both
crude as well as refined palm oil are fractionated in multi-
stage giving rise to several applications (Figs. 8, 9,
Tab. 1). The early reasons of fractionating palm oil have
less to do with product quality than with a simple political
choice of the Malaysian government aiming at rapidly
developing its local industry [16]. Since the early 1970s,
the export tax on palm oil being shipped from Malaysia
has been decreased, provided the oil had undergone fur-
ther processing. This policy naturally triggered a boom in
the production of processed palm oil. For a long time,
Malaysia has fractionated palm oil, mainly taking advan-
tage of such duty structure. The result has been the
creation of new commodities: palm olein and palm
stearin, both having broad specifications (olein not liquid
enough to resist low temperatures and stearin not suffi-
ciently tailored for direct use). Both had, however, the big
advantage of being cheap.
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Eur. J. Lipid Sci. Technol. 109 (2007) 336349 Dry fractionation of palm oil 343

Fig. 7. Flow sheet of a typical

dry fractionation plant oper-
ating with a membrane press
filter.

Fig. 8. Multistage dry fractionation process of

palm oil (PMF: palm mid fraction; IV: iodine
value).

Fig. 9. SFC profiles (SFC by pulsed NMR) of dif-

ferent palm oil fractions (Ol: olein, SOl: super olein,
MOl: mid olein, PO: palm oil, MSt: mid stearin,
SPMF: soft palm mid fraction, HPMF: hard palm
mid fraction, St: stearin, SSt: super stearin).

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344 M. Kellens et al. Eur. J. Lipid Sci. Technol. 109 (2007) 336349

Tab. 1. Some applications of palm oil fractions.

Product Palm oil Olein Stearin Super Middle Palm mid

olein stearin fraction

Shortenings 111 111 11 111 1

Margarines 11 111 1 111 1
Frying fats 111 111 111 11 1
Cooking oils 11 111
Salad oils 1 111
Specialty fats for coatings 1 11
Cocoa butter extenders 1 111
Ice cream 111
Icings 11 1 11
Biscuits 111 1 1 11
Cakes 111 1 11
Cookies 111 1 11
Crackers 111 1 1 11
Noodles 111 111 11
Fatty acids source 1 111
Hard coatings 11

111, highly suitable; 11, suitable; 1, limited application; , not suitable

Elsewhere, for example in Colombia, the reasons for Tab. 2. Percentages of palm liquid fraction allowed to be
fractionating have been very different. Unlike Malaysia, blended with soybean oil keeping cold test at 0 7C lower
Colombia is an importer of liquid oils (soybean and sun- than 5.5 h.
flower). Its palm production has increased continuously,
Iodine Mettler cloud Palm liquid
but most of the palm oil is being used locally. In order to
value point [7C] fraction [%]
bottle liquid oil for the Bogota market without running the
risk of having sediment formation, the Colombian refiner Olein 57 7.2
has to blend its palm olein with imported and taxed soy- Super olein 63 2.5 10
bean oil. The higher the quality of the olein (or superolein), Super olein 65 1.3 30
the more will be allowed in blends and the higher is the Top olein 71 24.5 100 (24 h min.
at 0 7C)
profit margin. According to olein (or superolein) quality,
this percentage can vary from 30 to 10% only (Tab. 2).

Oils and fats are complex mixtures of acylglycerols that Tab. 3. Correlation between chemical composition (in
are composed of a whole variety of different fatty acids: terms of TAG), physical state of the product and final
palmitic acid (P, C16:0), stearic acid (St, C18:0), oleic acid application (S: saturated fatty acid; U: unsaturated fatty
(O, C18:1), linoleic acid (L, C18:2), and linolenic acid (Ln, acid).
C18:3) are usually predominant. These fatty acids can be
Triacylglycerols Physical state of the Final application
broadly divided into saturated and unsaturated ones; in product
consequence, TAG are generally divided into four classes:
the trisaturated (SSS), the disaturated (SSU-SUS), the SSS Solid Fatty acid production
diunsaturated (SUU-USU), and the fully unsaturated Hard coatings
(UUU) ones. These TAG exhibit different physical and SSU-SUS Solid ? semi-solid Confectionery
chemical properties and specific potential for end-use SUU-USU Semi-solid ? liquid Margarines
UUU Liquid Salad (dressing) oils
applications (Tab. 3) [12]. Palm oil is principally made up
Liquid frying oils
of 610% SSS (mainly PPP, tripalmitoylglycerol), 4450%
SSU-SUS (mainly POP, dipalmitoyl-oleylglycerol, and
PLP, dipalmitoyl-linoleylglycerol), 3842% SUU-USU
(mainly POO, dioleyl-palmitoylglycerol, and PLO, palmi- cally, the goal of dry fractionation is to separate the
toyl-linoleyl-oleylglycerol) and 58% UUU (mainly OOO, trisaturated fraction first and then the disaturated and the
trioleylglycerol, and OOL, dioleyl-linoleylglycerol). Basi- diunsaturated ones. Due to intersolubility (closely linked

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Eur. J. Lipid Sci. Technol. 109 (2007) 336349
to polymorphism), it is clear that the trisaturated fraction
will inevitably contain also some SSU-SUS, SUU-USU
and UUU components. The first fractionation step of palm
oil will reduce the SSS content in the olein as much as
possible. When the crystallization is operated properly,
this content falls to zero in favor of higher levels of SUU-
USU and UUU, while SSU-SUS remains unchanged
(Tab. 4). When SSS is totally removed in the first step,
SSU-SUS begins to decrease selectively in the second
step, leading to higher iodine value (IV) and lower cloud
point (CP) super oleins. Further enrichments in POO and
PLO are responsible for the high drop in CP observed for
the top oleins (Fig. 10) [17].
On the other hand, palm oil is a valuable source of SUS; at
high levels of POP, it becomes after fractionation suitable
for CB replacement fats [principally the hard palm mid
fraction (PMF)] (Tabs 5, 6). The physicochemical char-
acteristics of CB equivalents (CBE) are relatively close to
the ones of CB with regard to crystallization, texture and
melting properties; this is due to similar TAG composition
(SSU-SUS components POP, POSt and StOSt), which
makes CBE fully compatible with CB and in consequence
usable in all types of applications to replace CB, partially
or totally. Production of high-quality CBE specialty fats is
delicate and can be faced by several problems that cause
failures in many confectionery products: (1) inadequate
removal of SSS with the effect of undesirable waxiness
between 35 and 40 7C, (2) high retention of SUU-USU and
UUU components with deterioration influence on the solid
fat content (SFC) profile, and (3) bad removal of diac-
ylglycerols (DAG) with detrimental effect on the crystal-
lization performance of the specialty fat [18]. Optimiza-
tions of the multistage dry fractionation route of palm oil,
together with the new developments in viscosity-resistant
crystallizers and in high-pressure membrane filter
presses, have led to a technology capable of producing
PMF as good as those obtained by solvent fractionation.
Classically, two routes (Fig. 8) are proposed for producing
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Dry fractionation of palm oil 345
the PMF: the olein route (more commonly followed in
Asia) and the stearin route, which is preferably used in
South America, because of the need of high-IV olein in the
first fractionation stage. Best CBE are obtained through
the olein route where SSU-SUS concentrates more
selectively in the soft PMF at the second fractionation
step; refractionation of this soft PMF produces an excel-
lent hard PMF particularly enriched in SSU-SUS with a
steep SFC profile. Practically, in the dry fractionated soft
PMF, SSU-SUS counts for more than 73%, the SSU-SUS/
SUU-USU ratio is 34 and the SSS content is low.
Refractionation of this soft PMF produces an excellent
hard PMF made of 8590% SSU-SUS, with an SSU-SUS/
SUU-USU ratio of 912 and less than a few percent of
SSS; the DAG content can be maintained sufficiently low
to avoid any adverse effect on the crystallization proper-
ties of the fraction [4].
Another main characteristic of palm oil is its red color due
to its particularly high content in b-carotene. Chemical
neutralization followed by deodorizing in mild conditions
is able to produce a refined palm red oil rich in carotenes,
tocopherols and tocotrienols. Fractionation is classically
operated on the fully refined oil, but the high vitamin con-
tent of crude palm oil makes the dry fractionation process
an attractive route for the specially refined oil; as a matter
of fact, carotenes, tocopherols and tocotrienols con-
centrate markedly in the liquid fractions.
Such specially refined oil can be fractionated giving solid
and liquid red fractions [19]. The pigment concentration in
the liquid fractions is particularly important: b-carotene in
top olein issued from the triple fractionation is nearly twice
the content in the neutralized oil, giving to this fraction
very high oxidative and cold stabilities and permitting
positive claims on the nutritional label. The red stearins as
well as red PMF find applications in the production of
margarines, shortenings and CBE rich in vitamins for die-
tetic use (Tab. 7).
Fig. 10. Correlation between IV and CP of liquid frac-
tions in a multistage dry fractionation process of palm
oil [17].
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346 M. Kellens et al. Eur. J. Lipid Sci. Technol. 109 (2007) 336349

Tab. 4. TAG composition (%) of palm oil, palm stearin, palm olein and palm super olein (M: myristic;
P: palmitic; St: stearic; O: oleic; L: linoleic; S: saturated fatty acid; U: unsaturated fatty acid; IV: iodine
value; nd: not detected).

Palm oil Palm stearin Palm olein Palm olein Palm super olein
IV 52.3 IV 34.3 IV 56.7 IV 58.9 IV 65.8

LLL 0.5 0.3 0.6 0.7 0.8

PLL/MOL 2.7 1.5 0.6 0.6 0.3
OOL 1.9 1.1 2.0 2.1 2.8
PLO/SLL 10.7 5.9 12.0 12.9 16.6
PLP/MOP 10.4 7.5 10.9 11.2 11.9
MPP 0.4 2.0 4.0 4.4 5.4
POO 22.7 12.9 24.5 26.3 33.4
POP/PLSt 30.3 27.5 30.2 28.7 19.0
PPP 6.1 26.5 1.7 nd nd
StOO 2.5 1.5 3.1 3.3 3.8
POSt 5.5 4.8 6.0 5.9 2.8
PPSt 1.2 5.3 0.2 nd nd
StOSt 0.7 0.5 0.4 0.3 nd
PStSt 0.1 0.6 nd nd nd
UUU 6.0 3.4 6.7 7.2 9.0
SUU-USU 38.6 21.8 42.9 46.1 57.1
SSU-SUS 47.5 40.7 48.3 46.7 34.0
SSS 7.9 34.1 2.1 nd nd

Tab. 5. Cocoa butter replacement fats (CBS: cocoa butter substitute; CBE: cocoa butter equivalent; CBR: cocoa butter
replacer) (La: lauric; M: myristic; P: palmitic; O: oleic; St: stearic; E: elaidic; S: saturated fatty acid; U: unsaturated fatty acid;
CB: cocoa butter).

CBS: lauric oils rich in C36C40 (LaLaLa, LaLaM, LaMM, etc.)

Palm kernel stearin fraction (solvent or dry fractionated)
? not compatible with CB in the solid state
CBE: non lauric-based oils rich in SSU-SUS (POP, POSt, StOSt)
Cocoa butter, Illipe (natural fats)
Palm oil fraction (hard PMF, solvent or dry fractionated)
Sal fat, shea butter (stearin fraction, usually solvent fractionated or panned and pressed).
? highly compatible with CB in the solid state
CBR: non lauric oils rich in trans monounsaturated fatty acids (StEE, PEE, etc.)
Partially hydrogenated oils (oils rich in SUU-USU triacylglycerols like soybean or sunflower).
? partially compatible with CB in the solid state

Minor components like DAG, which cannot be
removed during the refining process of palm oil, have
several disadvantages during fractionation; TAG and
DAG show eutectic interactions making separation dif-
ficult and fractionation incomplete [20]. High-melting
DAG (mainly 1,3-dipalmitoyl glycerol) develop cloudi-
ness upon storage of olein fractions at room tempera-
ture [21]. As mentioned before, they have a detrimental
effect on the crystallization performances of the speci-
alty fats [18]. The effects of the DAG content of RBD
olein on the IV and CP characteristics of super oleins
obtained after dry fractionation have been recently
studied [22]. It was shown that super olein obtained
from RBD olein with low DAG content (less than 1%)
prevented a higher amount of SUU-USU in correlation
with better IV and CP, compared with non-treated
superolein (5% DAG).
By removing minor components like free fatty acids and
monoacylglycerols during refining, modifications of the
physical properties of palm oil and fractions are observed.
Increased values of SFC, especially at lower tempera-
tures, are reported for refined palm oil compared to crude
oil [23]. Additionally, CP of refined palm oleins are usually

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Eur. J. Lipid Sci. Technol. 109 (2007) 336349 Dry fractionation of palm oil 347

Tab. 6. Different CBE qualities from palm oil mid fractions Tab. 8. Characteristics of palm fractions issued from
(HPMF: hard palm mid fraction). vacuum filtration, nozzle centrifuge separation and mem-
brane press filtration (IV: iodine value; SFC: solid fat con-
Iodine POP SFC [% max.] tent by pulsed NMR).
value content [%] at 35 7C
Vacuum Nozzle Membrane press
HPMF 1 2830 .80 6 filtration centrifuge filtration
HPMF 2 3235 .70 36 (rotary separation (squeezing
HPMF 3 3537 .60 25 drum) pressure: 16 bar)
HPMF 4 3740 .50 14
IV palm oil 52 52 52

By pulsed NMR using tempering method. IV palm olein 5657 5657 5657
IV palm stearin 4042 3638 3032
SFC of crystallized oil [%] 11 11 11
SFC of stearin cake [%] 43 65
Tab. 7. b-Carotene content of chemically refined red Olein yield [%] 72 76 82
palm oil and fractions [19].

b-Carotene [ppm]

Palm oil 382 by a lower IV (i.e. more saturated), a higher melting point
Palm olein 409 as well as a steeper SFC profile. The liquid phase, on the
Palm super olein 670 other hand, is of at least the same and in most cases of a
Palm top olein 854 better quality than that achieved in a vacuum filter. In case
Palm hard stearin 280 of palm fractionation (first stage), the yield of centrifugal
Palm soft PMF 235 separation is reported to be in between the yields
Palm hard PMF 80 obtained by a membrane press filter and a vacuum filter
(Tab. 8).

lower than CP of crude palm oleins. The influence of the

refining conditions has been studied, leading to the
observation that a tailing effect in the SFC profile was
observed in palm oleins subjected to severe refining
conditions. Although CP are generally reduced by deo-
dorizing, this tailing effect could be attributed to intra-
esterification of the fatty acids during refining, leading to
earlier crystallization of palm oleins upon storage. The
effect of time and temperature on the SUS/SSU ratio has
been deeply studied by Jeffrey [24]: long residence times
at high temperatures results in intra-esterification making
the processed palm oil unacceptable for production of
PMF.
6 Influence of filtration conditions on
qualities of palm fractions
6.1 Vacuum, centrifugal and membrane press
filtration
Compared with vacuum and centrifugal filtration, mem-
brane press filtration has some important advantages:
higher separation efficiency, higher tolerance to crystal
morphology changes, better protection against oxidation,
faster filtration, and much lower energy consumption. Due
to the improved separation, the stearin is characterized
6.2 Squeezing pressure in membrane press
filtration
As already said, it is not possible to remove all the liquid
phase from the solid phase with any of the commercial
separation techniques, due to liquid entrainment be-
tween and within the crystals. Removal of liquid from
the solid phase is more efficient in a membrane press
filter as compared to a vacuum filter. This is mainly due
to the larger differential pressure applied. In the case of
palm oil, with a standard membrane press filter operat-
ing at 6 bar pressure, the olein yield (calculated on the
olein fraction) easily increases by 10% compared with
vacuum filtration. However, the separation efficiency of
a filter press cannot be defined only in terms of the dif-
ferential pressure applied. The origin of the fatty matter,
as well as the conditions of crystallization and filtration,
also affect the residual olein content in a stearin cake.
The positive effect of squeezing pressure on the quality
of the solid palm fraction is shown in Tab. 9. The higher
the squeezing pressure, the less residual olein remains
in the cake. However, not all crystals can withstand high
squeezing pressures, resulting in partial or even total
passage of the stearin cake through the filter cloth. A
solution can be found in applying a lower pressure on a
thinner stearin cake.

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348 M. Kellens et al. Eur. J. Lipid Sci. Technol. 109 (2007) 336349

Tab. 9. Effect of squeezing pressure on separation effi- measure of the resistance of the liquid fraction against
ciency and quality of palm oil fractions (SFC: solid fat crystal formation at a certain temperature for a certain
content by pulsed NMR; IV: iodine value). period. When properly calibrated, the CP can be used to
predict the cold stability.
Squeezing SFC of Yield [%] IV
pressure stearin cake
The stearin fraction is more commonly characterized by
[%]
its melting behavior (e.g. slip melting point, clear melting
Stearin Olein Stearin Olein point, dropping point). These parameters, however, only
50 mm give an indication of the end of melting. They are not
6 bar 55 23.6 76.4 39.7 57.1 representative of the overall melting behavior. The deter-
15 bar 61 20.0 80.0 36.6 57.1 mination of the solid fat index (SFI) by dilatometry and the
30 bar 65 18.3 81.7 34.7 57.1 SFC by nuclear magnetic resonance (NMR) allows a more
25 mm quantitative definition of the solid-phase behavior of the
6 bar 60 20.6 79.4 36.8 57.2 different oil fractions. Today, the SFC method is more
15 bar 66 18.8 81.2 34.9 57.2 favored than the SFI method, due to its higher accuracy
30 bar 70 16.7 83.3 32.1 57.2
and its ease of application. NMR can also be applied to

follow quantitatively the crystallization behavior of the oil

Chamber plate width.
7 Analytical methods used to determine the
characteristics of palm fractions
A whole variety of analytical methods are used to deter-
mine the characteristics of the fractions obtained as well
as to qualify the performance of the fractionation process
[25]. Most of these methods can be found in the AOCS
Official Methods and Recommended Practices handbook
[26] or in the IUPAC Standard Methods for the Analysis of
Oils, Fats and Derivatives [27].
The IV is a measure of the degree of unsaturation, usually
made by titration (Wijs method). During crystallization, the
more saturated and hence higher-melting TAG con-
centrate in the solid phase, whereas the olein fraction
becomes enriched in more unsaturated TAG.
or fat during the fractionation process (see Fig. 4). Also, it
permits to quickly determine the yield in stearin, simply by
measuring the SFC of the slurry prior to filtration and of
the stearin cake after filtration.
SFC slurry
Yield stearin (%) = 6 100
SFC cake
Differential scanning calorimetry (DSC) reveals by far the
most direct information about the melting and crystal-
lization behavior of an oil or fat. The interpretation of the
DSC thermograms, however, is not easy, due to the
multiple polymorphic transitions that may occur during
melting and crystallization. Although the technique has
a large potential, standardization is necessary to use it
as a routine technique in the oils and fats processing
industry.

The change in IV is also a measure for the separation 8 Conclusions

efficiency as it can be used to quantify the separation:
IVolein IVinitial
Yield stearin (%) = 6 100
IVolein IVstearin
The fatty acid and TAG composition is usually determined
by gas-liquid chromatography (GLC) or high-pressure
liquid chromatography (HPLC). The fatty acid composi-
tion also allows the calculation of the IV:
IV = 0.9506C16:1 1 0.8606C18:1 1 1.7326C18:2 1
2.6166C18:3 1 0.7856C20:1 1 0.7236C22:1
The CP and the cold test (CT) reveal certain aspects of the
crystallization behavior. They are predominantly used to
define the properties of the liquid fraction. The CP is an
indication of the start of crystallization under the given
conditions of cooling. The CT, on the other hand, is a
The fractionation of oils, fats and their derivatives is
basically a rather simple technology, but it is based on a
complex crystallization process which, till today, is still
only partially understood. Especially the dry fractionation
process whereby the oils and fats are submitted to a
controlled cooling and hence crystallization, followed by
a selective separation using filtration, has largely
improved over the last years, enabling processors to dry
fractionate nearly any type of oil, fat or derivative. The
ongoing developments of more powerful dynamic crys-
tallizers and efficient high-pressure filter presses and the
implementation of new principles of fractionation, such
as controlled static crystallization, continuous counter-
current crystallization and centrifugal separation, are fur-
ther expanding the applicability of the fractionation
technology.

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Eur. J. Lipid Sci. Technol. 109 (2007) 336349
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[Received: December 22, 2006; accepted: February 28, 2007]
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