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DOI 10.1002/ejlt.200600309
Marc Kellens
Vronique Gibon
Marc Hendrix
Wim De Greyt
De Smet Technologies
and Services,
Zaventem, Belgium
Review Article
1 Introduction
Most of the natural oils and fats have only a limited application in their original forms, as a consequence of their
specific chemical composition. To extend their use in fatbased food products, oils therefore often undergo a
chemical or physical modification. The best known modification processes applied today in the edible oil industry
are hydrogenation, interesterification (chemical or enzymatic) and fractionation. The main purpose of these processes 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 separation of the triacylglycerols (TAG) through selective crystallization and filtration (fractionation) [1, 2].
At present, quite a number of questions arise with respect
to the effect of the chemical modification processes on
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2 Fractional crystallization
Hippolyte Mge Mouris (18171880) is most probably
the pioneer in fractionation with his famous patent concerning 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 oleodipalmitin) [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 process is known as Lipofrac concept. In solvent fractionation, 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 chemicals, no losses). In contrast to detergent or solvent fractionation, dry fractionation does not require any additional
substance. It simply consists in a controlled crystallization
of the melted oil, conducted according to a specific cooling 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
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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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M. Kellens et al.
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 crystalline 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 polymorph. 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.
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 fractional crystallization is not only dependent on the efficiency 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 unsaturation and positional isomers. Depending on their chemical
structure or polymorphic form, some TAG will be very soluble when mixed and form solid solutions; others will crystallize separately, being immiscible in the solid state and
giving rise to eutectic or monotectic interactions (Fig. 1) [4].
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4.1.3 Crystallization
Crystallization consists of successive stages: supercooling of the melt, nucleation, and crystal growth; crystals normally do not remain single but tend to agglomerate. 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 practical 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 temperature 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 essentially expressed in the geometry of the cooling surfaces
and in the agitation design (Fig. 3) [4].
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M. Kellens et al.
4.2 Separation
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Fig. 5. Separation technologies: (a) rotary drum, (b) Florentine belt filter, (c) membrane
press filter, (d) nozzle centrifuge,
(e) centrifugal filter, and (f) centrifuge decanter.
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M. Kellens et al.
Fig. 6. Filtration sequences in a membrane press filter: (a) filling, (b) squeezing, and (c) discharge.
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Fig. 9. SFC profiles (SFC by pulsed NMR) of different 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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M. Kellens et al.
Palm oil
Olein
Stearin
Super
olein
Middle
stearin
Palm mid
fraction
Shortenings
Margarines
Frying fats
Cooking oils
Salad oils
Specialty fats for coatings
Cocoa butter extenders
Ice cream
Icings
Biscuits
Cakes
Cookies
Crackers
Noodles
Fatty acids source
Hard coatings
111
11
111
111
11
111
111
111
111
111
1
111
111
111
11
1
1
111
11
1
1
1
1
1
111
11
111
111
111
111
111
11
1
1
1
11
11
11
11
11
1
1
1
11
111
11
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Iodine
value
Olein
Super olein
Super olein
Top olein
57
63
65
71
Mettler cloud
point [7C]
7.2
2.5
1.3
24.5
Palm liquid
fraction [%]
10
30
100 (24 h min.
at 0 7C)
Triacylglycerols
Final application
SSS
Solid
SSU-SUS
SUU-USU
UUU
Solid ? semi-solid
Semi-solid ? liquid
Liquid
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Fig. 10. Correlation between IV and CP of liquid fractions in a multistage dry fractionation process of palm
oil [17].
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M. Kellens et al.
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).
LLL
PLL/MOL
OOL
PLO/SLL
PLP/MOP
MPP
POO
POP/PLSt
PPP
StOO
POSt
PPSt
StOSt
PStSt
UUU
SUU-USU
SSU-SUS
SSS
Palm oil
IV 52.3
Palm stearin
IV 34.3
Palm olein
IV 56.7
Palm olein
IV 58.9
0.5
2.7
1.9
10.7
10.4
0.4
22.7
30.3
6.1
2.5
5.5
1.2
0.7
0.1
6.0
38.6
47.5
7.9
0.3
1.5
1.1
5.9
7.5
2.0
12.9
27.5
26.5
1.5
4.8
5.3
0.5
0.6
3.4
21.8
40.7
34.1
0.6
0.6
2.0
12.0
10.9
4.0
24.5
30.2
1.7
3.1
6.0
0.2
0.4
nd
6.7
42.9
48.3
2.1
0.7
0.6
2.1
12.9
11.2
4.4
26.3
28.7
nd
3.3
5.9
nd
0.3
nd
7.2
46.1
46.7
nd
0.8
0.3
2.8
16.6
11.9
5.4
33.4
19.0
nd
3.8
2.8
nd
nd
nd
9.0
57.1
34.0
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
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HPMF 1
HPMF 2
HPMF 3
HPMF 4
Iodine
value
POP
content [%]
SFC [% max.]
at 35 7C
2830
3235
3537
3740
.80
.70
.60
.50
6
36
25
14
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IV palm oil
IV palm olein
IV palm stearin
SFC of crystallized oil [%]
SFC of stearin cake [%]
Olein yield [%]
Vacuum
filtration
(rotary
drum)
Nozzle
Membrane press
centrifuge filtration
separation (squeezing
pressure: 16 bar)
52
5657
4042
11
43
72
52
5657
3638
11
76
52
5657
3032
11
65
82
b-Carotene [ppm]
Palm oil
Palm olein
Palm super olein
Palm top olein
Palm hard stearin
Palm soft PMF
Palm hard PMF
382
409
670
854
280
235
80
Compared with vacuum and centrifugal filtration, membrane 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
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M. Kellens et al.
Tab. 9. Effect of squeezing pressure on separation efficiency and quality of palm oil fractions (SFC: solid fat
content by pulsed NMR; IV: iodine value).
Squeezing
pressure
SFC of
stearin cake
[%]
Yield [%]
IV
55
61
65
23.6
20.0
18.3
76.4
80.0
81.7
39.7
36.6
34.7
57.1
57.1
57.1
60
66
70
20.6
18.8
16.7
79.4
81.2
83.3
36.8
34.9
32.1
57.2
57.2
57.2
SFC slurry
6 100
SFC cake
8 Conclusions
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
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IVolein
Yield stearin (%) =
IVolein
IVinitial
6 100
IVstearin
References
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