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1. Historical perspective
This kind of fractionation process has been applied for almost 150 years. In
most literature, Hippolyte Mège-Mouriès is credited with the invention of “a
patented method to produce certain fats of animal origin”. In fact, he concocted
the production of a sort of margarine fat, by separating a liquid fraction from
ordinary tallow after gentle cooling. But with only temperature difference as the
driving force, a fractional crystallization of a fat is a perfectly natural,
spontaneous phenomenon. So it was also observed that in palm (kernel) oil
harvested in tropical regions, small crystals would appear upon cooling and
form a crystal suspension in the wooden barrels during shipping to chillier
Western Europe. These slightly denser solids eventually settled, and such
fractions could effectively replace hardened fats in margarines [1]. In a more
evocative twist, we could therefore consider these wooden shipping drums the
very first oil crystallizers, with just the peaceful ocean waves providing the
necessary agitation to keep the mix in suspension. Moreover, the natural
fractional crystallization of fats when mildly cooled is echoed in the term
‘winterizationʼ, referring to the habit of leaving large oil tanks quiescent in
wintertime to induce some mild crystallization and obtain a liquid fraction with
improved cold stability, in an economic fashion [2].
Despite the apparent spontaneity of the process itself, it took until the 1960s for
the fractionation industry (and technology) to boom, when the production of
palm oil in Southeast Asia heavily increased and export taxes on processed
palm oil were reduced. At that time, however, the boundaries of the technology
were mainly determined by the phase separation. In the early stages of
fractionation technology, the olein and stearin fractions of oils and fats had to
be separated by settling, using only the force of gravity to bring about a
separation between the heavier solid phase and the lighter liquid phase, which
left the settled solid phase containing large quantities of entrained (trapped)
liquid oil, almost certainly more than 75% [3]. In the last decades, the
continuous development of separation techniques, from vacuum belt filtration
to centrifuges and membrane press filters, has put fractionation on the map as
a versatile and economic modification technique. Although some specific
techniques relying on use of detergents are still applied for very particular
production, actually only two main fractionation technologies are used in the
21st centuryʼs edible oil industry:
Principal concepts
If anything is clear from browsing through the Lipid Library, it is the fact that a
natural oil is a very complex mixture of different triglycerides (not to mention
diglycerides, free fatty acids, phospholipids, sterols, and uncountable other
minor constituents). The mix of triglycerides does have a repercussion on the
melting behavior of a fat: It does not exhibit a sharp melting point, but often
displays a steady softening (or increasing liquid content) with increasing
temperature, until it is completely liquid. The position and width of this melting
range on a temperature scale is determined by the type of constituting
triglycerides and compositional heterogeneity of the oil:
The type of the triglycerides: in a very simple approach, the longer the
fatty acid moieties, the larger the total molecule and consequently, the
more energy (i.e. higher temperature) will be required to convert such
triglycerides from a solid to a liquid ‘stateʼ. A double bond in the carbon
chain decreases the melting point dramatically, however, and this is why
oils containing a high proportion of unsaturated fatty acids are generally
liquid.
The broader the spectrum of triglycerides present in the oil, the broader
the melting range. Some of the triglycerides will only solidify (or melt) at
5°C, whereas others will still be hard as candle wax at room temperature.
The basic principles sketched in the former paragraphs help to explain the key
aspects of a crystallizer, the technological heart of the fractionation installation.
It should be able to gently cool down a mass of oil (up to 100 ton/batch) and
keep the resulting crystal suspension as homogeneous as possible. Note that
such gentle cooling means in fact imposing very low supercooling conditions,
and it will result in a formation of fewer and larger crystals, because the said
conditions simply rule out the existence of a mass of tiny crystals. Fat
crystallization is a fairly exothermic reaction (up to 180 kJ can be released for
every kg of crystals formed), so the efficiency with which this energy can be
removed is an important design feature. For most industrial crystallizers, this
ranges between 120 and 200 W/m2·K.
Figure 2. DSC cooling profile (-5°C/min) of palm oil and its derived palm
olein fraction. Exothermal peaks are shown upwards.
The upward peaks in the profile show at which temperatures and how much
heat of crystallization will be released upon cooling (here at 5°C/min!). For palm
oil, the sharp peak on the right is created by the fast solidification of
predominantly trisaturated triglycerides. It is largely (and not solely, as some
intersolubility will inevitably occur) this fraction that is crystallized in the first
step or ‘cutʼ in multistage palm oil fractionation. Although the absolute
temperatures in this diagram are not really relevant for fractionation because of
the high cooling rate, the diagram suggests clearly how simple fractional
crystallization can be: You put the temperature in between the two peaks and
wait for the solidification to take place. When this first trisaturated fraction is
removed, however, the remaining palm olein shows one large peak, and it is
instantly clear that a slow fractional crystallization of a distinct fraction is a lot
harder to accomplish in this matrix: There is a lot more material to crystallize in a
narrow temperature region, and intersolubility will have its say.
For a given cooling rate and heat exchange surface, the appropriate removal of
released crystallization heat to the cooling medium is also function of the
agitation and the viscosity of the bulk. The first being an externally imposed
process feature, the type and intensity of agitation is indeed a typical ‘designʼ
matter and linked with the concept of the crystallizer. It should be sufficient to
enhance heat transfer and favor crystal initiation and secondary crystallization,
but on the other hand excessive agitation could damage the structures of the
crystals being formed, which might present problems in the subsequent
filtration stage.
Viscosity, on the other hand, is an intrinsic state of the oil (though to be fully
correct, an edible oil crystal suspension does exhibit some shear-thinning
behavior). Excessive viscosities will reduce mass and heat transfer between
solid and liquid, hence decreasing the crystal growth rate, also by limiting
molecular diffusion. The flow properties of the oil not only are a function of
solids concentration present in the liquid, but are also greatly influenced by the
interactions between the different crystal entities such as network formation
and/or ‘gelly layersʼ [5]. In normal fractionation conditions, the viscosity of
crystal suspensions just prior to filtration ranges from 300 to 2000 mPa·s
depending on the application, though in palm kernel fatty acid fractionation,
viscosities over 50,000 mPa·s are not exceptional.
IV Palm oil 52 52 52
Solids in cake
46 - 65
(%)
Usually, the filter chambers are first filled with the crystal suspension, and in
doing so a large portion of the liquid olein is already passing through the filter
cloths. Then watertight membranes (one membrane per chamber) attached to
the internals of the plates are gradually inflated (with water, liquid oil or air) like
internal balloons to the desired pressures, reducing the chamber volume and
pushing out residual liquid, which is immediately evacuated via internal
channels in the plate towards collecting tanks. The volume reduction of the
chamber thus literally compacts and dries the cake. Typical final squeeze
pressures are 6 or 15 barg, 30 and even 50 barg membrane press filters are
available on the market to attain higher purity in speciality fat cakes. It is also
good to note that the mass fraction of solids in the filter cake decays
exponentially as a function of the distance to the filter cloth, and consequently
thinner filter chambers and longer squeezing times can be helpful (yet costly)
means to reduce the entrainment significantly.
The whole filtration plus squeezing operation can vary from 30 to 90 minutes.
After this, the filter plate package is opened so the solid cakes can just drop by
gravity into a stearin tank underneath the filter to melt.
The first step of dry fractionation of palm oil yields olein fractions with a cloud
point below 10°C. The olein fractions are used as a substitute for soft oils in
frying, cooking and salad oils or are being further fractionated. Together with a
further development of single-stage palm oil fractionation by technological
improvements, there is an increased tendency to execute a double or triple
fractionation of palm oil in order to produce fractions with specific
characteristics such as high IV superoleins (IV > 65) and hard palm-mid-
fractions (hard PMF) (IV < 36).
The latter fraction can serve as a feedstock for the production of typical cocoa
butter equivalents (CBE), which are non-lauric fats similar in their physical and
chemical properties to cocoa butter. They are often prepared by solvent
fractionation [7], though the more contemporary developments within dry
fractionation (better suited crystallizers, improved separation technologies) are
closing the gap between the quality of solvent- and dry-fractionated hard PMF.
Another technological field of interest is the use of plug flow reactors that allow
the fractional crystallization in a continuous fashion, offering considerable
reduction in operation costs (such as steam usage and cooling power). Indeed,
just as in any other edible oil processing technology, there is a continuous quest
for economization and process optimization. Heat recovery systems, crystal
seeding installations, optimized mixing procedures and elegant plant layouts
can all contribute to maximize capacity and minimize costs for a dry
fractionation plant.
One final comment is that the process technologist should always remember
that a fractionation process yields two products, and thus that the sum of the
value of the two fractions should always exceed the processing cost and
feedstock cost. This is why the feasibility of multistage fractionation is not only
a matter of technological know-how, but also a matter of having markets for all
‘by-productsʼ generated along the way.
References
t. Rossell, J.B. Fractionation of lauric oils. J. Am. Oil Chem. Soc., 62, 385-
389 (1985) (DOI: 10.1007/BF02541409).
v. Illingworth, D. Fractionation of fats. In: Physical Properties of Lipids, pp.
411-477 (A.G. Marangoni and S.S. Narine (eds.). Marcel Dekker, New York,
USA) (2002).
w. Hamm, W. Entrainment, are we making progress? Lecture Paper Series.
Society of Chemical Industry (2005).
y. Timms, R.E. Fractional crystallization - the fat modification process for the
21st century. Eur. J. Lipid Sci. Technol., 107, 48-57 (2005) (DOI:
10.1002/ejlt.200401075).
z. Calliauw, G., Fredrick, F., Gibon, V., De Greyt, W., Wouters, J., Foubert, I.
and Dewettinck, K. On the fractional crystallization of palm olein: Solid
solutions and eutectic solidification. Food Res. Int., 43, 972-981 (2010)
(DOI: 10.1016/j.foodres.2010.01.002).
{. Krishnamurthy, R. and Kellens, M. Fractionation and winterization. In:
Baileyʼs Industrial Oil and Fat Products, Volume 4, Edible Oil and Fat
Products: Processing Technology, pp. 301-337 (Y.H. Hui (ed.), John Wiley,
Champaign, USA) (1996).
|. Hashimoto, S., Nezu, T., Arakawa, H., Ito, T. and Maruzeni, S. Preparation of
sharp-melting hard palm midfraction and its use as hard butter in
chocolate. J. Am. Oil Chem. Soc., 78, 455-460 (2001) (DOI:
10.1007/s11746-001-0285-0).