Fractionation

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Fractionation Technology
Wolf Hamm, 38 The Uplands, Harpenden, Herts AL5 2NZ, UK whamm@btconnect.com This paper covers the following aspects of fractionation technology: 1. History 2. Developments 3. The Characteristics and Uses of Fractionated Products 4. Economics of Fractionation 5. Conclusions

1. History The production of oils from oilseeds and oil-rich fruits such as the olive and palm almost certainly pre-dates biblical times, but oil modification processes are generally not more than one hundred years old. The widespread use of the three oil modification processes - hydrogenation, interesterification and fractionation - in the twentieth century extended the range of applications of the triglyceride oils almost beyond recognition. These processes principally serve the purpose of modifying the melting properties of oils and fats in order to improve their functional properties in specific applications, but the processes are also used to improve the stability of the oils and fats thus processed. In the field of edible oil processing, fractionation almost always refers to the mechanical separation of the liquid from the solid, crystallised, constituents of a given oil or fat. The split between liquid and solid fractions depends on the temperature at which crystallisation is carried out. Fractionation is a process that has been known in industrial form for more than a century. Before then, the liquid (olein) and solid (stearin) fractions of certain oils and fats had been separated by settling, using only the force of gravity to bring about a separation between the heavier solid phase and the lighter liquid phase. Naturally this method of fractionating left the settled solid phase containing large quantities of entrained (trapped) liquid oil, almost certainly more than 75%. In later years a process of this type, using only indirect cooling of the oil but separating liquid from solid by filter or centrifuge, became known as 'dry fractionation'. The use of surface-active agents to assist in the separation of crystallised fat from the liquid fraction was originally proposed in patents issued at the beginning of the 20th century, and in the second half of the century the process was used on an industrial scale for the fractionation of oils such as palm oil and palm kernel oil as well as fatty acids. The use of disc centrifuges to improve the efficiency of separation, as in AlfaLaval's LIPOFRAC process, marked a further stage in the development of this

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process. Although fractionation of palm oil was not the first industrial application, it is convenient to use results obtained in fractionating this oil as a means of comparing the different process options. In the case of dry fractionation, the rotary vacuum filter became a common separating tool in the 1950s, and palm oil fractionated using this method led to olein yields of 60-65% when aiming at an increase of the Iodine Value (IV) of 4-5 units. In the LIPOFRAC process the enhanced separation allowed olein yields to be raised to between 75 and 80%. Thus the dry fractionation process had the disadvantage of lower olein yields - bearing in mind that in this case the liquid fraction was the more valuable - and of a solid fraction having a relatively low solids content. On the other hand, the LIPOFRAC process had the disadvantages of using relatively high levels of expensive chemicals and of creating an effluent problem, as the detergent solution used in the process had to be discharged as an effluent after it had lost its wetting power. In some countries the use of a wetting agent in the fractionation of an edible oil is not permitted. The use of solvent-based fractionation to produce a fat with melting properties similar to cocoa butter and compatible with it was developed in the 1950s. The fraction produced consists of the mid-fraction of palm oil; the top fraction comprising most of the trisaturated triglycerides present in the original oil, and the bottom fraction comprising much of the di- and tri-unsaturated components of the oil, having been removed. Although solvent fractionation is easily the most efficient fractionation process when considering separation performance and yield of the high-quality solid fraction, it has the disadvantage that the capital investment required is far greater than that required for the other fractionation processes. Moreover, the flammability of the solvents used requires process safety to be a major consideration in the design and operation of the plant, adding to the expenditure. For these reasons solvent fractionation has only been used for the production of fractions having high added value, production of palm mid-fraction and shea stearin being the prime examples. In the latter case it is essential to remove the isoprenoid gum-like material found in the crude oil before solvent fractionation. Since gum separation can also be carried out in acetone or hexane, it is advantageous to operate the total process without intermediate desolventising. Shea stearin, which has a high content of symmetrical, mono-unsaturated triglycerides, is a valuable component of cocoa butter equivalents. Solvent fractionation is not the most effective process for the fractionation of raw materials such as coconut oil, palm kernel oil and sal fat. For these oils dry fractionation, in some cases making use of hydraulic pressing to obtain good liquidsolid separation, has been shown to produce stearins in higher yields than those obtained by solvent fractionation and without sacrifice in quality. However for sal fat, fractionation from acetone is advantageous in separating diglycerides and other polar glycerides into the olein fraction. Back to Start 2. Developments The very remarkable growth of palm oil production in Malaysia and later in Indonesia, beginning in the 1970s, had a profound effect on developments in edible oil fractionation technology. Until this time, fractionation had been used on a relatively limited scale for the fractionation of palm oil in order to produce the functionally more useful palm olein, and for the fractionation of oils such as partially hardened soyabean oil to produce a stable liquid oil, where a mild hardening is used to eliminate the most

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unsaturated triglycerides and thereby improve stability. The fully saturated triglycerides formed during hardening are then removed by fractionation. The process was also used on a small scale to fractionate animal fats. The massive growth in palm oil supplies in the 1970s had two consequences. It became important to convert palm oil to palm olein (by fractionation), as palm olein had much better market prospects in the industrialised world than palm oil; it became attractive to the main palm oil producing country, Malaysia, to export fractions rather than the crude oil. The consequent growth in fractionation capacity in South East Asia was accompanied by significant developments in fractionation technology, these being intended for application to palm oil fractionation but obviously being equally suitable for the fractionation of other fats. In the first instance the relatively inefficient rotary vacuum filter was replaced by Tirtiaux's Florentine belt filter (see picture), which made it possible to handle far larger quantities of oil in a virtually fully continuous process. This company also studied the crystallisation of various oils in great detail, and developed a cooling procedure which ensured that filtration rates and solid-liquid separation could be optimised. As a result the dry fractionation process for palm oil became more competitive with the LIPOFRAC process than had previously been the case, while the disadvantages of the latter process meant that interest in its use declined sharply. Deffense (E Deffense, Fractionation of palm oil, J Amer Oil Chem Soc. 1985 62 376) provides a comprehensive overview of fractionation results comparing the various processes in use in the 1980s.

Picture: Florentine Filter manufactured by s.a. Fractionnement Tirtiaux The development of membranes for use in pressure filtration had a widespread effect on fractionation technology, making both vacuum filtration in dry fractionation as well as LIPOFRAC fractionation almost instantly redundant. By using membrane filter presses, olein yields in palm oil fractionation could be raised to close on 80% when aiming for an increase in Iodine Value of 5 units, and two-stage fractionation, which could be used to produce oleins of higher Iodine Values or stearins containing less entrained olein, became an attractive proposition. For the first time a real challenge to the dominance of solvent fractionation in the production of high-purity fractions was successfully challenged and thus provided an attractive alternative to a capital- and energy-intensive process became a reality, and it can therefore be said that the development of the membrane filter press virtually made LIPOFRAC and solvent fractionation redundant. The close resemblance in solid content and composition of

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palm mid-fraction produced by dry and solvent fractionation is shown in the Table 1. When first introduced, pressure filtration using membranes was carried out at pressures of 6-8 bar, but in more recent years higher pressures have been used. Kellens (M Kellens, Oil Modification Processes, in Edible Oil Processing, eds. Hamm and Hamilton, Sheffield Academic Press, 2000) shows that the use of high squeeze pressure (30 bar) in the filter makes it possible to produce a palm mid-fraction that matches in its principal characteristics the mid-fraction obtained by solvent fractionation. Kellens also demonstrates that by changing the sequence of the fractionation stages in a twostage process, different qualities of the fractions may be obtained, thus enhancing the versatility of the process. Table 1 Comparison Of Mid-Fractions Produced By Dry And Solvent Fractionation DRY 2 DRY 3 88.9 80.1 49.1 0.2 34 2.1 83.4 (69.0) 7.6 5.5 0.2 4.2 SOLVENT 2 85.9 75.0 44.0 2.5 34 3.7 82.7 (65.8) 6.9 7.1 0 2.4

No. of fractionations Solid fat content(%): 20 C 49.6 25 C 22.8 30 C 6.8 35 C 0 Iodine Value 46 Triglyceride composition(%): SSS 1.5 SOS 61.9 (of which POP) (49.2) SLinS 10.2 SUU 21.1 UUU 2.0 Diglycerides(%) 5.1

Source: Ian Stewart, Britannia Food Ingredients Ltd.

The fractionation process can either be used as a stand-alone process (it is normally applied to refined oils) or as part of a more complex process. Thus it can be coupled with hydrogenation, either with hydrogenation being a first stage followed by fractionation, e.g. in the case of hardening of soyabean oil to eliminate linolenic acid, followed by fractionation to separate the stearin formed, or with hydrogenation applied to one of the fractions produced in a fractionation process. An example of the latter combination is the hardening of palm kernel stearin produced by fractionation to nearzero Iodine Value. The fractionation process can also be coupled with interesterification, either in order to randomise a fraction obtained in a fractionation process or to interesterify a blend, one component of which is a fraction produced by fractionation. In the case of two-stage fractionation the decision whether to fractionate at the lower temperature followed by fractionation at the higher temperature, or to reverse this

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sequence, can have significant effects on the characteristics of the fractions produced. The fractions obtained when using these alternative routes to fractionate palm oil are shown in the figure.

Figure: Alternative routes to fractionate palm oil Key: CBE =cocoa butter equivalent, CBI = cocoa butter improver, PMF = palm midfraction
Source: M Kellens, Oil Modification Processes Fig. 5.21, in Edible Oil Processing, eds. Hamm and Hamilton, Sheffield Academic Press, 2000 by permission.

Back to Start 3. The Characteristics and Uses of Fractionated Products Since fractionation basically separates solid from liquid fractions of the oil or fat fractionated it is obvious that the process is primarily used to impart either improved liquid (flow) properties to the principal fraction or to produce a 'purer' solid fraction, where this is the principal fraction. However, the complexity of oils and fats, which consist of a large range of individual triglycerides, means that the fractions obtained will also be mixtures of various triglycerides, but enriched in either higher-melting or

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lower-melting components of the original oil. As the solidification of fats is also a very complex process, involving the formation of mixed crystals and eutectics, prediction of the melting properties of fractions is likely to be empirical rather than theoretical. Moreover, the problem of entrainment when separating liquid from solid adds to the difficulty of predicting fraction properties and their yield. It is well known that entrainment is strongly influenced by the crystallisation technique employed - the formation of highly irregular crystal agglomerates will result in much greater entrainment than when spherical crystals are produced. The production of oils that do not become cloudy (due to the formation of a suspension of a fine precipitate) on storage, particularly when the oil is to be stored in clear bottles for display in food stores, has long been an objective of oil refiners. In some cases the material precipitating from an oil consists of high-melting waxes, sunflower oil being an example of this type of precipitation, in other cases precipitation is due to the presence of fully saturated triglycerides. These may have been formed when lightly hydrogenating the oil in order to eliminate unstable triglycerides, as in the case of soyabean oil. Where only small proportions of less soluble components are to be removed the process is often referred to as winterisation, particularly in the USA. The crystallising and filtration conditions used to carry out this type of process resemble the older form of fractionation rather than the modern technology. Nowadays the production of palm olein is by far the most important fractionation process in which the liquid fraction is the principal product. Since palm olein is generally used as an industrial frying oil rather than as a competitor to seed oils as a salad oil, the purpose of fractionation is to improve the flow properties of the olein. For purposes of specification and quality control this is generally assessed by the Cloud Point of the oil, although the Iodine Value is also indicative of the reduction of the more saturated triglycerides in the oil. Most of the palm olein produced (principally in Malaysia) requires only a modest elevation of Iodine Value above that of the starting oil, e.g. an increase of 5 units, but it is possible, by means of a two-stage process, to achieve Iodine Value increases of 10 units and more. The number of fractions produced in a fractionation process obviously rises with the number of fractionation stages, although it is sometimes possible to design a process in which intermediate products are recycled. An important objective when fractionating an oil is to maximise the value of the secondary fraction, and this is particularly the case when fractionating palm oil. Palm stearin normally sells at a discount to palm oil, and the economics of processing this oil therefore relies on minimising the production of stearin and/or maximising the value of the stearin produced. In the past, palm stearin has found only a limited number of applications as an edible fat, but in more recent years the use of the membrane press filter has made it possible to refractionate the solid fraction from the first stage of fractionation to produce a second-stage fraction which may be suitable for confectionery fat blends, and is competitive in composition with palm mid-fraction as produced by solvent fractionation. The modern palm stearin is also suitable as a component of an interesterified blend, thus reducing or even eliminating the need for hydrogenation. Consequently palm stearin has become a more versatile feedstock or intermediate in the formulation of edible fat blends. By making use of different process routes and different pressures in the filter press it is possible to obtain palm oil fractions of different compositions, thus expanding the opportunities for making best use of the oil. The confectionery fat industry benefits to a considerable extent from the range of

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opportunities offered by fractionation. In addition to the production of palm midfraction, discussed earlier in this paper, fractionation is used to produce a number of important components of various confectionery fats. Shea oil, a fat of West African origin, is rich in symmetrical monounsaturated triglycerides, which can be concentrated by fractionation. As the crude oil contains significant amounts of unsaponifiable isoprenoid components (gums) which affect both refining and fractionation of the oil, it is necessary to remove this material before fractionation. Degumming of this oil is generally carried out in solvent (acetone or hexane), and subsequent fractionation is carried out in the same solvent. Separation of the gum fraction is easier when using acetone as the solvent than when using hexane, but in both cases it is imperative to choose operating conditions (time, temperature, agitation) that will cause the gums to precipitate without excessive entrainment of the oil component. The functional properties of the lauric fats are also improved by fractionation. In order to optimise their performance in a variety of products, fractionation may be followed by hydrogenation so as to remove the small proportion of unsaturated triglycerides left after fractionation. As the lauric fats are not compatible with cocoa butter care must be taken to avoid using both laurics and cocoa butter in the same product. Fat migration easily takes place in that case, leading to evidence of fat bloom. In the production of cocoa butter replacers (CBRs) fractionation is used to produce a midfraction from a hydrogenated soft oil such as rapeseed, soyabean or cottonseed oil. Although use of dairy butter has declined sharply in the industrialised world in the last 30 years, industrial use of butter has meant that the fractionation of butterfat has been a developing field. Butterfat fractions, obtained by multi-stage dry fractionation, have also found application in the production of spreadable butter. The fractionation of butterfat is more complex than the fractionation of, for example, palm oil, primarily due to the complexity of the butterfat triglyceride composition. Early work on the fractionation of this fat used the solvent-based process, but it was subsequently found that carefully controlled dry fractionation would also produce fractions which have a number of applications. A comprehensive review of butterfat fractionation has been provided by Deffense (E Deffense, Milk Fat Fractionation : A Review , J Amer Oil Chem Soc 1993 70 1193). Back to Start 4. Economics of Fractionation The dominant position of dry fractionation in today's oil processing world is not only due to the advances made in dry fractionation technology, but also to the fact that other fractionation processes, particular solvent fractionation, require far greater capital investment than dry fractionation. Dry fractionation has the advantage of basically only requiring crystallisers and filters, though filter costs have risen considerably as the separating performance of the filter has grown. Dry fractionation is also non-energy-intensive, which obviously is advantageous from the point of view of operating costs. Kellens (de Smet Group) has provided a detailed cost picture for dry fractionation, and this is shown in summary form in Table 2. It must be remembered, however, that in the case of fractionation the value of the secondary fraction(s) can play a significant role in the economics of production., and it

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is in this respect that fractionation is at a disadvantage when compared to the other oil modification processes, i.e. hydrogenation and interesterification, as these processes produce no secondary products that require marketing.

Table 2 Fractionation Plant Capital and Operating Costs (US$) INPUT: OUTPUT: Palm Olein 2, IV = 63 Palm Olein 1 Plant capacity Installed cost ($) Investment cost ($/t) Operating cost ($/year) Operating cost ($/t) Total Production Cost ($/t) 100 t/day 2,250,000 13.60 220,600 6.70 20.30 Palm Olein 2 50 t/day 2,250,000 27.30 150,700 9.10 36.40 Palm Oil, IV = 52 Palm Olein 1, IV = 57

Source: M Kellens, Oil Modification Processes, summary of data in Table 5.22, in Edible Oil Processing, eds. Hamm and Hamilton, Sheffield Academic Press, 2000 by permission.

5. Conclusions Fractionation of edible oils and fats has in the last twenty years become an important and very versatile oil modification process. Developments in the technology used have made it possible to improve the efficiency of separation achieved, and thereby increase the applicability of the process. The increasingly important role of palm oil in the global oil supply has played a key role in these developments. The mild operating conditions and relatively low operating costs constitute important advantages of the process, but it is important to remember that the overall economics of the process can be strongly influenced by the value of the secondary fraction produced. Copyright W Hamm 2000

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