NO141533B - PROCEDURE FOR THE PRODUCTION OF MARGARIN FAT WHICH IS FREE OF GREENNESS - Google Patents

Description

The invention relates to a method for producing

ing of a margarine fat which is free from graininess and which is based on palm oil.

Use of palm-based fats as the main component in fat mixtures such as e.g. is intended to be used as margarine fat, is often advantageous, as palm-based fats are often less expensive and much more readily available than various other fat raw materials of comparable quality. The widespread use of palm oil and its hydrogenated and/or fractionated derivatives in the production of fat mixtures, emulsions, etc. has been hampered in recent times, especially by the slow crystallization rate of the palm-based fats and the crystal defects of the crystallized products .

In order to overcome a major drawback often associated with palm-based fats, i.e. their slow rate of crystallization, which can cause packaging difficulties, the product being usually too soft when first produced and later becoming too hard, the palm-based fats are often corandomized fat with different fats.

Crystallized corandomized palm-based fat-containing fat mixtures quite often show even more deficiencies. In particular, the phenomenon of "graininess", by which one understands the formation of large grainy crystal aggregates in fat mixtures during storage, is often due to the presence of palm-based fat in corandomized form.

In "Fette, Seifen, Anstrichmittel" 61 (1959) 1040-6 is

it described a fat consisting of a corandomized mixture of 80% palm oil and 20% soybean oil. All of the palm oil is corandomized, while in the method according to the present invention 15-85% of the palm oil is corandomized with fat containing

specified triglycerides.

Other publications also indicate the production of fat products by corandomization of palm oil. Thus, British patent 903 141 and BRD-off.skrift 1 204 508 describe a corandomized mixture of palm oil and coconut oil or palm kernel oil. The two latter oils, however, mainly consist of triglycerides of C12~<C>14 fatty acids, so that the triglycerides have predominantly 36-42 carbon atoms in their fatty acid residues, while the method according to the present invention uses fat which predominantly consists of C^^- and higher triglycerides for corandomization of palm oil.

The margarine fat produced by the method according to the present invention contains 30-80% unhydrogenated, hydrogenated and/or fractionated palm oil. The method is characterized by the fact that 15-85% of the unhydrogenated, hydrogenated and/or fractionated palm oil is corandomized with one or more other fats that predominantly consist of C44 and higher triglycerides, after which the obtained corandomized fat mixture is mixed with the rest of the unhydrogenated, hydrogenated and /or fractionated palm oil and any other fat, with the proviso that within the given areas the proportions of the ingredients are selected so that the total fat mixture has a PUP:PPU ratio of less than 2.8, and the Case Content is greater than P2U minus 8.

The PUP:PPU ratio is to be understood as the weight ratio between 1,3-dipalmitoyl-2-unsaturated triglycerides (PUP) and the 1,2-dipalmitoyl-3-unsaturated triglycerides (PPU) in the fat mixture. By the unsaturated fatty acids in the PUP and PPU triglycerides are meant the cis-mono- and polyunsaturated fatty acids.

Sa^-triglycerides are triglycerides that have three saturated fatty acids with an average chain length of 44/3 or higher, especially triglycerides of palmitic acid, stearic acid and saturated fatty acids with longer chains.

It has surprisingly been found that margarine fat prepared according to the invention, with a PUP:PPU ratio of less than 2.8 and a Sa^ content of more than P2U t 8 as well as the emulsion or margarine prepared therefrom, do not becomes unacceptably grainy during storage.

Margarine fat produced according to the invention is well suited for the production of emulsions, especially margarine, which has expansion values at 10°C of no more than 1100, at 20°C of

at least 200 and at 35°C of not more than 175, especially less than 75.

The dilatation values stated in this description were measured according to H.A. Boekenoogen, "Analysis and Characterization of Oils, Fats and Fat Products", Volume I, 1964, Interscience Publishers, London, p.143 ff.

The term "fat" is used in this specification to include fatty acid triglycerides which are solid at 20°C and are usually referred to as "fats", as well as triglycerides which are liquid at the indicated temperature and which are usually referred to as "oils". The term "liquid oil", which is also used in this description, refers to triglycerides which are liquid at 5°C, preferably at 0°C. A "fat phase" is a fat or a fat mixture which may include liquid oils and which is suitable as the only fat mixture in the emulsions described here. Likewise, a "margarine fat" is a fat mixture which can also contain liquid oils and which is suitable as a fat phase in margarine. Unless otherwise stated, the terms "emulsion", "margarine", "spreadable foodstuff" etc. refer to water-in-fat emulsions containing fat prepared according to the invention, and also suitable amounts of fat-soluble emulsifiers, e.g. e.g. partial fatty acid glycerides such as monoglycerides, phosphatides and fractions thereof, etc. and/or water-soluble emulsifiers, e.g. partial glycerides, phosphatides, egg yolk, protein, etc.

The term "randomization" refers to the replacement of the fatty acid radicals in the glycerides in an arbitrary manner. This yield, when applied to at least two different fat sources, is called "corandomization" and can e.g. is carried out under the influence of an inter-esterification catalyst at temperatures of approx. 25-175°C, preferably 80-140°C. Suitable catalysts are alkali metals, their alloys, their hydroxides, their alkoxides, e.g. in proportions of 0.ol% to 0.3 or 0.5%, by weight.

Fat produced according to the invention is particularly important in emulsions containing from 40 or 50 and up to 85% of a fat phase, the rest of the emulsion being a water phase, which can be water, milk or skimmed milk adjusted to the required pH value, e.g. of approx. 4 or 4.5 to 6 or 7, and which may contain, apart from suitable water-soluble emulsifiers, various minor ingredients, e.g. salt, acid, protein, flavoring substances, preservatives.

In this description, all percentages, ratios and parts are by weight unless otherwise specified. The amount of fat in emulsion

is based on the weight of the emulsion, the amount of fat in the fat mixture is based on the weight of the fat mixture and fatty acid

the amount in a fat is based on the total amount of fatty acids in the fat, unless otherwise stated.

The term palm-based fat, as used in this description, includes both hydrogenated and unhydrogenated palm oil as well as solid and liquid fractions thereof. The palm-based fat must be present in both randomised and non-randomized form in the fat mixture produced according to the invention. 15-85% of the unhydrogenated, hydrogenated and/or fractionated palm oil is corandomized with one or more other fats which predominantly consist of C^- and higher triglycerides.

Fats that predominantly consist of C44 and higher triglycerides are understood to mean non-palm-based fats and liquid oils in which at least 90% of the triglycerides contain fatty acids with an average chain length of 44/3 and higher. Such fats can either be used as such or in the form of its hydrogenated and/or fractionated derivatives. Examples of "C44 and higher triglyceride" fats are soybean oil, safflower oil, sunflower oil, canola oil, marine oil, cottonseed oil, peanut oil, rice bran oil, etc., and their hydrogenated and/or fractionated derivatives. Preferably, 10-100% of the total fat content, which predominantly consists of C3 and higher triglycerides, is corandomized.

It will be obvious to the person skilled in the art that with a given number of raw materials, the amount of palm-based fat corandomized with the other fat can be easily determined by simple experiments to obtain a fat mixture with the required PUP:PPU ratio of less than 2 ,8, and where the amount of Sa^ is greater

than P2U?8. The amounts of PUP and PPU and Sa3-triglycerides in the fat mixture are calculated based on their content in the raw materials used. These contents can be calculated from the total fatty acid mixture and the fatty acid composition in the 2-mono-glycerides obtained by enzymatic hydrolysis with pancreatic lipase according to M.H. Coleman, J. of Am. Oil Chem. Soc. 38 (1961), 685-8.

It will also be obvious to the person skilled in the art that the type of fat and the amount of fat with which part of the palm-based fat is corandomized is likewise controlled by the factors mentioned above.

The rest of the fat mixture may consist of the rest of the palm-based fat, or it may include other fats mixed with this. The non-randomized fats can be of any type, provided that the requirement of P2Ur8 <Sa3 in the total margarine fat is met. Examples of such oils are coconut, palm kernel,

in

safflower, sunflower, soya oil, etc., which may be hydrogenated or fractionated.

Suitable proportions of corandomized components are from 25-98% of the total fat mixture.

The fat with which the palm-based fat is corandomized, i.e. the other fat which predominantly consists of C^- and higher triglycerides, is preferably partially hydrogenated to reduce its U content preferably without increasing the Sa content, since thereby the expansion value at 35°C can is influenced in a harmful direction, such a hydrogenation treatment is preferably carried out under trans-acid-causing conditions which are well known to those skilled in the art.

As already indicated, the content of the various triglycerides present in the fat mixture produced according to the invention can be calculated from the composition of the raw materials used.

The raw materials used in the accompanying examples have a triglyceride and a fatty acid composition as shown in Table I. In this table, Sa^ stands for a triglyceride having three saturated fatty acids with an average chain length of 44/3 or higher, and Sa for a fatty acid with chain length 44/3 or higher. The content of PUP, PPU and Sa^-triglycerides can be calculated as follows:

a. Fatty acid composition in the corandomized part of

on the total amount of fatty acids in the korandomized part

gr^= the quantity of raw material r in the randomized part i

calculated on the total amount of the Korandomized part

CP<r> = the amount of fatty acid P in the raw material r calculated for it

total amount of fatty acids in the raw material r.

b. Triglycerides in the corandomized part of the fat mixture:

where g. = the amount of corandomized part in the fat mixture m calculated on the total fat mixture

gr = the amount of non-randomized raw material r in the fat mixture m, calculated on the total fat mixture

PUP^ PPUi and Sa3i = the amounts of PUP, PPU and Sa3 in it

korandomized part

PUPr, PPUr and Sa3r = the amounts of PUP, PPU and Sa3 in the raw material r

PUP , PPU and Sa, = the amounts of PUP, PPU and Sa_ in it

m m w 3m J ^3

total fat mixture m.

The triglyceride composition in a margarine fat consisting of 24% palm oil

16% sunflower oil

60% of a corandomized mixture of

60 parts palm oil and

40 parts sunflower oil

can thus be calculated as follows:

a. Fatty acids in the corandomized part according to equation (1) (cf. table I) Pi = 0.6 x 44.5 + 0.4 x 6.5 = 29.2% U± = 0.6 x 49 .6 + 0.4 x 89.8 = 65.7% Sa±= 0.6 x 49.4 + 0.4 x 10.0 = 33.6% b. Triglycerides in the corandomized part according to the equations ( 2), (3) and (4) PUP± = 29.22 x 65.7/10,000 = 5.6% PPUj, = 2 x 5.6 = 11.2% Sa3± = 33.6<3>/ 10,000 = 3.8% c. Triglycerides in margarine fat according to equations (5), (6) and (7) (cf. table I).

PUPm = 0.6 x 5.6 + 0.24 x 35.8 + 0.16 x 1.0 = 12.1%

PPU = 0.6 x 11.2 + 0.24 x 6.0 + 0.16 x 0.1 = 8.3%

m

Sa3m = 0.6 x 3.8 + 0.24 x 7.0 + 0.16 x 0.0 = 4.0%

P_U = PUP + PPU = 20.4 3

2 m m m

PUP:PPU = 12.1 : 8.3 = 1.5

The margarines can be produced by emulsifying a suitable water phase in a suitable ratio in the fat mixture produced according to the invention and cooling and processing the mass in a conventional manner. The water phase may contain additives which are common for margarine, e.g. emulsifiers, salt and flavoring substances. Oil-soluble additives, e.g. flavoring compounds, vitamins, etc., can be included in the fat phase. In general, the proportion of fat phase in a margarine varies from 75 to 85% of the emulsion, depending on the local regulations for margarine. Alternatively, higher proportions of the water phase can be adapted in the production of so-called "light margarines" which can contain as little as 35, 40 or 50

and up to 60% fat by weight.

The emulsions, especially the margarine, can be produced in a conventional closed tubular heat exchanger with a scraped surface,

as described in "Margarine" by A.J.C. Andersen and P.N. Williams, Pergamon Press 1965, pp. 246 ff. "Votator" arrangements as described in GB patents n-r-, 639,743, 650,481 and 765,870 are particularly suitable. Alternatively, emulsions can be produced using a phase inversion process described in GB patent 1,215,868, or on conventional cooling drums as described in the same book by Andersen and Williams.

The invention shall be illustrated by means of examples.

Example I

A margarine was produced from a margarine fat which

consisted of palm oil, hardened to a melting point of 58°C and a corandomized mixture of 60% palm oil and 40% sunflower oil.

Table II shows the composition of the margarine fat and of a control sample. The margarines were prepared in the following way: The margarine fat mixture was melted and emulsified with a water phase which was prepared from acidified milk containing 0.1% mono/di-glyceride mixture so that an emulsion containing 80% fat was obtained.

The emulsion was crystallized and kneaded in a closed tubular heat exchanger with a scraped surface ("Votator" A unit),

which was allowed to stand at a temperature of 15-20°C. The cooling temperatures in the A unit were from -6 to -10°C, and 40% of the treatment emulsion was recycled. The crystallized emulsion was then passed through a resting tube ("Votator" B unit), where it further crystallized for 100-200 sec. and was packed.

The margarine sor<p>. produced according to the invention,

cg that produced from the control sample was stored for 8 weeks at 15°C and then assessed under the microscope for graininess according to the following scale:

1-2 = non-negligible graininess

3-4 = beginning graininess - acceptable graininess 5-6 = gritty - very gritty.

Examples II-IV

Margarines were produced as described in example I

of different margarine fats as shown in Table III. These margarines were assessed with respect to graininess, as described in Example I. The results are also shown in Table III.

Examples V- XXII

Margarines were produced as described in example I,

and these were assessed with regard to graininess after storage at 15°C, as described in example I. The results are reproduced in table IV.

All margarine fats that were produced had expansion values at 10°C below 1100, at 20°C above 200 and at 35°C

of less than 175.

The hydrogenated fats present in both the randomized and non-randomized portions of the fat mixtures described in the examples were hydrogenated to a melting point of 25-70°C.

With the exception of soybean oil, all fats were produced by hydrogenating the fats or liquid oils in a conventional iso-inducing manner to semi-solid or solid fats with melting points mostly between 25 and 45°C. Fats with such melting points generally have relatively few saturated fatty acids, in particular no more than 35%, and have a trans fatty acid content of at least 20%, preferably at least 30 or 40%. An iso-inducing, sulphur-poisoned hydrogenation catalyst was used in the hydrogenation of such clays (about 1.5% of a sulphur-poisoned nickel catalyst precipitated on diatomaceous earth), and the hydrogenation was carried out at temperatures varying from 140 to 180°C until the desired melting point was reached .

The hydrogenation treatment of soybean oil was carried out with non-poisoned nickel catalyst precipitated on diatomaceous earth. Soybean oil with a melting point above 30°C was hydrogenated in two stages, i.e. in the first stage with a fresh and in the second stage with a sulphur-poisoned catalyst, first at 90-120°C and then at 170-190°C

until the desired melting point was reached.

"vrr fractionation of the palm-based fats used

in the fat mixtures produced according to the invention, was carried out by heating the fat to a temperature of approx. 50 or 60°C, and cooling the liquid fat obtained to 40°C, followed by a gradual cooling during approx. 4 hours to 15. to 35°C. The mass obtained was then kept at this temperature for a period of approx. 1.5 to 3 hours, after which the solid fraction (stearin) was separated from the liquid fraction (olein) by filtration.

Wet fractionation of palm-based fats was carried out by mixing approx. 1 part fat with 1 part acetone, the mixture was allowed to stand at 2-15°C for several hours, and the stearins were separated from the oleins by filtration.

Claims (4)

1. Process for the production of a margarine fat which is free from graininess and which contains 30-80% unhydrogenated, hydrogenated and/or fractionated palm oil, characterized in that 15-85% of the unhydrogenated, hydrogenated and/or fractionated palm oil is corandomized with one or several other fats which predominantly consist of C^- and higher triglycerides, after which the obtained corandomized fat mixture is mixed with the rest of the unhydrogenated, hydrogenated and/or fractionated palm oil and any other fat, with the proviso that within the given areas the proportions of the raw materials are chosen as follows that the total fat mixture has a ratio between the amounts of 1,3-dipalmitoyl-2-unsaturated triglycerides and 1,2-dipalmitoyl-3-unsaturated triglycerides of less than 2.8, while the content (in percent) of triglycerides of saturated fatty acids that has an average chain length of 44/3 or higher, is greater than the total content (in percent) of the dipalmitoyl-monounsaturated triglycerides minus 8%. 2. Method as stated in claim 1, characterized in that 10-100% of the other fats which predominantly consist of C44~ and higher triglycerides are corandomized. 3. Method as stated in claim 1 or 2, characterized in that 25-98% randomised fats are mixed with 75-2% non-randomised fats. 4. Method as set forth in any one of claims 1 to 4, characterized in that the other fat, which predominantly consists of C44 and higher triglycerides, is partially hydrogenated.