CA1045893A

CA1045893A - Margarine fat

Info

Publication number: CA1045893A
Application number: CA196,043A
Authority: CA
Inventors: Theophil Wieske; Ingo Witte; Jacob Hannewijk; Marcel A. G. Willems
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1973-03-26
Filing date: 1974-03-26
Publication date: 1979-01-09
Also published as: DE2413726A1; JPS5026804A; IE39090L; SE8602473L; SE8602473D0; JPS5853894B2; NL7403963A; FR2222955B1; LU69711A1; IE39090B1; FR2222955A1; GB1455416A; NL173129C; NL173129B; AU6701274A; ZA741881B; BE812798A; DE2413726C2; CH590016A5

Abstract

Abstract of the Disclosure The invention relates to fat blends of a relative-ly high palm oil content which fat blends are suitable for the preparation of food spreads, particularly mar-garine, and comprise a co-randomized and a non-random-ized part, the co-randomized part comprising a palm-based fat, a lauric fat and a trans-containing fat, the non- randomized part containing such fats that the total fat blend contains well- efined proportions of saturated long-chain fatty acids, mono-trans long-chain fatty acids and saturated short-chain fatty acids. The fat blends of the invention are rapidly crystallizing even when they contain a relatively high proportion of slowly crystallizing palm oil.

Description

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~458~3 The present invention relates to fat blends con-taining palm-based fats, which fat blends are suitable for the preparation of food spreads, particularly marga-rine and which can also be applied in the production of shortenings.
The invention especially relates to margarine fats from which margarines of such a consistency can be made that they are suitable for packing in tubs.
The invention provides a fat blend suitable for the preparation of emulsions, particularly margarine, having dilatation values at 10C of at most 1000, at 20C of at least 200 and at 35C of no more than 75, which comprises a co-randomized and a non-randomized part, the co-randomized part comprising a palm-based ` 15 fat, a lauric fat and a trans-containing fat, the non-randomized part containing additional fats such that the fat blend comprises 18-50% H fatty acids,3-25% T fatty acids 3-30% M fatty acids, while the balance can be made up to L fatty acids. The dilatation values as described in this specification were measured as described in H.A. Boekenoogen "Analysis and Characterization of Oils, ~ats and ~at Products", Vol. I 1964, Interscience Pu-blishers London, pp. 143 et seq.
The term "fat" is used herein to include fatty acid triglycerides which are solid at 20C and are com-- monly described as "fats" as well as triglycerides which -~
are liquid at that temperature and which are commonly described as "oils". The term "liquid oil", which is also used in this specification refers to triglycerides -~
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which are liquid at 5C, preferably at 0C. A "fatty phase" is a fat or fat blend which can include liquid oils and which is suitable as the sole fat blend in the emulsions of the invention. Similarly a "margarine fat"
is a fat blend which can also contain liquid oils and which is suitable as the fatty phase in margarine. Un-less stated otherwise, the terms "emulsion", "margarine", "food spread" etc. refer to water-in-fat emulsions con-taining the fat blends of the invention and also suitable amounts of fat-soluble emulsifiers, e.g. partial fatty acid glycerides like monoglycerides, phosphatides, and fractions thereof, etc. and/or water-soluble emulsifiers, e.g. partial glycerides, phosphatides, egg yolk, protein etc.
In this specification by H fatty acids are understood saturated fatty acids with - 16-24 carbon atoms ~-T fatty acids: mono-trans unsaturated fatty acids with - 16-24 carbon atoms M fatty acids: saturated fatty acids with 12-14 carbon atoms L fatty acids: the remainder, being 100 - (H + T + M)%.
The term "randomizing" refers to the interchange of the fatty acid radicals of the glycerides on the glyc-eryl radicals in random fashion. This interchange, when applied to at least two different fat sources is called "co-randomizing" and can e.g. be effected under the in-fluence of an interesterification catalyst at tempera-tures of about 25-175C, preferably 80-140C. Suitable -~
interesterification catalysts are alkali metals, their ' 1~58~3 alloys, their hydroxides, their alkoxides, e.g. in pro-portions of 0.01% to 0.3 or 0.5~o by weight of the fat blend to be interesterified.
The fat blend according to the invention is partic-ularly of importance in emulsions containing from 40 or 50 up to 85% of a fatty phase, the balance of the emul-sion being an aqueous phase, which can be water, milk or skim milk adjusted to the required pH value e.g. of about 4 or 4.5 to 6 or 7 and which can contain, apart from suit-able water-soluble emulsifiers, various minor ingredients e.g. salt, acid, protein, flavours, preservatives, etc.
In this specification all percentages, proportions ~ -and parts are by weight unless otherwise specified. The amount of fat in the emulsion is based on the weight of the emulsion, the amount of fat in the fat blend is based on the weight of the fat blend and the amount of fatty acids in a fat is based on the total amount of fatty acids in said fat, unless stated otherwise.
The use of a palm-based fat, which term includes ;~
both hydrogenated and unhydrogenated palm oil as well as solid and liquid fractions thereof, preferably as a dom-; inating constituent in margarine fats, is of great im-portance, for reasons of availability and consistency of such fats and also because of economic considerations.
The presence of substantial amounts of palm-based fats in fat blends to be used in food spreads, e.g. mar-garines, often results in inadequate products, mainly because palm oilisaslowly crystallizing fat of a very specific glyceride distribution. The slow crystalliza-tion properties of palm oil can e.g. result in crystal ,:

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1~)4S8~3 defects, e.g. caused by "post-hardening", which means that on storage of the prepared product crystal growth proceeds, which e.g. can result in an unacceptable in-crease in hardness of the product and/or in the formation of large, grain-like crystal aggregates, which in turn are responsible for undesirable organoleptic properties of the finished product.
~he fat blend of the present invention can contain substantial proportions of palm-based fat, e.g. from 20, 30, 40 or 50 to about 80% by weight. ~he fat blends thus obtained are - as compared with the prior art products of the same palm-based fat content - more rapidly crystal-lizing, probably as a result of interaction of the various types of triglycerides which are formed as a result of -co-randomizing part, especially the major proportion, of the fat blend, and they can be used in margarines of out-standing consistency and organoleptic properties. A
particular advantage of the fat blends of the invention is that fractionating is an entirely optional process step. If suitable fat fractions are available, they can be incorporated in the fat blend, but if not, it is not necessary and certainly not preferred to carry out a complicated fractionation process, which always has the drawback that substantial proportions of fractions remain for which other outlets have to be found.
A further advantage is that in the fat blends of the invention liquid oils should not be subjected to a co-randomizing treatment, which process when applied to liquid oils may sometimes affect the organoleptic quality ~0 of the blend.
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1~)458~3 Preferably the fat blends of the invention contain a total of ~ and M fatty acids of 10-45% by weight, par-ticularly 12-40%~ the total of H and ~ fatty acids being preferably at most 60%. ~he co-randomized part of the fat blend may constitute from 10 or 20 to 80 or 95%,pre-ferably from 35 to 85% by weight of the total blend.
Preferably a co-randomized part is used containing from 5 to 35% by weight of lauric fats, 10 to 50%, es-pecially 15-45% by weight of palm-based fat and 10 to 50%
by weight of trans-containing fats based on the total weight of the fat blend to provide from 10 to 40% H, 4 to 25% ~ and 5 to 25% M fatty acids in the co-randomized part. In a particularly preferred embodiment of the in-vention the palm-based fats are the dominating fats in the co-randomized part. By "lauric fats" are understood fats containing substantial proportions of glycerides of ~ lauric acid (M acid), particularly coconut oil, palm f kernel oil, and babasu oil, which fats may have been sub-' jected to hydrogenation.
The non-randomized part of the fat blend of the in-; vention should be at least 5 or 7% by weight and prefer-ably contains 0 to 25% of lauric fats, 0 to 50% liquid oils, 0 to 25% palm-based fats and 0 to 35% of trans-containing fats. ~specially proportions of at least 10 or 20% liquid oils in the non-randomized part provide - suitable refrigeration type margarines.
Both in the randomized and the non-randomized part of the fat blend of the invention the palm-based fats can consist of or contain substantial proportions of hydrog nated palm oil, particularly hydrogenated palm .

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lV4SE~93 oil of a melting point of 40 to 48C, as well as frac-tions, particularly the liquid fractions, of hydrogenated or unhydrogenated palm oil obtained by dry fractionating or fractionating in the presence of organic solvents or detergent solutions. Unhydrogenated palm oil is general-ly preferred since thereby a complicating hydrogenating step can be avoided, without detrimentally affecting the ultimate quality of the fat blend of the invention.
The trans-containing fats can be present in both the randomized and the non-randomized part of the fat blend and hydrogenated oils of a melting point of 25-55C, particularly hydrogenated llquid oils of a melting point between 30 and 45C are preferred.
Suitably the high trans-containing fats are pre-pared by hydrogenating liquid oils in a conventional iso-promoting way to semi-solid fats having a melting point e.g. between 30 and 45C and generally having steep tem-perature/dilatation curves. Such fats generally have relatively few saturated fatty acids, particularly at most 35% and have a trans-fatty acid content of at least 20%, preferably at least 30 or 40%. The preferred range of the trans-fatty acid content of such hydrogenated oils is 50 to 70% and that of the saturated fatty acid content about 15 to 35%. Preferably an iso-promoting sulphur-poisoned hydrogenation catalyst is used in the hydrogena-tion of such oils, for example 1.5% of a sulphur-poisoned nickel catalyst precipitated on kieselguhr and the hydro-genation can be effected at temperatures varying from about 140C to 180C. In this way it is possible to ob-tain hydrogenated high trans-containing fats containing .
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~04S~9 3 40, 45 or 50 to 65, 70 or even 75% of trans-acids and no more than 10 or 15 to 25 or 30% of saturated fatty acids.
The hydrogenation treatment can also be carried out with non-poisoned nickel catalyst precipitated on kiesel-guhr. ~hese catalysts are especially used with oils, e.g. certain types of soya bean oil which do not remain stable as regards flavour after a treatment with an iso-promoting catalyst. Such oils therefore are preferably hydrogenated with a fresh nickel catalyst in two or more stages, or in the first stage with a fresh and the second stage with a sulphur-poisoned catalyst, first at about 90 to 120C and subsequently at about 170-190C. With these catalysts also high trans-fatty acid contents can be obtained, e.g. of 30, 35 or 40% up to 55 to 65% by weight and also low saturated fatty acid contents, e.g.
no more than 15, 20 or 25 to 30 or 35% by weight based on the total amount of fatty acids in the hydrogenated fats.
Fractions of hydrogenated oils can also be used to ; provide a suitable trans-containing fat for the fat blend of the invention. The fractionation treatment can be carried out by removing part of the tri-saturated glycer-ides and thus increasing the proportion of trans-acids, until a fraction of a high trans-acid content is obtained.
With a given trans-content of the trans-containing fats the total proportion of trans-containing fat in the -fat blend of the invention is preferably adjusted to provide a fat blend of a trans-fatty acid content of 3 to 25%, particularly 3 to 25% in the co-randomized part, .. . .

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1045~393 calculated on the total blend.
Fractionation of the hydrogenated fat and/or the palm-based fat to be used in the fat blend of the inven-tion, is preferably carried out by heating the fat to a temperature of about 50 or 60C, cooling the liquid fat obtained to 40C, followed by a gradual cooling in about 4 hours to about 32 to 38C in the case of hydrogenated fats or 15 to 35C in the case of a palm-based fat. ~he mass obtained is subsequently kept at this temperature for a period of about 1.5 to 3 hours, after which the solid fraction is separated, e.g. by filtration.
Oils which are suitable for the preparation of trans-containing fats are for instance groundnut, rape-seerl, sunflower, safflower, soyabean, fish and cotton-seed oil.
~he melting point referred to above is the "slip melting point" as defined in Bailey "Melting and Solid-` ification of Fats", Interscience Publishers Incorporated, New York, 1950, p. 110.
~he liquid oil component to be used in the fat blend of the invention is preferably one containing at t least 40% by weight of poly-unsaturated fatty acids, for example sunflower, safflower, cottonseed, wheat germ, soyabean, grapeseed, poppyseed, tobaccoseed, rye, walnut or corn oil.
According to a specific embodiment of the inven-tion, margarine fats are provided which are suitable for , ~ refrigerator-type margarines, i.e. those which are pre-ferably packed in tubs, having dilatation values at 10C
; 30 of no more than 700 and at 35C of no more than 50, said ,; ~',~. .
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margarine fats comprising about 45 to 7G% by weight of -~
co-randomized constituen-ts, the remainder being non-ran-domized constituents, the co-randomized part comprising 20-45% unhydrogenated palm oil, 5 to 30% of lauric fats, the balance being hydrogenated trans-containing fats.
The margarines can be prepared by emulsifying the suitable aqueous phase in a suitable proportion in the fat blend of the invention and chilling and working the mass in a conventional manner. The aqueous phase can con-tain additives which are customary for margarine, for example emulsifying agents, salt and flavours. Oil-soluble additives e.g. flavouring compounds, vitamins etc.
can be included in the fatty phase. Generally the pro-portion of fatty phase in a margarine varies from about 75 to 85% of the emulsion depending on local statutory requirements for margarine. Alternatively higher propor-tions of the aqueous phase can be adopted in the produc-tion of so-called low-fat spreads, which can contain as little as 35~ 40 or 50 up to 60% by weight of fat.
The emulsions, particularly the margarine, can be manufactured in a conventional closed tubular surface-scraped exchanger as described in "Margarine" by A.J.C.
Andersen and P.N Williams, Pergamon Press 1965 ~ pp. 246 et seq. Votator arrangements described in British patent specification 639~743~ British patent specification 650~481 and British patent specification 765~870 are particularly suitable. Alternatively, emulsions can be prepared by means of a phase inversion process as de-scribed in British patent specification 1, 215 ~ 868 or on 3G conventional cooling drums as described in the same book e. ~Q~

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1~458~3 by Andersen and Williams"
~he invention will be illustrated by the following examples:
EXA~PLES I -XXI I
Fat blends were prepared containing non-randomized and co-randomized constituents.
~he fat blends of Examples I-XIX were used for the preparation of margarine, the blend of Example XX for a low calorie spread and the blends of Examples XXI and XXII
were used as shortenings.
Margarines were prepared as follows: -~he margarine fat blend was melted and emulsified with an aqueous phase prepared from soured milk contain-ing 0.1% monodiglycerides to give an emulsion containing 80% of fat.
~he emulsion was crystallized and worked in a closed tubular surface-scraped heat exchanger (Votator A-unit), which was left at a temperature of 15C. The cooling temperatures in the A-unit were from -6 to -10C and 40% of the treatment emulsion was recirculated. There-after the crystallized emulsion was passed through a resting tube (Votator B-unit), where it crystallized further for 160 sec. and was then liquid-filled into tubs.
~he low calorie spread was prepared as follows:
~or the preparation of a low calorie spread with good spreadab,ility at refrigerator temperature and a very satisfactory melting behaviour, 4t of the fat blend of Example XVIII were mixed with 4 kg of a high-mel-ting distilled monoglyceride and 12.5 kg of a distilled sun-flower oil monoglyceride. ~his fat phase was mixed and .

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emulsified in a normal votator arrangement using less cooling, with 6t of a water phase containing 1% of salt and sufficient citric acid to maintain a pH in the emul-sion of 4.2.
The votated product was tub-filled and possessed ; the described properties in the fresh state and also after 6 weeks' storage at 15C.
The shortenings were prepared as follows:
A specially refined, rather white fat composition was continuously fed in the molten state into a tubular heat exchanger, in which the mass quickly crystallized while sufficient nitrogen (about 20 Vol%) was dosed into the solidifying fat stream, most of the gas being dis-solved under the pressure in the equipment. After heavy but short mechanical working in a high speed crystallizer -under almost normal pressure, the shortening mass was - ready for pack-filling. The final stiffening period was less than 1 minute.
~he co-randomization was carried out as follows:
The fats to be co-randomized were dried to a water content of about 0~01% by weight and subsequently co-randomized at 110C in a stirred vessel which was kept under a vacuum of 2 cm mercury, in the presence of 0.1%
by weight of sodium methoxide as a catalyst. After 20 minutes the mixture was cooled and the vacuum released.
The catalyst was destroyed by washing the co-randomized mixture with water and dried as before.
Preparation of hardened fats:
:
Palm ~, having a melting point of 38C, was heated in a hydrogenation vessel to 120C under hydrogen gas, .:

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10~5893 then 0.5% of a sulphurized Ni-on-guhr catalyst was added and the hydrogenation started. After 90 mins. at 180C
hydrogen supply was stopped and the oil was filtered free of catalyst. The hardened palm oil obtained had a melt-ing point of 42C, a trans-fatty acid content of 30%, and contained 50% H-, 1% M- and 29% L-fatty acids.
So~bean oil was treated in a similar way as de-scribed above; however, the initial hydrogenation temper-ature was held at 140C for 2 hours before the tempera-ture was allowed to rise to 180C after addition of 0.2%
of fresh Ni-on-guhr catalyst for a further 1.5 hours.
After filtration of the catalyst, the hardened bean oil ; had a melting point of 43C, and showed the followlng fatty acid class composition: ~ = 55%, H = 30%~ M ' oO5%
and L = 14.5%.
~ ~a-~e~eed Oil was hJ-drogenated with 0.3,~ of n^r-sulphurized active Ni-catalyst at 190C until the final iodine value was below 1. ~he melting point then was 70C.
20 kg of peruvian fish oil, iodine value 190, was hydrogenated at 145C in the presence of 0.5% of fresh Ni-on-guhr catalyst, said catalyst containing 60% of Ni on dry weight. After 90 minutes the iodine value had dropped to 150 and the temperature was then allowed to rise to 180-185C for a further 120 minutes. After that period the hydrogen gas supply was stopped and the oil filtered after cooling to 85C under an atmosphere of carbon dioxide. ~he final iodine value of the harden-ed fish oil was 70, and the m.p. 41C. ~he fatty acid oomposltion of the oil was ~ = 40%, H = 40.5% and M r 8%~ -' ' , ' ' ' , c~
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~i 1045~93 Neutralized and bleached so~bean oil, I.V. 132.8, was subjected to a first hydrogenation step at 10~C
using 0.1% Ni based on oil as a fresh, nonsulphurized on-guhr catalyst. After reaching of an iodine value of 95 and a m.p. of 28.5C, the catalyst was filtered off.
The fatty acid composition of the oil was H = 21%~ ~ =
r 22%, M = 0%.
j Part of this hydrogenated soybean oil was further ! hydrogenated at 1800C after addition of 0 4% of a sulphur-ized Ni-catalyst up to a m.p. of ~6C. After filtration the oil had a fatty acid composition of H = 22%, ~ = 56%, M = 0.
~he composition of the fat blends, expressed in proportions of fats and fatty acids, as well as t~e di-~; 15 latometric characteristics are compiled in the accompany-ing table.
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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Fat blend having dilatation values at 10°C of at most 1000, at 20°C at least 200 and at 35°C of no more than 75, and containing from 20-80% by weight of a palm-based fat, consisting essentially of hydrogenated or unhydrogenated palm oil, or solid or liquid fractions thereof, or mixtures thereof, which comprises from 35-85% by weight of a co-random-ised and the balance of a non-randomised part, the co-randomised part comprising the palm-based fat, an hydrogenated or unhydro-genated fat containing substantial proportions of glycerides of lauric acid, and a trans-containing fat prepared by hydro-genating liquid oils in an iso-promoting way to semi-solid fats having a trans-fatty acid content of 20-75% or fractions thereof, the non-randomised part containing such fats that the fat blend contains 18-50% saturated fatty acids with 16-24 carbon atoms, 3-25% mono-trans unsaturated fatty acids with 16-24 carbon atoms, and 3-30% saturated fatty acids with 12-14 carbon atoms.

2. Fat blend according to claim 1 containing in total 10-45% of saturated fatty acids of 12 to 14 carbons and mono-trans unsatured fatty acids of 16 to 24 carbons and no more than 60% of saturated and mono-trans unsaturated fatty acids of 16 to 24 carbons.

3. Fat blend according to claim 1 comprising a minor proportion of the non-randomised and a major proportion of the co-randomised part.

4. Fat blend according to claim 1 in which the co-randomised part contains 5 to 35% by weight of said fats con-taining substantial proportions of glycerides of lauric acid, 10 to 50% by weight of said palm-based fat, and 10 to 50% by weight of said trans-containing fat, based on the weight of the total fat blend.

5. Fat blend according to claim 4 in which the percentage of said palm-based fat in the co-randomised part is 15 to 45% by weight.

6. Fat blend according to claim 1 in which the non-randomised part comprises 0 to 25% of said fats containing substantial proportions of glycerides of lauric acid, 0 to 50% of liquid oils, 0 to 25% said palm-based fat and 0 to 35%
of said trans-containing fat.

7. Fat blend according to claim 1 in which unhydro-genated palm oil is used as said palm-based fat.

8. Fat blend according to claim 1 in which high trans-containing fats are used of a trans-content of 50 to 70%.

9. A margarine fat according to claim 1 which is suitable for refrigerator-type margarines, and having dilata-tion values at 10°C of no more than 700 and at 35°C of no more than 50, comprising 45 to 70% by weight of co-randomised consti-tuents, the remainder being non-randomised constituents, the co-randomised part comprising 20-45% of unhydrogenated palm oil, 5-30% of said fat containing substantial proportions of glycerides of lauric acid, the balance being hydrogenated trans-containing fats.