DE1070908B - - Google Patents

Description

GERMAN

kl. 53 h 1/01

INTERNAT. KL. A 23 d

PATENT OFFICE

U4723iVä / 53h

fcUjusj;

REGISTRATION DATE: 10th 1957

NOTICE

LOGIN ρ

AND ISSUE OF, '

EDITORIAL: DECEMBER 10, 1959

The invention relates in particular to a method for producing a cocoa butter-like fat for confectionery.

The invention is based on the knowledge that certain fractions of partially hardened palm oil 5 for the total or partial replacement of cocoa butter in products in which cocoa butter is usually used is processed, e.g. B. in couvertures for confectionery, can be used.

It is known that cocoa butter and palm oil both in their glyceride composition and in the Amount of triglycerides present show significant differences. As the behavior of fats is essentially influenced by these factors during melting, it was by no means foreseeable that a fat fraction could be obtained from palm oil, both on its own and in mixtures with cocoa butter Has properties that largely correspond to the characteristic properties of cocoa butter.

It is not yet known to use palm oil fractions as a cocoa butter substitute. It's a suggestion known to use slightly hardened palm oil for confectionery, but a slightly hardened palm oil is both with regard to its physical properties and to its behavior in mixtures with Cocoa butter is very different from the fractions provided according to the invention.

After all, it is the manufacture of a cocoa butter substitute from cottonseed oil through hydrogenation and then Fractionation has been described. In the known method, the lowest melting point Fraction used, the iodine numbers being between 44.8 and 53.9. That according to the known The product obtained in the process is only a conditionally useful cocoa butter substitute because it is mixed with cocoa butter a significant lowering of the melting point or the softening point brings about. The other properties that cocoa butter possesses are also used when it is used of the product of the known process mixed with cocoa butter.

According to the method according to the invention are partially hardened palm oil fractions with a Iodine number of at most 45, preferably not more than 42, a dilatation at 20 ° C of at least 1000 and a dilatation at 35 ° C of a maximum of 600. All values for the dilation, which are mentioned here, were determined according to the method described below.

According to the invention, it is expedient to work in such a way that palm oil is partially hardened and partially from it hardened oil by fractionating a fraction with an iodine number of 45 or less, preferably Process for the production of a fat similar to cocoa butter

Applicant: Unilever N.V., Rotterdam (Netherlands)

Representative: Dr. E. Wiegand, Munich 15,

and Dipl.-Ing. W. _Niemann,: .. '.

Hamburg 1, Ballindamm 26, patent attorneys ■ ::> ■

Claimed priority: Great Britain dated; 10. ^! August 1956, · ■■

Antony Crossley, Wallasey,

and Stanley Paul, Birkenhead (Great Britain), have been named as inventors

no more than 42, a dilatation at 20 ° C of at least 1000 and a dilatation at 35 ° C of at most 600. · ■■ · ■ · - ■■■■ '- ■ -. ■: ■■

For the production of products in which cocoa butter is usually processed, at least part of the cocoa butter can be obtained from a fraction obtained from partially hardened palm oil with an iodine number of at most 45, preferably not more than ^l42 , a dilatation at 20 ° C of at least 1000 and one Dilatation at 35 ° C of a maximum of 600 must be replaced. '

The execution of this process depends on the iodine number and the dilatation of the palm oil fraction used. There are z. As the kind of the product, the fraction to be incorporated werden'soll, ¹ in the cocoa butter replaced the desired quality of this product and the extent of the fraction into consideration. . _: . · -;

This is how it is, for example, with application. the fraction in chocolate as a substitute for a large part or virtually all of the commonly available cocoa butter required that dilation at 20 ° C the fraction is large enough to produce the To give chocolate the desired physical properties. The fraction must also be at body temperature practically melt completely. When it is used to add a smaller portion of the cocoa buttef replace, the dilation may be lower at 20 ° C,

909 688/241

and it is not necessary that the fraction completely melt at body temperature.

If the fraction z. The dilatation at 20 ° C of the partially hardened palm oil fraction of the invention, at least 1750 and the dilatation at 35 ⁰ C according to exceed 200; B. serves to replace almost completely the cocoa butter in chocolate must. If it is used to replace half of the cocoa butter, for example, good results are obtained with a dilatation at 20 ° C of at least 1500 and a dilatation at 35 ° C of at most 300, while replacing about 25% of the cocoa butter Fractions with a dilatation at 20 ° C of at least 1100 and with a dilatation at 35 ° C of at most 400 are suitable.

The most widely used are the fractions according to the invention with an iodine number of 30 to 40, preferably not higher than 35, a dilatation at 20 ° C of at least 1500, preferably not below 1750, and a dilatation at 35 ° C of no more than 30, preferably not more than 200.

The hardened palm oil fractions can be mixed with cocoa butter before processing and the invention also encompasses the preparation of mixtures of cocoa butter and a fraction with the above properties.

The hardness of the palm oil from which the fractions are made is to a large extent different from the for the fraction desired properties dependent. Usually the oil will have an iodine value of not less than 10, and preferably not less hardened than 25. The hardening is preferably carried out under such conditions that as little isooleic acids as possible form, e.g. B. using relatively low temperatures, e.g. B. below 120 ° C, and very active sulfur-free catalysts. However, you can also use catalysts such. B. by If sulfur is a bit poisoned, use it to harden the palm oil.

In order to obtain the fractions according to the invention from partially hardened palm oil, it is necessary to to remove either a high melting point fraction or a low melting point fraction or both, and depending on the degree of hydrogenation of the palm oil, the conditions under which hydrogenated and the properties desired for the fraction. From the iodine number and the dilatations of the hardened palm oil can be seen whether a substantially refractory fraction or an essentially low-melting fraction must be removed in order to obtain a fraction according to the invention or to obtain at least one fraction modified in this direction. From the iodine number and the dilatations of the products obtained, one can deduce which other fractions then, if necessary must be removed. In order to obtain the preferred fractions it is usually necessary to have both to remove high and low melting fractions from the hardened palm oil.

The easiest way of fractionation is to use a solvent. At the im Fractionation described below was essentially anhydrous acetone as the solvent used. But you can also use other practically anhydrous solvents, e.g. B. ether or light gasoline, apply, changing the solvent lengths and working conditions used accordingly are, which does not cause any particular difficulties. To remove a specific fraction, a simple crystallization will suffice, but it may be advantageous to carry this out in two or more stages.

An amount of acetone of 3 to 10 ml per gram of fat can be used to remove the low-melting glyceride fraction. This amount of acetone can be reduced if the number of crystallizations or wash operations \ ^r is ergrößert. The temperature during the crystallization depends on the conditions chosen, in particular on the amount

ίο of the solvent. At ratios of the order of magnitude indicated temperatures may be employed of from about -3 to +6 ⁰ C.

One can cool in different ways. The oil can be dissolved in acetone at 15 ° C or above and cool the solution to the desired temperature. The solution can be cooled down undisturbed but the time required to do this is significantly reduced (up to 20 to 30 minutes instead of many hours) if it is stirred vigorously. The cooling can also take place in that part of the Solvent is distilled off under reduced pressure. Another method is cold To mix acetone with hot oil, the temperatures of these substances being chosen so that the mixture receives the desired crystallization temperature.

The crystallization temperature becomes preferable

. Maintain this until no further precipitation takes place. The precipitate can then be filtered off preferably using vacuum or pressure. This can be done either on or after removal washed off the filter with chilled acetone at 1 to 2 ° C below the crystallization temperature will.

According to another method, which gives very satisfactory results, the mother liquor and the washing liquids are decanted instead of filtered. In order to obtain suitable crystals for this purpose, one should the acetone solution have a temperature above 30 ° C before the cooling starts and throughout Be stirred cooling. Under these conditions the crystals settle quickly and the Mother liquor to be decanted. The degree to which melting fractions from the crystal mass removed depends on the number of washing treatments; usually four to six are sufficient Washing processes. After each washing, the washing liquid is decanted; this can then be advantageous can be used for the crystallization of a new quantity of the material to be processed.

The removal of a high-melting glyceride fraction can be carried out by similar methods are, preferably 4 to 20 ml of acetone per gram of oil and a crystallization temperature of 15 to 30 ° C. If both high and fractions that melt at low temperatures are also to be removed, it does not matter which of the two fractions is removed first.

The product can be refined at any stage in the process, i.e. prior to hydrogenation or before or after fractionation.

The fractions obtained from hardened palm oil according to the invention can also offer advantages to be mixed with certain fats other than cocoa butter, and the invention also includes the manufacture of mixtures of these fats with the fractions of hardened palm oil.

Naturally occurring vegetable fats suitable for this purpose are Borneo alga, the common one under the name Illipebutter

comes and can be obtained from Shorea robusta and Shorea stenoptera, and that from Allanblackia floribunda, Allanblackia Stuhlmannii, Garcinia indica, Fats obtained from Pentadesma butyracea, Palaquium oleosum and Butyroepernum Parkii.

The. The proportions in which these fats can be added to the hardened palm oil fraction depend on on the type of fat and the palm oil fraction. The minimum ratio is usually around 20% Mix, but it can also be larger ίο Quantities, e.g. B. 50 to 75% or more can be used.

A method and an apparatus are used to determine the dilatations for the present purpose used, which in section C-IV3e (52) of the »D.G.F. Uniform methods «, published by the German Society for Fat Science V., are described.

Special measures are required to stabilize the fat before determining the dilation.

The dilatometer is filled with the grease sample and water according to the instructions and then turned on Water bath placed at a temperature of 60 ± 0.05 ° C, while the water level is about 3 cm above the top of the cut glass connection of the dilatometer. After the volume of the dilatometer has become constant, the meniscus is read. The dilatometer will now be on for IV2 hours Ice placed. The fat is then stabilized by gradually increasing its temperature up to 26 ° C leaves. To do this, the dilatometer is kept at this temperature for 40 hours, whereupon it is repeated IV is chilled on ice for 2 hours. The dilatometer is then placed on a water bath and its temperature is kept at 20 ± 5 ° C, and the meniscus, after a constant volume is reached, read again.

The D. G. F. Standard Methods procedure is then followed; the dilatations can be calculate in a lighter way.

The invention is explained in more detail below with the aid of a few examples.

example 1
a) Preparation of the catalyst

45

20 g of kieselguhr good quality (93.1 ^'1 Vo ash) were added 700 ml of distilled water was added and the mixture was heated to boiling. 15.4 ml of a 3.4 N solution of pure sodium carbonate were added to this boiling solution, and immediately thereafter a 10% aqueous nickel nitrate solution (Ni (NO ₃ ) ₂ · 6H ₉ O) and at the same time a 3.4N- Sodium carbonate solution. The latter solutions were added at a rate of 2 ml per minute, each of the solutions in a total amount of 400 ml. The reaction mixture was continuously boiled during the addition. The final mixture was filtered and the filter cake was washed with hot water until the filtrate reacted neutrally to phenolphthalein and no more precipitate formed with barium chloride solution. The filter cake was removed from the filter, dried at 110 to 120 ° C and finally pulverized.

9 g of the filter cake were converted into a pyrophoric catalyst with hydrogen at 500 ° C. for 75 minutes reduced, which was immediately added to 700 g of the palm oil to be hardened with an iodine number of 53.8 became. The palm oil contained 0.5% nickel.

b) hydrogenation '/

The catalyst-containing palm oil prepared in the above manner was subjected to atmospheric pressure at 100 ° C under vigorous. Stir hydrogenated for 45 minutes. The oil was then filtered off; it had one Iodine number of 27.8.

c) Fractionation . '■'. ■: ■

1. 350 g of the hardened palm oil with an iodine number of 27.8, that in the hydrogenation described under b) was dissolved in 3500 ml of anhydrous acetone at 48 ° C (in all in this description given examples, the acetone was practically anhydrous). The solution was under weak Stirring cooled down to 22 ° C; it was then left to stand for 20 minutes and then filtered off. Of the Filter cake was washed with 300 ml of acetone at 22 ° C, removed from the filter with 700 ml of acetone stirred at 22 ° C, filtered again and finally washed with 300 ml of acetone at 22 ° C. The first filtrate and the three washes were combined and the acetone removed, leaving a fraction of 182 g with an iodine number of 40.3 was obtained. The solid filter cake was discarded. . ,. '

2. 177 g of the product with an iodine number of 40.3 according to 1 were dissolved in 1770 ml of acetone at 50.degree. The solution was cooled to 0 ° C. with gentle stirring, allowed to stand for 20 minutes and then added filtered. The filter cake was washed with 300 ml of acetone at 0 ° C, removed from the filter, with Stirred 500 ml of acetone at 0 ° C, filtered again and finally washed with 300 ml of acetone at 0 ° C. The filtrate and washes were discarded. The filter cake freed from acetone passed from 112 g of a product with an iodine number of 32.4. , '■'

3. 111 g of the product with an iodine number of 32.4 according to 2 were dissolved in 1110 ml of acetone at 50.degree. The solution was cooled to 18 ° C. with gentle stirring and filtered off after standing for 20 minutes. The filter cake was washed with 200 ml of acetone at 18 ° C. The filtrate and washing liquids were united; after evaporation of the acetone was 79 g of a product with a Iodine number of 43.5 was obtained, corresponding to an overall yield of 23.4%. The solid filter cake was thrown away.

The product had a dilatation of 1880 at 20 ° C and 125 at 35 ° C.

Example 2

1. 401.5 g of the hardened palm oil, prepared according to Example 1, b), were dissolved in 4015 ml of anhydrous acetone dissolved at 48 ° C. The solution was cooled to 18 ° C. with gentle stirring and allowed to stand for 20 minutes and filtered off. The filter cake was washed off the filter with 300 ml of acetone at 18 ° C removed, stirred with 1000 ml of acetone at 18 ° C, filtered again and washed with 300 ml of acetone at 18 ° C. The filtrate and three washes were combined and the acetone removed, with 193.5 g of product were obtained. The solid filter cake was discarded.

2. All of the product obtained according to 1 was dissolved in 1935 ml of acetone at 50.degree. The solution was cooled to 0 ° C. with gentle stirring and filtered off after standing for 20 minutes. The filter cake was washed with 300 ml of acetone at 0 ° C, removed from the filter, stirred with 700 ml of acetone at 0 ° C, filtered again and finally with 300 ml

Acetone washed at 0 ° C. The filtrate and washes were discarded. After this the acetone had been removed, the filter cake consisted of 124.2 g of a product with an iodine number of 43.8.

3. 120 g of the product with an iodine number of 43.8, obtained after 2, were dissolved in 1200 ml of acetone at 49.degree. The solution was cooled to 16 ° C. with gentle stirring and filtered off after standing for 20 minutes. Of the The filter cake was washed with 50 ml of acetone at 16 ° C. After removing the acetone from the filtrate and the washing liquids, 102 g of a product with an iodine value of 35.5 were obtained. The total yield was thus 26.3%. The solid filter cake was discarded.

The product had a dilatation of 1905 at 20 ° C and 205 at 35 ° C.

Example 3

a) Preparation of the catalyst

18 g of catalyst cake, which was prepared and reduced according to Example 1, a), was melted directly into 700 g Introduced palm oil with iodine number 53.8, which contained 0.4 g of dissolved sulfur. The palm oil was hydrogenated at 180 ° C. with rapid stirring for 5 hours; the end product had an iodine number of 33.8.

The catalyst was then filtered off from the oil and washed on the filter with two portions of 50 g of molten palm oil with an iodine number of 53.8. The oil-containing catalyst cake was mixed with 700 g of palm oil with an iodine number of 53.8. The palm oil then contained 1.0% nickel.

b) hydrogenation

The catalyst-containing palm oil prepared in the above manner was heated at 180.degree. C. under atmospheric pressure Hydrogenated with vigorous stirring for IV2 hours. The oil was then filtered off and then had an iodine number 41.0.

^; c) fractionation

1. 370 g of a hardened palm oil with an iodine number of 41.0 according to b) were dissolved in 3700 ml of anhydrous acetone at 48.degree. The solution was cooled to 0 ° C. with gentle stirring, left to stand for ¹ minutes and then filtered off. The filter cake was washed with 300 ml of acetone at 0 ° C, removed from the filter, stirred with 700 ml of acetone at 0 ° C, filtered again and finally washed with 300 ml of acetone at 0 ° C. The filtrate and washes were discarded. The filter cake persisted. Removal of the acetone from 237 g of a product with an iodine number of 33.3.

; i2. 218g of a product with an iodine number of 33.3 according to 1 Were dissolved in 2180 ml of acetone at 50 ° C. The solution was allowed to rise to 25 ° C. with gentle stirring cooled and left to stand for 20 minutes, then filtered. The filter cake was washed with 400 ml of acetone at 25 ° C washed. The filtrate and the washing liquid were combined and the acetone removed, wherein. 136g fine product with iodine number 40.0 was obtained. Of the solid filter cake was discarded.

'S! 133 g of the product with an iodine number of 40.0 according to 2 were dissolved in 1330 ml of acetone at 50 ° C. The solution was brought to 0 ° C. with gentle stirring ■ chilled. It was allowed to stand for 20 minutes and then filtered. The filter cake was with 100 ml Acetone washed at 0 ° C, removed from the filter, "stirred with 250 ml of acetone, filtered again and closed, borrowed washed with 100 ml of acetone at 0 ° C. The filtrate and washes were discarded. Of the After removal of the acetone, the filter cake consisted of 111 g of a product with an iodine number of 37.8.

4. 102 g of the product with an iodine number of 37.8 according to 3 were dissolved in 1020 ml of acetone at 49.degree. the The solution was cooled to 20 ° C. with gentle stirring, left to stand for 20 minutes and filtered. Of the The filter cake was washed with 200 ml of acetone at 20 ° C. The filtrate and the washing liquid were combined and the acetone removed, 69.5 g of a product having an iodine number of 40.0 were obtained. The overall yield was 22.6%. The solid filter cake was discarded.

The product obtained had a dilatation of 2095 at 20 ° C and of 545 at 35 ° C.

Example 4

Milk chocolate was produced with the following composition:
ao 300 g "milk refiner paste" (76 g cocoa butter and

Containing 16g milk fat),
36 g extra fat.

The trough of a conche was heated to 40 ° C, whereupon the refiner paste and the additional fat slowly were supplied with heating. The chocolate mixture was heated up to 45 to 50 ° C and Maintained at this temperature for 2 hours. It was placed in a porcelain vaporizing dish with a Introduced in diameter of 22.5 cm, in which it was stirred in such a way that as few air bubbles as possible were formed. Stirring was continued until the mass became too stiff. The chocolate mixture was on top again carefully heated to a point where it could just be poured out, avoiding local overheating. The molten mixture was poured into molds cooled to 11 to 12 ° C, tapping to remove any air bubbles. The filled forms were at 11 to 12 ° C in a refrigerator. After 48 hours, the molded chocolate bars were made from the Molds removed, stored at room temperature (19 ° C) for 4 days and checked for it.

Chocolates were made in the above manner with the addition of the following fats:

a) a mixture of 10.2 g of cocoa butter and 25.8 of the product of Example 2, Section 3 with iodine number 35.5, a dilatation of 1905 at 2O ⁰ C and 205 g at 35 ° C;

b) a mixture of 10.2 g of cocoa butter and 25.8 g of the product according to Example 3, Section 4 with Iodine number 40.0, a dilatation of 2095 at 20 ° C and of 205 at 35 ° C.

Claims (5)

Patent claims: 1. A method for producing a cocoa butter-like fat, in particular for confectionery, thereby characterized in that palm oil is partially hardened and a lot of the go from it by fractionation low melting glycerides and also the highest melting glycerides removed that one a fraction is given which has an iodine number of at most 45, a dilatation at 20 ° C of at least 1000 and a dilatation at 35 ° C of no more than 600, and if necessary with cocoa butter mixes. 2. The method according to claim 1, characterized in that the palm oil has an iodine number of at least 10, preferably at least 25, is hardened before the fractionation takes place. 3. The method according to claim 1 or 2, characterized in that a fraction is produced which has an iodine number of no more than 42. 4. The method according to claim 1 to 3, characterized in that a fraction is produced which has a dilatation at 20 ° C of at least 1500, preferably at least 1750. 5. The method according to claim 1 to 4, characterized in that a fraction is produced which has a dilatation at 35 ° C of at most 300, preferably 200. Considered publications: German Auslegeschrift H 14530 IVa / 23a (published on May 24, 1956); Bailey, "Industrial oil and fat products," 1951, pp. 138-140; M. Loury, "Oleagineux," 1947, p. 185; Koch, "International Trade Journal for the Chocolate Industry", 1954, pp. 289 to 295; H. R. Jensen, “The Chemistry, Flavoring and Manufacture of Chocolate Confectionary and Cocoa ", 1931, pp. 183, 184. © 909 688/241 12.