CH666160A5 - PROCESS FOR TREATING COCOA BUTTER. - Google Patents

Description

DESCRIPTION

The object of the present invention is to improve the physical properties of cocoa butter.

Some cocoa butters are not directly usable in the manufacture of chocolate because their physical properties do not meet the required compliance criteria. Being too soft, they cannot give the chocolate the hard and brittle character desirable at room temperature. Having a too low solidification point and too wide a melting range, they do not provide the sensation of rapid melting in the mouth characteristic of chocolate. However, it would be desirable to be able to use them, given the world deficit in cocoa butter.

We have undertaken various tests to improve the melting behavior of these cocoa butters.

- Their deodorization had improved their organoleptic performance without influencing their physical properties.

- Their partial hydrogenation in the presence of nickel as catalyst had indeed increased the proportion of saturated fatty acids in the triglycerides, but had simultaneously caused the formation by isomerization of triglycerides of unsaturated fatty acids with high melting point, so that butter hardened cocoa had partly lost its ability to melt quickly, its melting range being too wide. In addition, the total elimination of the catalyst had required careful refining including neutralization and treatment with bleaching earth followed by deodorization.

- On the other hand, the addition of a compatible vegetable fat harder than cocoa butter such as illipe butter had improved both the hardness and the melting behavior of soft cocoa butter. However, the application of this method is limited by the fact that such addition is not allowed in many countries.

- Finally, fractionation by solvents, for example with acetone under the conditions described in the published French patent application No. 2,415,138 (corresponding to the British patent

No. 2.013.705) in conjunction with lactic fat or palm oil, had led to the production of a solid fraction and a semi-solid fraction at room temperature. It had not allowed the frank separation of a liquid fraction at room temperature despite prolonged crystallization under the temperature conditions indicated. The use under the same conditions of other solvents mentioned in general, for example isopropanol or hexane, did not lead either to a frank separation of a liquid fraction at room temperature or n 'had not allowed crystallization.

In the present description, by ambient temperature is meant a temperature of 20 to 30 ° C.

These difficulties are explained by the fact that cocoa butter is composed of a relatively small number of triglycerides of neighboring structure and physical properties in continuous equilibrium with each other. To simplify, it essentially comprises the mono-unsaturated triglycerides l, 3-dipalmitoyl-2-oleoyl-glycerol (POP), l-palmitoyl-2-oleoyl-3-stearoyl-glycerol (POS) and 1,3-di-stearoyl -2-oleoyl-glycerol (SOS), solid at room temperature, and the di-unsaturated triglycerides l-palmitoyl-2,3-dioleoyl-glycerol (POO) and l-stearoyl-2,3-dioleoyl-glycerol (SOO) , they are liquid at room temperature.

The tests carried out therefore tended to show that the fractionation into a liquid phase and into a solid phase at ambient temperature was a priori not possible by simple crystallization by solvents.

We have found that cocoa butters with a low solidification point can be split and fractions can be used, among others, in confectionery-chocolate.

The invention relates to a process for treating cocoa butter which is not directly usable in the manufacture of chocolate, characterized by the fact:

a) mixing the melted cocoa butter and, if necessary, pre-refined with hexane in the proportions by weight cocoa butter: hexane from 1: 2 to 1:10,

b) the mixture is cooled to -10 ° to 0 ° C. and kept at this temperature for at least 6 hours, until dense nodular crystals are formed,

c) that a fraction which is solid at room temperature and a fraction which is liquid at room temperature is separated at the crystallization temperature, and d) that the hexane is removed from the fractions obtained.

A cocoa butter which can serve as a raw material in the process according to the invention can be characterized by:

- a relatively high iodine index (IV), greater than 38,

- a solid fat index (SFI) at 30 ° C of less than 40% by weight, and

- a cooling curve (CC) showing a minimum temperature (T min.) Of around 16 ° C and a deviation of the minimum and maximum temperatures (A) from 3 to 5 ° C.

In this talk:

- The iodine index (IV) is the number of grams of iodine fixed per 100 g of fatty substance. It is a function of the degree of unsaturation of the fatty acids contained in the triglycerides. It is determined by titration with sodium thiosulfate of the iodine released by the addition of potassium iodide in a solution containing the fatty matter and

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666160

iodine chloride (reagent) by comparison with a reference solution of the reagent without fat (method 2.205,1.U.P.A.C. "Standard methods for the analysis of oils, fats and derivatives", Pergamon Press, 6th edition 1979).

- The solid fat index (SFI) is obtained by determining the fat melting curve. It is the percentage of solid fat existing in the partially melted fatty body at a given temperature, by NMR (nuclear magnetic resonance of the proton) drawn (I.U.P.A.C., 1st supplement, 1982,

method 2.323).

- The cooling curve (CC) is obtained by studying the behavior of the fat on cooling giving its solidification point under well-defined conditions (Shukoff method, reference temperature 0 ° C, I.U.P.A.C., method 2.132).

Such a raw material comes from the pressing of the roasted cocoa liquor from which the liquid part is collected.

Preferably, the raw material can be pre-refined. That is to say, it has undergone a treatment in molten form with activated carbon or other adsorbents, for example bleaching earths based on activated aluminum silicate such as montmorillonite or bentonite, followed by separation by filtration or spinning so as to remove the residual finely dispersed solids.

To carry out the process of the invention, the cocoa butter can be dissolved in hexane, preferably in the cocoa butter proportions of 1: 2 to 1: 5 and at a temperature of 40 to 60 ° C., then cool the solution by placing it in a thermostatically controlled crystallizer, preferably at a temperature of -10 to - 5 ° C with or without stirring.

Alternatively, the melted cocoa butter may be mixed, preferably at a temperature of 40 to 60 ° C, with the cooled hexane, preferably at a temperature of -10 to - 5 ° C.

We first observe the appearance of gelatinous crystals in milky mother liquors, then these become dense and appear in the form of nodules, while the mother liquors become clear. The minimum duration of crystallization is determined by this transformation of the crystals. It must be at least 6 hours and preferably around 24 hours. The nodular crystals can be collected by filtration using a vacuum filtration device or alternatively by decantation or spinning.

The crystals can be washed with cooled hexane, preferably during spinning, then melt the washed crystals, filter the solution if necessary and remove the hexane, for example by evaporation under vacuum. This collects the stearin.

The mother liquors of crystallization contain olein. They can be filtered if necessary, then the hexane is removed, for example by vacuum evaporation.

According to a variant of the process, which is preferred, the olein is crystallized from which the hexane has been removed. To do this, the molten olein is dissolved in pre-cooled hexane, preferably at a temperature of -10 to -5 ° C and in the olein: hexane proportions of approximately 1: 2, then the solution is maintained. at a temperature of -10 to -5 ° C, preferably with slow stirring, for example 10-20 rpm for at least 6 h. The additional stearin crystals are then separated, for example by wringing. The mother liquors of this second spin contain olein. Finally, the hexane is eliminated from the various fractions as above.

Preferably, the desolventized fractions are treated by vacuum steaming under conditions which do not cause isomerization, preferably under a pressure of 1.3 to 4 mbar and at a temperature below 220 ° C., for example of the order of 200 ° C, so as to eliminate all traces of hexane.

Stearin melts quickly at body temperature and, as a result, finds many applications in confectionery and biscuit making to replace cocoa butter, for example in pharmacies as a drug carrier, for example as a suppository.

In chocolate, it can be mixed with cocoa butter having a low solidification point with which it is perfectly compatible, preferably at a rate of 10 to 20% by weight, which allows this cocoa butter to be used to make chocolate.

Alone or mixed with cocoa butter which can be used directly, it makes it possible to make chocolates resistant to the conditions prevailing in hot and / or tropical countries.

Oleine is suitable for confectionery as an ingredient in spreads or pastry or praline furs, preferably at a rate of 8 to 15% by weight of the spread or fur. It can also be used in cosmetic compositions, for example in lip sticks, creams or lotions, preferably in an amount of 5 to 20% by weight of the composition.

The following examples, in which the proportions and percentages are by weight unless otherwise indicated, illustrate the invention.

Example 1:

21.5 kg of cocoa butter (IV = 40) is melted in a water bath at 60 ° C., 125 g of bleaching earth based on activated aluminum silicate are added thereto and the suspension is stirred for 10 min . After separation of the adsorbent by wringing, filtration of the liquid on paper using a Büchner funnel in the presence of 300 g of filtering earth and under a pressure of 20 mbar (15 mmHg), 21 kg of butter are obtained. pre-refined cocoa.

42 kg of hexane are mixed with pre-refined cocoa butter (fraction rectified at 65-69 ° C), the mixture is cooled to -5 ° C and kept at this temperature for 24 h without stirring. Abundant crystallization occurs. The crystals formed are then drained at 5 ° C while washing with 25 kg of hexane at 5 ° C. The crystals washed in a water bath at 80 ° C are then melted, the liquid is filtered on paper, then evaporate the hexane in a water bath at 60 ° C using a rotary evaporator under a pressure of 20 mbar (15 mmHg). 17.2 kg of a solid fraction at room temperature or stearin are thus collected (yield relative to pre-refined cocoa butter = 81.9%).

The mother-of-spin water contains the liquid fraction (olein) which is filtered on paper. The hexane contained in the filtrate is evaporated by means of a rotary evaporator brought to 60 ° C. in a water bath under a pressure of 20 mbar (15 mmHg). 2.7 kg of olein are thus obtained (yield relative to pre-refined cocoa butter = 12.8%).

The physical characteristics of the raw material and of the fractions obtained are indicated in Table I below:

Table I

Cocoa butter

Stearine

Olein

IV

40

36

59

SFI at 30 ° C (%)

40

58

-

CC (0 ° C)

T min.

16

18.6

-

AT

5.2

5.3

-

Example 2:

From 200 kg of cocoa butter (IV = 40), 189 kg of pre-refined cocoa butter are obtained by following the procedure of Example 1.

945 kg of hexane (rectified fraction at 65-69 ° C) previously cooled to -10 ° C are mixed with the pre-refined cocoa butter and the suspension is stirred using a rotary stirrer at 20 rpm. The temperature is maintained at -10 ° C while stirring continuously for 24 h. Crystals are formed which are wrung at -10 ° C. There is thus collected 272.5 kg of stearin containing the residual hexane.

Spin mother liquors representing 710.5 kg contain olein. After evaporating the hexane at 90 ° C under a pressure of 20 mbar, the remaining 56.5 kg of olein are treated with 113 kg of hexane previously cooled to -10 ° C, then the temperature is maintained

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of the mixture at -10: C for 24 h under slow stirring. Crystals are formed which are wrung at -10 ° C. The 23 kg of crystals collected contain residual hexane.

They are added to the 272.5 kg obtained previously during the first spin, then the whole is melted at 70 ° C. The hexane is then evaporated at 70 C under a pressure of 20 mbar, then at 60 ° C under a pressure of 2.7 mbar, so as to eliminate it completely. 148.3 kg of stearin are thus obtained.

The mother liquors of the second spin, representing 138 kg, contain olein. After evaporation of the hexane at 90 ° C under a pressure of 20 mbar, then at 60 ° C under a pressure of 2.7 mbar, so as to eliminate it completely, 37.7 kg of olein are obtained (yield compared to pre-refined cocoa butter = 20%).

The characteristics of the starting cocoa butter and of the fractions obtained are indicated in Table II below:

Example 3:

The stearin and olein obtained according to Example 2 are treated in a continuous falling film deodorizer so as to remove all traces of hexane at 200 "C in the presence of 10% water vapor under pressure 2.7 mbar with a fat flow rate of 1.5 kg / h, the fat remaining 3 min in the device.

After deodorization, the stearin is perfectly neutral and the olein has a typical taste and smell of roasted cocoa.

io Example 4-6:

One proceeds, as in Example 1, to the fractionation of a cocoa butter of iodine index 39 under the conditions indicated in Table III below. The physical characteristics of the fractions obtained and of the raw material are also indicated in Table IV below:

Table II

Cocoa butter

Stearine

Olein

IV

40

34

65

SFI at 30 ° C (%)

33

61

-

CC (0 ° C)

T min.

16.8

19.3

-

AT

4.4

5.2

-

Table III

Ex.

Temperature

Report

Crystallization time

Yield (%)

cocoa butter fractionation: hexane

(h)

(° C)

Stearine

Olein

4

-10

1:10

24

72

28

5

0

1: 5

24

54

46

6

-5

1: 3

24

78

22

Table IV

Ex.

Stearine

IV

Olein

IFC at 30 ° C (%) Stearin

CC (0 ° C) Stearin

T min.

AT

4

32

58

77

18.9

5

5

32

47

77

18.8

5

6

33

59

77

18.8

5

Raw materials

39

34

15.2

5.2

Comparative examples:

The fractionation of the same cocoa butter according to British Patent No. 2,013,705 is tried under the conditions detailed in Table V below:

Table V

Test

Solvent

Temperature

Report

Time to

Yield (%)

cocoa butter fractionation: solvent crystallization

(° C)

(weight: volume)

(h)

Stearine

Olein a

Acetone

15

1: 7.5

16

63

37

b

Isopropanol

15

1: 7.5

18

89

11

vs

Hexane

15

1: 7.5

no crystallization i

The iodine index of the fractions obtained in tests a and b is indicated in the table below:

Table VI

Test

1

IV

Stearine

Olein a

34

50

b

37

60

It appears from previous tests that, despite crystallization times much longer than those recommended in British Patent No. 2,013,705:

- in case a, the olein is not liquid at room temperature, and its too low IV indicates poor separation specificity,

- in case b, the IV of stearin is too high, which is also a sign of poor separation conditions, which is moreover confirmed by the low olein yield,

- in case c, there is no crystallization.

In addition, the solvents acetone and isopropanol are open to criticism from the point of view of food legislation, and acetone is difficult to remove, which is not the case with hexane.

Example 7:

Each of the stearins prepared according to Examples 1 and 2 is mixed in an amount of 20% to 80% of cocoa butter having served as a raw material for their fractionation and the mixtures are used in place of the cocoa butter which can be used directly for making chocolate with milk. The chocolates obtained have physical and organoleptic properties quite comparable to those of chocolates made from cocoa butter which can be used directly.

Example 8:

Stearin is used according to Example 2 in place of the cocoa butter which can be used directly to make milk chocolate at the rate of 20% of stearin for 80% of cocoa butter which can be used directly. The chocolate obtained is harder than a chocolate made from cocoa butter which can be used directly: at 30 ° C it is always hard and brittle. It unmolds more easily, but it also melts very quickly in the mouth. No fatty bleaching is observed. These properties make it suitable for hot and / or tropical countries.

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Example 9:

The olein according to Example 2 lends itself well to the preparation of spread or fur for pralines. 10% olein mixed with sugar, roasted hazelnuts, cocoa powder, skim milk powder, hydrogenated coconut fat and lecithin, the spreads have a smooth texture , a light brown color, a pleasant smell and flavor of cocoa and roasted hazelnuts.

Examples 10-11:

The olein according to Example 2 lends itself well, after having undergone extensive deodorization, for the preparation of the cosmetic compositions below:

Care cream (water-in-oil emulsion)% by weight

Isopropyl myristate 30

Paraffin oil 18

Cocoa butter olein 10

Ozokerite 4

Magnesium lanolate 14.4

Lanolin alcohol 3.6 Butylhydroxyanisole (BHA) + butylhydroxytoluene (BHT) 0.01

Water + preservative q.s.p. 100

Lipstick% by weight White body:

Microcrystalline wax 12

Candelilla wax 2

Synthetic heavy esters (Synchro wax ERLC® from Croda) 4

Castor oil 10

Cocoa butter olein 15

Isopropyl lanolate 15

Liquid lanolin 10

Acetylated lanolin 12

Vaseline 10

Cetyl Ricinoleate 9.8

BHA + BHT (50/50) 0.2

to which 5.4 parts by weight of the following pigments are added per 100 parts by weight of white body:,

Mineral and organic pigments:

Red iron oxide 1,2

Titanium oxide 1.3

D and C red N ° 9 2

D and C red N ° 27 0.4

Perfume 0.5

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Claims (11)

666,160 CLAIMS 1. Process for the treatment of cocoa butter not directly usable in the manufacture of chocolate, characterized by the fact: a) that the melted cocoa butter is mixed with hexane in the proportions by weight of cocoa: hexane from 1: 2 to 1:10, b) the mixture is cooled to -10 to 0 ° C. and kept at this temperature for at least 6 h, until dense nodular crystals are formed, c) that a fraction which is solid at room temperature and a fraction which is liquid at room temperature is separated at the crystallization temperature, and d) that the hexane is removed from the fractions obtained. 2. Method according to claim 1, characterized in that, prior to its mixing with hexane, the melted cocoa butter is treated with an adsorbent and then separated from said ad-sorbent. 3. Method according to claim I, characterized in that, in step a), the cocoa butter is dissolved in hexane at a temperature of 40 to 60 "C and that, in step b), the solution is cooled to a temperature of -10 to -5 C. 4. Method according to claim 1, characterized in that, in step a), the cocoa butter melted at a temperature of 40 to 60 C is mixed with the hexane cooled to a temperature of -10 to -5 vs. 5. Method according to claim 1, characterized in that, in step a), the cocoa butter and the hexane are mixed in the proportions by weight cocoa butter: hexane from 1: 2 to 1: 5. 6. Method according to claim 1, characterized in that the hexane is removed from the liquid fraction obtained in step c) and that it is then subjected to crystallization by subjecting it to the successive operations a) to d). 7. Solid fraction of cocoa butter obtained by implementing the method according to one of claims 1 to 6. 8. Liquid fraction of cocoa butter obtained by implementing the method according to one of claims 1 to 6. 9. A fatty composition usable in confectionery-chocolate comprising, by weight, 10 to 20% of a solid fraction according to claim 7 and 80 to 90% of cocoa butter. 10. Composition for pastry or praline fur or spread comprising 5 to 20% by weight of a liquid fraction according to claim 8. 11. Cosmetic composition comprising 5 to 20% by weight of a liquid fraction according to claim 8.