GB1595734A - Process for the production of vegetable fats - Google Patents

Description

(54) PROCESS FOR THE PRODUCTION OF MODIFIED VEGETABLE FATS (71) We, CADBURY INDIA LIMITED, a Company incorporated under the Indian Com- panies Act, of "Cadbury House" Bhulabhai Desai Road, Bombay 400 026, Maharashtra, India, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to the production of a modified vegetable fat from a natural vegetable fat which is solid or semi-solid.

The modified fat obtained according to the invention has a high melting stearine fraction capable of replacing at least part of the cocoa butter present in chocolate and other confectionary products and of raising the melting point of chocolates and chocolates products.

Cocoa butter, the natural fat of cocoa bean (Theobroma Cacao L) is an essential constituent of all chocolates and of many other confectionary products. In the manufacture of high quality chocolates the roasted cocoa bean is shelled and the nib ground. To this ground nib, which is called cocoa liquor, are added sugar, milk solids, cocoa butter, emulsifiers and flavourings. The physical characteristics of such chocolates arise mainly from the cocoa butter present. Cocoa butter melts completely at 35"C or slightly below body temperature; it is a hard brittle solid at normal room temperature. Cocoa butter is used in chocolates and confectionary products largely because its physical properties contrbute to glossy coatings, absence of waxiness and favourable volume changes in moulding operations.

A great deal of research work has been done by various workers to develop a substitute for at least part of the cocoa butter used during the manufacture of chocolates, i.e. a fat which can be used to make chocolates from partly or completely defatted ground cocoa bean or as a coating for confections. Oils and fats containing essentially C16 and C18 fatty acids would logically be preferred as raw materials for making cocoa butter substitutes. The most common of these are palm oil, cottonseed oil, Borneo tallow and mowrah fat.

The present invention provides a modified fat compatible with cocoa butter and having the following physical characteristics when admixed with cocoa butter and milk fat: - 1. A very short melting range, 2. melting readily in the mouth without having a waxy taste, 3. quick hardening, 4. resistance to formation of grey cast and surface bloom, 5. compatibility with defatted cocoa powder, cocoa liquor and milk fat individually or in mixture, and 6. controlled shrinkage during cooling for satisfactory mould release.

The essential characteristics and measurements necessary to determine the quality and suitability of a cocoa butter substitute for use in chocolate manufacture are: 1. Melting behaviour 2. Melting dilatation 3. Hardness 4. Solidification and super-cooling characteristics 5. Stability towards oxidative rancidity, and 6. Taste and appearance.

The modified fat of the invention does not contain undesirable tannins and phenols.

We have found that cocoa butter substitute meeting the above mentioned requirements can be prepared from vegetable fats, especially ShoreaRobusta Seed Fat, containing substantial quantities of both disaturated and diunsaturated glycerides of C16, C18 and C20 acids.

Sal, botanically known as Shorea Robusta, grows abundantly in the States of Madhya Pradesh, Uttar Pradesh, Orissa and Bihar in India.

Cocoa butter is hard and brittle at 300 C.

Unlike this, sal fat is greasy at this temperature.

This fat crystallises in a coarse and grainy crystalline mass, occluding some liquid fat which tends to separate out on standing. For this reason, sal fat cannot be used as a complete substitute for cocoa butter, even though it melts within a narrow range of 36"C-38"C.

The present invention provides a process for the production of a modified vegetable fat which comprises partially hydrogenating a refined, bleached and deodorised vegetable fat in the presence of a metal hydrogenation catalyst to produce a hardened fat, and subjecting the so-hardened fat to hydraulic pressure within a range of 200-700 p.s.i. at a controlled temperature in the range of 20"C to 350C to remove oily glycerides therefrom.

The vegetable fat prepared by this process contains a hard stenarine fraction uniform in its consistency and free from low melting triglycerides. The purpose of the partial hydrogentation is to harden the liquid fat that separates out from the crystallised sal fat thereby making the fat more stable towards rancidity and uniform in its consistency. The iodine value of raw sal fat varies from 38 to 45. This variation in iodine number is due to the varying amounts of glycerides of polyunsaturated fatty acids present in the raw fat.

The hydrogenation is carried out using a conventional metal catalyst such as nickel, copper, palladium, platinum or a complex catalyst such as copper-chromium using a support of Kieselguhr or any other diatomaceous earth.

The amount of catalyst used is not critical and may be varied, say from 0.02% to 5% by weight or even more, but the usual range is 0.01 to 2%.

The hydrogentation reaction is preferably carried out using a supported fresh nickel catalyst and the suitable temperature range is from about 100"C-190"C. The reaction is carried out at pressures preferably not exceeding 50 p.s.i. and more preferably between atmospheric and 35 p.s.i. The time of hydrogenation may vary e.g. from about 10 minutes to about an hour or more according to the iodine value of the raw material. The hydrogentated fat should preferably contain less than 2% of trisaturated glycerides. A suitable temperature range for solidifying the hardened fat lies between 20 C and 35"C at which temperature the hardened fat in a molten condition is held for 3 to 4 days for complete solification before subjecting it to hydraulic pressing.

Hydraulic pressing of the solidified fat is carried out using a conventional hydraulic press, at a controlled temperature and at a pressure preferably within the range 200-700 p.s.i. Pressure is applied for a sufficient length of time for drainage of liquid oil, e.g. from about 30 minutes to about an hour or more.

The hydraulic pressing of the solidified fat is carried out at a controlled temperature in a range similar to the melting range of the solidified fat itself i.e. 20"C to 35 c.

The hydraulic pressing of solidified fat according to our invention is so devised that 2% to 10 ,Ro of the low-melting triglycerides by weight of the solidified fat is removed. The resulting hard stearine fraction is compatible with cocoa butter and possesses excellent shelflife.

Undesirable tannins and phenols, especially ellagic acid, are present in the raw vegetable fats, for example in raw sal fat. Ellagitannins are complex ester glycosides and occur largely in myrobalans and oak galls.

According to the present invention, in order to remove ellagic acid and ellagitannins from raw vegetable fat, e.g. raw sal fat, a reagent containing sodium acetate and acetic acid buffer (pH 4.5) is used. This reagent is added to the raw sal fat to an extent of 0.5% to 2% by weight as a 10% solution as described and claimed in our copending Application No.

4126/78, Serial No: 1564681. This reagent complexes the ellagic acid present in raw sal fat and removes it. The removal of ellagic acid from raw sal fat by this procedure has been confirmed by using spectrophotometric techniques.

Other vegetable fats such as mowrah, phulwara, and mango kernel can also be used as starting materials individually or in combination with one another or with sal fat for preparation of a cocoa butter extender by adopting similar steps such as partial hydrogenation and solidification followed by hydraulic pressing.

The following Example in which all parts are by weight illustrates the invention: Example A sample of raw sal fat was treated with sodium acetate-acetic acid reagent and then washed with warm water.

On analysis by spectropho tome try it was noticed that after the pre-treatment of raw sal fat with sodium acetate-acetic acid reagent the absorbance at 255 m,u and 366 mu, with reference to phenols similar to ellagic acid and ellagitannins was found to have undergone a sharp reduction.

Neutralisation of the degummed sal fat was carried out successfully with 10% aqueous caustic soda solution at 400 C.

The acid value of the neutralised fat was 0.15. Bleaching of the neutralised fat was carried out at 80 C using activated earth (2% to 5%) and activated carbon (0.2 to 1%) under high vacuum.

The refined and bleached sal fat was then hydrogenated at 1480C in the presence of 0.2% of a fresh nickel catalyst containing 20% Ni on Kieselguhr of a gauge pressure of 25 p.s.i. for a period of 30 minutes in a pressure vessel with stirring, until the iodine value of the fat reached the desired range 35 to 38. Under these conditions of hydrogenation the transisomer content of the product, measured by infra-red absorption spectrophotometry was less than 5% of the total hydrogenated material.

The hydrogenated fat was filtered to remove the nickel catalyst and then post-bleached to remove traces of nickel using bleaching earth.

The hardened fat was completely melted and then solidified by cooling at controlled temperatures held for 4 days. The solidified fat was then subjected to a hydraulic pressure at 500 p.s.i. in order to squeeze out the liquid oil.

After a sufficient length of time for drainage of the oil, the pressure was released and the high melting stearine cake so obtained was subjected to deodorisation. Yield of the stearine fraction thus obtained was 95% to 98% in repeated trials on the basis of hydrogenated refined and bleached fat.

The high melting stearine so obtained melts sharply at about 38.5"C. This is higher than that of cocoa butter by about 3"-14"C, a desirable characteristic for tropical countries. The hard stearine fraction contains one-third unsaturated acids, mainly oleic, which gives it a similarity to cocoa butter although the palmitic-stearic acid ratio is reversed.

For some applications as a coating or confectionery fat, higher melting characteristics than those exhibited by cocoa butter may be required. By blending the hard stearine with cocoa butter, the melting range of cocoa butter can be raised effectively. The hard stearine fraction possesses many of the properties required for multipurpose confectionery and bakery fats. Its thermal characteristics indicate that it is compatible with cocoa butter in wide proportions. It is neutral and bland in flavour and low in polyunsaturated acids which should give it good oxidation stability. The hard stearine is distinguished by exceptional hardness and mechanical strength.

The hard stearine possesses superior resistance to blooming and dulling. This fat exhibited a temperature rise of4 C on solidification as compared with 4.9 C for cocoa butter.

The modified vegetable hard stearine was then tested for cooling curve (Figure 1 of the accompanying drawings), dilatation (Figure 2), fatty acid composition and thermal profile by differential scanning calorimetry (Figure 4) and compared with cocoa butter (Figure 3).

The melting properties of fats are commonly defined by their dilatations at the temperatures concerned, dilatation being the isothermal melting expansion expressed in cubic millimetres and referred to 25 grams of material.

The dilatation of a fat gives an indication of the solids content of the fat at a particular temperature within its melting range. The dilatation tests were carried out by cooling the melted fat to OOC for 90 minutes, tempering it for 48 hours at 26 C and again cooling to OOC before measuring the dilatation at various temperatures. The dilatation results for the hard butter extender along with that of cocoa butter are given in Table 1.

TABLE I Dt Modified Fat Cocoa Butter D20 2260 2040 D25 2020 1900 D30 1810 1490 D35 350 20 D40 85 1 D4s 0 0 The Jensen cooling curve of the hard butter extender was determined as follows:- About 75 g of sample was heated well above its melting point and placed in a test tube (length - 10 cm). A glass loop stirrer and a thermometer were inserted and the assembly was immersed in an air bath at 17 C. The sample was stirred at the rate of six strokes per minute until solidification occurred. A similar trial was carried out with a sample of cocoa butter and the cooling curves of temperature against time for each sample was plotted.These curves are shown in Figure 1 of the accompanying draw ings in which curve 1 indicates the temperature rise on solidification in the case of cocoa butter and curve 2 indicates the same for the modified fat.

The above mentioned modified vegetable fat comprising of high melting stearine fraction was used at various levels such as 5, 10, 15, 20 and 25% by replacing cocoa butter in the manufacture of chocolates. Chocolates so manufactured were found to have similar physical and moulding characteristics to those of standard chocolates.

WHAT WE CLAIM IS: 1. A process for the production of modified vegetable fat which comprises partially hydrogenating a refined, bleached and deodorised vegetable fat in the presence of a metal hydrogenation catalyst to produce a hardened fat, and subjecting the so-hardened fat to hydraulic pressure within a range of 200-700 p.s.i. at a controlled temperature in the range of 20 C to 350C to remove oily glycerides therefrom.

2. A process according to claim 1 wherein the vegetable fat is a fat of sal seed, mowrah, phulwara or mango kernel.

3. A process according to claim 1 wherein the vegetable fat is a mixture of sal seed fat with the fat of mowrah, phulwara and/or mango kernel.

4. A process according to claim 1 wherein the vegetable fat is a mixture of fat of mowrah, phulwara and mango kernel.

5. A process according to any of the preceding claims wherein the partial hydrogenation is carried out at about 100"C-1900C and at a pressure not exceeding 50 lb. p.s.i.

6. A process according to claim 5 wherein the pressure is between atmospheric pressure and 35 ib. p.s.i.

7. A process according to any of the preceding claims wherein the metal catalyst is a supported fresh nickel catalyst.

8. A process according to any of the preceding claims wherein the hardened or hydrogenated fat contains less than 5% trisaturated glycerides.

9. A process according to any of the preceding claims wherein the hydraulic pressure is applied for at least 30 minutes.

10. A process according to any of the preceding claims wherein the hydraulic pressure removes 2 to 10% of liquid oil by weight of the hydrogenated fat.

11. A process according to any of the preceding claims wherein the vegetable fat prior to partial hydrogenation is treated with a reagent containing sodium acetate and acetic acid buffer for removal of ellagic acid and ellagitannins.

12. A process according to any of the preceding claims wherein the vegetable fat is solid or semi-solid.

13. A process for the production of modi

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (17)

**WARNING** start of CLMS field may overlap end of DESC **. sharply at about 38.5"C. This is higher than that of cocoa butter by about 3"-14"C, a desirable characteristic for tropical countries. The hard stearine fraction contains one-third unsaturated acids, mainly oleic, which gives it a similarity to cocoa butter although the palmitic-stearic acid ratio is reversed. For some applications as a coating or confectionery fat, higher melting characteristics than those exhibited by cocoa butter may be required. By blending the hard stearine with cocoa butter, the melting range of cocoa butter can be raised effectively. The hard stearine fraction possesses many of the properties required for multipurpose confectionery and bakery fats. Its thermal characteristics indicate that it is compatible with cocoa butter in wide proportions. It is neutral and bland in flavour and low in polyunsaturated acids which should give it good oxidation stability. The hard stearine is distinguished by exceptional hardness and mechanical strength. The hard stearine possesses superior resistance to blooming and dulling. This fat exhibited a temperature rise of4 C on solidification as compared with 4.9 C for cocoa butter. The modified vegetable hard stearine was then tested for cooling curve (Figure 1 of the accompanying drawings), dilatation (Figure 2), fatty acid composition and thermal profile by differential scanning calorimetry (Figure 4) and compared with cocoa butter (Figure 3). The melting properties of fats are commonly defined by their dilatations at the temperatures concerned, dilatation being the isothermal melting expansion expressed in cubic millimetres and referred to 25 grams of material. The dilatation of a fat gives an indication of the solids content of the fat at a particular temperature within its melting range. The dilatation tests were carried out by cooling the melted fat to OOC for 90 minutes, tempering it for 48 hours at 26 C and again cooling to OOC before measuring the dilatation at various temperatures. The dilatation results for the hard butter extender along with that of cocoa butter are given in Table 1. TABLE I Dt Modified Fat Cocoa Butter D20 2260 2040 D25 2020 1900 D30 1810 1490 D35 350 20 D40 85 1 D4s 0 0 The Jensen cooling curve of the hard butter extender was determined as follows:- About 75 g of sample was heated well above its melting point and placed in a test tube (length - 10 cm). A glass loop stirrer and a thermometer were inserted and the assembly was immersed in an air bath at 17 C. The sample was stirred at the rate of six strokes per minute until solidification occurred. A similar trial was carried out with a sample of cocoa butter and the cooling curves of temperature against time for each sample was plotted.These curves are shown in Figure 1 of the accompanying draw ings in which curve 1 indicates the temperature rise on solidification in the case of cocoa butter and curve 2 indicates the same for the modified fat. The above mentioned modified vegetable fat comprising of high melting stearine fraction was used at various levels such as 5, 10, 15, 20 and 25% by replacing cocoa butter in the manufacture of chocolates. Chocolates so manufactured were found to have similar physical and moulding characteristics to those of standard chocolates. WHAT WE CLAIM IS:

1. A process for the production of modified vegetable fat which comprises partially hydrogenating a refined, bleached and deodorised vegetable fat in the presence of a metal hydrogenation catalyst to produce a hardened fat, and subjecting the so-hardened fat to hydraulic pressure within a range of 200-700 p.s.i. at a controlled temperature in the range of 20 C to 350C to remove oily glycerides therefrom.

2. A process according to claim 1 wherein the vegetable fat is a fat of sal seed, mowrah, phulwara or mango kernel.

3. A process according to claim 1 wherein the vegetable fat is a mixture of sal seed fat with the fat of mowrah, phulwara and/or mango kernel.

4. A process according to claim 1 wherein the vegetable fat is a mixture of fat of mowrah, phulwara and mango kernel.

5. A process according to any of the preceding claims wherein the partial hydrogenation is carried out at about 100"C-1900C and at a pressure not exceeding 50 lb. p.s.i.

6. A process according to claim 5 wherein the pressure is between atmospheric pressure and 35 ib. p.s.i.

7. A process according to any of the preceding claims wherein the metal catalyst is a supported fresh nickel catalyst.

8. A process according to any of the preceding claims wherein the hardened or hydrogenated fat contains less than 5% trisaturated glycerides.

9. A process according to any of the preceding claims wherein the hydraulic pressure is applied for at least 30 minutes.

10. A process according to any of the preceding claims wherein the hydraulic pressure removes 2 to 10% of liquid oil by weight of the hydrogenated fat.

11. A process according to any of the preceding claims wherein the vegetable fat prior to partial hydrogenation is treated with a reagent containing sodium acetate and acetic acid buffer for removal of ellagic acid and ellagitannins.

12. A process according to any of the preceding claims wherein the vegetable fat is solid or semi-solid.

13. A process for the production of modi

fied vegetable fat, substantially as hereinbefore described in the foregoing Example.

14. A vegetable fat derived from sal fat, by catalytic partial hydrogenation followed by subjection to hydraulic pressure to remove oily glycerides, and having a melting point of 38.5"C, a temperature rise on solidification of 4"C, a dilatation substantially a shown in the foregoing Table 1, and substantially free from tannins and phenols.

15. A fat as claimed in claim 14 when produced by the process of any of claims 1 to 13.

16. A mixture of a fat as claimed in claim 15 or 15 and cocoa butter, the proportion of the former being from 5 to 25% by weight of the mixture.

17. Chocolates made with a fat as claimed in claim 14 or 15 or a fat mixture as claimed in claim 16.