Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
  • C11C3/10—Ester interchange
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
  • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
  • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
  • A23G2200/08—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing cocoa fat if specifically mentioned or containing products of cocoa fat or containing other fats, e.g. fatty acid, fatty alcohol, their esters, lecithin, paraffins

Definitions

• This invention relates to improved food fats, particularly of the variety used in chocolate confectionery and to methods of making such fats.
• the present invention provides a method of improving fat fractions containing symmetrical disaturated glycerides which are separated from vegetable and animal fats for use as a substitute for cocoabutter, the outstanding melting characteristics of which are attributable to the presence of these glycerides.
• the invention provides a process for the preparation of fat fractions containing symmetrical disaturated glycerides by fractional crystallisation of edible fat comprising a mixture of saturated and unsaturated C 16 -C 18 fatty acid glycerides combined with interesterification m which an interesterification catalyst selectively active in the 1- and 3-posit ⁇ ons only is used to randomise the fatty acid residues of the glycerides in the fat at these positions only.
• Fractionation is more or less effective to remove trisaturated glycerides of a high-melting solid fraction, and also di- and tri-unsaturated glycerides as a lowermelting fluid fraction, from disaturated glycerides in fats, although complete separation may not be economically feasible and the isomeric, asymmetric disaturated glycerides are not normally separable at all by this means.
• the effect of the selective enzyme treatment in the process of the invention is to improve the fat fraction required by increasing the amount of symmetrical disaturated glycerides it contains and/or reducing the amount of asymmetric disaturated glycerides present with it. In doing so other glycerides may be increased in amount but being either more highly unsaturated or less unsaturated, are readily separated by fractionation.
• One effect of the invention may therefore be to improve the symmetry of fats, expressed as the ratio of the symmetrical to the asymmetrical disaturated glycerides present in the fat, i.e. GUG:GGU, without introducing new fatty acid residues. It can be calculated mathematically that this ratio will be increased in a fat consisting of the two isomers which is subjected to the selective enzyme treatment of the invention, provided that the ratio is initially at least 1:2 molar. Generally speaking, this minimum ratio is substantially exceeded in vegetable fats, on account of the preference of unsaturated fatty acids to occupy the 2-pos ⁇ tion on the glycerides present.
• palm oil contains sufficient of the asymmetric disaturated glycerides to be an embarrassment, affecting as it does the melting qualities of even the most carefully fractionated palm mid-fractions which are used in cocoabutter substitute fats.
• the invention improves palm mid-fractions by decreasing the amount of asymmetric disaturated glycerides present.
• Shea oil on the other hand contains very little asymmetric disaturated glycerides and the principal effect of the enzyme step in the application of the process of the invention to shea fractions is to increase the amount of the symmetrical isomer by conversion of the asymmetric GU 2 . Whether by this or the former mechanism described, the effect of the interesterification is to enhance the symmetry of the fat. In the subsequent fractionation of the interesterified fat a fraction is recovered rich in symmetrical disaturated glycerides.
• Fats or fat fractions subjected to the enzyme treatment should contain as little 2-saturated glycerides as possible, i.e. P 3 , UGU and GGU.
• the fatty acid residues of a vegetable fat are distributed in the glycerides of the fat in a 1-, 3-random -2-random pattern.
• the fatty acid residues in 1- and 3-positions are therefore already randomly distributed and the application of the invention to vegetable fats includes a preliminary step in which this random distribution in the 1- and 3- positions is changed, as for example by fractionation. Fractionation for this purpose may be carried out to recover the symmetrical disaturated glycerides in a fluid fraction substantially free from trisaturated glycerides, or in a crystallised fraction substantially free from di- and tri-unsaturated glycerides.
• any of the unsaturated fractions obtained may be subjected to the selective enzyme treatment step of the invention followed by fractionation.
• a mid-fraction rich in the disaturated glycerides may be recovered and this and/or the unsaturated fractions separated from it then subjected to the enzyme treatment followed by refractionation.
• the present invention provides a process for the preparation of an improved confectionery fat , characterised by the fact that a fat consisting substantially of saturated and unsaturated C 16 and C 18 fatty acid glycerides is rearranged by contact with an enzyme selectively active in the 1- and 3-pos ⁇ t ⁇ ons only and the rearranged fat is fractionated to recover a fraction comprising symmetrical disaturated C 16 and C 18 glycerides.
• Suitable vegetable fats include palm oil, shea, sal, pentadesma, aceituno, phulwara and mango kernel oils.
• suitable animal fats include tallow. Lard may contain too much asymmetric glyceride to be suitable, according to its source.
• Fat fractions which may be treated according to the invention include, for example, palm, shea and sal oleines, palm and tallow mid-fractions and cottonseed stearine. While the fats consist substantially of C 16 and C 18 fatty acid glycerides, minor amounts of other fatty acids may be present whether of shorter- or longer-chain, length. The fats of the lauric group.
• Suitable enzymes for catalysing the rearrangement in the 1- and 3-positions only are provided by lipase enzymes. These include those produced by Aspergillus niger, Rhizopus arrhizus, Rhizopus japonicus and Rhizopus niveus, Mucor javanicus and Mucor miehei. Such enzymes require the presence of water to initiate and sustain their activity and catalyse the reversible hydrolysis and este ⁇ fication reactions. The reaction is therefore carried out m the presence of small amounts of water, i.e. below 10%, preferably less than 5%, and more particularly not more than 1% by weight of the fat to minimise hydrolysis.
• reaction is also preferably carried out in the presence of a non-aqueous, substantially water-immiscible solvent for example hexane having a relatively low boiling point, i.e. below 100 ⁇ C to facilitate its removal from the interesterified fat.
• a non-aqueous, substantially water-immiscible solvent for example hexane having a relatively low boiling point, i.e. below 100 ⁇ C to facilitate its removal from the interesterified fat.
• the interesterification reaction is also preferably carried out m accordance with our co-pending patent application A.194 with the provision of means to control the water activity A W of the reaction system.
• the amount of catalyst is preferably from 0.1 to 10%, particularly 0.1 to 71 ⁇ 2% by weight of the fat.
• the catalyst is preferably supported on a Celite or other inert support as described in these Applications and may be dispersed in the reaction mass after being activated by contact with water. Alternatively the catalyst after activation may be supported in a fixed bed.
• the reaction terniperature is preferably from 0 to
• the reaction mass is separated from the catalyst and any solvent present removed prior to the further recrystallisation step.
• sufficient solvent may be left with the fat for the refractionation step.
• the fractionation is effected from an organic solvent, e.g. acetone, hexane or nitropropane.
• the fractionation may alternatively be carried out in the absence of solvent or by the so-called Lanza process.
• Shea oil was fractionated from acetone at 5°C to recover a solid stearine fraction containing principally disaturated glycerides and a fluid oleme fraction which was recovered from the solvent, refined and neutralised.
• the oleine fraction was dissolved in twice its weight of petroleum ether of boiling range 100 to 120°C and the solution percolated at 40 ⁇ C at a flow rate of 10.4 mls/hr through alternate layers of Celite and Celite-lipase catalyst packed in a bed in an upright reactor tube.
• the layers were previously wetted with water and the catalyst layers comprised Aspergillus mger lipase and were prepared m accordance with our patent Case A.189. A total amount of 7 grams of lipase was used.
• Table 2 shows the solids content of 20°C of the stearine product according to the invention and of a blend of equal parts with a typical palm mid-fraction, together with corresponding data for a typical commercial shea stearine product. From the data it is clear that the stearine from interesterified shea oleme is a useful confectionery fat and that as a result of the interesterification reaction a substantial amount of recoverable, symmetrical disaturated glyceride is generated. By contrast, the control test product contained only half the amount of SOS present in the interesterified stearine product of the invention and is very unsatisfactory as a confectionery fat.
• Example 2 a neutralised and refined mid fraction of palm oil used m cocoabutter substitutes was enzymatically interesterified as described in Example 1, with however, a flow rate of 21.0 ml/hr.
• the lipase was derived from Rhizopus japonicus.
• the interesterified fat was fractionated from a solution in 1.6 times its weight of hexane, maintained for 90 minutes at 8 ⁇ C.
• the solid, stearine fraction containing principally trisaturated glycerides was filtered and washed twice with hexane. After combining the filtrate and washings the solvent was removed from the fluid, oleine fraction which was recovered m 75.9% yield based on the interesterified fat.
• Example 1 was repeated on another neutralised and refined mid-fraction of palm oil as used in cocoabutter substitutes. A flow rate of 25 ml/hr was used and the lipase was derived from Rhizopus japonicus.
• the interesterified fat was analysed, redi ⁇ solved in 4 times its weight of acetone, and fractionated after maintaining for 2 hours at 20°C.
• the solid, stearine fraction containing principally t ⁇ saturated glycerides was filtered and washed with acetone. After combining the filtrate and wash the solvent was removed from the fluid, oleine fraction which was recovered in 89% yield based on the interesterified fat.
• the oleine fraction was further fractionated from a solution in 7.5 times its weight of acetone, maintained for 30 minutes at 5°C.
• the solid, stearine fraction from this second fractionation containing principally SOS glycerides was filtered and washed twice with acetone.
• the solvent was removed from the solid, stearine fraction of this second fractionation by evaporation in vacuo to give a mid-fraction in 59% yield based on the original interesterified fat.
• Tallow was fractionated from a solution in 3 times its weight of acetone, maintained for 1 hour at 17 ⁇ C.
• the solid, stearine fraction containing principally trisaturated glycerides was filtered and washed with acetone. After combining the filtrate and wash the solvent was removed from the fluid, oleine fraction which was recovered m 83% yield based on the tallow.
• the oleme fraction was further fractionated from a solution m 5 times its weight of acetone, maintained for 1 hour at 5°C.
• the solid, stearine fraction from this second fractionation containing principally symmetrical and asymmetrical disaturated glycerides (SOS and SSO) was filtered and washed twice with acetone.
• the solvent was removed from the solid, stearine fraction of this second fractionation by evaporation in vacuo to give a mid-fraction m 20% yield based on the original tallow.
• the interesterified fat was fractionated from a solution in 3 times its weight of acetone, maintained for 2 hour at 17°C.
• the oleine fraction was further fractionated from a solution in 5 times its weight of acetone, maintained for 1 hour at 5°C.
• the solid, stearine fraction from this second fractionation containing principally symmetrical disaturated glycerides (SOS) was filtered and washed twice with acetone.
• the solvent was removed from the solid, stearine fraction to give a mid-fraction in 39% yield based on the starting tallow mid-fraction.
• glyceride compositions are given for the tallow mid-fraction starting material and the mid-fraction derived from the interesterified tallow mid-fraction. From these data it will be seen that the mid-fraction from the interesterified fat contains substantially more of the desirable symmetrical disaturated cis-monounsaturated glycerides (SOS) and less of the undesirable asymmetrical disaturated cis-monounsaturated glycerides (SSO) than the starting tallow mid-fraction.
• SOS symmetrical disaturated cis-monounsaturated glycerides
• SSO asymmetrical disaturated cis-monounsaturated glycerides

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Food Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polymers & Plastics (AREA)
• Fats And Perfumes (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Edible Oils And Fats (AREA)
• Manufacture Of Tobacco Products (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
• Bakery Products And Manufacturing Methods Therefor (AREA)

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• 1982
  • 1982-07-07 CA CA000406801A patent/CA1241227A/en not_active Expired
  • 1982-07-08 ES ES513828A patent/ES513828A0/es active Granted
  • 1982-07-08 AU AU86822/82A patent/AU553171B2/en not_active Ceased
  • 1982-07-08 EP EP19820303580 patent/EP0069599B1/en not_active Expired
  • 1982-07-08 WO PCT/GB1982/000201 patent/WO1983000161A1/en unknown
  • 1982-07-08 JP JP57502055A patent/JPS58501066A/ja active Granted
  • 1982-07-08 ZA ZA824872A patent/ZA824872B/xx unknown
  • 1982-07-08 DE DE8282303580T patent/DE3273180D1/de not_active Expired
  • 1982-07-08 IE IE1647/82A patent/IE53399B1/en not_active IP Right Cessation
  • 1982-07-08 AT AT82303580T patent/ATE22113T1/de not_active IP Right Cessation
• 1983
  • 1983-03-07 DK DK112383A patent/DK158525C/da not_active IP Right Cessation
• 1987
  • 1987-03-02 SG SG211/87A patent/SG21187G/en unknown
  • 1987-12-30 MY MY353/87A patent/MY8700353A/xx unknown

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