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
• • 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
  • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids

Definitions

• This invention relates to edible fats and their preparation for use in particular in confectionery including chocolate, shortenings, margarine and other plastic emulsion food spreads.
• unsaturated vegetable oils for example sunflower oil
• unsaturated vegetable oils may be converted in the presence of saturated fatty acids themselves or alkyl esters thereof, to symmetrical disaturated triglycerides, particularly of palmitic and stearic acids, the presence of which in cocoa butter and other vegetable butters accounts for the sharp - melting and other physical attributes for which these expensive and often scarce products are so highly prized.
• the most beneficial of these glycerides are the 2-oleoyl homologues.
• the corresponding 2-linoleoyl and linoleneoyl disaturated triglycerides exhibit somewhat less satisfactory characteristics; being more highly unsaturated they are significantly softer and materially more susceptible to deterioration by oxidation.
• the present invention provides a process for the preparation of edible fats suitable for use in confectionery and like edible compositions by rearrangement of unsaturated glyceride oils and fats to more highly saturated fats by contact as rearrangement catalyst with lipase enzyme and in the presence of saturated fatty acids or esters thereof, wherein the oil or fat exhibits a high oleate content and preferably consists substantially of 2-unsaturated triglycerides at least 90% of which are 2-oleoyl triglycerides.
• the present invention also provides novel fats comprising symmetrical disaturated triglycerides of C16 and C18 fatty acids in which the saturated fatty acid residues are in random distribution between the 1 and 3-positions and the unsaturated fatty acid residues comprise at least 80% oleic acid residues, preferably at least 90% and more particularly at least 95% of such residues .
• Such fats are obtained by the rearrangement processes of the present invention using as rearrangement catalyst a 1, 3-regiospecific lipase, as described in US patent 4275081.
• High oleic sunflower varieties suitable for use on the present invention may be obtained by conventional plant breeding techniques, for example by crossing the naturally occurring high oleic varieties such as that reported by Horowitz and Winter (Nature 179:582 (1975)).
• High oleic mutants produced by artificial means, such as the mutagen treatment of seed can also be used and the Pervenets variety (reported by Kharachenk in Fisiologiya Rastenii 26:1226 (1979)) is an example. Progenies derived from such mutants are known, eg. those reported by Fick.
• sunflower seed is used from plant varieties giving oils with 10% or less eg.
• oils suitable for use in the present invention include selected olive oil, shea olein, sal olein and cottonseed olein, including winterised cottonseed oil.
• Enzyme rearrangement processes in accordance with the present invention are carried out in substantially non-aqueous and essentially water-immiscible liquid phase.
• a small amount of water is nevertheless necessary to activate the catalyst initially. This may be achieved either by contacting the catalyst first with water or by including a little water in the feedstock in batchwiese operations.
• a balance is required between the faster reaction rates provided by more water increasing the activity of the catalyst and correspondingly increased tendency to hydrolysis of the reactants and products, since the rearrangement process is reversible.
• the water activity of the system is maintained at between 0.2 and 0.6.
• the water activity of the system is maintained, preferably within these limits, by including a small amount of water in the feedstock supplied to the catalyst in a fixed bed.
• the water activity is preferably maintained at a level of which the rearrangement reaction is substantially completed with a contact time less than 2 hours, to minimise the effect by isomerisation of partial glyceride by-products leading to the appearance in the product of 2-saturated triglycerides, where 1, 3-regiospecific catalysts are used to produce symmetrical disaturated 2-oleoyl triglycerides.
• the rearrangement reaction may be carried out in the presence of a water-immiscible non-polar solvent eg. hexane or other hydrocarbon to maintain the reactants in liquid phase.
• a water-immiscible non-polar solvent eg. hexane or other hydrocarbon
• the concentration of reactants in the solvent is preferably from 20-50% by weight.
• the reaction may be operated at moderately elevated temperatures for example 40 to 80°C, at which the catalyst selected remains active and the reactants are wholly in liquid phase.
• the catalyst is preferably supported on an inert support for example Celite or other particulate siliceous, inert inorganic support or ion exchange medium, either organic for example a resin, or inorganic for example zeolitic.
• the amount of lipase is preferably 0.01-0.1% by weight of the support. Lipase is present in commercially available products in an amount of approximately 1% and sufficient commercial product is used to achieve this concentration of lipase on the support.
• Suitable 1, 3 regiospecific enzymes include Mucor miehei , Rhizopus , A. niger or other Aspergillus species.
• the acidolysis reactant used with the sunflower or other oil or fat in accordance with the invention may be in the form of a free saturated fatty acid , preferably palmitic or stearic acid, or a mixture of both. Alternatively, they may be present as esters, preferably of short chain saturated mono hydric alcohols, for example methyl and ethyl palmitate and stearate. Preferably from 1 to 5 moles of acidolysis reactant per mole of oil is used, more preferably 3-5 moles per mole.
• the rearranged triglyceride product of the invention is preferably recovered from the reactant mixture after first separating any free fatty acid and any reactant solvent this has been used, by fractional crystallisation at a temperature, preferably from 10-40°C, at which the unsaturated acid or ester by-products are liquid and can be separated from the crystallised product.
• the fractionation may be effected from suitable solvent for example acetone.
• these by-products may be distilled off, preferably at reduced pressure using conventional acid refining methods.
• the by-products may be hydrogenated to the corresponding stearic acid or ester thereof and recycled for use as the acidolysis reactant.
• a mixture of equal parts of high oleic sunflower oil and stearic acid was dissolved in twice its weight of hexane.
• Half the feedstock obtained was saturated with water by passage through a column containing a bed of wet silica gel and was then recombined with the remainder of the feedstock.
• the combined feedstock was pumped at a flow rate of 6 Kg per hour at 50°C, through a reactor column containing 1 Kg of interesterification catalyst consisting of Mucor miehei lipase supported on Celite, prepared as described in British patent 1577933 and pre-activated with 10% water prior to use. Residence time was approximately 15 minutes.
• the free fatty acids were separated using a falling film evaporator and the reaction product fractionated at -5°C in acetone using a solvent to oil ratio 5:1, in a scraped-surface heat exchanger to recover a stearin fraction rich in StOSt.
• the substantially greater SOS content of the stearine fraction and lower content of SLnS is apparent from Table 1.
• the enzyme and shea stearines were evaluated for confectionery fats, both alone and in blends of equal parts of mid-fraction, by Jensen Cooling Curve determination in Table 2.
• the enzymatically produced stearine exhibited excellent confectionery fat characteristics and was similar to shea stearine.
• Example I was repeated using as feedstock the olein by-product recovered from Example I, the catalyst in this case being supported on a phenol-formaldehyde weak anion exchange resin.
• the deacidified product was first fractionated in acetone with a solvent:oil ratio of 5:1 at a temperature of 0°C, to remove an olein fraction in 56% yield.
• the stearine fraction remaining was then redispersed in acetone at a 3:1 ratio and a second stearine fraction separated in 10% yield overall at a temperature of 25°C, consisting substantially of saturated glycerides and leaving a mid-fraction recovered in 34% overall yield from the solvent.
• the saturated glycerides of the upper stearine fraction result from the presence of partial glycerides in the recycled olein undergoing isomerisation followed by interesterification in the reactor.
• a reactant mixture of high oleate sunflower oil (2.5 parts by wt) and myristic acid (1.0 parts by wt) dissolved in 100-120° petroleum ether (8 parts by wt) was saturated with water at 40°C by passage through a bed of acid washed celite (4.0g) containing 80% by wt of water.
• the water saturated reaction mixture was pumped at 40°C using a flow rate of 15m/hr ⁇ 1 through a bed of catalyst (2.0g) consisting of Rhizopus japonicus lipase suppored on celite.
• the catalyst prepared as described in our patent GB 1577933, contained 1700 lipase units per gm, and was activated with 10% water prior to use.
• the mean residence time of the reactant mixture in the catalyst bed was approximately 15 mins.
• the interesterification reaction product contained 58% triglyceride, 6% diglyceride and 36% free fatty aic.
• the triglyceride fraction was isolated and analysed. The results given in Table 3 show that myristate was incorporated into the sunflower oil triglycerides and valuable SOS triglycerides were generated.
• a mixture of high oleate sunflower oil (2.5 parts by wt) and methyl palmitate (2.4 parts by wt) dissolved in 100-120° petroleum ether (8 parts by wt) was reacted as described in Example 3 using a catalyst ved of Rhixopus niveus lipase supported on celite and a flow rate of 4ml hr ⁇ 1.
• the catalyst contained 1500 lipase units per gm.
• the mean residence time of the reactant mixture in the catalyst bed was approximately 1 hour.
• the reaction product contained 50% triglyceride, 4% diglyceride, 43% methyl esters and 3% free fatty acid. Analysis of the triglyceride fraction showed that extensive interesterification occurred. Palmitate was incorporated into the sunflower oil triglycerides and valuable SOS triglycerides were produced (Table 1).

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Edible Oils And Fats (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Fats And Perfumes (AREA)

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Cited By (16)

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• 1986
  • 1986-05-06 GB GB08610979A patent/GB2190394A/en not_active Withdrawn
• 1987
  • 1987-05-04 AU AU72481/87A patent/AU596411B2/en not_active Ceased
  • 1987-05-05 SE SE8701847A patent/SE467860B/sv not_active Application Discontinuation
  • 1987-05-05 EP EP87303996A patent/EP0245076A3/de not_active Withdrawn
  • 1987-05-06 JP JP62110393A patent/JPS6317697A/ja active Granted
  • 1987-05-06 ZA ZA873239A patent/ZA873239B/xx unknown

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