Method for preparing a randomly transesterified fat product

Abstract

A method for preparing an edible randomly interesterified fat product comprises the steps of: a) providing a fat composition comprising 0.5% to 25% by weight of free fatty acids; and b) enzymatically reacting the fat composition provided in step a) with 0.5% to 10% by weight of a polyol compound, based on the fat composition, wherein the weight ratio of free fatty acids in the fat composition to the polyol composition is 0.1 to 20.0, and the resulting randomly interesterified fat product has less than 1.0% by weight of free fatty acids.

Description

Technical Field

[0001] The present invention relates to a method for preparing a randomly transesterified fat product and its use.

Background Art

[0002] Fats and oils are important raw materials for foods such as confectionery products, bakery products, and cooking products.

[0003] Transesterification brings about complete randomization of fatty acid acyl groups, changing the physical properties of fats or oils so that they can meet the requirements in various applications. Chemical transesterification often requires an alkali catalyst such as sodium methoxide. However, in the presence of a large amount of free fatty acids, transesterification cannot be carried out or cannot be carried out completely. Therefore, additional deacidification steps such as distillation and neutralization are required before transesterification.

[0004] The transesterification reaction can also be catalyzed by enzymes. The presence of a large amount of free fatty acids may not affect the reaction catalyzed by enzymes. However, after transesterification and before purification, it is necessary to remove them by additional deacidification steps such as distillation and neutralization.

[0005] WO 2005 / 010136 A2 relates to a method capable of significantly improving the productivity of enzymatic transesterification or esterification by only deodorization or by deodorizing and purifying the initial substrate to extend the service life of the enzyme.

[0006] WO 2006 / 124818 A2 discloses a method capable of significantly improving the productivity of enzymatic esterification, transesterification or interesterification by purifying the substrate oil to extend the service life of the enzyme.

[0007] International Publication No. WO 2013 / 131862 A1 relates to a glyceride composition obtained from shea oil, which contains at least 75% by weight of triglycerides and 5 to 25% by weight of diglycerides, based on the total weight of the composition, and has an oleic acid content of at least 65% by weight, a total content of stearic acid and palmitic acid of 10 to 20% by weight, based on the total of C12 to C20 fatty acids present in the glycerides, and wherein oleic acid, stearic acid, and palmitic acid are present as acyl groups of monoglycerides, diglycerides or triglycerides.

[0008] International Publication No. WO 2019 / 020714 A1 discloses a non-hydrogenated fat composition containing stearic acid (C18:0) fatty acid residues of more than 28% by weight, oleic acid (C18:1) fatty acid residues of more than 44% by weight, and palmitic acid (C16) fatty acid residues of less than 10% by weight, based on the total C8 - C24 fatty acid residues, and having a total amount of more than 30% by weight and a weight ratio of (StOSt + StStO) / (StOO + OStO) of 0.6 - 1.5, based on the total glycerides present in the composition, and containing StOSt, StSto, StOO and OStO triglycerides.

[0009] International Publication No. WO 2017 / 133895 A1 relates to a method for preparing a self-emulsifying fat composition.

[0010] European Patent Application Publication No. EP 0516542 A1 relates to a process which is a combination of fractionation, purification and transesterification, and wherein the crucial step is the fractionation of a fat fraction containing free fatty acids at a temperature of -5 to -30°C.

[0011] European Patent Application Publication No. EP 0257388 A2 discloses a transesterified fat using an enzyme preparation containing a lipase having thermal stability at a high temperature sufficient to melt the reactive substrate, without using a solvent and removing water from the reaction system during the reaction. Summary of the Invention Problems to be Solved by the Invention

[0012] There is still a need to improve the efficiency of the process of random transesterification of fats, especially when the content of free fatty acids in the raw material is high. There is also a need to improve the quality of randomly transesterified fat products in terms of various aspects such as desirable crystallization properties and appearance.

Means for Solving the Problems

[0013] According to the present invention, there is provided a method for preparing an edible randomly transesterified fat product, comprising: a) providing a fat composition containing 0.5% to 25% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting this fat composition with 0.5% to 10% by weight of a polyol compound based on the weight of this fat composition, wherein the weight ratio of free fatty acids in the fat composition to the polyol compound is from 0.1 to 20.0, and the resulting randomly transesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0014] The method of the present invention has been found to be particularly useful for randomly transesterifying fat compositions containing large amounts of free fatty acids, for example, free fatty acids of 0.5% by weight or more. The transesterification method according to the present invention does not require removal of free fatty acids. In contrast, conventional randomization methods require removal of free fatty acids, for example, before transesterification. Therefore, since there is no need to remove free fatty acids during the transesterification process, this method can significantly improve efficiency and greatly limit losses throughout the transesterification. Furthermore, since removal of free fatty acids is not required, there is less waste of free fatty acids generated when the method according to the present invention is applied.

[0015] Furthermore, surprisingly, the randomly transesterified fat products produced according to the method of the present invention have been found to have particularly good crystallization behavior and a desirable appearance, especially a bright color. These improved properties make the random transesterified fat products produced according to the method particularly suitable for various applications such as confectionery, bakery or cooking, compared to similar fat products manufactured by conventional methods.

Brief Description of the Drawings

[0016]

Figure 1

Embodiments for Carrying Out the Invention

[0017] The term "fat" refers to glyceride oils containing fatty acid acyl groups and does not imply any specific melting point. The term "oil" is used synonymously with "fat". The term "free fatty acid" refers to a fatty acid that is not bound to any alcohol (e.g., glycerol) as part of an ester molecule. The free fatty acid content can be determined by titration with a standard alkali according to the AOCS official method Ca 5a-40. The free fatty acid concentration is calculated and expressed, for example, as a percentage of oleic acid. Thus, the molar mass of oleic acid (282 g / mol) is used in the formula shown in the AOCS official method Ca 5a-40 for calculating the percentage of free fatty acids. In the AOCS Ca 5a-40 method, it is assumed that the number of moles of the titrated acid groups corresponds to oleic acid in the following calculation. FFA% as oleic acid = (titration molar base x 282 g / mol) / sample weight (g) x 100%

[0018] The resulting weight value of the FFA is an approximate value, and in the case of naturally occurring fats and oils, the actual free fatty acids are a mixture of various fatty acids with different molecular weights.

[0019] The term "random transesterification" refers to the random non-specific redistribution of the fatty acid moieties present on the glycerol moiety in triglyceride oils.

[0020] The term "polyol composition" refers to a composition consisting of one or more organic compounds containing two or more hydroxyl groups, such as glycerol, propylene glycol, polyglycerol, sugar alcohols, polyethylene glycol, polypropylene glycol, etc.

[0021] The term "fatty acid" refers to a straight-chain saturated or unsaturated (including monounsaturated and polyunsaturated) carboxylic acid having 8 to 24 carbon atoms. A fatty acid having x carbon atoms and y double bonds can be represented as Cx:y. For example, palmitic acid can be represented as C16:0, and oleic acid can be represented as C18:1. The fatty acid profile can be determined by fatty acid methyl ester analysis (FAME) using gas chromatography in accordance with ISO12966-2 and ISO12966-4. Accordingly, the percentage of fatty acids in the compositions referred to herein (e.g., palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1), etc.) includes both acyl groups and free fatty acids (excluding unsaponifiables) such as triglycerides, diglycerides, and monoglycerides, and is based on the total weight of the fatty acid residues from C8 to C24.

[0022] According to the present invention, the weight ratio of the free fatty acids in the fat composition provided in step a) to the polyol composition in step b) is preferably from 0.2 to 18.0, more preferably from 0.3 to 15.0, even more preferably from 0.5 to 15.0, and most preferably from 0.5 to 10.0. The method according to the present invention is particularly efficient and involves an improved yield when the preferred weight ratio is used.

[0023] In step a) of the method according to the invention, the fat composition provided preferably contains from 0.5% to 20% by weight of free fatty acids, calculated as a percentage of oleic acid and measured according to AOCS Ca 5a-40, more preferably from 0.5% to 18% by weight, even more preferably from 0.8% to 17% by weight, and most preferably from 1.0% to 15% by weight of free fatty acids.

[0024] In step a) of the method according to the invention, the fat composition provided is preferably selected from cupuaçu butter, cocoa butter, illipe butter, mango kernel oil, illipe butter, kokum butter, murumuru butter, high stearic acid high oleic acid sunflower oil, fractions thereof, and mixtures thereof. More preferably, the fat composition provided is selected from cupuaçu butter, cupuacuolein, cupuacustearin, cocoa butter, and mixtures thereof. Even more preferably, the fat composition provided is a single fat composition such as cupuaçu butter, cupuacuolein, or cocoa butter. Alternatively, the fat composition provided is more preferably a mixture of cupuaçu butter and cupuacuolein with a weight ratio of cupuaçu butter to cupuacuolein from 20:80 to 80:20, or a mixture of cupuaçu butter and cupuacustearin with a weight ratio of cupuaçu butter to cupuacustearin from 20:80 to 80:20.

[0025] In step a) of the method according to the invention, the fat composition provided preferably contains at least 15% by weight of stearic acid (C18:0), the percentage of said acid being with respect to the acid bound as an acyl group in the glyceride and any free fatty acids present in the fat composition, and being based on the total weight of C8 to C24 fatty acids. The fat composition provided more preferably contains from 20% to 80% by weight of stearic acid (C18:0), even more preferably from 25% to 75% by weight, and most preferably from 25% to 70% by weight of stearic acid.

[0026] Accordingly, in a preferred embodiment, in step a) of the method according to the invention, the fat composition provided comprises from 0.5% to 20% by weight of free fatty acids, calculated as a percentage of oleic acid and measured according to AOCS Ca 5a-40, and at least 15% by weight of stearic acid (C18:0), the percentage of said acid being based on the total weight of C8 to C24 fatty acids and relating to the acids bound as acyl groups in the glycerides and any free fatty acids present in the fat composition.

[0027] In a more preferred embodiment, in step a) of the method according to the invention, the fat composition provided comprises from 0.5% to 18% by weight of free fatty acids, calculated as a percentage of oleic acid and measured according to AOCS Ca 5a-40, and from 20% to 80% by weight of stearic acid (C18:0), the percentage of said acid being based on the total weight of C8 to C24 fatty acids and relating to the acids bound as acyl groups in the glycerides and any free fatty acids present in the fat composition.

[0028] In an even more preferred embodiment, in step a) of the method according to the invention, the fat composition provided comprises from 0.8% to 17% by weight of free fatty acids, calculated as a percentage of oleic acid and measured according to AOCS Ca 5a-40, and from 25% to 75% by weight of stearic acid (C18:0), the percentage of said acid being based on the total weight of C8 to C24 fatty acids and relating to the acids bound as acyl groups in the glycerides and any free fatty acids present in the fat composition.

[0029] In the most preferred embodiment, in step a) of the method according to the invention, the fat composition provided comprises from 1.0% to 16% by weight of free fatty acids, calculated as a percentage of oleic acid, measured according to AOCS Ca 5a-40, and from 25% to 70% by weight of stearic acid (C18:0), the percentage of said acid being with respect to the acids bound as acyl groups in the glycerides and any free fatty acids present in the fat composition and being based on the total weight of C8 to C24 fatty acids.

[0030] The term "unsaponifiable matter" refers to substances present in fats and oils that are not saponified by alkali hydroxide and are extractable into ether. The unsaponifiable matter content can be measured according to AOCS Ca 6a-40.

[0031] In step a) of the method according to the invention, the fat composition provided preferably comprises at least 1% by weight of unsaponifiable matter, more preferably at least 2% by weight, even more preferably from 3% to 15% by weight, even more preferably from 4% to 12% by weight, and most preferably from 5% to 10% by weight of unsaponifiable matter. The method according to the invention is considered to be particularly suitable for fat compositions containing the indicated amounts of unsaponifiable matter.

[0032] Thus, in a preferred embodiment, in step a) of the method according to the invention, the fat composition provided comprises from 0.5% to 20% by weight of free fatty acids, calculated as a percentage of oleic acid, measured according to AOCS Ca 5a-40, and at least 15% by weight of stearic acid (C18:0), the percentage of said acid being with respect to the acids bound as acyl groups in the glycerides and any free fatty acids present in the fat composition and being based on the total weight of C8 to C24 fatty acids, and further comprises at least 2% by weight of unsaponifiable matter.

[0033] In a more preferred embodiment, in step a) of the method according to the invention, the fat composition provided contains, as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, from 0.5 wt% to 18 wt% free fatty acids and from 20 wt% to 80 wt% stearic acid (C18:0) (the percentage of said acid being with respect to the acids bound as acyl groups in the glyceride and any free fatty acids present in the fat composition and being based on the total weight of C8 to C24 fatty acids), and further contains from 3 wt% to 15 wt% unsaponifiables.

[0034] In an even more preferred embodiment, in step a) of the method according to the invention, the fat composition provided contains, as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, from 0.8 wt% to 17 wt% free fatty acids and from 25 wt% to 75 wt% stearic acid (C18:0) (the percentage of said acid being with respect to the acids bound as acyl groups in the glyceride and any free fatty acids present in the fat composition and being based on the total weight of C8 to C24 fatty acids), and further contains from 4 wt% to 12 wt% unsaponifiables.

[0035] In the most preferred embodiment, in step a) of the method according to the invention, the fat composition provided contains, as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, from 1.0 wt% to 16 wt% free fatty acids and from 25 wt% to 70 wt% stearic acid (C18:0) (the percentage of said acid being with respect to the acids bound as acyl groups in the glyceride and any free fatty acids present in the fat composition and being based on the total weight of C8 to C24 fatty acids), and further contains from 5 wt% to 10 wt% unsaponifiables.

[0036] According to the present invention, in step b) of the method, the provided fat composition preferably reacts with 0.5% to 8% by weight of the polyol composition, more preferably 0.5% to 6% by weight, even more preferably 1% to 5% by weight, and most preferably 1% to 3% by weight of the polyol composition, based on the weight of the provided fat composition.

[0037] In a preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 20% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with 0.5% to 8% by weight of the polyol composition, based on the weight of the provided fat composition, wherein the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.2 to 18.0, and the resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0038] In a more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with 0.5% to 6% by weight of the polyol composition, based on the weight of the provided fat composition, wherein the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.3 to 15.0, and the resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0039] In an even more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.8% to 17% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 5% by weight based on the weight of the provided fat composition, wherein the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.5 to 15.0, and the resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0040] In the most preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0% to 16% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 3% by weight based on the weight of the provided fat composition, wherein the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.5 to 10.0, and the resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0041] In step b) of the method according to the invention, the polyol composition is preferably selected from glycerol, propylene glycol, polyglycerol, sugar alcohols, polyethylene glycol, polypropylene glycol, and mixtures thereof; more preferably selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof; even more preferably selected from glycerol, propylene glycol, and mixtures thereof. Most preferably, in step b) of the method according to the invention, the polyol composition consists of glycerol. Alternatively, in step b) of the method according to the invention, the polyol composition is preferably a mixture of glycerol and propylene glycol, where the weight ratio of glycerol to propylene glycol is from 1:3 to 3:1.

[0042] In step b) of the method according to the invention, the reaction is preferably catalyzed by a lipase, more preferably an immobilized lipase, even more preferably an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae. For example, Novozym® 40086 is a commercially available immobilized lipase derived from Rhizomucor miehei immobilized on a microporous anion resin. Novozym® 435 is a commercially available immobilized lipase derived from Candida antarctica immobilized on a microporous acrylic resin. Lipozyme® TL IM is a commercially available immobilized lipase derived from Thermomyces lanuginosus immobilized on a non-compressible silica gel support. These enzymes have been found to be particularly stable in their reuse for the method according to the invention.

[0043] In step b) of the method according to the present invention, the reaction is preferably carried out in a temperature range of 20°C to 85°C, more preferably 30°C to 80°C, even more preferably 40°C to 80°C, and most preferably 50°C to 75°C. Further, the reaction is preferably carried out in a dry environment such as bubbling (mixing) with nitrogen gas or under vacuum. The reaction time is preferably from 1 hour to 48 hours, more preferably from 3 hours to 36 hours, and even more preferably from 7 hours to 30 hours.

[0044] After step b) of the method according to the present invention, the obtained random ester-exchanged fat product is preferably subjected to purification, more preferably to physical purification such as bleaching and deodorization. Physical purification is well-known in the art and mainly reduces free fatty acids in the deodorization step without accompanying alkali neutralization. It is considered that the combination of physical purification and the method according to the present invention further improves the yield and efficiency of the entire process for producing the random ester-exchanged fat product.

[0045] Accordingly, in a preferred embodiment, a method for preparing an edible random ester-exchanged fat product according to the present invention comprises: a) providing a fat composition containing 0.5 wt% to 20 wt% free fatty acids as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; b) enzymatically reacting the provided fat composition with a polyol composition of 0.5 wt% to 8 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol composition is from 0.2 to 18.0, and the obtained random ester-exchanged fat product has less than 1.0 wt% free fatty acids as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0046] In a more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 0.5% to 6% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae. The polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol composition is from 0.3 to 15.0. The resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0047] In an even more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.8% to 17% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 5% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae. The polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol composition is from 0.5 to 15.0. The resulting random interesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0048] In the most preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol, the weight ratio of free fatty acids to glycerol in the provided fat composition is 0.5 to 10.0, and the resulting random interesterified fat product has less than 1.0 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0049] In an additional preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol, the weight ratio of free fatty acids to glycerol in the provided fat composition is 0.5 to 10.0, and the resulting random interesterified fat product has less than 1.0 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and c) purifying the resulting random interesterified fat product, preferably by physical purification.

[0050] In another preferred embodiment, a method for preparing an edible random transesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, calculated as a percentage of oleic acid, and 3 wt% to 15 wt% unsaponifiables, measured according to AOCS Ca 5a-40; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol, and the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 10.0, and the resulting random transesterified fat product has less than 1.0 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0051] In an alternative preferred embodiment, a method for preparing an edible random transesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, calculated as a percentage of oleic acid, measured according to AOCS Ca 5a-40; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is a mixture of glycerol and propylene glycol, and the weight ratio of free fatty acids to the polyol composition in the provided fat composition is from 0.5 to 10.0, and the resulting random transesterified fat product has less than 1.0 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid.

[0052] According to the present invention, the random transesterified fat product obtained by this method preferably has less than 0.80% by weight, preferably from 0.01% to 0.50% by weight, more preferably from 0.01% to 0.40% by weight, even more preferably from 0.01% to 0.30% by weight of free fatty acids, calculated as a percentage of oleic acid and measured according to AOCS Ca 5a-40.

[0053] The degree of randomization of the random transesterified fat can be calculated based on the triglyceride that decreased the most during the reaction. "TAGd" refers to the content of this triglyceride (the triglyceride that decreased the most during the reaction) after the reaction. "TAGi" refers to the content of that triglyceride before the reaction. When the same fat is chemically transesterified, it is considered to be completely randomized. "TAGe" refers to the content of that triglyceride that has undergone chemical transesterification. Therefore, the degree of randomization can be calculated based on the following formula. Degree of randomization % = (TAGi - TAGd) / (TAGi - TAGe) x 100%

[0054] When the degree of randomization is calculated to exceed 100%, when the randomization is completed, the degree of randomization can be regarded as 100%. This may be due to the allowable error of the analysis method.

[0055] According to the present invention, the random transesterified fat product obtained by this method preferably has a degree of randomization of at least 70%, more preferably at least 75%, even more preferably from 80% to 100%, even more preferably from 84% to 100%, and most preferably from 90% to 98%.

[0056] Accordingly, in a preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 20% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 0.5% to 8% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol composition is from 0.2 to 18.0, and the resulting random interesterified fat product has less than 0.80% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of at least 75%.

[0057] In a more preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 0.5% to 6% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.3 to 15.0, and the resulting random interesterified fat product has from 0.01% to 0.50% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of from 80% to 100%.

[0058] In an even more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.8% to 17% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 5% by weight based on the weight of the provided fat composition, using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, and the weight ratio of free fatty acids in the provided fat composition to the polyol compound is from 0.5 to 15.0, and the resulting random interesterified fat product has 0.01% to 0.40% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of 84% to 100%.

[0059] In the most preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0% to 16% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 3% by weight based on the weight of the provided fat composition, using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol, and the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.5 to 10.0, and the resulting random interesterified fat product has 0.01% to 0.30% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of 90% to 98%.

[0060] In a further preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol and the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.5 to 10.0, and the resulting random interesterified fat product has 0.01 wt% to 0.30 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of 80% to 100%; c) purifying the resulting random interesterified fat product, preferably by physical purification.

[0061] In another preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and 3 wt% to 15 wt% unsaponifiables; b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol and the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.5 to 10.0, and the resulting random interesterified fat product has 0.01 wt% to 0.30 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of 80% to 100%.

[0062] In an alternative preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is a mixture of glycerol and propylene glycol, the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 10.0, and the resulting random interesterified fat product has 0.01 wt% to 0.30 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and has a degree of randomization of 80% to 100%.

[0063] According to the present invention, the random interesterified fat product obtained by this method preferably has a weight ratio of stearic acid (C18:0) to oleic acid (C18:1) of from 0.3:1 to 3:1, more preferably from 0.4:1 to 2.5:1, even more preferably from 0.4:1 to 2:1, and most preferably from 0.5:1 to 1.5:1.

[0064] The amount of triglyceride defined herein is the weight percentage based on the total triglyceride present in the fat composition. The notation triglyceride XYZ represents a triglyceride having fatty acid acyl groups X, Y, and Z at any of the 1, 2, and 3 positions of the glyceride. The notation A2B includes both AAB and ABA, and AB2 includes both ABB and BAB. The triglyceride content can be determined, for example, by GC (ISO23275).

[0065] The random transesterified fat product obtained by the method according to the present invention preferably contains at least 1% by weight of StStSt (tristearin triglyceride), more preferably at least 1.5% by weight, even more preferably from 2.0% to 50% by weight, and preferably from 2.1% to 20% by weight of StStSt.

[0066] Accordingly, in a preferred embodiment, a method for preparing an edible random transesterified fat product according to the present invention comprises: a) providing a fat composition containing from 0.5% to 20% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition in an amount of from 0.5% to 8% by weight based on the weight of the provided fat composition, using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.2 to 18.0, the resulting random transesterified fat product has less than 0.80% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.3:1 to 3:1, and has at least 1% by weight of StStSt (tristearin triglyceride).

[0067] In a more preferred embodiment, the method for preparing an edible random ester-exchanged fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition in an amount of 0.5% to 6% by weight based on the weight of the provided fat composition, using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.3 to 15.0, the resulting random ester-exchanged fat product has 0.01% to 0.50% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.4:1 to 2.5:1, and has at least 1.5% by weight of StStSt (tristearin triglyceride).

[0068] In an even more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.8 wt% to 17 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 5 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof, the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 15.0, the resulting random interesterified fat product has 0.01 wt% to 0.40 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.4:1 to 2:1, and has 2.0 wt% to 50 wt% StStSt (tristearin triglyceride).

[0069] In the most preferred embodiment, the method for preparing an edible random ester-exchanged fat product according to the present invention comprises: a) providing a fat composition containing 1.0% to 16% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 3% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is glycerol, the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 10.0, the resulting random ester-exchanged fat product has 0.01% to 0.30% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.5:1 to 1.5:1, and has 2.1% to 20% by weight of StStSt (tristearin triglyceride).

[0070] In an additional preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; b) enzymatically reacting the provided fat composition with a polyol composition in an amount of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosa, or Rhizopus oryzae, wherein the polyol composition is glycerol and the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.5 to 10.0, and the resulting random interesterified fat product has 0.01 wt% to 0.30 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, a weight ratio of stearic acid (C18:0) to oleic acid (C18:1) of from 0.5:1 to 1.5:1, and 2.1 wt% to 20 wt% StStSt (tristearin triglyceride); and c) purifying the resulting random interesterified fat product, with physical purification being more preferred.

[0071] In another preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, and 3 wt% to 15 wt% unsaponifiables; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is glycerol, the weight ratio of free fatty acids in the provided fat composition to glycerol is 0.5 to 10.0, the resulting random interesterified fat product has 0.01 wt% to 0.30 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is 0.5:1 to 1.5:1, and has 2.1 wt% to 20 wt% StStSt (tristearin triglyceride).

[0072] In an alternative preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition comprising from 1.0 wt% to 16 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of from 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition is a mixture of glycerol and propylene glycol, the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 10.0, the resulting random interesterified fat product has less than 1.0 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.5:1 to 1.5:1, and has from 2.1 wt% to 20 wt% StStSt (tristearin triglyceride).

[0073] The term "triglyceride (TAG)" refers to a glyceride consisting of three fatty acid chains covalently bonded to a glycerol molecule. The term "diglyceride (DAG)" refers to a glyceride consisting of two fatty acid chains covalently bonded to a glycerol molecule and is not necessarily limited to a specific position (position 1 and 3 or position 1 and 2) on the glycerol backbone. The term "monoglyceride (MAG)" refers to a glyceride consisting of one fatty acid chain covalently bonded to a glycerol molecule and is not necessarily limited to a specific position (position 1, 2 or 3) on the glycerol backbone. The triglyceride content, diglyceride content and monoglyceride content can be determined, for example, by high performance size exclusion chromatography according to ISO 18395:2005(E).

[0074] According to the present invention, the random transesterified fat product obtained by this method preferably contains 0.01% to 5% by weight of monoglycerides, more preferably 0.05% to 4% by weight, even more preferably 0.1% to 3% by weight, and most preferably 0.2% to 3% by weight of monoglycerides.

[0075] The random transesterified fat product obtained by the method according to the present invention preferably contains 1% to 35% by weight of diglycerides, more preferably 5% to 35% by weight, even more preferably 10% to 35% by weight, and most preferably 10% to 32% by weight of diglycerides.

[0076] The presence of monoglycerides and diglycerides generated in situ in the random transesterified fat product produced according to the method of the present invention provides an additional emulsifying function to the random transesterified fat product without adding an emulsifier. This property is particularly suitable for applications involving emulsification such as margarine.

[0077] When propylene glycol is used in the polyol composition in step b) of the method according to the present invention, propylene glycol esters can also be generated in situ in the obtained random transesterified fat product. Polyglycerol esters of fatty acids can also be generated in situ in the obtained random transesterified fat product produced according to the method of the present invention when polyglycerol is used. The variously generated emulsifiers such as propylene glycol esters and polyglycerol esters provide emulsifying properties to the obtained random transesterified fat product without adding any additional emulsifier.

[0078] Accordingly, in a preferred embodiment, a method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5 wt% to 20 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 0.5 wt% to 8 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol and the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.2 to 18.0, and the resulting random interesterified fat product has less than 0.80 wt% free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, a weight ratio of stearic acid (C18:0) to oleic acid (C18:1) of from 0.3:1 to 3:1, at least 1 wt% of StStSt (tristearin triglyceride), from 0.01 wt% to 5 wt% of monoglyceride, and from 1 wt% to 35 wt% of diglyceride.

[0079] In a more preferred embodiment, the method for preparing an edible random esterified fat product according to the present invention comprises: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 0.5% to 6% by weight based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol, and the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.3 to 15.0, and the resulting random esterified fat product has 0.01% to 0.50% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, a weight ratio of stearic acid (C18:0) to oleic acid (C18:1) of from 0.4:1 to 2.5:1, at least 1.5% by weight of StStSt (tristearin triglyceride), from 0.05% to 4% by weight of monoglyceride, and from 5% to 35% by weight of diglyceride.

[0080] In an even more preferred embodiment, the method for preparing an edible random interesterified fat product according to the present invention comprises: a) providing a fat composition containing 0.8% to 17% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1% to 5% by weight based on the weight of the provided fat composition, using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol and the weight ratio of free fatty acids to glycerol in the provided fat composition is from 0.5 to 15.0, and the resulting random interesterified fat product has 0.01% to 0.40% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, a weight ratio of stearic acid (C18:0) to oleic acid (C18:1) of from 0.4:1 to 2:1, 2.0% to 50% by weight of StStSt (tristearin triglyceride), 0.1% to 3% by weight of monoglyceride, and 20% to 35% by weight of diglyceride.

[0081] In the most preferred embodiment, the method for preparing an edible random ester-exchanged fat product according to the present invention comprises: a) providing a fat composition containing 1.0 wt% to 16 wt% of free fatty acids as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; and b) enzymatically reacting the provided fat composition with a polyol composition of 1 wt% to 3 wt% based on the weight of the provided fat composition using an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae, wherein the polyol composition consists of glycerol and the weight ratio of free fatty acids in the provided fat composition to glycerol is from 0.5 to 10.0, and the obtained random ester-exchanged fat product has 0.01 wt% to 0.30 wt% of free fatty acids as measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) is from 0.5:1 to 1.5:1, and has 2.1 wt% to 20 wt% of StStSt (tristearin triglyceride), 0.2 wt% to 3 wt% of monoglyceride, and 10 wt% to 32 wt% of diglyceride.

[0082] The present invention also relates to the use of an edible random ester-exchanged fat product produced according to the method of the present invention in food applications such as confectionery, bakery or cuisine. Preferably, the edible random ester-exchanged fat product produced according to the method of the present invention is used in cream, spread, filling, coating, margarine or shortening.

[0083] In one aspect, a confectionery product manufactured from an edible random interesterified fat product produced according to the method of the present invention is typically a chocolate-like product and can be selected, for example, from bars, fillings, biscuit creams, and confectionery coatings. A filling is preferred. The confectionery product preferably contains one or more additional ingredients such as skim milk powder, cocoa butter, nut-based materials (e.g., hazelnut pieces and / or hazelnut paste), and emulsifiers (e.g., lecithin, PGPR, sorbitan tristearate, or mixtures thereof). Further optional ingredients include flavors (e.g., vanilla, vanillin, mint, orange, etc.), colorants, and inclusions such as confectionery and fruit pieces.

[0084] In another aspect, margarine can be formed by mixing an edible random interesterified fat product produced according to the method of the present invention with an aqueous phase to form an oil-in-water emulsion. Preferably, no additional emulsifier is required. The amounts of the fat and aqueous phases are typically in the range of 10 to 90 wt% fat and 90 to 10 wt% aqueous phase, for example, 20 to 80 wt% fat and 80 to 20 wt% aqueous phase, or 30 to 70 wt% fat and 70 to 30 wt% aqueous phase. Further components of the margarine include one or more of colorants (such as beta-carotene), flavoring agents (e.g., salt and / or citric acid), and preservatives (e.g., potassium sorbate), and typically these components are present in an amount of less than 5 wt% (e.g., 0.1 to 3 wt%) based on the weight of the margarine. The preparation of margarine from vegetable fat and an aqueous phase is well known to those skilled in the art. Margarine typically contains about 80 to 90 wt% of a fat phase. The margarine can be packaged, for example, in a tub-type container or wrapping paper.

[0085] In a further aspect, an edible random transesterified fat product produced according to the method of the present invention can be used for the use of whipped cream. Whipped cream is typically an oil-in-water emulsion that incorporates a suspended gas such as air. Whipped cream can include an edible random transesterified fat product produced according to the method of the present invention, water, and, optionally, one or more of sugar, non-fat milk powder, and, optionally, an emulsifier. Typically, whipped cream contains 10% to 50% by weight of sugar, 20% to 50% by weight of fat, 10% to 40% by weight of water, and, optionally, up to 10% by weight of non-fat dry milk, and, optionally, up to 5% by weight of an emulsifier.

[0086] A list or discussion of documents clearly disclosed previously herein is not necessarily to be construed as an admission that such document is part of the prior art or common general knowledge.

[0087] Priority and options for a given aspect, embodiment, feature, or parameter of the present invention are to be considered as disclosed in combination with all priorities and options for all other aspects, embodiments, features, and parameters of the present invention, unless otherwise indicated in context.

[0088] The following non-limiting examples illustrate the present invention and are not intended to limit its scope in any way. In the examples and throughout this specification, all percentages, parts, and ratios are by weight unless otherwise indicated.

Examples

[0089] Throughout these examples: FFA as oleic acid refers to the free fatty acid content measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid, Cx:y refers to a fatty acid having x carbon atoms and y double bonds, and the levels are measured by GC-FAME (ISO12966-2 and ISO12966-4), O, P, St, and L refer to oleic acid, palmitic acid, stearic acid, and linoleic acid respectively, Triglyceride compositions such as POSt are measured by GC (ISO23275) and include triglycerides having the same fatty acid at different positions (e.g., POSt includes PStO and StPO), US-Nx refers to the solid fat content measured by NMR (ISO8292-1) of non-stabilized fat at x °C, The percentage of unsaponifiables is measured according to AOCS Ca 6a-40, Yellow and red indicate the color measurement of a 1-inch (25.4 mm) cuvette using a Lovibond Tintometer (ISO15305), TAG / DAG / MAG is determined according to ISO18395:2005(E).

[0090] Example 1 Crude cacao olein is obtained by solvent fractionation of crude cacao butter. 800 g of crude cacao olein containing 16 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acid in the fat composition to glycerol is calculated as 15 / 2 and is 7.5. The reaction was catalyzed by an immobilized lipase derived from Rhizomucor miehei immobilized on a macroporous anion resin (Novozym® 40086). After about 24 hours, after the reaction was complete, the product was filtered.

[0091] A commercially available fat Creamelt® Stand obtained from Bunge Loders Croklaan BV of the Netherlands was regarded as a reference. Creamelt® Stand is a chemically interesterified cacao olein, and during processing, excess free fatty acid was removed by distillation before chemical interesterification. Table 1 shows the analysis results of the crude cacao olein, the reference product, and the product obtained by the method of the present invention.

Table 1

[0092] This result shows that according to the method of the present invention, for the random transesterified fat product, without removing free fatty acids from crude cacao butter, a triglyceride composition and solid fat content profile similar to those of conventional chemically transesterified cacao butter can be obtained. The degree of randomization of fat product 1 can be calculated based on the triglyceride that decreased the most during the reaction (StOO in this example), considering 100% randomization of the reference sample. Thus, the degree of randomization is (StOO (crude cacao butter) - StOO (fat product 1)) / (StOO (crude cacao butter) - StOO (reference 1)) x 100%, that is, 84%.

[0093] Comparative Example 1 300 g of crude cacao butter containing 6 g of glycerol (2% by weight based on the total fat composition) was prepared, heated to 110 °C, and dried under vacuum at a pressure of about 10 mbar for 30 minutes. Sodium methoxide (0.10% by weight concentration) was added to this dried oil, and the mixture was stirred at about 10 mbar for 30 minutes. Thereafter, the reaction was stopped by adding citric acid, and the formed soap was removed by silica gel. The analysis results of the crude cacao butter, reference product, and comparative example product are shown in Table 2. [Table 2]

[0094] This result indicates that without removing free fatty acids, crude cacao olein cannot be chemically transesterified, as no significant change in the triglyceride composition and / or solid fat content profile was observed between the crude cacao olein and the comparative fat product 1. The degree of randomization of the comparative fat product 1 can be calculated based on the triglyceride that decreased the most during the reaction (StOO in this example), considering 100% randomization of the reference sample. Thus, the degree of randomization is (StOO (crude cacao olein) - StOO (comparative fat product 1)) / (StOO (crude cacao olein) - StOO (reference 1)) x 100, which is only 5.5%.

[0095] Example 2 800 g of crude cacao olein containing 16 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. The reaction was catalyzed by an immobilized lipase derived from Rhizomucor miehei immobilized on a macroporous anion resin (Novozym® 40086). After about 24 hours, when the reaction was complete, the product was filtered. The filtered enzyme was reused again when preparing a new 800 g of crude cacao olein containing 16 g of glycerol. The filtered enzyme was reused 12 times. In each batch of the product, the solid fat content profile was measured to monitor the performance of the enzyme stability. The results are shown in Table 3 below. [Table 3]

[0096] This result shows that the enzyme performance is quite good and stable in this method, despite the high free fatty acid content in the starting material (crude cacao olein).

[0097] Example 3 600 g of crude cacao butter containing 12 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids in the fat composition to glycerol was calculated as 14.47 / 2 and was 7.2. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, when the reaction was complete, the product was filtered. Subsequently, the product was bleached at 90 °C for 30 minutes using 1.5% acid-activated bleaching earth and deodorized at 230 °C for 4 hours under a vacuum of 0.05 - 0.2 mbar using a batch deodorizer. Table 4 shows the analysis results of the crude cacao butter and the product obtained by the method of the present invention. [Table 4]

[0098] Comparative Example 3.1 The same crude cacao butter from Example 3 was first distilled to remove excess free fatty acids and then subjected to chemical transesterification by short-path distillation at a temperature of about 200 °C and a pressure of about 8 × 10 -3 mbar. About 300 g of distilled cacao butter was prepared, heated to 110 °C, and dried under a vacuum of about 10 mbar for 30 minutes. Sodium methoxide (0.2% by weight concentration) was added to this dried oil, and the mixture was stirred at about 10 mbar for 30 minutes. Thereafter, the reaction was stopped by adding citric acid, and the soap formed was removed by silica gel. Subsequently, the product was bleached at 90 °C for 30 minutes using 1.5% acid-activated bleaching earth and deodorized at 230 °C for 4 hours under a vacuum of 0.05 - 0.2 mbar using a batch deodorizer. Table 5 shows the analysis results of the crude cacao butter, the distilled cacao butter, and Comparative Example Product 3.1. [Table 5]

[0099] Comparative Example 3.2 The same crude chia olein from Example 3 was first distilled to remove excess free fatty acids and then subjected to enzymatic transesterification by short-path distillation at a temperature of about 200 °C and a pressure of about 8 × 10 -3 mbar. A total of about 400 g of distilled chia olein was prepared and heated to 60 °C. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, when the reaction was complete, the product was filtered. Subsequently, the product was bleached at 90 °C for 30 minutes using 1.5% acid-activated bleaching earth and deodorized at 230 °C for 4 hours under a vacuum of 0.05 - 0.2 mbar using a batch deodorant. The analysis results of the crude chia olein, distilled chia olein, and Comparative Example Product 3.2 are shown in Table 6.

Table 6

[0100] This result shows that the product of Example 3, where deacidification (distillation of free fatty acids) was not performed before enzymatic transesterification by the method of the present invention, has unexpectedly preferable yellow and red colors after purification compared to the product of Comparative Example 3.1, where deacidification (distillation of free fatty acids) was performed before chemical transesterification, and the product of Comparative Example 3.2, where deacidification was performed before enzymatic transesterification. The method according to the present invention not only improves the efficiency of the process without losing a significant amount of fatty acids (improvement in yield by about 15%) but also enables the production of high-quality fat products with desirable bright colors.

[0101] Example 4 600 g of crude chia butter containing 12 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids to glycerol in the fat composition was calculated as 6.27 / 2 and was about 3.1. The reaction was catalyzed by an immobilized lipase derived from Rhizomucor miehei immobilized on a macroporous anion resin (Novozym® 40086). After about 24 hours, when the reaction was complete, the product was filtered.

[0102] The chemically transesterified shea butter is regarded as a reference for indicating the degree of transesterification based on the triglyceride composition. Before chemical transesterification, it is necessary to remove free fatty acids by distillation / deodorization, as is well known in the art. The analysis results of crude shea butter, the product by the method of the present invention, and the reference are shown in Table 7. [Table 7]

[0103] This result shows that according to the method of the present invention, without removing free fatty acids from crude shea butter, for random transesterified fat products, triglyceride compositions and solid fat content profiles similar to those of conventional chemically transesterified shea butter can be obtained. The degree of randomization of fat product 4 can be calculated based on the triglyceride (StOSt in this example) that decreased the most during the reaction, considering 100% randomization of the reference sample. Therefore, the degree of randomization is (StOSt (crude shea butter) - StOSt (fat product 4)) / (StOSt (crude shea butter) - StOSt (reference 2)) x 100%, that is, 93.4%.

[0104] Example 5 560 g of crude shea olein and 240 g of shea stearin containing 16 g of glycerol (2% by weight based on the total fat composition) were prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids in the fat composition to glycerol is calculated as 11 / 2 and is 5.5. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, after the reaction was completed, the product was filtered. The analysis results of the crude shea olein / shea stearin blend and the product obtained by the method of the present invention are shown in Table 8. [Table 8]

[0105] Example 6 600 g of crude cacao olein (the same crude cacao olein as in Example 1) containing 12 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70°C. Thus, the weight ratio of free fatty acid in the fat composition to glycerol was calculated as 15 / 2 and was 7.5. The reaction was catalyzed by an immobilized lipase derived from Rhizopus oryzae immobilized on polypropylene (Accurel®). After about 24 hours, after the reaction was completed, the product was filtered. The analysis results of the product obtained by the method of the present invention are shown in Table 9. [Table 9]

[0106] Example 7 600 g of crude cacao olein (the same crude cacao olein as in Example 1) containing 24 g of glycerol (4% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70°C. Thus, the weight ratio of free fatty acid in the fat composition to glycerol was calculated as 15 / 4 and was approximately 3.8. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, after the reaction was completed, the product was filtered. The analysis results of the product obtained by the method of the present invention are shown in Table 10. [Table 10]

[0107] Example 8 600 g of cocoa butter containing 6 g of glycerol (1 wt% based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids to glycerol in the fat composition was calculated to be 1.01 / 1 and was approximately 1.0. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, when the reaction was complete, the product was filtered.

[0108] The chemically interesterified cocoa butter is regarded as a reference for indicating the degree of interesterification based on the triglyceride composition. Before chemical interesterification, as is well known in the art, it is necessary to remove free fatty acids either by distillation / deodorization or chemical neutralization. The analysis results of cocoa butter, the product obtained by the method of the present invention, and the reference are shown in Table 11.

Table 11

[0109] This result shows that according to the method of the present invention, a similar random interesterified fat product can be obtained without removing free fatty acids from cocoa butter. Furthermore, monoglycerides and diglycerides are also produced in this process, and the content of monoglycerides in the fat product is 2.1 wt%. The produced monoglycerides and diglycerides may provide additional emulsifying properties to the random interesterified fat product. The degree of randomization of fat product 8 can be calculated based on the triglyceride that decreased the most during the reaction (POSt in this example), considering 100% randomization of the reference sample. Thus, the degree of randomization is (POSt (cocoa butter) - POSt (fat product 8)) / (POSt (cocoa butter) - POSt (reference 3)) x 100%, that is, 94.1%.

[0110] Example 9 600 g of cocoa butter containing 12 g of glycerol (2% by weight based on the total fat composition) was prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids in the fat composition to glycerol was calculated to be 1.01 / 1 and was approximately 0.5. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, after the reaction was complete, the product was filtered.

[0111] Chemically transesterified cocoa butter is regarded as a reference for indicating the degree of transesterification based on the triglyceride composition. Before chemical transesterification, as is well known in the art, it is necessary to remove free fatty acids either by distillation / deodorization or chemical neutralization. The analysis results of cocoa butter, the product obtained by the method of the present invention, and the reference are shown in Table 12.

Table 12

[0112] This result shows that according to the method of the present invention, a similar randomly transesterified fat product can be obtained without removing free fatty acids from cocoa butter. Furthermore, monoglycerides and diglycerides are also produced from this process, and the content of monoglycerides in the fat product is 2.6% by weight. The produced monoglycerides and diglycerides provide additional emulsifying properties to the randomly transesterified fat product. The degree of randomization of fat product 9 can be calculated based on the triglyceride that decreased the most during the reaction (POSt in this example), taking into account the 100% randomization of the reference sample. Therefore, the degree of randomization is (POSt (cocoa butter) - POSt (fat product 9)) / (POSt (cocoa butter) - POSt (reference 3)) x 100%, that is, 92.2%.

[0113] Example 10 480 g of crude shea olein and 320 g of crude shea butter containing 12 g of glycerol and 12 g of propylene glycol (3% by weight of the polyol compound based on the total fat composition) were prepared in a glass container and mixed with nitrogen gas from the bottom at 70 °C. Thus, the weight ratio of free fatty acids to the polyol compound (glycerol and propylene glycol) in the fat composition was calculated as 15 / 3 and was 5.0. The reaction was catalyzed by an immobilized lipase derived from Candida antarctica B immobilized on a macroporous acrylic resin (Novozym® 435). After about 24 hours, after the reaction was complete, the product was filtered. The analysis results of the crude shea olein / sheastearin blend and the product obtained by the method of the present invention are shown in Table 13.

Table 13

[0114] This result shows that according to the present invention, random transesterified fat products can be produced by using various polyol compounds.

[0115] Example 11 The initial crystallization curves of fat product 1 and reference 1 (Creamelt® Stand) at 20 °C were measured up to 40 minutes using pulsed NMR conforming to ISO 8292-1. Both curves are shown in Figure 1. This result shows that fat product 1 has a faster initial crystallization rate and forms more initial solids, which is particularly desirable for various applications such as creams, spreads, fillings, margarines, shortenings.

Claims

Claim 1 A method for preparing a randomly transesterified fat product for consumption, comprising: a) providing a fat composition containing 0.5% to 18% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; b) enzymatically reacting the fat composition provided in step a) with a polyol composition in an amount of 0.5% to 10% by weight based on the weight of the fat composition, wherein the weight ratio of the free fatty acids in the fat composition to the polyol composition is from 0.1 to 20.0; wherein the obtained randomly transesterified fat product has less than 1.0% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid; in step a), the fat composition is selected from shea butter, cocoa butter, sal fat, mango kernel oil, illipe butter, kokum butter, murumuru butter, high-stearic acid high-oleic acid sunflower oil, fractions thereof and mixtures thereof. Claim 2 The method according to claim 1, wherein the weight ratio of the free fatty acids in the fat composition of step a) to the polyol composition of step b) is from 0.2 to 18.

0. Claim 3 The method according to claim 1 or claim 2, wherein in step a), the fat composition contains 0.8% to 17% by weight of free fatty acids, measured according to AOCS Ca 5a-40 and calculated as a percentage of oleic acid. Claim 4 The method according to any one of claims 1 to 3, wherein in step a), the fat composition is selected from cocoa butter, shea butter, shea olein, shea stearin and mixtures thereof. Claim 5 The method according to any one of claims 1 to 4, wherein in step a), the fat composition contains at least 15% by weight of stearic acid (C18:0), and the percentage of the free fatty acids relates to the acids bonded as acyl groups in the glycerides and any free fatty acids present in the fat composition, and is based on the total weight of the fatty acids from C8 to C24. Claim 6 The method according to any one of claims 1 to 5, wherein in step a), the fat composition contains at least 1% by weight of unsaponifiables. Claim 7 The method according to any one of claims 1 to 6, wherein in step b), the provided fat composition reacts with 0.5% to 8% by weight of the polyol composition based on the weight of the provided fat composition. **Claim 8** The method according to any one of claims 1 to 7, wherein in step b), the polyol composition is selected from glycerol, propylene glycol, polyglycerol, and mixtures thereof. **Claim 9** The method according to claim 8, wherein in step b), the polyol composition consists of glycerol. **Claim 10** The method according to any one of claims 1 to 9, wherein in step b), the reaction is catalyzed by lipase. **Claim 11** The method according to claim 10, wherein in step b), the reaction is catalyzed by immobilized lipase. **Claim 12** The method according to claim 11, wherein in step b), the reaction is catalyzed by an immobilized lipase derived from Rhizomucor miehei, Candida antarctica, Thermomyces lanuginosus, or Rhizopus oryzae. **Claim 13** The method according to any one of claims 1 to 12, wherein the randomly transesterified fat product obtained has less than 0.80% by weight of free fatty acids, calculated as a percentage of oleic acid, as measured according to AOCS Ca 5a-40. **Claim 14** The method according to any one of claims 1 to 13, wherein the randomly transesterified fat product obtained has a degree of randomization of at least 70%. **Claim 15** The method according to any one of claims 1 to 14, wherein the randomly transesterified fat product obtained contains 0.01% to 5% by weight of monoglycerides. **Claim 16** The method according to any one of claims 1 to 15, wherein the randomly transesterified fat product obtained contains 1% to 35% by weight of diglycerides. **Claim 17** The method according to any one of claims 1 to 16, wherein the weight ratio of stearic acid (C18:0) to oleic acid (C18:1) in the randomly transesterified fat product obtained is from 0.3:1 to 3:

1. **Claim 18** The method according to any one of claims 1 to 17, wherein the remembered randomly transesterified fat product contains at least 1% by weight of StStSt (tristearin triglyceride). **Claim 19** Use of an edible randomly transesterified fat product produced according to the method according to any one of claims 1 to 18 in food applications such as confectionery, bakery or cooking.

Images