Method for producing interesterified fat

Abstract

To provide a method for efficiently producing diacylglycerol-rich interesterified fat while performing a glycerolysis reaction at a low temperature by enhancing the initial reaction rate.SOLUTION: A method for producing interesterified fat includes a step of reacting fat with glycerol in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, wherein a mixture of glycerol and the calcium-based catalyst that has been pre-mixed is added after heating the fat to 90°C or higher.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing interesterified fats and oils rich in diacylglycerol. [Background technology]

[0002] Diacylglycerol is used in various industrial fields such as food and cosmetics. Generally, diacylglycerol is produced by an esterification reaction between glycerin and a fatty acid, or a glycerolysis reaction between glycerin and fats and oils. These production methods are roughly divided into chemical methods using chemical catalysts such as hydroxides and alkoxides of alkali metals or alkaline earth metals, and enzymatic methods using enzymes such as lipase (e.g., Patent Documents 1 and 2). In the glycerolysis method using a chemical catalyst, a chemical catalyst is added to fats and oils and glycerin, and then the temperature is raised to the reaction temperature to produce a glyceride composition containing diacylglycerol.

[0003] The glycerolysis method can produce diacylglycerol with fewer steps than the esterification method. However, the glycerolysis method has a high reaction temperature, which makes it easy for unsaturated fatty acids to be converted into trans acids, resulting in the production of a large amount of trans acids. This is particularly noticeable in polyunsaturated fatty acids with a large number of unsaturated bonds. Therefore, treatment at a lower temperature is desirable. On the other hand, a low reaction temperature is inefficient because it takes time to start the reaction and to reach reaction equilibrium. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2005-504862 [Patent Document 2] JP 2004-222595 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a method for efficiently producing transesterified fats and oils rich in diacylglycerol by carrying out a glycerolysis reaction at a low temperature while increasing the initial reaction rate. [Means for solving the problem]

[0006] The present inventors have conducted intensive research in view of the above problems and have found that if glycerin and a calcium-based catalyst are mixed in advance, and the mixture of glycerin and a calcium-based catalyst is added and reacted after the oil or fat reaches a predetermined temperature, the initial reaction rate is increased even at a low reaction temperature, and transesterified oil or fat rich in diacylglycerol can be efficiently obtained.

[0007] That is, the present invention provides a method for producing transesterified fats and oils, which includes a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, and after the fats and oils are heated to 90°C or higher, a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. Effect of the Invention

[0008] According to the present invention, transesterified oils and fats rich in diacylglycerol can be efficiently obtained by a glycerolysis reaction at a low temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The method for producing interesterified fats and oils of the present invention includes a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, and after heating the fats and oils to 90°C or higher, a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. In this specification, "fat" and "oil" are synonymous. In addition, substances constituting fats and oils (oils) include not only triacylglycerols but also monoacylglycerols and diacylglycerols. In other words, fats and oils (oils) contain at least one of monoacylglycerols, diacylglycerols, and triacylglycerols.

[0010] In the present invention, the fats and oils to be reacted with glycerin are generally those mainly composed of triacylglycerol, and examples thereof include soybean oil, rapeseed oil, safflower oil, rice oil, corn oil, sunflower oil, cottonseed oil, olive oil, sesame oil, peanut oil, pearl barley oil, wheat germ oil, perilla oil, linseed oil, perilla oil, chia seed oil, sacha inchi oil, walnut oil, kiwi seed oil, salvia seed oil, grape seed oil, macadamia nut oil, and hazelnut oil. Examples of the oils and fats include vegetable oils and fats such as tallow oil, pumpkin seed oil, camellia oil, tea seed oil, borage oil, palm oil, palm olein, palm stearin, coconut oil, palm kernel oil, cacao butter, monkey fat, shea butter, and algae oil; animal oils and fats such as fish oil, seal oil, whale oil, lard, beef tallow, and butter fat; microbial oils such as oils and fats derived from microorganisms producing polyunsaturated fatty acids such as zygomycetes; and oils and fats such as transesterified oils, hydrogenated oils, and fractionated oils of these. The oils and fats can be used alone or in combination of two or more. Among them, the oil and fat is preferably a liquid oil and fat from the viewpoint of the emulsification characteristics of the transesterified oil and fat and ease of handling. Note that the liquid oil and fat refers to an oil and fat that is liquid at 20°C when a cooling test according to the Standard Fats and Oils Analysis Test Method 2.3.8-27 is carried out. In addition, in the present invention, since the production of trans acids is suppressed by the reaction at a low temperature, unlike a normal glycerolysis reaction, it is preferable to use fatty acids with a carbon chain length of 18 or more and the number of double bonds of 3 or more, which are expected to have various physiological functions. In particular, it is preferable to use one or more types of oils and fats selected from oils and fats rich in ω3 unsaturated fatty acids, such as perilla oil, linseed oil, perilla oil, chia seed oil, sacha inchi oil, algae oil, fish oil, seal oil, whale oil, and oils and fats derived from microorganisms producing polyunsaturated fatty acids.

[0011] Fish oil can be extracted from raw materials such as sardines, herring, pacific saury, mackerel, bonito, tuna, squid, cod liver, etc. Algal oil can be extracted from algae belonging to the Chlorophyceae, Bacillariophyceae, etc. It is preferable to appropriately carry out known separation and purification means such as liquid-liquid separation, filtration, and centrifugation to remove impurities before the reaction. In addition, so-called concentrated oils may be used, which are produced by selectively hydrolyzing fish oil or the like using lipase to increase the ratio of unsaturated fatty acids such as eicosapentaenoic acid (C20:5, EPA) and docosahexaenoic acid (C22:6, DHA) in the fatty acids that make up the oil.

[0012] The triacylglycerol content in the oil may be 100% by mass, but is preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 89% by mass or less in order to easily concentrate highly unsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid in the transesterified oil, and is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more in terms of production efficiency. In order to make the triacylglycerol content in the oil to be reacted with glycerin less than 100% by mass, it is preferable to partially hydrolyze the oil by acting lipase on the oil, and then remove the resulting fatty acid by distillation. By this operation, it is possible to selectively remove saturated fatty acids with carbon numbers of 16 and 18 in the constituent fatty acids, and it is possible to further concentrate highly unsaturated fatty acids in the oil to be reacted with glycerin. In addition, the content of free fatty acids or salts thereof in the fats and oils is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 4% by mass or less, and even more preferably 1% by mass or less in terms of preventing catalyst deactivation, and is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more in terms of production efficiency.

[0013] The constituent fatty acids constituting the oil or fat are not particularly limited, and may be either saturated fatty acids or unsaturated fatty acids. From the viewpoints of handling properties and industrial productivity of the oil, the content of unsaturated fatty acids in the fatty acids constituting the oil is preferably 60 to 100% by mass, more preferably 70 to 98% by mass, and even more preferably 80 to 96% by mass. From the viewpoint of physiological effects, the number of carbon atoms of the unsaturated fatty acids is preferably 14 to 24, more preferably 16 to 22, and even more preferably 18 to 22. In this specification, the amount of fatty acid is calculated as the amount of free fatty acid.

[0014] In view of their physiological activity, it is preferable that the fatty acids constituting the oils and fats contain a large amount of fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more. Furthermore, according to the method of the present invention, it is possible to obtain an interesterified oil and fat having a high ratio of fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more in the reacted oil, while preventing the ratio of the fatty acids in the reacted oil from being lower than the ratio of the fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more in the reacting raw material oil and fat. The total content of fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more in the fatty acids constituting the oil is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and even more preferably 30% by mass or more from the viewpoint of physiological activity, and is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less from the viewpoint of suppressing by-production of trans fatty acids. The total content of fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more in the fatty acids constituting the oil is preferably 15 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 25 to 80% by mass, and even more preferably 30 to 80% by mass. Examples of fatty acids that have a carbon chain length of 18 or more and a double bond number of 3 or more in the fatty acids that compose the oils and fats include α-linolenic acid (C18:3), γ-linolenic acid (C18:3), arachidonic acid (C20:4), eicosapentaenoic acid (C20:5, EPA), docosapentaenoic acid (C22:5), docosahexaenoic acid (C22:6, DHA), etc. Among them, ω3 unsaturated fatty acids having a double bond at the third position counting from the methyl end of the carbon chain are preferred in terms of physiological activity and ease of enjoying the effects of the present invention.

[0015] The glycerin used in the present invention preferably has a purity of 95% by mass or more in terms of improving reactivity.

[0016] In the present invention, the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups when reacting fats and oils with glycerin [FA / GLY] is preferably 0.60 or more, more preferably 0.65 or more, even more preferably 0.70 or more, even more preferably 0.75 or more, and even more preferably 0.80 or more, from the viewpoint of reducing glycerin that does not dissolve in the oil phase, and is preferably 2.0 or less, more preferably 1.7 or less, and even more preferably 1.4 or less, from the viewpoint of producing diacylglycerol. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups when reacting fats and oils with glycerin [FA / GLY] is preferably 0.60 to 2.0, more preferably 0.65 to 1.7, even more preferably 0.70 to 1.7, even more preferably 0.75 to 1.4, and even more preferably 0.80 to 1.4. The ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] is expressed by the following formula. FA / GLY = (moles of fatty acids + moles of monoacylglycerol + moles of diacylglycerol x 2 + moles of triacylglycerol x 3) / (moles of glycerin + moles of monoacylglycerol + moles of diacylglycerol + moles of triacylglycerol)

[0017] The reaction between the fat or oil and glycerin is carried out in the presence of a calcium-based catalyst. The calcium catalyst used in the present invention is not particularly limited as long as it catalyzes the glycerolysis reaction, and examples thereof include calcium halides such as calcium hydroxide, calcium carbonate, calcium oxide, and calcium silicate, calcium alkoxides such as calcium methoxide, etc. These may be used alone or in combination of two or more. Among these, calcium hydroxide is preferred since it can shorten the time from addition of the catalyst to the start of the reaction.

[0018] In the present invention, the amount of calcium-based catalyst added (total amount added) is, from the viewpoint of improving reactivity, preferably such that the ratio of the molar amount of calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] is 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, still more preferably 3.0 or more, still more preferably 4.0 or more, and still more preferably 5.0 or more, and from the viewpoint of reducing the amount of neutralizing agent, is preferably 490 or less, more preferably 300 or less, still more preferably 150 or less, still more preferably 100 or less, still more preferably 50 or less, and still more preferably 20 or less. The amount of calcium-based catalyst added is preferably 0.5 to 490, more preferably 1.0 to 300, even more preferably 2.0 to 150, still more preferably 3.0 to 100, still more preferably 4.0 to 50, and even more preferably 5.0 to 20, in terms of the ratio of the molar amount of calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin].

[0019] The amount of calcium catalyst added (total amount added) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, even more preferably 0.04% by mass or more, and even more preferably 0.06% by mass or more, based on the total of fats and oils and glycerin, from the viewpoint of improving reactivity, and is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less, based on the total of fats and oils and glycerin, from the viewpoint of reducing the amount of neutralizer. The amount of calcium catalyst added is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, even more preferably 0.03 to 3.0% by mass, even more preferably 0.04 to 2.0% by mass, and even more preferably 0.06 to 1.5% by mass.

[0020] In the present invention, glycerin and a calcium-based catalyst are mixed in advance, and the mixture of glycerin and a calcium-based catalyst is added after the temperature of the oil or fat is raised to 90° C. or higher to react the oil or fat with the glycerin. Hereinafter, in this specification, the "mixture of glycerin and a calcium-based catalyst" may be simply referred to as the "mixture". The method for mixing glycerin and the calcium catalyst can be an appropriate method such as stirring, shaking, etc. It is preferable to mix while dehydrating the mixture, in order to reduce the time lag from the addition of the catalyst to the start of the reaction and to reduce the moisture content in the system. The mixing may be performed under reduced pressure or normal pressure. When the mixing is performed under reduced pressure, the pressure is not particularly limited, but is preferably 13000 Pa or less, more preferably 7000 Pa or less, and even more preferably 700 Pa or less, from the viewpoint of reducing the moisture content in the reaction system. When the mixing is performed under normal pressure, it is preferable to perform the mixing under a nitrogen atmosphere in which nitrogen is circulated in order to suppress oxidation of the resulting transesterified oil or fat.

[0021] The mixing temperature of glycerin and the calcium catalyst is preferably 20° C. or higher, more preferably 30° C. or higher, even more preferably 40° C. or higher, and even more preferably 50° C. or higher, from the viewpoint of reducing the time lag from the addition of the catalyst to the start of the reaction, and is preferably 165° C. or lower, more preferably 160° C. or lower, and even more preferably 155° C. or lower, from the viewpoint of industrial productivity. The mixing temperature of glycerin and the calcium catalyst is preferably 20 to 165° C., more preferably 30 to 160° C., even more preferably 40 to 155° C., and even more preferably 50 to 155° C.

[0022] The mixing time of glycerin and calcium catalyst is not particularly limited, but from the viewpoint of uniform dissolution, it is preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, and even more preferably 20 minutes or more, and from the viewpoint of maintaining a uniform dissolution state and industrial productivity, it is preferably 300 minutes or less, more preferably 240 minutes or less, even more preferably 180 minutes or less, and even more preferably 120 minutes or less. The mixing time of glycerin and calcium catalyst is preferably 1 minute or more and 300 minutes or less, more preferably 5 minutes or more and 240 minutes or less, even more preferably 10 minutes or more and 180 minutes or less, and even more preferably 20 minutes or more and 120 minutes or less.

[0023] The amount of the calcium-based catalyst pre-mixed with glycerin is preferably 5% by mass or more of the total amount of calcium-based catalyst added, from the viewpoint of reducing the time lag from the addition of the catalyst to the start of the reaction, more preferably 10% by mass or more, even more preferably 50% by mass or more, and even more preferably 100% by mass. When the amount of calcium-based catalyst premixed with glycerin is less than 100% by mass of the total amount of calcium-based catalyst added, the remaining amount may be added to fats and oils below 90° C. or to fats and oils at 90° C. or higher, but in terms of reducing the amount of neutralizing agent and facilitating purification of the transesterified fats and oils produced, it is preferable to add as little calcium-based catalyst as possible at less than 90° C. Specifically, the amount of calcium-based catalyst added at less than 90° C. varies depending on the type of catalyst, but is preferably 8% by mass or less, more preferably 4% by mass or less, even more preferably 1.2% by mass or less, and even more preferably 0% by mass, based on the total amount of fats and oils and glycerin.

[0024] Moreover, the amount of glycerin pre-mixed with the calcium-based catalyst is preferably 5% by mass or more of the total amount of glycerin, more preferably 10% by mass or more, even more preferably 50% by mass or more, and even more preferably 100% by mass, from the viewpoint of reducing the time lag from the addition of the catalyst to the start of the reaction. When the amount of glycerin to be mixed in advance with the calcium-based catalyst is less than 100% by mass of the total amount of glycerin, the remaining amount may be mixed with fats and oils at less than 90° C. Also, the glycerin may be mixed with fats and oils at less than 90° C. in the form of a mixture with the calcium-based catalyst.

[0025] The mixture is added to the fat after the fat reaches 90°C or higher. In the present invention, it is preferable to add the mixture to the fat at the temperature at which it is mixed, in order to reduce the time lag from the addition of the catalyst to the start of the reaction. If the temperature of the mixture is less than 90°C, it is preferable to adjust the temperature of the fat so that the temperature of the mixture after mixing is 90°C or higher. The temperature of the oil or fat when the mixture is added is preferably 95°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher, from the viewpoint of reducing the time lag from the addition of the catalyst to the start of the reaction, suppressing the deactivation of the catalyst, and improving the purity of diacylglycerol in the reaction oil, and is preferably 165°C or lower, more preferably 160°C or lower, even more preferably 155°C or lower, and even more preferably 150°C or lower, from the viewpoint of improving the quality. The temperature of the oil or fat when the mixture is added is preferably 90 to 165°C, more preferably 95 to 160°C, even more preferably 100 to 155°C, and even more preferably 110 to 150°C. From the same viewpoint, the temperature of the oil or fat when the mixture is added is preferably in the range of reaction temperature -15°C to reaction temperature, more preferably in the range of reaction temperature -10°C to reaction temperature, even more preferably in the range of reaction temperature -5°C to reaction temperature, and even more preferably at the reaction temperature. After adding the mixture to the oil or fat, the temperature is raised to a reaction temperature as necessary to carry out a glycerolysis reaction between the oil or fat and glycerin.

[0026] The reaction temperature is 90° C. or higher and 165° C. or lower, but from the viewpoint of improving the reaction rate, it is preferably 95° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher, and from the viewpoint of reducing the content of by-products, it is preferably 160° C. or lower, more preferably 155° C. or lower, and even more preferably 150° C. or lower. The reaction temperature is 90 to 165° C., preferably 95 to 160° C., more preferably 100 to 155° C., and even more preferably 110 to 150° C.

[0027] When the temperature is raised to the reaction temperature of the oil and glycerin as necessary after the mixture is added, the rate of temperature rise is preferably 0.1° C. / min or more, more preferably 0.15° C. / min or more, and even more preferably 0.2° C. / min or more from the viewpoint of suppressing deactivation of the catalyst and industrial productivity, and is preferably 20° C. / min or less, more preferably 10° C. / min or less, and even more preferably 3° C. / min or less from the viewpoint of a large heating load on the equipment. The rate of temperature rise to the reaction temperature of the oil and glycerin is preferably 0.1 to 20° C. / min, more preferably 0.15 to 10° C. / min, and even more preferably 0.2 to 3° C. / min.

[0028] In the present invention, the reaction time is preferably 0.5 hours or more, more preferably 0.75 hours or more, and even more preferably 1.0 hours or more from the viewpoint of diacylglycerol production, and is preferably within 14.5 hours, more preferably within 11.5 hours, and even more preferably within 8.5 hours from the viewpoint of industrial productivity. By mixing glycerin and a calcium catalyst in advance, the initial reaction rate is increased, and the reaction time can be shortened. The reaction time is preferably 0.5 hours to 14.5 hours, more preferably 0.75 hours to 11.5 hours, and even more preferably 1.0 hours to 8.5 hours from the viewpoint of diacylglycerol production, and is preferably within 14.5 hours, more preferably 0.75 hours to 11.5 hours, and even more preferably 1.0 hours to 8.5 hours from the viewpoint of industrial productivity.

[0029] In order to improve the reactivity and to prevent a decrease in catalytic performance, it is preferable to carry out the reaction between the fat or oil and glycerin after removing water contained in the fat or oil and glycerin by reducing pressure, bubbling with nitrogen, or the like. The reaction may be carried out under reduced pressure or normal pressure. When the reaction is carried out under reduced pressure, the pressure is not particularly limited, but is preferably 13,000 Pa or less in order to reduce the moisture content in the reaction system. When the reaction is carried out under normal pressure, the reaction is preferably carried out under a nitrogen atmosphere in which nitrogen is circulated in order to suppress oxidation of the resulting transesterified oil or fat. After completion of the glycerolysis reaction, it is preferable to neutralize the calcium catalyst and remove it by filtration or the like.

[0030] After the glycerolysis reaction, a purification process that is normally used for fats and oils may be carried out. Specifically, the process may include distillation, acid treatment, washing with water, decolorization, deodorization, etc. In the present invention, after the glycerolysis reaction, an enzymatic esterification reaction may be further carried out, but from the viewpoint of increasing the ratio of diacylglycerol in the reaction oil, it is preferable to carry out a distillation treatment without carrying out an esterification reaction.

[0031] According to the method of the present invention, the initial reaction between fats and oils and glycerin is promoted, so that transesterified fats and oils rich in diacylglycerol can be efficiently produced. In the present invention, the triacylglycerol concentration 0.5 hours after the start of the reaction (the point in time when the reaction temperature is reached after the mixture is added to the oil or fat) is preferably at least 2% by mass lower, and more preferably at least 5% by mass lower, than when glycerin and the catalyst are added separately (including the case where the catalyst is added after the mixture of the oil or fat and glycerin is heated to the reaction temperature; the same applies below), although the effect varies depending on the amount of catalyst.

[0032] In the present invention, the mass % of TAG is analyzed 0.5 hours after the start of the reaction, and the TAG reduction rate (% / h / mol of catalyst / kg) is calculated by the following formula. TAG reduction rate (% / h / catalyst amount mol / kg)=(100-a) / b / c a: mass% of TAG after 0.5 hours of reaction b: Amount of catalyst added to the total of fats and oils and glycerin (mol / kg-raw material) c: Reaction time 0.5 hours The TAG reduction rate (% / h / mol catalyst amount / kg) is preferably 2000 (% / h / mol catalyst amount / kg) or more, more preferably 3500 (% / h / mol catalyst amount / kg) or more, and even more preferably 5500 (% / h / mol catalyst amount / kg) or more, from the viewpoint of diacylglycerol production, and is preferably 30000 (% / h / mol catalyst amount / kg) or less, more preferably 20000 (% / h / mol catalyst amount / kg) or less, and even more preferably 15000 (% / h / mol catalyst amount / kg) or less, from the viewpoint of industrial productivity. In addition, the relative value, taking the TAG reduction rate (% / h / mol catalyst / kg) in the comparative example (catalyst added after heating a mixture of fats and oils to the reaction temperature) as 1, is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more in terms of diacylglycerol production, and is preferably 12 or less, more preferably 9 or less, and even more preferably 6 or less in terms of industrial productivity.

[0033] The interesterified oils and fats obtained by the method of the present invention contain triacylglycerols in addition to diacylglycerols, and also contain unreacted glycerin, fatty acids, and monoacylglycerols, although in smaller amounts compared to the above. The transesterified oil obtained by the method of the present invention is rich in diacylglycerol, and the content is preferably 40% by mass or more in terms of improving physiological activity. The time from the start of the reaction until diacylglycerol reaches 40% by mass (equilibrium composition) can be shortened by preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, compared to the case where glycerin and the catalyst are added separately.

[0034] In relation to the above-mentioned embodiment, the present invention further discloses the following method for producing interesterified oils and fats. <1> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the fats and oils are heated to 95°C or higher, and then a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. <2> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 100°C or higher and 155°C or lower, in which the fats and oils are heated to 100°C or higher, and then a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. <3> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 110°C or higher and 150°C or lower, in which the fats and oils are heated to 110°C or higher, and then a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. <4> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the fats and oils are heated to 90°C or higher, and then a mixture of glycerin and a calcium-based catalyst, which has been previously mixed at 30°C or higher and 160°C or lower, is added to the fats and oils. <5> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the fats and oils are heated to 90°C or higher, and then a mixture of glycerin and a calcium-based catalyst, which has been mixed in advance so that the molar ratio of the calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] is 1.0 to 300, is added. <6> A method for producing transesterified fats and oils, comprising the step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] is 0.65 or higher and 1.7 or lower, and after the fats and oils are heated to 90°C or higher, a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. <7> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the fats and oils are heated to 95°C or higher, and then a mixture of glycerin and a calcium-based catalyst, which has been previously mixed at 30°C or higher and 160°C or lower, is added to the fats and oils. <8> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the fats and oils are heated to 95°C or higher, and then a mixture of glycerin and a calcium-based catalyst, which has been mixed in advance so that the molar ratio of the calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] is 1.0 to 300, is added. <9> A method for producing transesterified fats and oils, comprising the step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, in which the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] is set to 0.65 or higher and 1.7 or lower, and after the fats and oils are heated to 95°C or higher, a mixture of glycerin and a calcium-based catalyst that has been previously mixed is added to the fats and oils. <10> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium catalyst at a reaction temperature of 90°C or higher and 165°C or lower, in which the fats and oils are heated to 90°C or higher, and then a mixture of glycerin and a calcium catalyst, which has been mixed in advance at 30°C or higher and 160°C or lower, with the ratio of the molar amount of the calcium catalyst to the molar amount of glycerin [mmol-calcium catalyst / mol-glycerin] being 1.0 to 300, is added. <11> A method for producing transesterified fats and oils, comprising the step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, wherein the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] is 0.65 or higher and 1.7 or lower, and after the fats and oils are heated to 90°C or higher, a mixture of glycerin and a calcium-based catalyst, which has been previously mixed at 30°C or higher and 160°C or lower, is added to the fats and oils. <12> A method for producing transesterified fats and oils, comprising a step of reacting fats and oils with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, in which the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] is set to 0.65 or higher and 1.7 or lower, and after the fats and oils are heated to 90°C or higher, a mixture of glycerin and a calcium-based catalyst that has been premixed in such a way that the ratio of the molar amount of calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] is 1.0 to 300 is added. EXAMPLES

[0035] In the following examples, "%" means "% by mass."

[0036] [Analysis method] (i) Determination of fatty acid composition The samples were converted into fatty acid methyl esters according to the "Methyl Esterification Method (Boron Trifluoride Methanol Method) (2.4.1.2-1996)" in the "Standard Methods for the Analysis of Fats, Oils and Related Materials, 2003 Edition" compiled by the Japan Oil Chemists' Society, and the obtained samples were subjected to gas chromatography (GC).

[0037] (ii) Measurement of the glyceride composition (MAG, DAG and TAG composition) of the total glyceride of interesterified oils and fats when using linseed oil Approximately 10 mg of transesterified oil and 0.5 mL of trimethylsilylation agent ("Silylation Agent TH", Kanto Chemical) were added to a glass sample bottle, sealed, and heated at 70°C for 15 minutes. 1.5 mL of water and 1.5 mL of hexane were added to the bottle and shaken. After standing, the upper layer was subjected to gas chromatography (GC) to analyze the glyceride composition.

[0038] (iii) Measurement of the glyceride composition (MAG, DAG and TAG composition) of the total glyceride of interesterified oils using algae oil Because the detection sensitivity of gas chromatography (GC) decreases when EPA or DHA is included, a thin-layer chromatography detector was used for the analysis. After TLC development using a mixed solvent of 70 vol% hexane and 30 vol% ethyl acetate, the analysis was performed using an Iatroscan (manufactured by LSI Medience).

[0039] During the glycerolysis reaction, samples were taken over time (at 0.5, 1.0, 2.0, 3.0 and 4.0 hours) to analyze the transesterified oil. The reaction oil was collected in a test tube capable of centrifugation, cooled to 40°C, and centrifuged at 3000 r / min for 10 minutes to remove the precipitated glycerin and catalyst to obtain the transesterified oil. The TAG reduction rate (% / h / mol catalyst / kg) was calculated from the TAG concentration value 0.5 hours after the start of the reaction. The relative value was calculated and compared, taking the TAG reduction rate (% / h / mol catalyst / kg) of the comparative example (a mixture of oil and glycerin was heated to the reaction temperature and then a catalyst was added). The time at which the DAG concentration reached 40% by mass was defined as the time to reach equilibrium composition, and this time was calculated.

[0040] Example 1 100.0 g of glycerin (Kao), the raw material for the glycerolysis reaction, was placed in a 200 mL 4-neck flask equipped with a stirring blade (50 mm x 20 mm). Next, 0.41 g of calcium hydroxide (Kanto Chemical) was added as a catalyst, and the mixture was dehydrated under reduced pressure at 80°C and 400 Pa for 60 minutes while stirring at 300 r / min. The pressure was returned to normal while introducing nitrogen, and a mixture was obtained. The mixture became clear and no longer cloudy. 351.7 g of algae oil (trade name: Life's omega 60, manufactured by DSM) as the raw oil for the glycerolysis reaction was placed in a 1000 mL 4-neck flask equipped with a stirring blade (75 mm x 20 mm). The mixture was dehydrated under reduced pressure for 30 minutes at 70 ° C and 400 Pa while stirring at 400 r / min. After that, the pressure was returned to normal while introducing nitrogen, and the reaction temperature was raised to 150 ° C while circulating nitrogen in the space inside the flask. Next, 48.5 g of a mixture at 80 ° C was added, and the glycerolysis reaction was carried out at a temperature of 150 ° C and normal pressure (nitrogen flow). The reaction started when the temperature reached 150 ° C after the addition of the mixture. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.05 mass% relative to the total of the raw oil and glycerin.

[0041] Comparative Example 1 351.7 g of algae oil and 48.3 g of glycerin, which are raw materials for the glycerolysis reaction, were placed in a 1000 mL 4-neck flask equipped with a stirring blade (75 mm x 20 mm). The mixture was dehydrated under reduced pressure for 30 minutes at 70 ° C and 400 Pa while stirring at 400 r / min. After that, the mixture was returned to normal pressure while introducing nitrogen, and heated to the reaction temperature of 150 ° C while circulating nitrogen in the space inside the flask. Next, 0.20 g of calcium hydroxide was added as a catalyst, and the glycerolysis reaction was carried out at a temperature of 150 ° C and normal pressure (nitrogen flow). The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.05 mass% of the total of the raw material oil and glycerin.

[0042] Example 2 A mixture was prepared in the same manner as in Example 1, except that the amount of calcium hydroxide was 0.83 g. The mixture became transparent and no longer cloudy. The glycerolysis reaction was carried out in the same manner as in Example 1, except that 48.7 g of the mixture was added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.10 mass% based on the total amount of the raw material oil and glycerin.

[0043] Comparative Example 2 The same operation as in Comparative Example 1 was carried out, except that 0.40 g of calcium hydroxide was added as a catalyst. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.10% by mass based on the total amount of the raw material oil and glycerin.

[0044] Comparative Example 3 100.0 g of glycerin, which is the raw material for the glycerolysis reaction, was placed in a 200 mL 4-neck flask equipped with a stirring blade (50 mm x 20 mm). Next, 0.45 g of sodium hydroxide granules (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 10 g of distilled water as a catalyst, and the entire amount was added, and the mixture was dehydrated under reduced pressure for 60 minutes at 80 ° C. and 400 Pa while stirring at 300 r / min, and returned to normal pressure while introducing nitrogen to obtain a mixture. The mixture became transparent without turbidity. The glycerolysis reaction was carried out in the same manner as in Example 1, except that 48.5 g of the mixture was added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.054 mass% relative to the total of the raw oil and glycerin.

[0045] Comparative Example 4 The same operation as in Comparative Example 1 was carried out, except that 0.22 g of sodium hydroxide granules was added as a catalyst. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.25, and the amount of catalyst added was 0.054 mass% based on the total of the raw material oil and glycerin.

[0046] Example 3 A mixture was prepared in the same manner as in Example 1, except that the amount of calcium hydroxide was 0.29 g. The mixture became transparent and no longer cloudy. The glycerolysis reaction was carried out in the same manner as in Example 1, except that 331.1 g of undeodorized linseed oil (manufactured by ADM) and 69.1 g of the mixture were added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.00, and the amount of catalyst added was 0.05 mass% based on the total of the raw material oil and glycerin.

[0047] Comparative Example 5 The glycerolysis reaction was carried out in the same manner as in Comparative Example 1, except that 331.1 g of undeodorized linseed oil and 69.1 g of glycerin were used as a catalyst and 0.20 g of calcium hydroxide was added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.00, and the amount of catalyst added was 0.05% by mass based on the total amount of the raw material oil and glycerin.

[0048] Comparative Example 6 A mixture was prepared in the same manner as in Comparative Example 3, except that sodium hydroxide and granules were used at 0.29 g. The mixture became transparent and no longer cloudy. The glycerolysis reaction was carried out in the same manner as in Example 1, except that 331.1 g of undeodorized linseed oil and 69.1 g of the mixture were added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.00, and the amount of catalyst added was 0.05 mass% based on the total of the raw material oil and glycerin.

[0049] Comparative Example 7 The glycerolysis reaction was carried out in the same manner as in Comparative Example 1, except that 331.1 g of undeodorized linseed oil, 69.1 g of glycerin, and 0.20 g of sodium hydroxide granules as a catalyst were added. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.00, and the amount of catalyst added was 0.05% by mass based on the total amount of the raw material oil and glycerin.

[0050] The reaction conditions, the reaction raw materials, and the analytical values ​​of the obtained transesterified oil are shown in Table 1. The glyceride composition of the algae oil subjected to the reaction with glycerin was 0.1 mass% fatty acid, 99.9 mass% TAG. Similarly, the glyceride composition of the undeodorized linseed oil was 0.1 mass% fatty acid, 1.0 mass% MAG, 2.4 mass% DAG, and 96.5 mass% TAG. The fatty acid composition of the interesterified oil was the same as that of the raw oil, so no data was shown.

[0051] [Table 1]

[0052] As is clear from Table 1, when a glycerolysis reaction was carried out by adding a mixture of glycerin and a calcium-based catalyst premixed after the fats and oils reached 90°C or higher, the TAG reduction rate was greater and the initial reaction rate was improved compared to when the calcium-based catalyst was added after the fats and oils and glycerin reached 90°C or higher. It was also confirmed that the time required to reach the equilibrium composition could be shortened, particularly when the amount of calcium-based catalyst added was increased. On the other hand, when using a sodium-based catalyst, even if a mixture of glycerin and a calcium-based catalyst was added after the oil had reached 90°C or higher, there was no change in the initial reaction rate, nor was there any shortening of the time it took to reach the equilibrium composition.

Claims

1. The method for producing an interesterified oil or fat includes a step of reacting an oil or fat with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 90°C or higher and 165°C or lower, and after heating the oil or fat to 90°C or higher, a mixture of glycerin and a calcium-based catalyst that has been mixed in advance is added to the oil or fat.

2. 2. The method for producing transesterified oils and fats according to claim 1, wherein glycerin and a calcium-based catalyst are mixed while being dehydrated.

3. 3. The method for producing transesterified oils and fats according to claim 1 or 2, wherein glycerin and a calcium-based catalyst are mixed in advance at a temperature of 20° C. or higher and 165° C. or lower.

4. The method for producing transesterified oils and fats according to any one of claims 1 to 3, wherein the ratio of the molar amount of the calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] is 0.5 to 490.

5. The method for producing interesterified oils and fats according to any one of claims 1 to 4, wherein the calcium-based catalyst is calcium hydroxide.

6. The method for producing an interesterified oil or fat according to any one of claims 1 to 5, wherein the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] during the reaction of the oil or fat with glycerin is 0.60 or more and 2.0 or less.

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