Method for producing interesterified fat

Abstract

To provide a method for producing interesterified fat with a high diacylglycerol purity by performing a glycerolysis reaction at a low temperature while suppressing the formation of byproducts.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 the calcium-based catalyst is added after heating the fat and glycerol 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 diacylglycerol.

[0003] The glycerolysis method can produce diacylglycerol with fewer steps than the esterification method. However, in the glycerolysis method, in order to increase the purity of diacylglycerol, it is necessary to increase the ratio of glycerin to fats and oils in the reaction raw material, but this results in a large amount of monoacylglycerol being produced in the reaction oil, which increases the purification load. On the other hand, there is a problem that if the ratio of glycerin to fats and oils in the reaction raw material is reduced, the yield of diacylglycerol is low. In addition, the glycerolysis method has a high reaction temperature, so unsaturated fatty acids are easily converted to trans acids, resulting in a large amount of trans acids being produced, which is particularly noticeable in polyunsaturated fatty acids with a large number of unsaturated bonds. [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] In addition, it has been found that when the glycerolysis reaction is carried out at high temperatures, many by-products other than trans fatty acids are also produced, so that a process at a lower temperature is desirable. Therefore, the present invention relates to providing a method for producing transesterified oils and fats having high diacylglycerol purity in high yields while suppressing the production of by-products by carrying out a glycerolysis reaction at a low temperature. [Means for solving the problem]

[0006] The present inventors have found that if fats and oils and glycerin are reacted by contacting them with a calcium-based catalyst after they have reached a predetermined temperature, the reaction proceeds at a low temperature while suppressing the production of by-products, and transesterified fats and oils having a high diacylglycerol purity can be obtained in good yield.

[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 which adds the calcium-based catalyst after the fats and oils and glycerin are heated to 90°C or higher. Effect of the Invention

[0008] According to the present invention, transesterified oils and fats having high diacylglycerol purity can be obtained in high yields by a glycerolysis reaction at low temperatures. Furthermore, according to the present invention, the production of by-products can be suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the present invention, "transesterified fats and oils" refers to fats and oils obtained by reacting a raw material fat and oil with glycerin, removing the catalyst by neutralization, filtration, etc., and removing unreacted phase-separated glycerin, and "reacted oil" refers to fats and oils obtained by reacting a raw material fat and oil with glycerin, but before removing the catalyst and unreacted phase-separated glycerin. In addition, in the present invention, "reacting step" refers to the step after the reaction temperature is reached, and does not include the step of raising the temperature to the reaction temperature.

[0010] The method for producing an interesterified oil or fat of the present invention is a method for producing an interesterified oil or fat, comprising 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 more and 165° C. or less, and adding the calcium-based catalyst after heating the oil or fat and glycerin to 90° C. or more. At this time, the oil or fat and glycerin may be heated to 90° C. or more as a reaction raw material in which they are mixed in advance, or the reaction raw materials, the oil or fat and glycerin, may be heated separately to 90° C. or more and then mixed, but from the viewpoint of ease of production, it is preferable to heat the reaction raw material in which the oil or fat and glycerin are mixed to 90° C. or more. 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.

[0011] 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.

[0012] 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.

[0013] 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, particularly 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.

[0014] 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.

[0015] 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 in terms of physiological activity and the ease of enjoying the effects of the present invention, and is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less in terms of suppressing the 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.

[0016] The glycerin used in the present invention preferably has a purity of 95% by mass or more in terms of improving reactivity.

[0017] 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, and even more preferably 0.70 or more, from the viewpoint of reducing the amount of 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, and even more preferably 0.70 to 1.4. The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] is expressed by the following formula (1). 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) (1)

[0018] 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 hydroxide, calcium carbonate, calcium oxide, 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, calcium oxide, and calcium silicate are preferred, and calcium hydroxide is more preferred, because they can significantly suppress the production of glycidol fatty acid esters as a by-product and can improve the purity of diacylglycerol in the reaction oil.

[0019] In the present invention, the calcium-based catalyst is added to the fats and oils and glycerin at a temperature of 90° C. or higher when the temperature is increased to the reaction temperature. Here, adding the calcium-based catalyst at 90° C. or higher does not mean that the calcium-based catalyst is not added to the reaction raw materials at a temperature lower than 90° C., but means that the amount required to catalyze the reaction is added at 90° C. or higher. The temperature of the fats and oils and glycerin when the calcium catalyst 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 suppressing the deactivation of the catalyst and improving the diacylglycerol purity of 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 suppressing the generation of by-products and improving quality. The temperature of the fats and oils and glycerin when the calcium catalyst is added is 90° C. or higher, preferably 95 to 165° C., more preferably 100 to 155° C., and even more preferably 110 to 150° C. From the same viewpoint, the temperature of the fat or oil and glycerin when the calcium-based catalyst is added is preferably in the range of reaction temperature −15° C. to the reaction temperature, more preferably in the range of reaction temperature −10° C. to the reaction temperature, even more preferably in the range of reaction temperature −5° C. to the reaction temperature, and even more preferably at the reaction temperature. After adding a calcium-based catalyst to the reaction raw materials, the temperature is raised to a reaction temperature as necessary to carry out a glycerolysis reaction with the oils and fats and glycerin.

[0020] In the present invention, examples of the pattern of "adding a calcium-based catalyst after heating the fats and oils and glycerin to 90° C. or higher" include a pattern in which the reaction raw material in which the fats and oils and glycerin are mixed in advance is added after heating to 90° C. or higher, a pattern in which the reaction raw materials fats and oils and glycerin are added separately after heating to 90° C. or higher, a pattern in which the fats and oils are heated to 90° C. or higher and then glycerin and the calcium-based catalyst are added separately or mixed and then added, etc. When the fats and oils are heated to 90° C. or higher and then glycerin and the calcium-based catalyst are added, it is not necessary to raise the temperature of glycerin to 90° C. or higher before adding it, and it is sufficient that the fats and oils and glycerin are heated to 90° C. or higher when the glycerin and calcium-based catalyst are added. When the fat or oil is heated to 90° C. or higher and then glycerin and the calcium-based catalyst are added separately, it is preferable to dehydrate the glycerin and the calcium-based catalyst in advance, in order to prevent the catalyst from being deactivated and to improve the purity of diacylglycerol in the reaction oil. Similarly, it is also preferable to dehydrate the fat or oil in advance.

[0021] In the present invention, the amount of calcium-based catalyst added to the reaction raw material at 90°C or higher is 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 preferably 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, still more preferably 5.0 or more, and still more preferably 8.0 or more, in terms of improving reactivity, and is preferably 490 or less, more preferably 300 or less, still more preferably 150 or less, and still more preferably 100 or less, in terms of being able to reduce the amount of neutralizing agent. The amount of calcium-based catalyst added to the reaction raw material at 90°C or higher 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 100, still more preferably 5.0 to 100, and still more preferably 8.0 to 100, 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].

[0022] The amount of calcium-based catalyst added to the reaction raw materials at 90°C or higher is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, even more preferably 0.03 mass% or more, still more preferably 0.04 mass% or more, still more preferably 0.06 mass% or more, still more preferably 0.1 mass% or more, and still more preferably 0.15 mass% or more, relative to the reaction raw materials, from the viewpoint of improving reactivity, and is preferably 10 mass% or less, more preferably 5 mass% or less, even more preferably 3.0 mass% or less, still more preferably 2.0 mass% or less, and still more preferably 1.5 mass% or less, from the viewpoint of reducing the amount of neutralizing agent. The amount of calcium-based catalyst added to the reaction raw materials at 90°C or higher is preferably 0.01 to 10 mass%, more preferably 0.02 to 5 mass%, even more preferably 0.03 to 3.0 mass%, still more preferably 0.04 to 2.0 mass%, still more preferably 0.06 to 1.5 mass%, still more preferably 0.1 to 1.5 mass%, and still more preferably 0.15 to 1.5 mass%, based on the reaction raw materials.

[0023] The amount of calcium catalyst added at less than 90° C. varies depending on the type of catalyst, but is preferably as small as possible from the viewpoints of reducing the amount of neutralizing agent and facilitating purification of the produced transesterified oil / fat. Specifically, the amount of calcium catalyst added at less than 90° C. 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 reaction raw materials.

[0024] 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. In addition, in the present invention, from the viewpoint of suppressing the generation of by-products, it is preferable that the step of reacting at more than 165°C is not substantially included. "Substantially not included" is preferably 10% or less of the time required for the reaction step, more preferably 5% or less, even more preferably 2.5% or less, and even more preferably 0%. In addition, "substantially not included" is preferably 24 minutes or less, more preferably 12 minutes or less, even more preferably 6 minutes or less, and even more preferably 0 minutes in terms of specific time.

[0025] The rate of temperature rise to the reaction temperature of the reaction raw materials, when the temperature is raised to the reaction temperature as necessary after adding a calcium catalyst, 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 reaction raw materials 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.

[0026] The reaction time is preferably 0.1 hours or more, more preferably 0.25 hours or more, and even more preferably 0.5 hours or more from the viewpoint of diacylglycerol production, and is preferably 15 hours or less, more preferably 12 hours or less, and even more preferably 9 hours or less from the viewpoint of industrial productivity. The reaction time is preferably 0.1 hours or more and 15 hours or less, more preferably 0.25 hours or more and 12 hours or less, and even more preferably 0.5 hours or more and 9 hours or less.

[0027] In order to improve the reactivity and prevent a decrease in catalytic performance, it is preferable to carry out the reaction between fats and oils and glycerin after removing water contained in the reaction raw materials 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 remove the calcium catalyst by neutralization, filtration, or the like.

[0028] After the glycerolysis reaction, a purification process that is generally 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 industrial productivity, it is preferable to carry out a distillation treatment without carrying out an esterification reaction.

[0029] The interesterified oils and fats obtained by the method of the present invention contain, in addition to diacylglycerol, monoacylglycerol and triacylglycerol, and also contain dissolved unreacted glycerin, although in a smaller amount than these. On the other hand, according to the method of the present invention, it is possible to suppress the production of 3-chloropropane-1,2-diol ester (3-MCPD-E), as well as the total amount of 3-chloropropane-1,2-diol (3-MCPD), 3-chloropropane-1,2-diol ester (3-MCPD-E), glycidol, and fatty acid esters of glycidol (MCPD-FS). MCPD-FS can be measured by the method described in the German Society for Lipid Science (hereinafter also referred to as "DGF") Standard Method C-III 18(09) (DGF Standard Methods 2009(14. Supplement), C-III 18(09), "Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and glycidol (glycidyl esters)"). In the present invention, in order to quantify glycidol esters, the method described in Option A of the standard method 7.1 ("7.1 Option A: Determination of the sum of ester-bound 3-MCPD and glycidol") is used. Furthermore, 3-MCPD-E can be measured by the method described in the German Society for Lipid Science Standard Method C-VI 18(10) (DGF Standard Methods 2010(16.Supplement), C-VI 18(10), "Fatty-acid-bound 3-chloropropane-1,2-diol (3-MCPD) and 2,3-epoxi-propane-1-ol (glycidol)"). In the present invention, the value obtained by the standard method, assay B, is regarded as the 3-MCPD-E content. The details are described in the Examples.

[0030] The content of MCPD-FS in the interesterified oil obtained by the method of the present invention is preferably 15 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less from the viewpoint of improving quality. Also, the content of 3-MCPD-E in the interesterified oil is preferably 6 ppm or less, more preferably 4 ppm or less, and even more preferably 2 ppm or less from the same viewpoint.

[0031] In the present invention, when fats and oils containing a large amount of ω3 unsaturated fatty acids in the constituent fatty acids are used as the reaction raw material fats and oils, the amount of reduction in ω3 unsaturated fatty acids in the interesterified fats obtained by the method of the present invention is preferably 2% by mass or less, and more preferably 1% by mass or less, relative to the ω3 unsaturated fatty acids in the fatty acids constituting the reaction raw material fats and oils, in order to suppress the production of trans fatty acids.

[0032] The interesterified oil obtained by the method of the present invention is rich in diacylglycerol, and from the viewpoint of improving physiologically active functions, the diacylglycerol content is preferably 35 to 55% by mass, more preferably 40 to 53% by mass. From the same viewpoint, the content of monoacylglycerol in the transesterified oil is preferably 20 to 50% by mass, more preferably 25 to 45% by mass. The transesterified oil obtained by the method of the present invention can be used in the same manner as general edible oils and fats, by removing monoacylglycerol by distillation or the like, as necessary.

[0033] In the transesterified oil obtained by the method of the present invention, the free fatty acid content is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and even more preferably 2% by mass or less, from the viewpoints of reducing the load of the refining process and industrial productivity. Also, from the viewpoint of efficient reaction, the free fatty acid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more.

[0034] In the interesterified oil or fat, the total content of diacylglycerol and triacylglycerol is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, from the viewpoints of physiological effects and industrial productivity.

[0035] In the interesterified oil obtained by the method of the present invention, the purity of diacylglycerol is preferably 55% by mass or more, more preferably 60 to 90% by mass, even more preferably 65 to 90% by mass, and still more preferably 69 to 90% by mass, from the viewpoints of physiological effects and industrial productivity. Here, the purity of diacylglycerol is [diacylglycerol / (diacylglycerol+triacylglycerol)×100].

[0036] 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 an interesterified oil or fat, comprising the step of reacting an oil or fat 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 calcium-based catalyst is added after the oil or fat and glycerin are heated to 95°C or higher. <2> A method for producing an interesterified oil or fat, comprising the step of reacting an oil or fat 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 calcium-based catalyst is added after the oil or fat and glycerin are heated to 100°C or higher. <3> A method for producing an interesterified oil or fat, comprising the step of reacting an oil or fat 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 calcium-based catalyst is added after the oil or fat and glycerin are heated to 110°C or higher. <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 and glycerin are heated to 90°C or higher, and then a calcium-based catalyst is added in a molar ratio of calcium-based catalyst to glycerin [mmol-calcium-based catalyst / mol-glycerin] of 1.0 to 300. <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 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 the fats and oils and glycerin are heated to 90°C or higher, and then the calcium-based catalyst is added. <6> A method for producing an interesterified oil having a diacylglycerol purity of 60 to 90% by mass, comprising the step of reacting an oil with glycerin in the presence of a calcium catalyst at a reaction temperature of 95°C or higher and 160°C or lower, wherein the oil and glycerin are heated to 90°C or higher, and then the calcium catalyst is added. <7> 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 more and 160°C or less, wherein the total content of fatty acids having a carbon chain length of 18 or more and having three or more double bonds in the fatty acids constituting the fats and oils is 15 mass% or more, and the fats and oils and glycerin are heated to 90°C or more, and then the calcium-based catalyst is added. <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 and glycerin are heated to 95°C or higher, and then a calcium-based catalyst is added in a molar ratio of calcium-based catalyst to glycerin [mmol-calcium-based catalyst / mol-glycerin] of 1.0 to 300. <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 0.65 or higher and 1.7 or lower, and the fats and oils and glycerin are heated to 95°C or higher, and then the calcium-based catalyst is added. <10> The method for producing an interesterified oil or fat having a diacylglycerol purity of 60 to 90% by mass includes a step of reacting an oil or fat with glycerin in the presence of a calcium-based catalyst at a reaction temperature of 95°C or higher and 160°C or lower, and the calcium-based catalyst is added after the oil or fat and glycerin are heated to 95°C or higher. <11> 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 more and 160°C or less, wherein the total content of fatty acids having a carbon chain length of 18 or more and a double bond number of 3 or more among fatty acids constituting the fats and oils is 15 mass% or more, and the fats and oils and glycerin are heated to 95°C or more, and then the calcium-based catalyst is added. <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, 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 and glycerin are heated to 90°C or higher, a calcium-based catalyst is added in a ratio of the molar amount of calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] of 1.0 to 300. <13> The present invention relates to a method for producing an interesterified oil having a diacylglycerol purity of 60 to 90% by mass, comprising the step of reacting an oil with glycerin at a reaction temperature of 90°C or higher and 165°C or lower in the presence of a calcium catalyst, and after the oil and glycerin are heated to 90°C or higher, a calcium catalyst is added in such a way that the molar ratio of the calcium catalyst to the molar amount of glycerin [mmol-calcium catalyst / mol-glycerin] is 1.0 to 300. <14> 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 more and 165°C or less, wherein the total content of fatty acids having a carbon chain length of 18 or more and 3 or more double bonds in the fatty acids constituting the fats and oils is 15% by mass or more, and after the fats and oils and glycerin are heated to 90°C or more, a calcium-based catalyst is added in a ratio of the molar amount of calcium-based catalyst to the molar amount of glycerin [mmol-calcium-based catalyst / mol-glycerin] of 1.0 to 300. <15> The method for producing an interesterified oil or fat having a diacylglycerol purity of 60 to 90% by mass includes a step of reacting an oil or fat with glycerin at a reaction temperature of 90°C or higher and 165°C or lower in the presence of a calcium-based catalyst, the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] being 0.65 or higher and 1.7 or lower, and the oil or fat and glycerin are heated to 90°C or higher, and then the calcium-based catalyst is added. <16> 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 more and 165°C or less, wherein the total content of fatty acids having a carbon chain length of 18 or more and having 3 or more double bonds in the fatty acids constituting the fats and oils is 15 mass% or more, 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 more and 1.7 or less, and the calcium-based catalyst is added after the fats and oils and glycerin are heated to 90°C or more. <17> The present invention relates to a method for producing an interesterified oil having a diacylglycerol purity of 60 to 90% by mass, the method including a step of reacting an oil with glycerin in the presence of a calcium catalyst at a reaction temperature of 90°C or higher and 165°C or lower, the total content of fatty acids having a carbon chain length of 18 or higher and having three or more double bonds in fatty acids constituting the oil is 15% by mass or higher, and the calcium catalyst is added after the oil and glycerin are heated to 90°C or higher. EXAMPLES

[0037] In the following examples, "%" means "% by mass."

[0038] [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).

[0039] (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.

[0040] (iii) Measurement of the glyceride composition (MAG, DAG and TAG composition) of the total glyceride of interesterified oils and fats when using fish oil or 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).

[0041] (iv) Measurement of MCPD-FS (based on the German Society for Lipid Science (DGF) standard method C-III 18(09) option A) Approximately 100 mg of the transesterified oil sample was weighed in a test tube with a lid, and 50 μL of the internal standard (3-MCPD-d5 / t-butyl methyl ether), 500 μL of a mixed solution of t-butyl methyl ether / ethyl acetate (volume ratio 8:2), and 1 mL of 0.5N sodium methoxide were added and stirred, and then the tube was left to stand for 10 minutes. 3 mL of hexane and 3 mL of a 3.3% acetic acid / 20% aqueous sodium chloride solution were added and stirred, and then the upper layer was removed. Another 3 mL of hexane was added and stirred, and then the upper layer was removed. 250 μL of a mixed solution of 1 g of phenylboronic acid / 4 mL of 95% acetone was added and stirred, and then the tube was sealed and heated at 80 ° C for 20 minutes. 3 mL of hexane was added to this and stirred, and the upper layer was subjected to a gas chromatography-mass spectrometer (GC-MS) to quantify the glycidol fatty acid esters.

[0042] (v) Measurement of 3-MCPD-E (based on the German Society for Lipid Science (DGF) standard method C-VI 18(10)assay B) Approximately 100 mg of the transesterified oil sample was weighed in a test tube with a lid, and 100 μL of the internal standard (3-MCPD-d5-dipalmitate / t-butyl methyl ether), 100 μL of t-butyl methyl ether, and 200 μL of 0.5N sodium methoxide were added and stirred, and then the mixture was left to stand for 5 minutes. 600 μL of isohexane and 600 μL of 8.75% by mass sulfuric acid / 60% by mass sodium bromide aqueous solution were added and stirred, and then the upper layer was removed. Further, 600 μL of isohexane was added and stirred, and then the upper layer was removed. 100 μL of saturated phenylboronic acid / diethyl ether solution was added to the extract obtained by extracting three times with 600 μL of a diethyl ether / ethyl acetate mixed solution (volume ratio 3:2) from the lower layer and stirred. After distilling off the organic solvent under a nitrogen stream, 500 μL of isooctane was added to this and stirred, and then the mixture was subjected to a gas chromatograph-mass spectrometer (GC-MS) to quantify 3-MCPD-E.

[0043] The values ​​quantified in the above (iv) and (v) were converted into the glycidol (G) content by the following formula (2). G[mg as G / kg]=(MCPD-FS[mg / kg] - 3-MCPD-E[mg / kg])×74 / 110 (2)

[0044] Example 1 300.0 g of fish oil (DD Oil Type 2, Nippon Suisan Co., Ltd.) and 100.0 g of glycerin were placed in a 1000 mL 4-neck flask equipped with a stirring blade (75 mm x 20 mm). The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 0.70. The mixture was dehydrated under reduced pressure at 70°C and 400 Pa for 30 minutes while stirring at 400 r / min. The pressure was then adjusted to 9300 Pa, and the mixture was heated to the reaction temperature of 110°C at a heating rate of 1°C / min. Next, the mixture was returned to normal pressure while introducing nitrogen, and 4.0 g of calcium hydroxide was added as a catalyst to carry out a glycerolysis reaction at a temperature of 110°C and a pressure of 9300 Pa. Five hours after the start of the reaction, the mixture was returned to normal pressure while introducing nitrogen, and the reaction oil was sampled. The reaction oil was collected in a test tube capable of centrifugation, centrifuged at 3000 r / min for 10 minutes, and the precipitated glycerin and catalyst were removed to obtain an interesterified oil.

[0045] Example 2 The feed consisted of 300 g of fish oil (Omega Oil 1812TG Gold, manufactured by BASF) and 101.9 g of glycerin. After the reaction temperature reached 125°C, 0.241 g of calcium hydroxide was added, and the reaction time was set to 7 hours. The glycerolysis reaction was carried out in the same manner as in Example 1 to obtain an interesterified oil.

[0046] Example 3 A glycerolysis reaction was carried out in the same manner as in Example 2, except that the reaction temperature was 150° C. and the reaction time was 2 hours, to obtain an interesterified oil.

[0047] Example 4 A glycerolysis reaction was carried out in the same manner as in Example 3, except that the amount of calcium hydroxide added was 0.402 g, to obtain an interesterified oil.

[0048] Example 5 The feed consisted of 302.6 g of algae oil (manufactured by DSM) and 97.4 g of glycerin. After the reaction temperature reached 150° C., 0.60 g of calcium hydroxide was added, and the reaction time was set to 4 hours. A glycerolysis reaction was carried out in the same manner as in Example 1 to obtain an interesterified oil.

[0049] Comparative Example 1 A glycerolysis reaction was carried out in the same manner as in Example 2, except that the temperature at which calcium hydroxide was added was 70° C., to obtain an interesterified oil.

[0050] Comparative Example 2 A glycerolysis reaction was carried out in the same manner as in Example 3, except that the temperature at which calcium hydroxide was added was 70° C., to obtain an interesterified oil.

[0051] Comparative Example 3 A glycerolysis reaction was carried out in the same manner as in Example 4, except that the temperature at which calcium hydroxide was added was 70° C., to obtain an interesterified oil.

[0052] Comparative Example 4 A glycerolysis reaction was carried out in the same manner as in Example 4, except that the reaction temperature was 175° C., the calcium hydroxide addition temperature was 175° C., and the reaction time was 1.5 hours, to obtain an interesterified oil.

[0053] Comparative Example 5 A glycerolysis reaction was carried out in the same manner as in Comparative Example 4, except that the temperature at which calcium hydroxide was added was 70° C., to obtain an interesterified oil.

[0054] The reaction conditions, the reaction raw materials, and the analytical values ​​of the obtained transesterified oils and fats are shown in Table 1. Note that the values ​​of the above-mentioned (v) 3-MCPD-E were all zero, so it is not shown in Table 1. In addition, the glyceride composition of the oils and fats subjected to the reaction with glycerin was 100 mass% triacylglycerol in all cases.

[0055] [Table 1]

[0056] Example 6 331.1 g of undeodorized linseed oil (ADM) and 68.9 g of glycerin (Kao) were placed in a 1000 mL 4-neck flask equipped with a stirring blade (75 mm x 20 mm). The ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups [FA / GLY] was 1.00. The mixture was dehydrated under reduced pressure at 70°C and 400 Pa for 30 minutes 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 at a heating rate of 1°C / min while circulating nitrogen in the space inside the flask. Next, 0.20 g of calcium hydroxide (manufactured by Kanto Chemical) was added as a catalyst, and a glycerolysis reaction was carried out at a temperature of 150°C and normal pressure (nitrogen flow). After 3 hours from the start of the reaction, the reaction oil was sampled. The reaction oil was collected in a test tube capable of centrifugation, centrifuged at 3000 r / min for 10 minutes, and the precipitated glycerin and catalyst were removed to obtain an interesterified oil.

[0057] Example 7 A glycerolysis reaction was carried out in the same manner as in Example 6, except that the amount of catalyst added was 0.60 g, to obtain an interesterified oil.

[0058] Example 8 A glycerolysis reaction was carried out in the same manner as in Example 6, except that the amount of catalyst added was 0.994 g, to obtain an interesterified oil.

[0059] Comparative Example 6 A glycerolysis reaction was carried out in the same manner as in Example 7, except that the temperature at which calcium hydroxide was added was 70° C., to obtain an interesterified oil.

[0060] Comparative Example 7 A glycerolysis reaction was carried out in the same manner as in Example 6, except that the catalyst was changed to sodium hydroxide and the amount of the catalyst added was changed to 0.536 g, to obtain an interesterified oil.

[0061] The reaction conditions, the reaction raw materials, and the analytical values ​​of the obtained interesterified oils and fats are shown in Table 2. Note that, since the values ​​of the above-mentioned (v)3-MCPD-E were all zero, it is not shown in Table 2. The glyceride composition of the oil and fat subjected to the reaction with glycerin was 0.1 mass % fatty acid, 1.0 mass % MAG, 2.4 mass % DAG, and 96.5 mass % TAG.

[0062] [Table 2]

[0063] As is clear from Tables 1 and 2, it was confirmed that when a calcium-based catalyst was added to carry out a glycerolysis reaction after the reaction raw materials reached 90° C. or higher at a low reaction temperature, the diacylglycerol purity was higher than when the catalyst was added at 70° C. On the other hand, when a sodium-based catalyst was used, the by-production of 3-MCPD-E and MCPD-FS could not be suppressed even when the catalyst was added after the reaction raw materials reached 90° C. or higher at a low reaction temperature (comparison between Example 8 and Comparative Example 7). In addition, when the reaction temperature was high, the purity of diacylglycerol increased, but the by-production of 3-MCPD-E and MCPD-FS could not be suppressed regardless of the catalyst addition temperature (comparison between Comparative Examples 4 and 5).

Claims

1. A method for producing an interesterified oil or fat, comprising 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, in which the calcium-based catalyst is added after the oil or fat and glycerin are heated to 90°C or higher.

2. The method for producing transesterified oils and fats according to claim 1, wherein the amount of calcium catalyst added is 0.5 to 490 in terms of the molar ratio of calcium catalyst to glycerin [mmol-calcium catalyst / mol-glycerin].

3. 3. The method for producing interesterified oils and fats according to claim 1 or 2, wherein the calcium-based catalyst is one or more selected from the group consisting of calcium hydroxide, calcium oxide and calcium silicate.

4. 3. The method for producing interesterified oils and fats according to claim 1 or 2, wherein the ratio of the number of moles of fatty acid groups to the number of moles of glycerin groups in the reaction raw materials [FA / GLY] is 0.60 or more and 2.0 or less.

5. 3. The method for producing transesterified oils and fats according to claim 1 or 2, wherein the rate of temperature rise up to the reaction temperature of the reaction raw materials is 0.1° C. / min or more and 20° C. / min or less.

6. The method for producing interesterified oils and fats according to claim 1 or 2, wherein the interesterified oils and fats have a diacylglycerol purity of 55% by mass or more.

7. 3. The method for producing an interesterified oil or fat according to claim 1 or 2, wherein the total content of fatty acids constituting the oil or fat, each of which has a carbon chain length of 18 or more and a double bond number of 3 or more, is 15 mass% or more.

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