Method for producing transesterified oils and fats

Abstract

Provided is a method for producing a transesterified oil or fat having a high purity of diacylglycerol while carrying out a glycerol alcoholysis reaction at a low temperature. A method for producing a transesterified oil or fat, said method comprising a step in which an oil or fat and glycerol are reacted at a reaction temperature of 90-165 DEG C (inclusive) with the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] being 0.30-1.7 (inclusive) in the presence of a calcium-based catalyst.

Description

Technical Field

[0001] This invention relates to a method for manufacturing transesterified fats rich in diacylglycerols. Background Technology

[0002] Diacylglycerol is used in various industries such as food and cosmetics.

[0003] Diacylglycerols are typically manufactured through esterification of glycerol with fatty acids or glycerol alcoholysis of glycerol with oils. These methods are broadly classified into chemical methods using chemical catalysts such as alkali metal or alkaline earth metal hydroxides or alkoxides, and enzymatic methods using enzymes such as lipases. For example, Patent Document 1 describes a method for producing oils with a high diacylglycerol content by adding calcium hydroxide as a catalyst to undeodorized rapeseed oil and glycerol, and carrying out glycerol alcoholysis at a temperature of 210°C.

[0004] Compared to esterification, glycerol hydrolysis can produce diacylglycerols with fewer steps.

[0005] Patent Document 1: Japanese Patent Application Publication No. 2010-59406 Summary of the Invention

[0006] The present invention provides a method for manufacturing an transesterified fat, comprising: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 or more and 1.7 or less in the presence of a calcium-based catalyst, and reacting the fat with glycerol at a reaction temperature of 90°C or more and 165°C or less.

[0007] However, in glycerol hydrolysis, to improve the purity of diacylglycerols [diacylglycerol / (diacylglycerol + triacylglycerol) × 100], it is necessary to increase the ratio of glycerol to fat in the reaction feedstock. But if this ratio is increased, a large amount of monoacylglycerols will be generated when the equilibrium composition is reached—this is common technical knowledge. Monoacylglycerols are easily emulsified, have a high purification load, and also possess a distinctive odor. Therefore, it is desirable to reduce monoacylglycerols. Consequently, in existing glycerol hydrolysis methods, the ratio of glycerol to fat is reduced, thereby suppressing the formation of monoacylglycerols while sacrificing some purity of diacylglycerols.

[0008] Therefore, the present invention relates to a method for producing transesterified fats rich in diacylglycerols with a high reaction rate while suppressing the formation of monoacylglycerols.

[0009] The inventors of this invention have discovered that when the ratio of glycerol to oils that are previously thought to generate large amounts of monoacylglycerol is high, the generation of monoacylglycerol can be suppressed by reacting at low temperatures in the presence of a calcium-based catalyst, and transesterified oils rich in diacylglycerol can be obtained with a high reaction rate.

[0010] According to the present invention, the formation of monoacylglycerol can be suppressed by glycerol alcoholysis at low temperature, and transesterified oils rich in diacylglycerol can be obtained with a high reaction rate. Detailed Implementation

[0011] In this invention, "ester-exchange oil" refers to the oil after reacting the oil as a raw material with glycerol, removing the catalyst through neutralization, filtration, etc., and removing unreacted, phase-separated glycerol. "Reaction oil" refers to the oil after reacting the oil as a raw material with glycerol, before removing the catalyst and phase-separated unreacted glycerol. Furthermore, in this invention, "reaction process" refers to the process after reaching the reaction temperature, excluding the process of heating to the reaction temperature.

[0012] The method for manufacturing the transesterified oil of the present invention includes a process in which the ratio of the molar number of fatty acid groups to the molar number of glycerol groups [FA / GLY] is set to 0.30 or more and 1.7 or less in the presence of a calcium-based catalyst, and the oil and glycerol are reacted at a reaction temperature of 90°C or more and 165°C or less.

[0013] In this specification, "grease" and "oil" are synonymous. Furthermore, the substances constituting grease (oil) include not only triacylglycerols, but also monoacylglycerols and diacylglycerols. That is, grease (oil) includes any one or more of monoacylglycerols, diacylglycerols, and triacylglycerols.

[0014] In this invention, the oils that react with glycerol are typically predominantly triacylglycerols, and examples include: soybean oil, rapeseed oil, safflower oil, rice oil, corn oil, sunflower seed oil, cottonseed oil, olive oil, sesame oil, peanut oil, coix seed oil, wheat germ oil, perilla oil, flaxseed oil, perilla oil, chia seed oil, sacha inchi oil, walnut oil, kiwi seed oil, sage seed oil, grapeseed oil, macadamia nut oil, hazelnut oil, pumpkin seed oil, camellia oil, tea seed oil, borage oil, palm oil, palm oil extract, palm stearin, coconut oil, palm kernel oil, cocoa butter, and shorea(sal) seed oil. Vegetable oils such as butter, shea butter, and algal oil; animal oils such as fish oil, seal oil, whale oil, lard, tallow, and butter; microbial oils such as those produced by microorganisms that produce polyunsaturated fatty acids from zygosaccharidosis bacteria; or their transesterified oils, hydrogenated oils, fractionated oils, etc. Oils may be used in one or in combination with two or more types.

[0015] From the perspective of the emulsification characteristics and ease of operation of transesterified oils, liquid oils are preferred. Liquid oils refer to oils that are liquid at 20°C when subjected to the cooling test according to Standard Oil Analysis Test Method 2.3.8-27.

[0016] Furthermore, in this invention, from the viewpoint of suppressing the formation of trans acids by conducting the reaction at a lower temperature than that of conventional glycerol hydrolysis, it is preferable to use fatty acids with a carbon chain length of 18 or more and a double bond number of 3 or more, which are expected to perform various physiological functions. Particularly preferred are oils rich in ω3 unsaturated fatty acids, such as one or more oils selected from perilla oil, flaxseed oil, perilla seed oil, chia seed oil, Sacha inchi oil, algae oil, fish oil, seal oil, whale oil, and oils from microorganisms that produce polyunsaturated fatty acids.

[0017] Fish oil can be obtained from sources such as sardines, herring, saury, mackerel, bonito, tuna, squid, and cod liver. Algal oil can be collected from algae belonging to the classes Chlorophyta and Diatomaceousta. They are preferably purified before reaction using known separation or purification methods such as liquid-liquid separation, filtration, or centrifugation to remove impurities.

[0018] In addition, by selectively hydrolyzing fish oil and other oils using lipases, it is also possible to use so-called concentrated oils, which 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 oils.

[0019] The triacylglycerol content in the oil can be 100% by mass, but from the viewpoint of easy concentration in transesterified oils, especially highly unsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid, is preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 89% by mass or less. Furthermore, from the viewpoint of production efficiency, it is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. To ensure that the triacylglycerol content in the oil reacting with glycerol is less than 100% by mass, it is preferable to partially hydrolyze the oil with lipase and then remove the resulting fatty acids beforehand by distillation. This operation allows for the selective removal of saturated fatty acids with 16 and 18 carbon atoms constituting the fatty acids, and further concentrates the highly unsaturated fatty acids in the oil reacting with glycerol.

[0020] Furthermore, from the viewpoint of suppressing catalyst deactivation, the content of free fatty acids or their salts in the oil 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 addition, from the viewpoint of production efficiency, it 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.

[0021] There are no particular limitations on the fatty acids that make up fats and oils; they can be either saturated or unsaturated fatty acids.

[0022] From the viewpoint of the operability and industrial productivity of oils, the content of unsaturated fatty acids in the fatty acids constituting the oils is preferably 60-100% by mass, more preferably 70-98% by mass, and even more preferably 80-96% by mass. From the viewpoint of physiological effects, the number of carbon atoms in the unsaturated fatty acids is preferably 14-24, more preferably 16-22, and even more preferably 18-22.

[0023] Furthermore, the fatty acid content in this specification is a conversion of free fatty acids.

[0024] From the viewpoint of physiological activity, fatty acids constituting oils are preferably fatty acids with 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, the proportion of fatty acids with a carbon chain length of 18 or more and a double bond number of 3 or more in the reaction oil can be suppressed to be lower than the proportion of such fatty acids in the oil used as a reaction raw material, thereby obtaining an transesterification oil with a high proportion of fatty acids with a carbon chain length of 18 or more and a double bond number of 3 or more in the reaction oil.

[0025] From the viewpoint of physiological activity, the total content of fatty acids constituting the oil with a carbon chain length of 18 or more and a double bond number of 3 or more is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and even more preferably 30% by mass or more. Furthermore, from the viewpoint of inhibiting the formation of trans fatty acid byproducts, it is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. The total content of fatty acids constituting the oil with a carbon chain length of 18 or more and a double bond number of 3 or more is preferably 15 to 99% by mass, more preferably 20 to 90% by mass, further preferably 25 to 80% by mass, and even more preferably 30 to 80% by mass.

[0026] Examples of fatty acids constituting oils and fats that have a carbon chain length of 18 or more and have 3 or more double bonds include α-linolenic acid (C18:3), γ-linolenic acid (C18:3), eicosapentaenoic acid (C20:4), eicosapentaenoic acid (C20:5, EPA), docosapentaenoic acid (C22:5), and docosahexaenoic acid (C22:6, DHA). From the viewpoint of physiological activity and ease of achieving the effects of this invention, ω3-series unsaturated fatty acids having a double bond at the third position from the methyl terminus of the carbon chain are preferred.

[0027] From the viewpoint of improving reactivity, the glycerol used in this invention is preferably glycerol with a purity of 95% by mass or higher.

[0028] In this invention, the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] during the reaction of oil and glycerol is 0.30 to 1.7.

[0029] 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 (1).

[0030] FA / GLY = (moles of fatty acids + moles of monoacylglycerol + moles of diacylglycerol × 2 + moles of triacylglycerol × 3) / (moles of glycerol + moles of monoacylglycerol + moles of diacylglycerol + moles of triacylglycerol)

[0031] From the viewpoint of reducing the amount of glycerol insoluble in the oil phase, the molar ratio of fatty acid groups to glycerol groups [FA / GLY] is 0.30 or more, preferably 0.35 or more, and more preferably 0.40 or more. Furthermore, from the viewpoint of increasing the ratio of diacylglycerol to monoacylglycerol in the reaction oil and improving the reaction rate, it is 1.7 or less, preferably 1.6 or less, and more preferably 1.5 or less. The molar ratio of fatty acid groups to glycerol groups [FA / GLY] is 0.30 to 1.7, preferably 0.35 to 1.6, and more preferably 0.40 to 1.5.

[0032] In this invention, the reaction between oils and glycerol is carried out in the presence of a calcium-based catalyst. By using a calcium-based catalyst, it is possible to both increase the reaction rate and suppress the formation of monoacylglycerols.

[0033] The calcium-based catalyst used in this invention is only required to catalyze the glycerol alcoholysis reaction. Examples of calcium-based catalysts include calcium hydroxide, calcium carbonate, calcium oxide, calcium silicate, calcium methoxide, and calcium alkoxides. One type or two or more types can be used. From the viewpoint of improving the purity of the diacylglycerol in the reaction oil, calcium hydroxide, calcium oxide, and calcium silicate are preferred.

[0034] When the calcium-based catalyst is calcium hydroxide and calcium oxide, from the viewpoint of improving reactivity, the amount of calcium-based catalyst added relative to the reactants (total of oils and glycerol) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.03% by mass or more, and even more preferably 0.04% by mass or more. Furthermore, from the viewpoint of reducing the amount of neutralizing agent, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. When the calcium-based catalyst is calcium hydroxide and calcium oxide, the amount added relative to the reactants is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 1.5% by mass, further preferably 0.03 to 1.5% by mass, and even more preferably 0.04 to 1.0% by mass.

[0035] Similarly, when the calcium-based catalyst is calcium silicate, from the viewpoint of improving reactivity, the amount of calcium-based catalyst added relative to the reactants (the total of oils and glycerol) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more. Furthermore, from the viewpoint of reducing the amount of neutralizing agent, it is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less. When the calcium-based catalyst is calcium silicate, the amount added relative to the reactants is preferably 0.5 to 20.0% by mass, more preferably 1.0 to 15.0% by mass, further preferably 1.5 to 15.0% by mass, and even more preferably 2.0 to 10.0% by mass.

[0036] Furthermore, when the calcium-based catalyst is calcium hydroxide or calcium oxide, from the viewpoint of improving reactivity, the molar ratio of the calcium-based catalyst to the molar ratio of glycerol [mmol-calcium-based catalyst / mol-glycerol] is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.2 or more, even more preferably 3.0 or more, even more preferably 10.0 or more, and even more preferably 15.0 or more. Additionally, from the viewpoint of reducing the amount of neutralizing agent, it is preferably 340 or less, more preferably 170 or less, and even more preferably 80 or less. In the case of calcium hydroxide and calcium oxide, the molar ratio of the calcium-based catalyst to the molar ratio of glycerol [mmol-calcium-based catalyst / mol-glycerol] is preferably 0.2 to 340, more preferably 0.5 to 340, further preferably 1.2 to 170, even more preferably 3.0 to 170, even more preferably 10.0 to 80, and even more preferably 15.0 to 80.

[0037] Similarly, when the calcium-based catalyst is calcium silicate, from the viewpoint of improving reactivity, the molar ratio of the calcium-based catalyst to the molar ratio of glycerol [mmol-calcium-based catalyst / mol-glycerol] is preferably 30 or more, more preferably 60 or more, further preferably 90 or more, even more preferably 120 or more, even more preferably 150 or more, and even more preferably 180 or more. Furthermore, from the viewpoint of reducing the amount of neutralizing agent, it is preferably 900 or less, more preferably 700 or less, and even more preferably 500 or less. The molar ratio of the calcium-based catalyst to the molar ratio of glycerol [mmol-calcium-based catalyst / mol-glycerol] when using calcium silicate is preferably 30 to 900, more preferably 60 to 900, further preferably 90 to 700, even more preferably 120 to 700, even more preferably 150 to 500, and even more preferably 180 to 500.

[0038] In this invention, there is no particular limitation on the timing of adding the calcium-based catalyst to the reactants. From the viewpoints of suppressing catalyst deactivation and improving the purity of the diacylglycerol in the reaction oil, it is preferable to carry out the reaction at a temperature of 50°C or higher. However, carrying out the reaction at a temperature of 50°C or higher does not mean that no calcium-based catalyst is added to the reactants at temperatures below 50°C; rather, it means adding the amount required for the catalytic reaction at a temperature of 50°C or higher.

[0039] From the viewpoint of suppressing catalyst deactivation and improving the diacylglycerol purity of the reaction oil, the temperature at which the calcium-based catalyst is added to the reactants is preferably 60°C or higher, more preferably 75°C or higher, and even more preferably 90°C or higher. Furthermore, from the viewpoint of improving quality, it is preferably 165°C or lower, more preferably 160°C or lower, and even more preferably 155°C or lower. The temperature at which the calcium-based catalyst is added to the reactants is preferably 60–165°C, more preferably 75–160°C, and even more preferably 90–155°C.

[0040] After adding a calcium-based catalyst to the reaction raw materials, the temperature is raised to the required reaction temperature to carry out the glycerol hydrolysis reaction of oils and glycerol.

[0041] In this invention, the reaction temperature is above 90°C and below 165°C. The reason why this invention can achieve its effects under such low temperature conditions compared to conventional glycerol alcoholysis is not yet certain, but it is thought to be due to the following mechanism.

[0042] If the glycerol hydrolysis reaction of oils and glycerol is carried out at high temperatures, glycerol has high solubility in oils, and monoacylglycerols become easily stabilized in the reaction oil. Therefore, the reaction equilibrium is biased towards the formation of monoacylglycerols. On the other hand, if the glycerol hydrolysis reaction is carried out at low temperatures below 165°C, glycerol has low solubility in oils, and monoacylglycerols are difficult to stabilize in the reaction oil. Therefore, this equilibrium is considered to be hindered, and the formation of monoacylglycerols is inhibited. This allows for both an increase in the reaction rate and an increase in the ratio of diacylglycerols to monoacylglycerols in the reaction oil.

[0043] Regarding the reaction temperature, from the viewpoint of increasing the reaction rate, it is preferably 90°C or higher, more preferably 95°C or higher, and more preferably 100°C or higher. Furthermore, from the viewpoint of increasing the ratio of diacylglycerol to monoacylglycerol in the reaction oil, it is preferably 165°C or lower, more preferably 160°C or lower, and more preferably 155°C or lower. The reaction temperature is 90–165°C, preferably 95–160°C, and more preferably 100–155°C. Furthermore, from the viewpoint of increasing the ratio of diacylglycerol to monoacylglycerol in the reaction oil, it is preferable that steps involving reactions at temperatures exceeding 165°C are substantially excluded. "Substantially excluded" preferably means 10% or less of the time consumed by the reaction steps, more preferably 5% or less, further preferably 2.5% or less, and even more preferably 0%. In terms of specific time, "substantially excluded" is preferably 24 minutes or less, more preferably 12 minutes or less, further preferably 6 minutes or less, and even more preferably 0 minutes.

[0044] Regarding the heating rate of the reactants to the reaction temperature, from the viewpoint of suppressing catalyst deactivation and for industrial production purposes, it 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. Furthermore, from the viewpoint of reducing the heating load on the equipment, it is preferably 20 °C / min or less, more preferably 10 °C / min or less, and even more preferably 3 °C / min or less. The heating rate of the reactants to the reaction temperature is preferably 0.1–20 °C / min, more preferably 0.15–10 °C / min, and even more preferably 0.2–3 °C / min.

[0045] Regarding the reaction time, from the viewpoint that extending the reaction time can increase the ratio of diacylglycerol to monoacylglycerol in the reaction oil, and from the viewpoint that reducing catalyst activity can suppress the reverse reaction during cooling, a reaction time of 0.1 hours or more is preferred, more preferably 0.25 hours or more, and even more preferably 0.5 hours or more is preferred. Furthermore, from the viewpoint of industrial production, a reaction time of 15 hours or less is preferred, more preferably 12 hours or less, and even more preferably 9 hours or less is preferred. 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.

[0046] From the perspective of improving reactivity and inhibiting the decline in catalyst performance, the reaction of oils and glycerin is preferably carried out after removing the water contained in the reaction raw materials by means of depressurization or nitrogen bubbling.

[0047] From the perspective of industrial productivity and to prevent the degradation of catalyst performance, the moisture concentration of the reaction feedstock before the addition of the calcium-based catalyst is preferably 0.01 to 0.5% by mass, more preferably 0.03 to 0.4% by mass, and even more preferably 0.05 to 0.3% by mass.

[0048] Furthermore, the reaction can generally be carried out under reduced pressure or at atmospheric pressure. When carried out under reduced pressure, the pressure is not particularly limited, but from the viewpoint of reducing moisture in the reaction system, a pressure of 13000 Pa or less is preferred. However, when carried out at atmospheric pressure, in order to suppress the oxidation of the obtained transesterified fat, it is preferable to carry out the reaction under a nitrogen atmosphere with flowing nitrogen gas.

[0049] After the glycerol alcoholysis reaction is completed, a calcium-based catalyst, which is used as a catalyst, is mixed in the reaction oil. Therefore, after the glycerol alcoholysis reaction is completed, it is preferable to neutralize the calcium-based catalyst and remove it by filtration or the like.

[0050] There are no particular limitations on the neutralizing agent. From the viewpoint that the neutralized product is insoluble in water or oil and can be easily removed by filtration, acids such as sulfuric acid, hydrochloric acid, and phosphoric acid are preferred, and phosphoric acid is more preferred.

[0051] In this invention, during the neutralization of the calcium-based catalyst, from the viewpoint of suppressing the decrease in diacylglycerol concentration due to transesterification during subsequent post-distillation, it is preferable to add a neutralizing agent at least 1.2 molar times, more preferably at least 1.25 molar times, and even more preferably at least 1.3 molar times, relative to the calcium-based catalyst. Furthermore, there is no particular upper limit to the molar ratio; from the viewpoint of suppressing the increase in the acid value of the neutralized oil, it is preferably 3.0 molar times or less, more preferably 2.6 molar times or less, and even more preferably 2.2 molar times or less. The amount of neutralizing agent relative to the calcium-based catalyst is preferably 1.2 to 3.0 molar times, more preferably 1.25 to 2.6 molar times, and even more preferably 1.3 to 2.2 molar times.

[0052] Regarding the temperature of the neutralization process, i.e., the process from adding the neutralizing agent to the reaction oil containing the calcium-based catalyst until the stirring is stopped (hereinafter the same), from the viewpoint of fully generating the neutralized product, it is preferably 40°C or higher, more preferably 70°C or higher, and even more preferably 100°C or higher. Furthermore, from the viewpoint of suppressing the reverse reaction and suppressing oxidation, it is preferably 165°C or lower, more preferably 160°C or lower, and even more preferably 150°C or lower.

[0053] Regarding the time of the neutralization process, from the viewpoint of fully generating neutralized matter, it is preferably 1 to 240 minutes, more preferably 3 to 180 minutes, and even more preferably 10 to 120 minutes.

[0054] In the neutralization process, from the viewpoint of fully generating neutralized products, it is preferable to carry out neutralization while stirring. There are no particular restrictions on the means of stirring.

[0055] In this invention, after the glycerol alcoholysis reaction, diacylglycerol concentration or conventional oil purification processes can be performed. Specifically, processes such as distillation, acid treatment, water washing, decolorization, and deodorization can be included. In this invention, after the glycerol alcoholysis reaction, an enzymatic esterification reaction can also be performed; however, from the viewpoint of increasing the ratio of highly unsaturated fatty acids in the reaction oil, distillation is preferred instead of esterification.

[0056] The transesterified oil obtained by the method of the present invention contains not only diacylglycerol, but also triacylglycerol, monoacylglycerol, and dissolved unreacted glycerol, but the ratio of diacylglycerol to monoacylglycerol is high.

[0057] In the transesterified oil obtained by the method of the present invention, from the viewpoint of suppressing emulsification and reducing purification load, the ratio of diacylglycerol to monoacylglycerol [diacylglycerol / monoacylglycerol mass ratio] is preferably 1.08 or more, more preferably 1.10 or more, even more preferably 1.12 or more, and preferably 2.2 or less, more preferably 2.0 or less, even more preferably 1.8 or less. The ratio of diacylglycerol to monoacylglycerol [diacylglycerol / monoacylglycerol mass ratio] is preferably 1.08 to 2.2, more preferably 1.10 to 2.0, and even more preferably 1.12 to 1.8.

[0058] The transesterified oil obtained by the method of the present invention is rich in diacylglycerol, and its content, from the viewpoint of improving physiological activity, is preferably 38-56% by mass, more preferably 40-54% by mass, and even more preferably 42-52% by mass.

[0059] Furthermore, from the viewpoint of enhancing physiological activity, the content of monoacylglycerol in the transesterified oil is preferably 22-45% by mass, more preferably 23-43.5% by mass, and even more preferably 24-42% by mass. The transesterified oil obtained by the method of the present invention can have monoacylglycerol removed by distillation or other processes as needed, and can be used in the same way as ordinary edible oils.

[0060] In the transesterified oil obtained by the method of the present invention, from the viewpoint of reducing the load on the purification process and improving industrial productivity, the free fatty acid content is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, and even more preferably 2% by mass or less. Furthermore, from the viewpoint of efficiently carrying out the 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.

[0061] In transesterified oils, from the viewpoint of suppressing emulsification and reducing purification load, the reaction rate (diacylglycerol + monoacylglycerol content) is preferably 72-96% by mass, more preferably 75-94% by mass, and even more preferably 77-92% by mass.

[0062] Furthermore, in the transesterified oil obtained by the method of the present invention, from the viewpoint of physiological effects and industrial productivity, the purity of diacylglycerol is preferably 55% by mass or more, more preferably 60-90% by mass, even more preferably 65-90% by mass, and even more preferably 69-90% by mass. The purity of diacylglycerol is [diacylglycerol / (diacylglycerol + triacylglycerol) × 100].

[0063] In addition to the above embodiments, the present invention also discloses the following method for manufacturing transesterified grease.

[0064] <1>

[0065] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 or more and 1.6 or less in the presence of a calcium-based catalyst, and reacting the fat with glycerol at a reaction temperature of 95°C or more and 160°C or less.

[0066] <2>

[0067] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 to 1.6 and the molar ratio of calcium catalyst to glycerol [mmol-calcium catalyst / mol-glycerol] to 3.0 to 170 in the presence of calcium hydroxide or calcium oxide as a calcium catalyst, and reacting the fat with glycerol at a reaction temperature of 90°C to 165°C.

[0068] <3>

[0069] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 to 1.6 in the presence of calcium silicate as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 90 to 700, and reacting the fat with glycerol at a reaction temperature of 90°C to 165°C.

[0070] <4>

[0071] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 to 1.6 in the presence of a calcium-based catalyst, and reacting the fat with glycerol at a reaction temperature of 90°C to 165°C, wherein the total content of fatty acids constituting the fat reacting with glycerol having a carbon chain length of 18 or more and a double bond number of 3 or more is 15 to 99% by mass.

[0072] <5>

[0073] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 to 1.6 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the mass ratio of diacylglycerol to monoacylglycerol in the obtained transesterified oil is 1.10 to 2.2.

[0074] <6>

[0075] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.35 to 1.6 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0076] <7>

[0077] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of calcium hydroxide or calcium oxide as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 3.0 to 170, and reacting the fat with glycerol at a reaction temperature of 95°C to 160°C.

[0078] <8>

[0079] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of calcium silicate as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 90 to 700, and reacting the fat with glycerol at a reaction temperature of 95°C to 160°C.

[0080] <9>

[0081] A method for manufacturing an transesterified fat includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of a calcium-based catalyst, and reacting the fat with glycerol at a reaction temperature of 95°C to 160°C, wherein the total content of fatty acids constituting the fat reacting with glycerol having a carbon chain length of 18 or more and a double bond number of 3 or more is 15 to 99% by mass.

[0082] <10>

[0083] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 95°C to 160°C, wherein the mass ratio of diacylglycerol to monoacylglycerol in the obtained transesterified oil is 1.10 to 2.2.

[0084] <11>

[0085] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 95°C to 160°C, wherein the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0086] <12>

[0087] A method for manufacturing an transesterified fat includes: in the presence of calcium hydroxide or calcium oxide as a calcium-based catalyst, setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 3.0 to 170, and reacting the fat with glycerol at a reaction temperature of 90°C to 165°C, wherein the total content of fatty acids constituting the fat reacting with glycerol having a carbon chain length of 18 or more and a double bond number of 3 or more is 15 to 99% by mass.

[0088] <13>

[0089] A method for manufacturing an transesterified fat includes: in the presence of calcium silicate as a calcium-based catalyst, setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 90 to 700, and reacting the fat with glycerol at a reaction temperature of 90°C to 165°C, wherein the total content of fatty acids constituting the fat reacting with glycerol having a carbon chain length of 18 or more and a double bond number of 3 or more is 15 to 99% by mass.

[0090] <14>

[0091] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 and the molar ratio of calcium catalyst to glycerol [mmol-calcium catalyst / mol-glycerol] to 3.0 to 170 in the presence of calcium hydroxide or calcium oxide as a calcium catalyst; and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the mass ratio of diacylglycerol to monoacylglycerol in the obtained transesterified oil is 1.10 to 2.2.

[0092] <15>

[0093] A method for manufacturing an transesterified grease includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of calcium silicate as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 90 to 700, and reacting the grease with glycerol at a reaction temperature of 90°C to 165°C, wherein in the obtained transesterified grease, the mass ratio of diacylglycerol to monoacylglycerol is 1.10 to 2.2.

[0094] <16>

[0095] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of calcium hydroxide or calcium oxide as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 3.0 to 170, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0096] <17>

[0097] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of calcium silicate as a calcium-based catalyst, setting the molar ratio of calcium-based catalyst to glycerol [mmol-calcium-based catalyst / mol-glycerol] to 90 to 700, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0098] <18>

[0099] A method for manufacturing an transesterified oil includes: a step of reacting an oil with glycerol at a reaction temperature of 90°C to 165°C in the presence of a calcium-based catalyst, wherein the total content of fatty acids constituting the oil reacting with glycerol, wherein the fatty acids have a carbon chain length of 18 or more and a double bond number of 3 or more, is 15 to 99% by mass, and the mass ratio of diacylglycerol to monoacylglycerol in the obtained transesterified oil is 1.10 to 2.2.

[0100] <19>

[0101] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the total content of fatty acids constituting the oil reacting with glycerol having a carbon chain length of 18 or more and a double bond number of 3 or more is 15 to 99% by mass, and the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0102] <20>

[0103] A method for manufacturing an transesterified oil includes: setting the molar ratio of fatty acid groups to glycerol groups [FA / GLY] to 0.30 to 1.7 in the presence of a calcium-based catalyst, and reacting the oil with glycerol at a reaction temperature of 90°C to 165°C, wherein the mass ratio of diacylglycerol to monoacylglycerol in the obtained transesterified oil is 1.10 to 2.2, and the reaction rate (diacylglycerol + monoacylglycerol content) in the obtained transesterified oil is 72 to 96% by mass.

[0104] Example

[0105] In the following embodiments, "%" refers to "mass %".

[0106] [Analysis Methods]

[0107] (i) Determination of fatty acid composition

[0108] According to the "Methyl Esterification Method (Boron Trifluoride Methanol Method) (2.4.1.2-1996)" in the "Test Methods for Analysis of Standard Oils and Fats 2003 Edition" compiled by the Japan Oil Chemistry Society, the sample was subjected to fatty acid methyl esterification, and the resulting sample was subjected to gas chromatography (GC).

[0109] (ii) Determination of the total glycerol composition (MAG, DAG and TAG components) of transesterified oils when using flaxseed oil

[0110] In a glass sample vial, add approximately 10 mg of transesterified oil and 0.5 mL of trimethylsilylating reagent (“Silylating Reagent TH”, manufactured by Kanto Chemical), seal tightly, and heat at 70°C for 15 minutes. Add 1.5 mL of water and 1.5 mL of hexane, and shake. After standing, send the supernatant to a gas chromatograph (GC) for analysis of the glycerol ester composition.

[0111] (iii) Determination of the total glycerol composition (each component of MAG, DAG, and TAG) of transesterified lipids when using algal oil

[0112] The detection sensitivity of gas chromatography (GC) is reduced when EPA or DHA is present, so thin-layer chromatography (TLC) was used for analysis. TLC was performed using a mixture of 70 vol% hexane and 30 vol% ethyl acetate, followed by analysis with an IATROSCAN (manufactured by LSI MEDIENCE).

[0113] [Example 1]

[0114] 263.1 g of decolorized linseed oil (ADM grade) and 136.9 g of glycerol, which will serve as feedstock for the glycerol hydrolysis reaction, were placed in a 1000 mL four-necked flask equipped with a stirring blade (75 mm × 20 mm). The molar ratio of fatty acid groups to glycerol groups [FA / GLY] was 0.50.

[0115] While stirring at 400 rpm, the mixture was dehydrated under reduced pressure at 70°C and 400 Pa for 30 minutes. Then, while passing nitrogen gas through the mixture at atmospheric pressure, the mixture was heated to the reaction temperature of 140°C at a heating rate of 4°C / min. Next, 0.6 g of calcium hydroxide was added as a catalyst, and the glycerol alcoholysis reaction was carried out while passing nitrogen gas through the mixture at 140°C and atmospheric pressure. Four hours after the start of the reaction, the mixture was cooled to 95°C, and phosphoric acid was added followed by stirring for 30 minutes to obtain a neutralized oil. The neutralized oil was collected in a centrifugable test tube and centrifuged at 3000 rpm for 10 minutes to remove the precipitated glycerol and catalyst, yielding the transesterified oil.

[0116] [Example 2]

[0117] The amount of decolorized linseed oil (made with ADM) used as the feedstock for the glycerol hydrolysis reaction was set at 304.8 g, the amount of glycerol was set at 95.2 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 0.75. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain the transesterified oil.

[0118] [Example 3]

[0119] The amount of decolorized linseed oil (made with ADM) used as the feedstock for the glycerol hydrolysis reaction was set at 331.1 g, the amount of glycerol was set at 68.9 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.00. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain the transesterified oil.

[0120] [Example 4]

[0121] The amount of decolorized linseed oil (made with ADM) used as the feedstock for the glycerol hydrolysis reaction was set at 349.1 g, the amount of glycerol was set at 50.9 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.25. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain the transesterified oil.

[0122] [Example 5]

[0123] The amount of decolorized linseed oil (made with ADM) used as the feedstock for the glycerol hydrolysis reaction was set to 362.3 g, the amount of glycerol was set to 37.7 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set to 1.50. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain the transesterified oil.

[0124] [Comparative Example 1]

[0125] The amount of decolorized linseed oil (made with ADM) used as the feedstock for the glycerol hydrolysis reaction was set at 372.3 g, the amount of glycerol was set at 27.7 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.75. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain the transesterified oil.

[0126] [Example 6]

[0127] The amount of algal oil (trade name: Life'somega 60, manufactured by DSM) used as feedstock for the glycerol hydrolysis reaction was set at 302.6 g, the amount of glycerol was set at 97.4 g, the molar ratio of fatty acid groups to glycerol groups [FA / GLY] was set at 0.70, the catalyst addition temperature and the reaction temperature were set at 150°C, and the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain transesterified oil.

[0128] [Example 7]

[0129] The amount of algal oil (trade name: Life'somega 60, manufactured by DSM) used as feedstock for the glycerol hydrolysis reaction was set at 334.5 g, the amount of glycerol was set at 65.5 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.00. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain transesterified oil.

[0130] [Example 8]

[0131] The amount of algal oil (trade name: Life'somega 60, manufactured by DSM) used as the feedstock for the glycerol hydrolysis reaction was set at 351.7 g, the amount of glycerol was set at 48.3 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.25. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain the transesterified oil.

[0132] [Example 9]

[0133] The algal oil (trade name: Life'somega 60, manufactured by DSM), which will serve as the feedstock for the glycerol hydrolysis reaction, was set at 364.3 g, and the glycerol was set at 35.7 g. The ratio of the molar number of fatty acid groups to the molar number of glycerol groups [FA / GLY] was set at 1.50. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain the transesterified oil.

[0134] [Comparative Example 2]

[0135] The amount of algal oil (trade name: Life'somega 60, manufactured by DSM) used as the feedstock for the glycerol hydrolysis reaction was set at 373.8 g, the amount of glycerol was set at 26.2 g, and the ratio of the number of moles of fatty acid groups to the number of moles of glycerol groups [FA / GLY] was set at 1.75. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain the transesterified oil.

[0136] [Example 10]

[0137] The addition of calcium hydroxide as a catalyst was performed after the feedstock was dehydrated under reduced pressure and the pressure was reduced to 9300 Pa. The temperature was then increased to the reaction temperature of 140°C at a heating rate of 1°C / min. Otherwise, the transesterified oil was obtained under the same conditions as in Example 1.

[0138] [Example 11]

[0139] The addition of calcium hydroxide as a catalyst was performed after the feedstock was dehydrated under reduced pressure and the pressure was reduced to 9300 Pa. The temperature was then increased to the reaction temperature of 140°C at a heating rate of 1°C / min. Otherwise, the transesterified oil was obtained under the same conditions as in Example 2.

[0140] [Example 12]

[0141] The addition of calcium hydroxide as a catalyst was performed after the feedstock was dehydrated under reduced pressure and the pressure was reduced to 9300 Pa. The temperature was then increased to the reaction temperature of 140°C at a heating rate of 1°C / min. Otherwise, the transesterified oil was obtained under the same conditions as in Example 3.

[0142] [Comparative Example 3]

[0143] 0.882 g of sodium methoxide as a catalyst was added at 70 °C, and the glycerol alcoholysis reaction was carried out at 150 °C for 5 hours. Otherwise, the transesterified oil was obtained under the same conditions as in Example 3.

[0144] [Comparative Example 4]

[0145] 0.536 g of sodium hydroxide as a catalyst was added at 150 °C, and otherwise transesterified oil was obtained under the same conditions as in Comparative Example 3.

[0146] [Comparative Example 5]

[0147] The addition of 0.4 g of calcium hydroxide as a catalyst was scheduled after the raw material was dehydrated under reduced pressure. The mixture was then heated to a reaction temperature of 210°C at a heating rate of 1°C / min and subjected to glycerol alcoholysis for 1 hour. Otherwise, the transesterified oil was obtained under the same conditions as in Example 3.

[0148] [Example 13]

[0149] The algal oil (trade name: Life'somega 60, manufactured by DSM) used as feedstock for the glycerol hydrolysis reaction was set at 334.5 g, glycerol was set at 65.5 g, the molar ratio of fatty acid groups to glycerol groups [FA / GLY] was set at 1.00, calcium hydroxide used as catalyst was set at 4.0 g, and the catalyst addition temperature and reaction temperature were set at 100°C. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain transesterified oil.

[0150] [Example 14]

[0151] The algal oil (trade name: Life'somega 60, manufactured by DSM), which will be the feedstock for the glycerol hydrolysis reaction, was set at 334.5 g, and glycerol was set at 65.5 g. The molar ratio of fatty acid groups to glycerol groups [FA / GLY] was 1.00. Calcium hydroxide, which serves as a catalyst, was set at 4.0 g, and the catalyst addition temperature and reaction temperature were set at 110°C. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain the transesterified oil.

[0152] [Example 15]

[0153] The algal oil (trade name: Life'somega 60, manufactured by DSM), which will be the feedstock for the glycerol hydrolysis reaction, was set at 334.5 g, and glycerol was set at 65.5 g. The molar ratio of fatty acid groups to glycerol groups [FA / GLY] was 1.00. Calcium hydroxide, which serves as a catalyst, was set at 0.16 g, and the catalyst addition temperature and reaction temperature were set at 160°C. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 6 to obtain the transesterified oil.

[0154] [Example 16]

[0155] The amount of decolorized linseed oil (made with ADM) used as feedstock for the glycerol hydrolysis reaction was set at 331.1 g, the amount of glycerol was set at 68.9 g, the molar ratio of fatty acid groups to glycerol groups [FA / GLY] was set at 1.00, the amount of calcium oxide used as catalyst was set at 0.44 g, and the catalyst addition temperature and reaction temperature were set at 150°C. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain transesterified oil.

[0156] [Example 17]

[0157] The amount of decolorized linseed oil (made with ADM) used as feedstock for the glycerol hydrolysis reaction was set at 331.1 g, the amount of glycerol was set at 68.9 g, the molar ratio of fatty acid groups to glycerol groups [FA / GLY] was set at 1.00, the amount of calcium silicate used as catalyst was set at 20.00 g, and the catalyst addition temperature and reaction temperature were set at 150°C. Otherwise, the glycerol hydrolysis reaction was carried out in the same manner as in Example 1 to obtain transesterified oil.

[0158] [Table 1]

[0159]

[0160] As shown in Table 1, when a calcium-based catalyst is used as the catalyst, the glycerol alcoholysis reaction is carried out at a low [FA / GLY] molar ratio and a low reaction temperature. Compared with the case of a high reaction temperature, the ratio of diacylglycerol to monoacylglycerol in the reaction oil becomes higher. Compared with the case of a high [FA / GLY] molar ratio, this indicates that the total reaction rate of diacylglycerol and monoacylglycerol is higher, and it is confirmed that more triacylglycerol remains (Examples 1-17, Comparative Examples 1 and 2).

[0161] In addition, if a catalyst is added before heating the reaction raw materials, although there is a slightly higher amount of triacylglycerol residue, the mass ratio of diacylglycerol to monoacylglycerol becomes higher (Examples 10-12 and Examples 1-3).

[0162] On the other hand, when using a sodium-based catalyst, a large amount of monoacylglycerol was generated, indicating that the diacylglycerol / monoacylglycerol ratio was lower (Comparative Examples 3-4 and Example 3).

[0163] Furthermore, when calcium hydroxide is used as a catalyst and the reaction is carried out at a low [FA / GLY] ratio and a high temperature, a large amount of monoacylglycerol is generated, indicating that the diacylglycerol / monoacylglycerol ratio becomes lower (Comparative Example 5 and Example 3).

Claims

1. A method for manufacturing an transesterified grease, wherein, include: A process in which oils and glycerol are reacted at a reaction temperature of 90°C to 165°C in the presence of a calcium-based catalyst, with the ratio of the molar number of fatty acid groups to the molar number of glycerol groups (FA / GLY) set to 0.30 or higher and 1.7 or lower.

2. The method for manufacturing transesterified grease as described in claim 1, wherein, The amount of calcium hydroxide or calcium oxide used as a calcium-based catalyst is 0.01% by mass or more relative to the total amount of oil and glycerol.

3. The method for manufacturing transesterified grease as described in claim 1, wherein, The amount of calcium silicate used as a calcium-based catalyst is 0.5% by mass or more relative to the total amount of oil and glycerol.

4. The method for manufacturing transesterified oil according to any one of claims 1 to 3, wherein, The fatty acids constituting the oil include fatty acids with a carbon chain length of 18 or more and a double bond number of 3 or more.

5. The method for manufacturing transesterified grease as described in claim 4, wherein, The fatty acids constituting the oil contain at least 15% by mass of fatty acids with a carbon chain length of 18 or more and a double bond number of 3 or more.

6. The method for manufacturing transesterified oil according to any one of claims 1 to 5, wherein, The mass ratio of diacylglycerol to monoacylglycerol in the oil after transesterification is 1.08 or higher, and the total mass of diacylglycerol and monoacylglycerol is 72% or higher.

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