JP5973530B2 - Glyceride composition and method for producing the glyceride composition - Google Patents

Description

  The present invention relates to a glyceride composition, a method for producing a glyceride composition, a method for reducing the content of glycidol fatty acid ester and / or 3-chloropropane-1,2-diol fatty acid ester in the glyceride composition, and glycidol The present invention relates to a method for suppressing the production of fatty acid esters and / or fatty acid esters of 3-chloropropane-1,2-diol.

  In recent years, various attempts have been made to improve the flavor and stability of fats and oils. Various factors are related to the deterioration of quality such as the flavor and stability of fats and oils, and methods according to each factor have been reported. For example, Patent Document 1 discloses a method of containing ascorbic acid or the like, which is an antioxidant, in fats and oils as an attempt to suppress the deterioration odor of frying fats and oils accompanying the generation of thermal oxidative decomposition products. According to this, it is possible to add an antioxidant to the fat by adding a poorly fat-soluble organic acid such as ascorbic acid to the fat in the form of an aqueous solution and dehydrating under high temperature and high vacuum. It is difficult to produce a heat-deteriorating odor even after long-term use.

  By the way, an oxirane structure which is a three-membered ether is known to be chemically unstable and rich in reactivity, and causes a chemical reaction such as polymerization. In addition, 3-chloropropanes to which halogen is bonded are likely to react. In some glyceride compositions, a fatty acid ester of glycidol, which is one of epoxides having such an oxirane structure, is present in a trace amount, and is highly likely to cause a chemical change such as polymerization. In addition, fatty acid esters of 3-chloropropane-1,2-diol, which may be derived from fatty acid esters of glycidol, are likely to cause similar chemical reactions. The presence of fats and oils deteriorated by polymerization or the like is not preferable because they cause foaming and unpleasant odor when fried.

  However, the method of adding an antioxidant as in Patent Document 1 cannot reduce the fatty acid ester of glycidol or the fatty acid ester of 3-chloropropane-1,2-diol already present in the oil or fat. Further, in other conventional methods, there has been no report on a method for reducing the fatty acid ester of glycidol or fatty acid ester of 3-chloropropane-1,2-diol in fats and oils. It was desired.

International Publication No. 01/096506 Pamphlet

  This invention is made | formed in view of this situation, The glyceride composition with little fatty acid ester of glycidol and / or 3-chloropropane-1, 2-diol fatty acid ester, the manufacturing method of this glyceride composition, glyceride Method for reducing the content of fatty acid ester of glycidol and / or 3-chloropropane-1,2-diol fatty acid ester in the composition, and fatty acid ester of glycidol and / or 3-chloropropane-1,2-diol fatty acid It aims at providing the method of suppressing the production | generation of ester.

  The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems. As a result, 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol, and fatty acid ester of glycidol. A glyceride composition containing at least one selected from the group consisting of and / or containing 3% by mass or more of a diglyceride is deodorized under specific temperature conditions, and is exposed to an acidic condition. By deodorizing at a lower temperature or by heat treatment with the acid value within a specified range, the fatty acid ester of glycidol and the fatty acid ester of 3-chloropropane-1,2-diol in the glyceride composition can be reduced. By the same method, reduction of glycidol and 3-chloropropane-1,2-diol having the same functional group is also expected. It found that can be, and have completed the present invention. Specifically, the following are provided.

  (1) contains at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol, and / or diglyceride A method for producing a glyceride composition, comprising deodorizing a glyceride composition containing 3% by mass or more under a temperature condition of 100 to 240 ° C.

  (2) The said glyceride composition is a manufacturing method of the glyceride composition as described in (1) containing the fatty acid ester of glycidol and / or the fatty acid ester of 3-chloropropane- 1, 2-diol.

  (3) The said glyceride composition is a refined oil, The manufacturing method of the glyceride composition as described in (1) or (2).

  (4) The glyceride composition has an acid value of 2 to 30, and the glyceride composition according to any one of (1) to (3), wherein the glyceride composition is heat-treated before the deodorization treatment. Method.

  (5) The method for producing a glyceride composition according to any one of (1) to (3), wherein the glyceride composition is exposed to acidity before the deodorization treatment.

  (6) The method for producing a glyceride composition according to any one of (1) to (3), wherein the glyceride composition is exposed to acidity after the deodorizing treatment.

  (7) The method for producing a glyceride composition according to (5) or (6), wherein the exposure under the acidic condition is to contact the glyceride composition with an acidic processing aid.

  (8) The method for producing a glyceride composition according to (7), wherein the acidic processing aid is at least one selected from the group consisting of activated clay, acidic activated carbon, and inorganic acid.

  (9) The method for producing a glyceride composition according to (8), wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid.

  (10) The method for producing a glyceride composition according to any one of (5) to (9), wherein the exposure under acidic conditions is performed at 20 to 260 ° C.

  (11) A glyceride composition obtained by the production method according to any one of (1) to (10).

  (12) It contains at least 3% by mass of diglyceride and is selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol A glyceride composition comprising one kind as a 3-chloropropane-1,2-diol equivalent amount in total less than 10 ppm.

  (13) A food containing the glyceride composition according to (11) or (12).

  (14) contains at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol, and / or diglyceride Of glycidol in the glyceride composition and / or fatty acid of 3-chloropropane-1,2-diol by deodorizing the glyceride composition containing 3% by mass or more of the glyceride composition at a temperature of 100 to 240 ° C. A method of reducing esters or suppressing their formation.

  (15) contains at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol, and / or diglyceride The fatty acid ester of glycidol and / or 3 in the glyceride composition according to (14), wherein the glyceride composition containing 3% by mass or more of the glyceride composition is exposed to acidity and deodorized at a temperature of 100 to 240 ° C. -A method for reducing fatty acid esters of chloropropane-1,2-diol or suppressing their production.

  According to the present invention, it is possible to obtain a glyceride composition with less fatty acid ester of glycidol and / or fatty acid ester of 3-chloropropane-1,2-diol.

  Hereinafter, embodiments of the present invention will be specifically described. In the present invention, glycerides are glycerin in which 1 to 3 fatty acids are ester-bonded, and in addition to triglyceride (triacylglycerol), which is the main component of fats and oils, diglyceride (diacylglycerol), monoglyceride (monoacylglycerol) ).

  The method for producing the glyceride composition of the present invention comprises 3-chloropropane-1,2-diol (hereinafter referred to as 3-MCPD), a fatty acid ester of 3-chloropropane-1,2-diol (hereinafter referred to as 3-MCPD). A glyceride composition containing at least one selected from the group consisting of glycidol and a fatty acid ester of glycidol and / or containing 3% by mass or more of diglyceride, at a temperature of 100 to 240 ° C. It is characterized by deodorizing treatment. That is, in the method for producing a glyceride composition of the present invention, (A) 3-MCPD, a fatty acid ester of 3-MCPD, a glyceride composition containing at least one selected from the group consisting of glycidol and a fatty acid ester of glycidol, B) a glyceride composition containing 3% by mass or more of diglyceride, or (C) 3-MCPD, a fatty acid ester of 3-MCPD, glycidol, and at least one selected from the group consisting of fatty acid esters of glycidol, and Any glyceride composition containing 3% by mass or more of diglyceride is deodorized at a temperature of 100 to 240 ° C. When the glyceride composition before the deodorization treatment contains 3% by mass or more of diglyceride, the content of diglyceride is more preferably 10 to 98% by mass, and 60 to 93% by mass. More preferably. Here, the content of diglyceride in the glyceride composition can be measured by, for example, a gas chromatography method (AOCS Official Method Cd 11b-91).

When the glyceride composition before the deodorizing treatment contains at least one selected from the group consisting of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester, The total content of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester is preferably 3 ppm or more, and more preferably 10 ppm or more, as 3-MCPD equivalent by an analysis method described later. 10 to 200 ppm is more preferable, and 10 to 100 ppm is most preferable. In addition, since the manufacturing method of the glyceride composition of this invention has the effect of reducing the fatty acid ester of glycidol and the fatty acid ester of 3-MCPD, the fatty acid ester of glycidol and / or the fatty acid of 3-MCPD in the said glyceride composition. More useful when esters are included.
Further, glycidol and 3-MCPD whose structure is similar to fatty acid ester of glycidol and fatty acid ester of 3-MCPD are not included in normal edible fats and oils. And 3-MCPD also have the effect of reducing.

  In the present invention, as a method for measuring the content of glycidol, fatty acid ester of glycidol, fatty acid ester of 3-MCPD and 3-MCPD, the German official method (DGF Standard Methods C-III) which measures these as 3-MCPD equivalent amount 18 (09)) was used.

  Specifically, sample oils and fats are collected, an internal standard substance is added, a methanol solution of sodium methoxide is added and reacted at room temperature, and ester saponification decomposition is performed. Next, a salt solution containing a small amount of acetic acid and hexane are added to and mixed with this, and then hexane is removed. At this time, 3-MCPD, 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester are all converted to 3-MCPD. Then, it is derivatized with phenylboric acid, extracted with hexane, and measured with a gas chromatograph mass spectrometer. And using the chromatogram obtained by the measurement of a gas chromatograph mass spectrometer, the internal standard and the ionic strength of 3-MCPD are compared, so that glycidol in fats and oils, fatty acid ester of glycidol, 3-MCPD, 3-MCPD, The total amount of MCPD fatty acid ester is calculated in terms of free 3-MCPD.

  Thus, in the preparation method of the measurement sample in the German official method, 3-MCPD, 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester are all converted to 3-MCPD. For this reason, the measured value according to the German official method is a 3-MCPD conversion value of the total content of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester. In addition, since a to-be-measured object is glyceride compositions, such as vegetable oil, what is measured by the said German official method is estimated to be the fatty acid ester of glycidol and the fatty acid ester of 3-MCPD.

  In the method for producing a glyceride composition of the present invention, any one of the glyceride compositions (1) to (3) above is used at a temperature lower than the deodorizing temperature 240 to 260 ° C. used in the usual method for producing fats and oils. The deodorizing treatment is performed under a temperature condition of 0 ° C., preferably 100 to 235 ° C., more preferably 160 to 225 ° C., and most preferably 200 to 215 ° C. In addition, the manufacturing method of the glyceride composition of this invention is 100-240 degreeC again after the steam distillation process (normal deodorizing process) at 240-260 degreeC, when manufacturing a glyceride composition with favorable flavor. It is preferable that a deodorizing process is performed on temperature conditions. Conditions other than the deodorization temperature are not particularly limited, but reduced pressure or steam blowing is preferred, and steam blowing is more preferred at reduced pressure. Further, the deodorization time is preferably 15 to 150 minutes, and more preferably 40 to 100 minutes.

  In the method for producing a glyceride composition of the present invention, purified oil may be used as the glyceride composition. By using refined oil, a glyceride composition having a better flavor can be produced. Refined oils include, for example, rapeseed oil, soybean oil, rice oil, safflower oil, grape oil, sunflower oil, wheat germ oil, corn oil, cottonseed oil, sesame oil, peanut oil, flux oil, Vegetable oils such as sesame oil, olive oil, palm oil, palm oil, mixed vegetable oils that are a mixture of two or more of these, or edible fractionated oils such as palm olein, palm stearin, palm super olein, palm mid fraction, etc. In addition to hydrogenated oil, transesterified oil, etc., edible oil produced by direct esterification reaction such as medium-chain fatty acid triglyceride can be used. There are chemical refining (chemical refining) and physical refining (physical refining) as methods for refining vegetable oil, and any refining method may be used. The former chemical refining is a method usually used for refining vegetable oils. Crude oil obtained by squeezing and extracting the plant as raw material is degummed, deoxidized, decolorized, and dewaxed. After being deodorized, it is refined and becomes refined oil. On the other hand, the latter physical refining is a method that is often performed with palm oil, palm oil, etc., and crude oil obtained by squeezing palm or palm as a raw material is subjected to degumming treatment, decolorization treatment, deoxidation / It is refined through deodorizing treatment and becomes refined oil.

  In the manufacturing method of the glyceride composition of this invention, it is preferable to heat-process the said glyceride composition whose acid value is 2-30 before the said deodorizing process. For the glyceride composition having an acid value of 2 to 30, a glyceride composition having a high acid value or a glyceride composition having an acid value adjusted by adding an acid can be used. Preferably, the glyceride composition is 15. In addition, it is preferable that the acid used when adjusting an acid value is a free fatty acid. Here, free fatty acid means free fatty acid and its salt. Although it does not specifically limit as a free fatty acid, A C12-C22 fatty acid is preferable, for example, a palmitic acid, an oleic acid, a linoleic acid, a stearic acid, a linolenic acid etc. are mentioned.

  Moreover, it is preferable that the temperature at the time of heat processing is 100-260 degreeC, It is more preferable that it is 160-245 degreeC, It is still more preferable that it is 200-225 degreeC. In the method for producing a glyceride composition of the present invention, the heat treatment is not particularly limited as long as it is heated, but specifically, heating is performed, heating is performed under reduced pressure, and heating is performed while blowing water vapor. And heating while blowing water vapor under reduced pressure. Conditions other than temperature are not particularly limited, but reduced pressure or steam blowing is preferred, and steam blowing is more preferred at reduced pressure. Moreover, although the time of heat processing is not specifically limited, 40 to 100 minutes are preferable.

  In the method for producing a glyceride composition of the present invention, the glyceride composition may be exposed to acidity before the deodorization treatment or after the deodorization treatment. Exposure to an acidic condition prior to the deodorizing treatment is preferable in terms of flavor, and when exposed to an acidic condition after the deodorizing treatment, the effect of reducing the fatty acid ester of glycidol and 3-chloropropane-1,2-diol is high. In the method for producing a glyceride composition of the present invention, the method for exposing the glyceride composition to an acidic condition is not particularly limited. For example, the glyceride composition is brought into contact with an acidic processing aid. The method of adding a C1-C22 organic acid to a composition is mentioned, These methods can also use 2 or more types together.

  Moreover, it is preferable that exposure under acidic conditions is performed at 20-260 degreeC, and in the case of the method made to contact an acidic processing aid, it is more preferable to be performed at 20-200 degreeC, and 100- Most preferred is 180 ° C. Moreover, in the case of the method of adding a C1-C22 organic acid, it is more preferable to carry out at 100-260 degreeC, and it is most preferable to carry out at 180-260 degreeC.

  In the method of bringing the glyceride composition into contact with an acidic processing aid, the acidic processing aid is not particularly limited. For example, the processing aid showing acidity, the processing aid showing aqueous acidity, Examples thereof include a processing aid containing an acidic gas and a processing aid in which an acid remains. Specific examples include clay, activated carbon, silica gel, ion exchange resin, filter aid, zeolite, fiber, catalyst, enzyme, acid-treated products thereof, inorganic acids, and the like, which can be used alone or in combination. . In the present invention, white clay refers to clay mainly composed of montmorillonite. The white clay is not particularly limited, and includes any one of acidic white clay or activated white clay that has been activated. In the present invention, as a raw material of activated carbon, for example, coke, artificial graphite, charcoal, bone charcoal, glassy carbon, carbon fiber, carbon black, silk, or the like can be used. In particular, those derived from plants such as wood, seed coat, grain residue, bark and cocoon pattern are preferred, and wood is most preferred. Moreover, as an activation method, various methods, such as water vapor activation, gas activation, and chemical activation, are known, Even if it activates by any method, it can use suitably. Of these, those chemically activated are preferred. Among the chemical activations, those activated with zinc chloride, phosphoric acid, sulfuric acid, calcium chloride, etc. are more preferred, and those activated with phosphoric acid are most preferred. Moreover, even if it activated by alkali, if it was processed so that it might show acidity after that, it can use suitably. In the present invention, diatomaceous earth, cellulose, perlite, etc. can be used as the filter aid. As the fiber, chemical fiber, plant fiber, animal fiber or the like can be used. Among these, as the acidic processing aid of the present invention, acidic clay or acidic activated carbon is preferable, and combined use of activated clay and acidic activated carbon is more preferable. The amount of processing aid added is not particularly limited, but in the case of processing aids other than inorganic acids, 0.01 to 10% by weight, preferably 1 to 7% by weight, based on the glyceride composition. Further preferred. Processing aids other than inorganic acids are generally solid and are preferably removed by filtration after contact.

  In the method using an inorganic acid as an acidic processing aid, the type of the inorganic acid is not particularly limited, and examples thereof include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and these are used alone or in combination. be able to. Among these, sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid are preferable in terms of easy availability. Moreover, although it is preferable to add and use the inorganic acid with respect to the said glyceride composition, since there are few addition amounts, adding an inorganic acid as aqueous solution is preferable when controlling addition amount. The addition of the aqueous solution of the inorganic acid to the glyceride composition is immediately after the deodorization treatment, and the temperature of the glyceride composition is preferably 100 ° C. or higher, more preferably 100 to 200 ° C. Although the addition amount of an inorganic acid is not specifically limited, 0.001-0.7 mass% is preferable with respect to a glyceride composition, and 0.001-0.05 mass% is still more preferable. Moreover, after adding and contacting an inorganic acid, it is preferable to remove an inorganic acid by water washing etc.

  In the method of adding an organic acid having 1 to 22 carbon atoms to the glyceride composition, the organic acid is not particularly limited. For example, citric acid, acetic acid, malic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and the like can be mentioned, and these can be used alone or in combination. Among these, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, and linolenic acid are preferable in that they have good solubility in fats and oils. In addition, it is preferable to add a water-soluble organic acid such as citric acid or malic acid as an aqueous solution in order to enhance dispersibility. The addition of the aqueous organic acid solution to the glyceride composition is preferably immediately after the deodorization treatment. The temperature of the glyceride composition is preferably 100 ° C. or higher, more preferably 100 to 260 ° C., and most preferably 180 to 260 ° C. The addition amount of the organic acid is not particularly limited, but is preferably in the range of 10 ppm to 20% by mass with respect to the glyceride composition, and the acid value of the glyceride composition may be added to be 2 to 30. More preferred. In addition, after the exposure under acidic conditions, it is preferable to remove the organic acid having 1 to 4 carbon atoms by filtration or water washing, and to remove the organic acid having 5 or more carbon atoms by means such as distillation.

  The glyceride composition of the present invention is obtained by the above-described method for producing the glyceride composition of the present invention. According to the glyceride composition of the present invention, glycidol fatty acid ester, 3-MCPD fatty acid ester, glycidol, and 3-MCPD can be reduced, or the formation of glycidol fatty acid ester and 3-MCPD fatty acid ester can be suppressed. Therefore, it can be expected that the obtained glyceride composition is less likely to cause foaming and a decrease in flavor during frying.

  The glyceride composition of the present invention contains 3% by mass or more of diglyceride, and at least one selected from the group consisting of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester is converted into 3-MCPD The total content is less than 10 ppm. Although the glyceride composition of the present invention contains a certain amount or more of diglyceride, it can be expected that glycidol and glycidol fatty acid esters are less likely to cause foaming and a decrease in flavor during frying. The diglyceride content is preferably 60 to 98% by mass, and at least one selected from the group consisting of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester is 3- It is preferable to contain less than 3 ppm in total as the MCPD equivalent.

  The food of the present invention is characterized by containing the above-described glyceride composition of the present invention. According to the food of the present invention, since the fatty acid ester of glycidol and the fatty acid ester of 3-MCPD in the glyceride composition used as a raw material are small, it can be expected that foaming and flavor reduction during frying are unlikely to occur. As food, any food that can contain fats and oils can be targeted. Examples include seasoning oil, mayonnaise, chocolate, dressing, margarine, fat spread, cream and the like.

  The method of the present invention is a method for reducing the content of the fatty acid ester of glycidol and / or the fatty acid ester of 3-MCPD in the glyceride composition or suppressing the production thereof. This method comprises a glyceride composition containing at least one selected from the group consisting of 3-MCPD, fatty acid ester of 3-MCPD, glycidol and fatty acid ester of glycidol, and / or containing 3% by mass or more of diglyceride. The fatty acid ester of glycidol and / or the fatty acid ester of 3-MCPD in the glyceride composition is reduced or the production thereof is suppressed by performing a deodorizing treatment at a temperature condition of 100 to 240 ° C. The conditions for the deodorization treatment are the same as in the method for producing the glyceride composition described above. In addition, the glyceride fatty acid ester and / or 3-MCPD fatty acid ester in the glyceride composition is further reduced by exposing the glyceride composition to an acidic condition and further deodorizing it at a temperature of 100 to 240 ° C. Or generation | occurrence | production of these can be suppressed.

  Hereinafter, although it demonstrates still in detail based on the Example of this invention, this invention is not limited to these description at all.

  The possibility of reducing 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester contained in the glyceride composition was examined.

<Examination of acid exposure conditions>
[Raw material glyceride composition 1]
To 1600 g of soybean / rapeseed mixed refined oil refined by a conventional method (mixed oil of soybean decolorized oil and rapeseed decolorized oil), 0.256 g of fatty acid ester of glycidol (Glycidol Stearate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.192 g of A fatty acid ester of 3-MCPD (1-Stearyl-3-chloropropandiol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed to obtain a raw glyceride composition 1 (85.35 ppm as 3-MCPD equivalent). It was.

[Comparative Example 1]
The raw glyceride composition 1 was stirred at 110 ° C. under reduced pressure for 20 minutes to obtain a glyceride composition of Comparative Example 1.

[Example 1]
5% by mass of activated carbon (phosphoric acid activated activated carbon: CA1, manufactured by Nippon Norit Co., Ltd.) with respect to the amount of the raw glyceride composition 1 is added to the raw glyceride composition 1 and stirred at 110 ° C. for 20 minutes under reduced pressure. Then, the activated carbon was removed by filtration to obtain a glyceride composition of Example 1.

[Example 2]
The glyceride composition of Example 2 was prepared in the same manner as in Example 1 except that 5% by mass of activated clay (sulfuric acid-treated clay: manufactured by Mizusawa Chemical Co., Ltd.) was used instead of 5% by mass of activated carbon. Obtained.

[Example 3]
5% by mass of activated clay (sulfuric acid-treated clay: manufactured by Mizusawa Chemical Co., Ltd.) with respect to the amount of the raw glyceride composition 1 is added to the raw glyceride composition 1, and 20% at normal temperature (28 ° C) under reduced pressure. After stirring for 5 minutes, the activated clay was removed by filtration to obtain a glyceride composition of Example 3.

[Raw material glyceride composition 2]
Raw material glyceride composition 1 and soybean decolorized oil were mixed at a weight ratio of 83:17 to obtain raw material glyceride composition 2 (14.30 ppm as 3-MCPD equivalent).

[Example 4]
5% by mass of activated carbon (phosphoric acid activated activated carbon: CA1, manufactured by Nippon Norit Co., Ltd.) is added to the raw material glyceride composition 2 and stirred for 20 minutes at 110 ° C. under reduced pressure. Thereafter, the activated carbon was removed by filtration to obtain a glyceride composition of Example 4.

[Example 5]
The glyceride composition of Example 5 was prepared in the same manner as in Example 4 except that 5% by mass of activated clay (sulfuric acid-treated clay: manufactured by Mizusawa Chemical Co., Ltd.) was used instead of 5% by mass of activated carbon. Obtained.

[Raw material glyceride composition 3]
Raw material glyceride composition 1 and soybean decolorized oil were mixed at a weight ratio of 86:14 to obtain raw material glyceride composition 3 (11.65 ppm as 3-MCPD equivalent).

[Example 6]
5% by mass of activated carbon (phosphoric acid activated activated carbon: CA1, manufactured by Nippon Norit Co., Ltd.) is added to the raw glyceride composition 3 with respect to the amount of the raw glyceride composition 3 and stirred at 110 ° C. for 20 minutes under reduced pressure. Then, the activated carbon was removed by filtration to obtain a glyceride composition of Example 6.

[Example 7]
The glyceride composition of Example 7 was prepared in the same manner as in Example 6 except that 5% by mass of activated clay (sulfuric acid-treated clay: manufactured by Mizusawa Chemical Co., Ltd.) was used instead of 5% by mass of activated carbon. Obtained.

(Quantitative method)
The quantification of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester in the glyceride composition was carried out in accordance with the German official method (DGF Standard Methods C-III 18 (09)). In this method, since the fatty acid ester of glycidol and the fatty acid ester of 3-MCPD are converted into 3-MCPD when preparing the measurement sample, the fatty acid ester of 3-MCPD, 3-MCPD, glycidol and glycidol All were measured as free 3-MCPD.
After adding 50 μL of an internal standard substance (3-MCPD-d5 20 μg / mL solution) to 100 mg of the samples of the raw glyceride compositions 1 to 3, Examples 1 to 7 and Comparative Example 1, 1 mL of sodium methoxide solution (0.5 mol / L methanol) was added and reacted at room temperature to saponify and decompose the ester. Next, 3 mL of brine (20%) containing a small amount of acetic acid and 3 mL of hexane were added to and mixed with this, and then hexane was removed. At this time, glycidol is converted into 3-MCPD, and the fatty acid ester of glycidol is converted into 3-MCPD as the ester bond is broken. Thereafter, it was derivatized with 250 μL of an aqueous phenylboric acid solution (25%), extracted with 2 mL of hexane, and measured with a gas chromatograph mass spectrometer.
By using the chromatogram obtained by the measurement of the gas chromatograph mass spectrometer and comparing the ionic strength of 3-MCPD-d5 which is an internal standard and 3-MCPD, the glycidol and glycidol in the glyceride composition The total amount of fatty acid esters of fatty acid ester, 3-MCPD and 3-MCPD was calculated in terms of free 3-MCPD.

(GC-MS analysis conditions)
Analytical device: Agilent Technology, model name 6890GC
Column: manufactured by Restek, product name Rtx-5MS (length 30 m, diameter 0.25 mm)
Column temperature: 60 ° C. (1 minute) to 190 ° C. (temperature increase rate 6 ° C./min) to 280 ° C. (temperature increase rate 20 ° C./min)
Detector: MS (EI, SIM mode)
Splitless: 1 μL injection Carrier gas: He

  The total amount of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester (3-MCPD equivalent amount) in the glyceride composition by treatment with activated carbon activated with inorganic acid or clay treated with sulfuric acid. ) Was confirmed to be significantly reduced (Table 1: Examples 1 to 7, raw material triglyceride compositions 1 to 3, Comparative Example 1). In view of the amount of glycidol fatty acid ester and 3-MC added to the glyceride composition, it is clear that glycidol fatty acid ester and 3-MCPD were reduced.

[Raw material glyceride composition 4]
160 g of soybean / rapeseed mixed oil refined by a conventional method (mixed oil of soybean decolorized oil and rapeseed decolorized oil), 20.8 mg of glycidol fatty acid ester (Glycidol Stearate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 16.0 mg of 3 -Fatty acid ester of MCPD (1-Stearyl-3-chloropropandiol, manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed to obtain raw material glyceride composition 4 (70.61 ppm as 3-MCPD equivalent). .

<Examination of acid treatment>
[Example 8]
0.025 mass% sulfuric acid was added to the raw material glyceride composition 4, and the mixture was stirred at 150 ° C. for 10 minutes under normal pressure to obtain a glyceride composition of Example 8.

  It was confirmed that the total amount of 3-MCPD, fatty acid ester of 3-MCPD, glycidol and fatty acid ester of glycidol (converted amount of 3-MCPD) of the glyceride composition treated with sulfuric acid was significantly reduced (Table 2: Example 8). In view of the amount of fatty acid ester of glycidol and fatty acid ester of 3-MCPD added to the glyceride composition, it is clear that both were reduced.

<Examination of deodorizing conditions>
[Example 9]
Example 9 The glyceride composition of the raw material glyceride composition 1 was deodorized at 210 ° C. for 90 minutes under reduced pressure (4 torr) while blowing water vapor (total amount: 3 mass% with respect to the glyceride composition amount). A glyceride composition was obtained.

  The calculation of the 3-MCPD equivalent amount was in accordance with the description of the above quantitative method. By performing the deodorization treatment at a low temperature, a decrease in the total amount of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester was confirmed (Table 3: Example 9).

<Examination of deodorizing conditions, acid value and heat treatment conditions>
Samples prepared by reducing the total content of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester by preparing a glyceride composition containing a large amount of diglyceride and treating it with activated clay It was. And the influence which the temperature in heat processing and the presence or absence of free fatty acid addition has on the production | generation suppression of 3-MCPD, the fatty acid ester of 3-MCPD, glycidol, and the fatty acid ester of glycidol was examined.

[Raw material glyceride composition 5]
A mixed oil of soybean bleaching oil and rapeseed bleaching oil purified by a conventional method was partially hydrolyzed with lipase and subjected to molecular distillation. Furthermore, 5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added to the glyceride composition deodorized at 250 ° C. for 1.5 hours, and the pressure was reduced at 110 ° C. for 20 minutes. After stirring, the activated clay was removed by filtration, and the raw glyceride composition 5 (glyceride composition was 0.6% by weight of monoglyceride, 88.7% by weight of diglyceride, 10.7% by weight of triglyceride, and 0 as 3-MCPD conversion amount) .76 ppm).

[Example 10]
The glyceride composition 5 (acid value of the glyceride composition: 0.2) was treated at 220 ° C. for 90 minutes under normal pressure to obtain the glyceride composition of Example 10.

[Example 11]
The glyceride composition of Example 11 was obtained in the same manner as in Example 10 except that palmitic acid was added so that the acid value of the glyceride composition was 5.8.

[Example 12]
The glyceride composition of Example 12 was obtained in the same manner as in Example 10 except that palmitic acid was added so that the acid value of the glyceride composition was 10.9.

[Example 13]
A glyceride composition of Example 13 was obtained in the same manner as in Example 10 except that the temperature was 230 ° C.

[Example 14]
A glyceride composition of Example 14 was obtained in the same manner as in Example 11, except that the temperature was 230 ° C.

[Example 15]
A glyceride composition of Example 15 was obtained in the same manner as in Example 12, except that the temperature was 230 ° C.

[Comparative Example 2]
A glyceride composition of Comparative Example 2 was obtained in the same manner as in Example 10 except that the temperature was 240 ° C.

[Example 16]
A glyceride composition of Example 16 was obtained in the same manner as in Example 11, except that the temperature was 240 ° C.

[Example 17]
A glyceride composition of Example 17 was obtained in the same manner as in Example 12, except that the temperature was 240 ° C.

  The calculation of the 3-MCPD equivalent amount was in accordance with the description of the above quantitative method. In the heat treatment, the lower the temperature, the lower the total amount of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol fatty acid ester (converted amount of 3-MCPD) (Table 3: Raw material glyceride composition 5 Examples 10-17, Comparative Example 2). When palmitic acid is added so that the acid value becomes 5.8 or 10.9 during high temperature treatment such as deodorization treatment, 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol associated with temperature It was confirmed that the production | generation of fatty acid ester was suppressed notably (Table 3: Examples 10-12, Examples 13-15, Comparative Example 2, and Examples 16-17).

[Raw material glyceride composition 6]
Rice oil extracted by a conventional method is partially hydrolyzed with lipase, deoxidized, and then 2% by weight of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) with respect to the deacidified rice oil. After stirring at 105 ° C. for 20 minutes under reduced pressure, the activated clay was removed by filtration to obtain decolored rice oil. Next, the decolorized rice oil was deodorized for 90 minutes at 240 ° C. under reduced pressure (4 torr) while blowing steam (3% by mass of oil) to obtain a refined oil (raw glyceride composition 6). In addition, it was 7 mass% when the diglyceride content in the raw material glyceride composition 6 was measured by the gas chromatography method (AOCS Official Method Cd 11b-91).

[Reference Example 1]
0.1% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added to the raw glyceride composition 6, stirred at 110 ° C. for 20 minutes under reduced pressure, and then activated clay was filtered. Was removed to obtain a recolored oil (glyceride composition of Reference Example 1).

[Example 18]
To the raw material glyceride composition 6, 0.5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 20 minutes under reduced pressure, followed by filtration. Was removed to obtain a recolored oil. Subsequently, the recolored oil was deodorized for 90 minutes at 240 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of oil) to obtain a glyceride composition of Example 18.

[Example 19]
To the raw material glyceride composition 6, 0.5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 20 minutes under reduced pressure, followed by filtration. Was removed to obtain a recolored oil. Subsequently, the recolored oil was deodorized for 90 minutes at 230 ° C. under reduced pressure (4 torr) while blowing water vapor (3 mass% with respect to oil) to obtain a glyceride composition of Example 19.

[Example 20]
1% by weight of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) is added to the raw material glyceride composition 6 and stirred at 110 ° C. for 20 minutes under reduced pressure, and then the activated clay is removed by filtration. And re-bleaching oil was obtained. Subsequently, the recolored oil was deodorized for 90 minutes at 220 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of oil) to obtain a glyceride composition of Example 20.

[Example 21]
1% by weight of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) is added to the raw material glyceride composition 6 and stirred at 110 ° C. for 20 minutes under reduced pressure, and then the activated clay is removed by filtration. And re-bleaching oil was obtained. Then, the recolored oil was deodorized for 90 minutes at 200 ° C. under reduced pressure (4 torr) while blowing water vapor (3 mass% with respect to oil) to obtain a glyceride composition of Example 21.

  The calculation of the 3-MCPD equivalent amount was in accordance with the description of the above quantitative method. In Examples 18 to 21, it was confirmed that the amount of 3-MCPD equivalent in the refined oil could be reduced, and further, an edible oil with good flavor could be produced. In addition, the 3-MCPD conversion amount reduction effect was so high that the re-deodorization temperature was low, and the 3-MCPD conversion amount reduction effect was high when the amount of activated clay at the time of re-decoloration was 0.5 mass%.

[Raw material glyceride composition 7]
Rapeseed decolorized oil (manufactured by Nisshin Oillio Group Co., Ltd.) was mixed with 85% by mass and glyceride composition 5 was mixed with 15% by mass, and steam was blown into the resulting mixed oil (3% by mass against oil). ) And deodorized at 240 ° C. for 90 minutes under reduced pressure (4 torr) to obtain a refined oil (raw glyceride composition 7). In addition, when the diglyceride content in the raw material glyceride composition 7 was measured by a gas chromatography method (AOCS Official Method Cd 11b-91), it was 13.3% by mass.

[Reference Example 2]
0.1% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) is added to the raw material glyceride composition 7, and the mixture is stirred at 110 ° C. for 20 minutes under reduced pressure, followed by filtration. Was removed to obtain a recolored oil (glyceride composition of Reference Example 2).

[Example 22]
To the raw material glyceride composition 7, 0.5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 20 minutes under reduced pressure, followed by filtration. Was removed to obtain a recolored oil. The decolorized oil was then deodorized for 90 minutes at 240 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of oil) to obtain a glyceride composition of Example 22.

[Example 23]
To the raw material glyceride composition 7, 0.5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 20 minutes under reduced pressure, followed by filtration. Was removed to obtain a recolored oil. The decolorized oil was then deodorized for 90 minutes at 230 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of the oil) to obtain a glyceride composition of Example 23.

[Example 24]
1% by weight of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) is added to the raw material glyceride composition 7, and the mixture is stirred at 110 ° C. for 20 minutes under reduced pressure, and then the activated clay is removed by filtration. And re-bleaching oil was obtained. The decolorized oil was then deodorized for 90 minutes at 220 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of oil) to obtain a glyceride composition of Example 24.

[Example 25]
1% by weight of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd.) is added to the raw material glyceride composition 7, and the mixture is stirred at 110 ° C. for 20 minutes under reduced pressure, and then the activated clay is removed by filtration. And re-bleaching oil was obtained. Subsequently, the recolored oil was deodorized for 90 minutes at 200 ° C. under reduced pressure (4 torr) while blowing water vapor (3% by mass of oil) to obtain a glyceride composition of Example 25.

  The calculation of the 3-MCPD equivalent amount was in accordance with the description of the above quantitative method. In Examples 22 to 25, it was confirmed that the amount of 3-MCPD equivalent in the refined oil can be reduced, and further, an edible oil having a good flavor can be produced. In addition, the 3-MCPD conversion amount reduction effect was so high that the re-deodorization temperature was low, and the 3-MCPD conversion amount reduction effect was high when the amount of activated clay at the time of re-decoloration was 0.5 mass%.

Claims (4)

It contains at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol, and / or 3 mass of diglyceride % Of the glyceride composition containing at least 100% at 240 to 240 ° C.
A method for producing a glyceride composition, wherein the glyceride composition is exposed to acidity by the method of (1) before, during and / or after the deodorization treatment.
(1) The said glyceride composition is made to contact with 0.01-10 mass% phosphoric acid activation activated carbon or 0.001-0.7 mass% inorganic acid at 100-180 degreeC.   The method for producing a glyceride composition according to claim 1, wherein the glyceride composition is a refined oil.   The method for producing a glyceride composition according to claim 2, wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid. It contains at least one selected from the group consisting of 3-chloropropane-1,2-diol, fatty acid ester of 3-chloropropane-1,2-diol, glycidol and fatty acid ester of glycidol, and / or 3 mass of diglyceride % Of the glyceride composition containing at least 100% at 240 to 240 ° C.
Before the deodorization treatment, during the deodorization treatment and / or after the deodorization treatment, the glyceride composition is exposed to acidity by the method of (1), whereby a fatty acid ester of glycidol in the glyceride composition and / or 3- A method for reducing or suppressing the production of chloropropane-1,2-diol fatty acid esters.
(1) The said glyceride composition is made to contact with 0.01-10 mass% phosphoric acid activation activated carbon or 0.001-0.7 mass% inorganic acid at 100-180 degreeC.