JP2023162681A - Method for producing oil and fat composition - Google Patents

Abstract

To provide an oil and fat composition that has sufficiently low levels of 3-MCPD and glycidol and also reduced vitamin K, and is used in formulated milk for childcare, and a method for producing the same.SOLUTION: A method for producing an oil and fat composition includes a decolorization step. The decoloration step is performed using activated carbon that has not undergone hydrochloric acid treatment.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an oil and fat composition, particularly a method for producing an oil and fat composition used in infant formula.

3-MCPD, which is produced when the fatty acid ester of 3-MCPD (3-monochloropropane-1,2-diol) contained in edible oils and fats is metabolized in the body, is suspected of being carcinogenic and toxic. In addition, it has been reported that oils and fats that contain high concentrations of DAG (diacylglycerol) contain glycidol fatty acid esters, and there are concerns that glycidol, which is produced when glycidol fatty acid esters are metabolized in the body, is also carcinogenic and toxic. has been done. Therefore, it is desired to reduce 3-MCPD, glycidol, and their fatty acid esters from edible oils and fats, particularly from oil and fat compositions used in infant formula.
Vitamin K is one of the fat-soluble vitamins and is known to have effects related to blood coagulation and bone formation. Vitamin K is synthesized in the intestine by intestinal bacteria, and can also be ingested from food. A lack of vitamin K causes a decline in blood coagulation, leading to symptoms such as nosebleeds and gastrointestinal bleeding. It is known that newborn infants are susceptible to vitamin K deficiency hemorrhage because their intestinal bacteria are underdeveloped and their breast milk contains little vitamin K. Therefore, vitamin K is administered to newborn infants immediately after birth, and the vitamin K content of formula milk for infants is adjusted by adding vitamin K preparations.
In addition, for infant formula, there are standards for permission to label infant formula (Consumer Affairs Agency) as well as the content of linoleic acid and α-linolenic acid, and in order to meet these standards, large quantities of edible fats and oils are required. You need to use bean oil or rapeseed oil.
Soybean oil and rapeseed oil also contain a lot of vitamin K. However, the vitamin K content varies greatly depending on the origin and harvest of the raw material. Therefore, when soybean oil and rapeseed oil are blended to contain a certain amount of linoleic acid and α-linolenic acid necessary for infant formula, it is difficult to control vitamin K within a certain range.
As a method for removing vitamin K from fats and oils, for example, it is described that in the decolorization process of fats and oils, vitamin K is reduced when a treatment is performed using activated clay:activated carbon = 4:1 (Non-Patent Document 1). ).
Additionally, a method has been reported for producing a fat for formula milk powder with a reduced content of vitamin K by using transesterified oil containing at least one of soybean oil and rapeseed oil as a raw material for transesterification ( Patent Document 1).

JP2020-162444A

Journal of Japan Oil Chemists' Society Vol. 48, No. 11 (1999) 1271-1274

An object of the present invention is to provide an oil and fat composition used for infant formula, which has sufficiently low concentrations of 3-MCPD and glycidol and reduced vitamin K, and a method for producing the same. It is.

The present inventors discovered that when activated carbon is used to reduce vitamin K in the decolorization process of oil and fat compositions, 3-MCPD increases during the treatment, and that this phenomenon also occurs when certain activated carbons are used. We found that this occurs when using That is, the present invention was completed based on the discovery that when activated carbon that has been treated with hydrochloric acid among activated carbons is used, the 3-MCPD concentration increases during the purification process.

Embodiments of the invention may be as follows.
[1] A method for producing an oil or fat composition including a decoloring step, wherein the decoloring step is carried out using activated carbon that has not been treated with hydrochloric acid.
[2] The production method according to [1] above, wherein the oil and fat composition is an oil and fat composition for infant formula.
[3] The production according to [1] or [2] above, wherein the activated carbon that has not been treated with hydrochloric acid is used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the fat composition used in the decolorizing step. Method.
[4] The activated carbon that has not been treated with hydrochloric acid is selected from the group consisting of gas-activated activated carbon and chemically activated activated carbon, and the activated carbon that has not been treated with hydrochloric acid has a chlorine concentration (total of free residual chlorine and combined chlorine) of 200 μg/g. The manufacturing method according to any one of the following [1] to [3].
[5] The content of vitamin K in 100 g of the fat composition after the bleaching step is reduced by 10 μg or more compared to the content of vitamin K in 100 g of the fat composition before the bleaching step, [1] to The manufacturing method according to any one of [4].
[6] The production method according to any one of [1] to [5] above, wherein a deodorizing step is performed following the decoloring step.
[7] The production method according to [6] above, wherein the 3-MCPD concentration of the oil and fat composition after the deodorizing step is 0.42 ppm or less.
[8] The production method according to [6] or [7] above, wherein the glycidol concentration of the oil and fat composition after the deodorizing step is 0.17 ppm or less.
[9] An oil and fat composition for infant formula, which has a 3-MCPD concentration of 0.42 ppm or less, a glycidol concentration of 0.17 ppm or less, and a vitamin K concentration of 20 to 100 μg/100 g.

By the method of the present invention, it is possible to reduce the vitamin K content in the oil and fat composition, and at the same time, the concentrations of 3-MCPD, glycidol, and their fatty acid esters, whose intake should be reduced from a safety perspective, are sufficiently reduced. It is possible to provide a method for producing an oil and fat composition. The above method is particularly suitable as a method for producing an oil and fat composition for infant formula, and the vitamin K content is adjusted, and the concentration of 3-MCPD, glycidol, and their fatty acid esters whose intake is desired to be reduced from a safety standpoint. It is possible to produce an oil and fat composition for infant formula in which the

<Method for producing oil and fat composition>
The method for producing an oil or fat composition of the present invention is characterized in that it includes a decoloring step, and the decoloring step is carried out using activated carbon that has not been treated with hydrochloric acid.
More specifically, the oil and fat composition that has gone through the process of arbitrarily mixing the oil and fat compositions is subjected to a decoloring treatment using activated carbon that has not been treated with hydrochloric acid. After the decolorization step, a deodorization treatment may be performed. The oil and fat composition may be a deacidified oil and fat composition.

<Bleaching process>
In the decolorizing step of the oil and fat composition in the method of the present invention, it is necessary to use activated carbon that has not been treated with hydrochloric acid. This is because if activated carbon treated with hydrochloric acid is used, the concentration of 3-MCPD and its fatty acid esters will increase after the decolorization step.

Methods for producing activated carbon are broadly divided into gas activation methods and chemical activation methods. Activation (treatment) refers to a reaction or operation that generates nanometer-sized micropores inside a carbon material that is a raw material. Through this treatment, the internal surface area increases due to the generation of micropores, which increases the adsorption capacity of the carbon material. (Ikuo Abe, “Method for producing activated carbon,” Carbon, No. 225, pp. 373-381 (2006)).
The gas activation method is a method in which a carbide obtained by carbonizing various carbon raw materials, preferably organic raw materials, is treated using an activation gas.Steam and carbon dioxide are industrially used as the activation gas. ing. More preferred is steam-activated activated carbon. The gas-activated activated carbon may be a commercially available product, or it may be activated by a known method (for example, Ikuo Abe, "Manufacturing method of activated carbon", Carbon, No. 225, pp. 373-381 (2006)). Activated carbon may also be used.
The chemical activation method is a method that uses chemicals such as zinc chloride and phosphoric acid as an activator. Since carbonization and activation usually proceed at the same time, the starting material is a woody material rather than a charred material. For example, chemically activated activated carbon can be produced by impregnating sawdust with a concentrated zinc chloride aqueous solution and firing it at 550 to 750°C in an inert gas atmosphere. The chemical activation method also includes an alkali activation method using potassium hydroxide, sodium hydroxide, etc.

In the production of activated carbon by gas activation method or chemical activation method, a process is known in which after activation treatment, washing is performed using water or diluted hydrochloric acid, etc., followed by drying and sieving (Ikuo Abe, ``Activated Carbon "Manufacturing Method", Carbon, No. 225, pp. 373-381 (2006)). The treatment using hydrochloric acid is said to be carried out to adjust the pH since activated carbon exhibits alkalinity after activation.
The term "activated carbon that has not been treated with hydrochloric acid" in the present invention refers to activated carbon that has not been treated with hydrochloric acid after the activation step in the method for producing activated carbon. More preferably, the "activated carbon that has not been treated with hydrochloric acid" of the present invention is one that is produced by a gas activation method or a chemical activation method, and is not subjected to a cleaning treatment after the activation process, or is one that is not subjected to a cleaning treatment after the activation process. Examples include dilute hydrochloric acid or those that do not use hydrochloric acid. Furthermore, activated carbon that does not use hydrochloric acid in other steps is also more preferred. Preferably, the "activated carbon not treated with hydrochloric acid" has a chlorine concentration of 200 μg/g or less, more preferably 500 μg/g or less, and even more preferably 1000 μg/g or less.
The activated carbon of the present invention is produced by a method including carbonizing raw materials, optionally crushing and sizing, activating the raw materials, optionally washing and drying, and then sieving and crushing.

The step of decolorizing an oil and fat composition using the "activated carbon that has not been treated with hydrochloric acid" of the present invention may be carried out, for example, in a batch manner, followed by filtration, or by filling a column etc. with activated carbon and discoloring the oil and fat composition. It may also be carried out by a method of contact. In order to perform the decolorization process efficiently and in a short time, it may be heated to a temperature of about 90 to 120°C. Further, it is preferable to perform the mixing and stirring under reduced pressure (generally 6.7 kPa or less), and the mixing and stirring may be performed for 10 to 60 minutes, generally about 30 minutes, although it varies depending on the processing amount and the like.

The amount of activated carbon that has not been treated with hydrochloric acid is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the fat composition used in the decolorizing step. This is because within this range, the vitamin K content can be significantly reduced, while 3-MCPD is not increased. The amount is more preferably 0.05 to 5.0 parts by weight, and even more preferably 0.1 to 3.0 parts by weight.

When the above bleaching step is performed, the content of vitamin K in 100 g of the fat composition after the bleaching step is reduced by 10 μg or more compared to the content of vitamin K in 100 g of the fat composition before the bleaching step. preferable. That is, the amount of vitamin K per 100 g of the oil and fat composition reduced by the decolorization step with respect to the content of vitamin K in the oil and fat composition before the decolorization step is preferably 10 μg or more, more preferably 20 μg or more, More preferably it is 30 μg or more, even more preferably 50 μg or more. The upper limit of the amount of vitamin K reduced by the decolorization process per 100 g of the oil and fat composition is not particularly limited, but is, for example, about 200 μg, 150 μg, or 100 μg.

In the decolorization step using activated carbon that has not been treated with hydrochloric acid, clay may be further used in addition to activated carbon. When using white clay, activated carbon and white clay may be mixed in advance and brought into contact with the fat composition, or activated carbon and white clay may be brought into contact with the fat composition in this order.
Types of clay include activated clay and acid clay.
The amount of clay is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7.0 parts by mass, and The amount is more preferably .1 to 5.0 parts by weight, and even more preferably 1.0 to 3.0 parts by weight.
The mass ratio of activated carbon to white clay used may be, for example, 1:0 to 20, or 1:0.01 to 15.0. 1: preferably about 0.1 to 10.0.
In order to perform the decolorization process efficiently and in a short time, it is preferable to heat the mixture to a temperature of about 90 to 120°C and mix and stir under reduced pressure (generally 6.7 kPa or less). Generally, mixing and stirring may be performed for about 30 minutes.

<Deodorizing process>
After the above-mentioned decolorization step, a deodorization step may be performed. The deodorizing step is not particularly limited except for the temperature conditions (180 to 230° C.), and a vacuum steam distillation deodorizing method commonly used for deodorizing edible fats and oils may be used.
In the present invention, the deodorizing step is carried out at a lower temperature than the normal temperature during refining fats and oils, that is, preferably at 180°C or more and 230°C or less, more preferably 200°C or more and 220°C or less, and even more preferably 210°C or more and 220°C or less. . Glycidol can be further reduced if the deodorizing temperature is less than 180°C, but considering the flavor of the oil or fat, if deodorizing is performed at less than 180°C, odor components cannot be removed sufficiently and the product will lose its marketability, so the deodorizing temperature should be less than 180°C. It is not desirable to do so.
On the other hand, if the deodorizing temperature exceeds 230°C, glycidol will increase, which is not preferable. In particular, if the temperature is 260°C or higher, these components will increase significantly, which is extremely undesirable.

The oil and fat composition of the present invention obtained by the above production method has low concentrations of 3-MCPD, glycidol, and their fatty acid esters even after the deodorizing treatment step. The 3-MCPD concentration after decolorization and deodorization treatment is preferably 0.42 ppm or less, more preferably 0.35 ppm or less. The glycidol concentration after decolorization and deodorization treatment is preferably 0.17 ppm or less, more preferably 0.10 ppm or less.
The concentration of vitamin K in the oil and fat composition after the deodorizing step is preferably 20 to 100 μg/100g, more preferably 30 to 95 μg/100g, more preferably 30 to 91 μg/100g, and even more preferably is 35 to 75 μg/100g, more preferably 35 to 50 μg/100g. Further, it is also preferable that the amount is about 70 to 95 μg/100g.
Note that 3-MCPD and glycidol exist in the oil and fat compositions in the form of 3-MCPD fatty acid ester and glycidol fatty acid ester, respectively, but in this specification, the values measured as 3-MCPD and glycidol are are used to express "3-MCPD concentration" and "glycidol concentration" in the oil and fat composition.

<Oil and fat composition used in infant formula>
The oil and fat composition of the present invention is particularly suitable for use in infant formula.
Infant formula is powdered or liquid milk used as a substitute for breast milk, and is often made to mimic the composition of breast milk as closely as possible. The main components of human milk are proteins, fats, and carbohydrates, and the fats contain a certain amount of essential fatty acids such as linoleic acid, α-linolenic acid, arachidonic acid, and docosahexaenoic acid, which are necessary for infant growth. include.
According to the Consumer Affairs Agency, the permissible standards for labeling infant formula include 4.4 to 6.0 g of fat, 0.3 to 1.4 g of linoleic acid, and 0.3 to 1.4 g of α-linolenic acid per 100 kcal. It shows that it is 0.05g or more. The term "oil and fat composition used for infant formula" in the present invention means an oil and fat composition that satisfies such nutritional standards.

The raw material oil for the oil and fat composition of the present invention can be selected and used so that the produced oil and fat composition satisfies the above-mentioned characteristics. In particular, it is preferable to use a combination of various fats and oils such that linoleic acid and α-linolenic acid meet the above-mentioned permission criteria.
For example, fractionated palm oil such as palm oil, palm olein, palm double olein, palm stearin, palm mid-fraction, fractionated palm kernel oil such as palm kernel oil, palm kernel olein, palm kernel stearin, coconut oil, etc. Lauric oil, soybean oil, rapeseed oil, corn oil, sunflower oil, safflower oil, perilla oil, linseed oil, high oleic sunflower oil, high oleic rapeseed oil, high oleic safflower oil, cottonseed oil, rice bran oil, sesame oil, olive oil, Examples include vegetable oils such as liquid fats and oils such as peanut oil, animal oils such as fish oil, beef tallow, pork fat, etc., and fractionated oils of these fats and oils can also be used.
The raw material fats and oils for the oil and fat composition of the present invention include, for example, 20 to 80 parts by mass (preferably 30 to 70 parts by mass) of palm oil or its fractionated oil, and 20 to 80 parts by mass (preferably 25 to 65 parts by mass) of lauric fats and oils. 0 to 45 parts by mass (preferably 10 to 35 parts by mass) of other fats and oils, preferably liquid fats and oils.

The raw material oil for producing the oil and fat composition of the present invention may be selected from deacidified palm oil and its fractionated oil.
Deacidification treatment usually uses an alkaline aqueous solution as described below, but in alkaline deacidification treatment, palm oil with a high acid value, coconut oil and palm kernel oil containing a lot of lauric acid produce a large amount of soap. However, since the oil is removed along with the soap as alkaline fats, there is a problem that the yield is reduced, so purification by distillation is often used, and these fats and oils are usually not deoxidized.

In this specification, when referring to "deacidified palm oil" with respect to raw material fats and oils, it is sufficient that the oil has been at least deacidified, and after deacidification, decolorization and/or deodorization treatment is performed by a known method. may also be performed. Preferably, it is an oil or fat that has been subjected to deoxidation treatment, decolorization treatment, and deodorization treatment. In this specification, the decolorization treatment and deodorization treatment after the deacidification treatment of the raw material fats and oils are distinguished from the decolorization treatment performed in the presence of activated carbon of the present invention performed in a later step and the deodorization treatment that may be performed thereafter. Therefore, the former may be referred to as "first decolorization treatment" and "first deodorization treatment", and the latter may be referred to as "second decolorization treatment" and "second deodorization treatment".

The "deacidification treatment" can be performed by a method known in the art, for example, by treating the crude oil with an aqueous alkaline solution such as an aqueous sodium hydroxide solution. More specifically, the treatment may be performed by adding an alkaline aqueous solution having a concentration of about 5% to 30%, for example. The amount of alkali added can be appropriately determined depending on the amount of free fatty acids mixed. The time required for treatment with an alkaline aqueous solution is approximately 10 to 30 minutes, depending on the alkali concentration and treatment temperature. The temperature for treatment with the alkaline aqueous solution can be about 60 to 80°C, but it is preferable to carry out the treatment at a temperature as low as possible. For example, stirring can be performed at 70 to 75°C for about 20 minutes. Alternatively, the treatment time may be shortened by performing the treatment at a high temperature of about 80 to 90°C.

In another aspect of the present invention, the oil and fat composition of the present invention comprises a mixture of an oil and fat selected from deacidified palm oil and its fractionated oil, and one or more other optionally included fats and oils. These oils and fats are produced as a mixture of these oils and fats, or each oil and fat is subjected to decolorization and deodorization treatments. The deodorizing treatment is preferably carried out at a temperature of 180°C or higher and 230°C or lower.

<Childcare formula>
The infant formula of the present invention contains the above-mentioned oil and fat composition of the present invention, and also contains any other components contained in infant formula.
Optional ingredients include, for example, protein sources, carbohydrate sources, vitamins, minerals, and other nutritional elements.
The oil and fat composition of the present invention can be contained, for example, in an amount of 10 to 30% by mass in infant formula, but is not limited thereto.

(Example 1)
45 parts by mass of deoxidized palm olein, 35 parts by mass of palm kernel olein, and 25 parts by mass of soybean oil were mixed, and 100 parts by mass of oil and fat were mixed with steam-activated activated carbon (activated carbon A (no hydrochloric acid treatment (chlorine concentration 130 μg/g)) and activated carbon. 0.4 parts by mass of B (treated with hydrochloric acid (chlorine concentration 1600 μg/g)) (chlorine concentration was measured by the ion chromatography method described below) and activated clay (trade name: Galleon Earth V2 (manufactured by Mizusawa Chemical Industry Co., Ltd.) )) was added and decolorized under normal pressure at 100°C for 60 minutes with stirring.Activated carbon and activated clay were filter paper (trade name: Toyo Roshi No. 2, manufactured by Advantech). and a filter aid (trade name: Silica #600H, manufactured by Chuo Silica Co., Ltd.) to obtain a decolorized oil. 15 kg of this decolorized oil was blown at 210°C for 75 minutes under a vacuum of 0.4 kPa or less. Deodorization treatment was carried out under the condition that the amount of water vapor incorporated was 3.0% (wt% of oil), and 25 ppm of citric acid was added during cooling to obtain deodorized oil.

(Examples 2 and 3)
Each fat and oil composition was produced by decoloring and deodorizing the fat and oil having the composition according to the description in Table 1 under the same conditions as in Example 1, except for changing the points listed in Table 1.

(Comparative Examples 1 and 2)
Each fat and oil composition was produced by decoloring and deodorizing the fat and oil having the composition according to the description in Table 1 under the same conditions as in Example 1, except for changing the points listed in Table 1.

For each fat and oil obtained in Examples and Comparative Examples, the vitamin K concentration, 3-MCPD concentration, and glycidol concentration were measured using the analysis method described below. The analysis results are shown in Table 1.

(Vitamin K analysis method)
Measurements were made in accordance with "Food Labeling Standards (Attachment: Nutrition labeling-related 'Vitamin K (1) High Performance Liquid Chromatography Method'") and Mitsuaki Mori's "Vitamin Analysis Method for Foods in Japan."
1. Standard reagent 1) Phylloquinone standard product (isomer mixture) (Wako Pure Chemical Industries, Ltd., 99%) Dissolved in isooctane Phylloquinone standard stock solution (approximately 100 ppm)
2) Menaquinone-7 standard product (Wako Pure Chemical, 98%) Dissolved in ethanol Menaquinone-7 standard stock solution (approximately 100 ppm)
2. Standard solution Dilute phylloquinone standard stock solution and menaquinone-7 standard stock solution with 2-propanol to a combined total of 10, 40, and 400 ng/mL, respectively.

3. Reagent 1) 2,2,4-trimethylpentane (isooctane) (Wako, for HPLC)
2) Ethanol (manufactured by Wako Pure Chemical Industries, for HPLC)
3) 2-propanol (manufactured by Wako Pure Chemical Industries, for LC/MS)
4) Methanol (manufactured by Wako Pure Chemical Industries, for HPLC)

5. Analysis method 1) Collect 1.0 g (±0.02 g) of fat and oil into a 10 mL volumetric flask and make up the volume with 2-propanol.
2) After filtering 1.0 mL of the dissolved oil and fat, measurement was performed using HPLC.

5. Equipment/Analysis conditions Equipment: HPLC (manufactured by Shimadzu Corporation)
Column: L-columns ODS inner diameter 4.6mm x 250mm (manufactured by the Chemical Evaluation and Research Organization)
Reduction column: Platinum column RC-10 inner diameter 4.0mm x 15mm (manufactured by Osaka Soda)
Cartridge type guard column: L-column ODS Cat.No.652050 (manufactured by the Chemical Evaluation and Research Organization)
Injection volume: 20μL
Column temperature: 40℃
Flow rate: 1.0mL/min
Measurement wavelength: excitation 240 nm, fluorescence 430 nm Mobile phase: methanol:ethanol (7:3, v/v)

(3-Analysis methods such as MCPD)
It was measured according to "DFG Standard Methods Section C-Fats C-IV 18 (10)".
1. Standard solution The following standard stock solutions and solutions all used toluene as a solvent.
1) 3-MCPD-1,2-palmitoyl ester (manufactured by Wako Pure Chemical Industries, ≧98%)
3-MCPD-1,2-palmitoyl ester standard stock solution (approximately 1000 ppm)
3-MCPD-1,2-palmitoyl ester standard solution (approximately 40 ppm)
2) d5-3-MCPD-1,2-palmitoyl ester (manufactured by Wako Pure Chemical Industries, ≧98%)
*Used as a surrogate d5-3-MCPD-1,2-palmitoyl ester standard stock solution (approximately 1000 ppm)
d5-3-MCPD-1,2-palmitoyl ester standard solution (approximately 40 ppm)
3) Glycidyl stearate (manufactured by TCI, 96%≧)
Glycidyl stearate standard stock solution (approximately 1000ppm)
Glycidyl stearate standard solution (approximately 40 ppm)

2. Reagent 1) Ultrapure water 2) Toluene (manufactured by Kanto Kagaku, for agricultural residue use, 5000 times concentrated)
3) t-Butyl methyl ether (t-BME) (manufactured by Kanto Chemical, for agricultural residue use, 5000 times concentrated)
4) Methanol (manufactured by Kanto Chemical, for agricultural residue use, 5000 times concentrated)
5) Hexane (manufactured by Kanto Chemical, for agricultural residue use, 5000 times concentrated)
6) Ethyl acetate (manufactured by Kanto Chemical, for agricultural residue use, 5000 times concentrated)
7) Diethyl ether (manufactured by Kanto Chemical, for agricultural residue use, 5000 times concentrated)
8) Isooctane 9) Sodium methoxide 10) Sodium methoxide-methanol solution (25 g/L): Dissolve 0.25 g in 10 mL with methanol (* Prepared for use (cannot be stored for long periods as it easily decomposes with moisture))
11) Sodium chloride (manufactured by Kanto Chemical, special grade)
12) Sodium chloride solution (NaCl 200g/L solution): Dissolve 50g of sodium chloride in ultrapure water to make 250mL 13) Sodium bromide (manufactured by Kanto Kagaku, special grade)
14) Sodium bromide aqueous solution (NaBr 600g/L solution)
15) Sulfuric acid (25%, 6N): Dilute sulfuric acid (96%, 36N) 6 times ex) Add 10 mL of sulfuric acid (96%, 36 N) to 50 mL of ultrapure water, then adjust the volume to 60 mL 16) Acidic sodium chloride Aqueous solution (200 g/L): Add 35 mL of sulfuric acid (25%) to 1 L of sodium chloride aqueous solution ex) 20 mL of sodium chloride aqueous solution + 700 μL of sulfuric acid (25%)
17) Acidic sodium bromide aqueous solution (chloride-free saline solution): Add 35 mL of sulfuric acid (25%) to 1 L of sodium bromide aqueous solution (600 g/L) ex) 20 mL of sodium bromide aqueous solution + 700 μL of sulfuric acid (25%)
18) Phenylboronic acid (PBA, phenylboronic acid)
19) Derivatization reagent: Dissolve phenylboronic acid in diethyl ether and bring it to a saturated state with precipitation.

3. Equipment 1) Pasteur pipette 2) Graduated cylinder 25mL, 50mL, 100mL
3) Volumetric flask 5mL, 10mL
4) Pipetman P-5000, P-1000, P-200
5) Screw vial (glass, 1.5mL capacity)
6) Syringe 7) Filter (hydrophobic)

4. Analysis method 1) 100 mg (±0.5 mg) of the sample was collected into a 1.5 mL screw vial.
2) As a surrogate, 100 μL of d5-3-MCPD-1,2-palmitoyl ester standard solution (about 50 ppm) and 100 μL of t-butyl methyl ether were added and stirred.
*To confirm contamination, samples in which 3-MCPD etc. were not detected (ex. extra virgin olive oil) were analyzed. In addition, 100 μL of 3-MCPD-1,2-palmitoyl ester standard solution (approximately 40 ppm) was added to the spike sample together with the surrogate to check the recovery rate.
3) 200 μL of sodium methoxide-methanol solution was added, stirred, and reacted at room temperature for 3.5 to 5.5 minutes.
4) To stop the reaction in (A) 3), 600 μL of an acidic sodium chloride aqueous solution was added (Analysis [A]). After this, the following steps 5) to 8) were performed.
(B) To stop the reaction in 3), 600 μL of an acidic sodium bromide aqueous solution was added (Analysis [B]). After this, the following steps 5) to 8) were performed.
5) After adding 600 μL of hexane and stirring, let stand for 5 minutes or more and remove the hexane layer. 600 μL of hexane was added again and the same operation was repeated.
6) After adding 600 μL of diethyl ether/ethyl acetate (6:4) mixture and stirring, the solvent layer was collected in a vial containing sodium sulfate (anhydrous). The same operation was repeated two more times.
7) After adding 100 μL of PBA solution and derivatizing it, nitrogen gas was blown to dry it.
8) After redissolving with 1 mL of isooctane and filtering, measurement was performed using GC/MS.

5. Equipment/Analysis conditions Equipment: GC/MS (Agilent 5975C/7890A)
Column: DB-17MS, inner diameter 0.25mm x 30m, film thickness 0.25μm
Injection volume: 2μL
Inlet temperature: 240℃
Splitless time: 1.5 minutes Split flow rate: 20mL/min
Carrier gas: helium, 1.2 mL/min, constant flow Oven temperature: 85°C (0.5min) → 6°C/min → 150°C → 12°C/min → 180°C → 25°C/min → 280°C (7 min)
Ionization: EI (positive)
Measurement ion: 3-MCPD m/z = 147 (for quantification), 146, 196, 198 (for confirmation)
3-MCPD-d5 m/z=150 (surrogate), 149/201/203 (for confirmation)
Ion source temperature: 250℃
Quadrupole: 150℃

6. Quantification method
[Internal standard method]
The d5-3-MCPD-1,2-palmitoyl ester added as a surrogate is converted to the d5-3-MCPD concentration, and the area ratio obtained by dividing the area value of 3-MCPD by the area value of the surrogate is multiplied by the surrogate concentration. - MCPD concentration was calculated.
Quantitative value = Surrogate concentration x 3 - MCPD area value / Surrogate area value
The concentration in the sample was determined by dividing the quantitative value obtained above by the amount of sample collected.
3-MCPD concentration [ppm] = quantitative value [μg/L] / sample collection amount [mg]
*In analysis [A], 3-MCPD-FS concentration (3-MCPD equivalent released from 3-MCPD fatty acid ester and glycidol fatty acid ester) can be measured, and in analysis [B], 3-MCPD concentration (from 3-MCPD fatty acid ester) can be measured. Only the free 3-MCPD equivalents) can be measured.
Using the measurement results of Analysis [A] and Analysis [B], the 3-MCPD concentration was subtracted from the 3-MCPD-FS concentration, and the glycidol concentration was calculated by multiplying by the glycidol conversion coefficient.
Glycidol concentration [ppm] = (3-MCPD-FS concentration [A] - 3-MCPD concentration [B]) x glycidol conversion coefficient t

<Calculation of glycidol conversion coefficient>
The conversion coefficient from glycidol to 3-MCPD is calculated by creating a calibration curve in analysis [A] in the presence of chloride. Multiple concentrations of glycidol (as glycidol ester) were added to uncontaminated fat and oil samples and processed according to analysis [A]. The reciprocal of the slope of the resulting calibration curve y=mx+n is equal to the glycidol conversion factor t.
Glycidol conversion coefficient t=1/m

(Method for measuring chlorine concentration)
Standard reagent: Chloride ion standard solution 1000mg/L (for JCSS chemical analysis) (Kanto Chemical)

1) Activated carbon was burned in a combustion furnace at 1350° C. in an oxygen stream, and the chlorine gas generated at that time was absorbed into a sodium hydroxide solution as an absorption liquid.
2) After the absorbed sodium hydroxide solution was brought to a fixed volume with water, chloride ions were separated by ion chromatography using the following apparatus.

Equipment combustion furnace: Yoshida Seisakusho 1091-II
Ion chromatograph: Thermo Scientific Dionex Integrion
Column: Dionex Ion Pac AS20 (0.4mm x 250mm)
Guard column: Dionex Ion Pac AG20 (0.4mm x 50mm)

(result)
In all of the fats and oils of Examples 1 to 3, the concentration of vitamin K decreased by 10 μg/100 g or more compared to before the decolorization process, and the concentrations of 3-MCPD and glycidol were sufficiently low. .
On the other hand, in the method of Comparative Example 1, although the amount of vitamin K decreased was high, the concentration of 3-MCPD increased significantly compared to the raw material.

Claims (9)

A method for producing an oil or fat composition including a decoloring step, wherein the decoloring step is carried out using activated carbon that has not been treated with hydrochloric acid. The manufacturing method according to claim 1, wherein the oil and fat composition is an oil and fat composition for infant formula. The manufacturing method according to claim 1, wherein the activated carbon that has not been treated with hydrochloric acid is used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the fat composition used in the decolorizing step. The manufacturing method according to claim 1, wherein the activated carbon that has not been treated with hydrochloric acid is selected from the group consisting of gas-activated activated carbon and chemically activated activated carbon, and the chlorine concentration in the activated carbon that has not been treated with hydrochloric acid is 200 μg/g or less. . Any one of claims 1 to 4, wherein the content of vitamin K in 100 g of the fat composition after the bleaching step is reduced by 10 μg or more with respect to the content of vitamin K in 100 g of the fat composition before the bleaching step. The manufacturing method according to item 1. The manufacturing method according to claim 1, wherein the decoloring step is followed by a deodorizing step. 7. The production method according to claim 6, wherein the 3-MCPD concentration of the oil and fat composition after the deodorizing step is 0.42 ppm or less. 7. The manufacturing method according to claim 6, wherein the glycidol concentration of the oil and fat composition after the deodorizing step is 0.17 ppm or less. 3-An oil and fat composition for infant formula milk, which has a MCPD concentration of 0.42 ppm or less, a glycidol concentration of 0.17 ppm or less, and a vitamin K concentration of 20 to 100 μg/100 g.