JP2019183169A - Manufacturing method of oil and fat - Google Patents

Abstract

To provide a method for effectively manufacturing oil and fat having content of palmitic acid binding at 2 position of triglyceride in total amount of palmitic acid contained in constituent fatty acid of the triglyceride of 50 mass% or more.SOLUTION: There is provided a manufacturing method of oil and fat including following processes: (a) a process (a) for obtaining a mixture containing a raw material oil and fat having content of palmitic acid in total amount of fatty acid binding at 2 position of triglyceride of 30 to 100 mass%, and fatty acid or fatty acid lower alkyl ester having content of unsaturated fatty acid with 18 or more carbon atoms of 70 mass% or more, at a ratio that content of the palmitic acid in total amount of the fatty acid binding at 1,3 positions of the triglyceride of the raw material oil and fat after 1,3 position selective transesterification is 0.15 to 0.65 times as before transesterification, and (b) a process (b) for conducting transesterification of a mixture using 1,3 position selective lipase to obtain a transesterification reaction product having reaction rate of 70% or more.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing fats and oils containing abundant triglycerides having palmitic acid at the 2-position.

  Human milk is rich in triglycerides with palmitic acid at the 2-position. Palmitic acid is a major saturated fatty acid occupying about 20 to 25% of the fatty acid constituting the fat of human milk. And about 70 to 75% of palmitic acid contained in human milk is bound to the 2-position of triglyceride. Triglyceride having palmitic acid bonded at the 2-position is said to be an important fat for infants because it has a better digestibility than the triglyceride bonded at the 1- or 3-position.

  Fat compositions similar to the fatty acids that make up human milk fat can be derived from oils and fats of plant origin. However, there is a significant difference between the composition of human milk substitute fat and the composition of human milk fat derived from plant-derived oils (vegetable oils and fats). This difference is caused by the unsaturated fatty acid at the 2-position of many glycerides constituting vegetable oils. Therefore, in order to make triglyceride obtained from vegetable oils and fats closer to the structure of triglyceride contained in human milk fat, it is necessary to control the distribution of fatty acid residues depending on the position of the glycerin skeleton of triglyceride.

  Japanese Patent Application Laid-Open No. 6-70786 describes a method for producing a triglyceride having a high β-palmitic acid content. According to the production method, first, fatty acid triglyceride is chemically transesterified using a catalyst to increase the content of palmitic acid at the β-position (2-position) of the triglyceride. Next, this is transesterified with an arbitrary fatty acid enzymatically using a lipase that selectively acts at the α-position (1, 3 position), and the fatty acid is introduced into the α position (1, 3 position).

  JP-T-2009-507480 describes a method for producing a composition containing 1,3-dioleoyl-2-palmitoyl glyceride (OPO). The production method includes the step of subjecting palm oil stearin having an iodine number (IV) of about 2 to about 12 to enzymatic transesterification with oleic acid or a non-glyceride ester thereof.

Japanese Patent Laid-Open No. 6-70786 Special table 2009-507480

  However, in the above production method, it is necessary to perform fractionation after transesterification. Therefore, the above production method could not efficiently increase the concentration of triglyceride having palmitic acid at the 2-position.

  An object of the present invention is to provide a method for efficiently producing fats and oils in which the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of triglyceride is 50% by mass or more. It is.

  The present inventors have intensively studied to solve the above problems. Then, a 1,3-position selective lipase is obtained by mixing a mixture containing a fat and oil rich in palmitic acid as a constituent fatty acid and an unsaturated fatty acid having 18 or more carbon atoms and / or a lower alkyl ester of unsaturated fatty acid in a specific ratio. It has been found that the above-mentioned problems can be solved by transesterifying to a specific reaction rate. Thus, the present invention has been completed.

That is, this invention provides the following manufacturing methods.
(1) By transesterifying a mixture containing a raw oil and fat containing palmitic acid as a constituent fatty acid and an unsaturated fatty acid and / or an unsaturated fatty acid lower alkyl ester with a lipase having 1,3-position selectivity , A method for producing fats and oils, in which the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of the triglyceride is 50% by mass or more, the following steps:
(A) The content of palmitic acid in the total amount of fatty acids bonded to the 2-position of triglyceride is 30 to 100% by mass, and the content of unsaturated fatty acids having 18 or more carbon atoms is 70% by mass or more. A fatty acid or a fatty acid lower alkyl ester,
In a ratio that the content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of the triglycerides of the raw fats and oils is 0.15-0.65 times before the transesterification after the 1,3-position selective transesterification Containing, obtaining a mixture,
(B) a step of transesterifying the mixture using a 1,3-position selective lipase to obtain a transesterification product having a reaction rate of 70% or more;
The manufacturing method of the said fats and oils containing.
(2) Further, the following steps:
(C) removing fatty acid or fatty acid lower alkyl ester from the transesterification product,
The manufacturing method of the fats and oils as described in (1) containing.
(3) The method for producing fats and oils according to (2), wherein a group of steps including the steps (a), (b) and (c) is one cycle, and the obtained fats and oils are repeated two or more cycles as raw material fats and oils.
(4) The content of palmitic acid that binds to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of the triglyceride of the fat obtained in the first cycle is 50 to 65% by mass; The fat and oil according to (3), wherein the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the fatty acid constituting the triglyceride is 70 to 85% by mass. Manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing efficiently the fats and oils whose content of the palmitic acid couple | bonded with 2 position of the triglyceride which occupies for the whole quantity of the palmitic acid contained in the fatty acid of a triglyceride is 50 mass% or more can be provided.

The present invention produces fats and oils in which the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of triglyceride (hereinafter also referred to as β-palmitoyl ratio) is 50% by mass or more. On how to do. And this invention includes the following process (a) and (b).
(A) The content of palmitic acid in the total amount of fatty acids bonded to the 2-position of triglyceride is 30 to 100% by mass, and the content of unsaturated fatty acids having 18 or more carbon atoms is 70% by mass or more. A fatty acid or a fatty acid lower alkyl ester,
In a ratio that the content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of the triglycerides of the raw fats and oils is 0.15-0.65 times before the transesterification after the 1,3-position selective transesterification A step of obtaining a mixture (b), a step of transesterifying the mixture using a 1,3-position selective lipase, and obtaining a transesterification product having a reaction rate of 70% or more. Will be described in detail.

Step (a)
In step (a), the content of palmitic acid in the total amount of fatty acids bound to the 2-position of triglyceride is 30 to 100% by mass (hereinafter also referred to as P2FT), and unsaturated fatty acids having 18 or more carbon atoms. This is a step of preparing a mixture containing a fatty acid and / or a fatty acid lower alkyl ester in a specific ratio, the content of which is 70% by mass or more. The content of palmitic acid in the total amount of fatty acids bound to the 2-position of triglyceride in P2FT is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the content of palmitic acid in the total amount of fatty acids bound to the 2-position of triglyceride in P2FT is in the above range, the content of palmitic acid bound to the 2-position of triglycerides in the total amount of palmitic acid contained in the constituent fatty acids is Oils and fats (hereinafter also referred to as P2OL) that are 50% by mass or more can be produced efficiently. Moreover, P2FT has content of the palmitic acid which occupies for the fatty-acid total fatty-acid total amount, Preferably it is 20-100 mass%, More preferably, it is 25-90 mass%, More preferably, it is 30-85 mass%. It is.

  As one of the preferable embodiments of the P2FT, fats and oils containing palm oil and / or palm fractionated oil can be mentioned. Palm fractionated oil is an oil derived from palm oil by fractionation. Examples of the palm fractionated oil include palm olein, palm stearin, palm super olein, palm middle melting point, palm hard stearin, and soft palm. P2FT may contain 1 type, or 2 or more types chosen from palm oil and palm fractionation oil. P2FT may include palm hard stearin, which is a solid part obtained by further separating palm stearin. In this case, the content of palmitic acid in the total amount of constituent fatty acids of P2FT is preferably 65 to 95% by mass, more preferably 70 to 90% by mass, and further preferably 75 to 85% by mass. In this case, the iodine value of P2FT is preferably 8 to 20, more preferably 11 to 17, and still more preferably 13 to 15. The fat and oil containing palm oil and / or palm fractionated oil contained in P2FT may be a fat and oil subjected to random transesterification.

  Another preferred embodiment of the P2FT is palmitic acid that binds to the 2-position of triglyceride at least once through a group of steps including steps (a), (b), and (c) described later. The aspect which uses P2OL in which the ratio of this was raised as P2FT is mentioned. In this case, the content of palmitic acid in the total amount of constituent fatty acids of P2FT is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and further preferably 27 to 40% by mass. In this case, the content of palmitic acid bonded to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of P2FT is preferably 50 to 80% by mass, more preferably 55 to 75% by mass. More preferably, it is 60-70 mass%. That is, P2OL obtained through a group of steps including steps (a), (b) and (c) is the content of palmitic acid which binds to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids. Can be used in step (a) as P2FT to obtain a higher P2OL.

The above fatty acid and / or fatty acid lower alkyl ester contains 70% by mass or more of unsaturated fatty acid having 18 or more carbon atoms and / or lower alkyl ester of unsaturated fatty acid. The content of unsaturated fatty acid and / or unsaturated fatty acid lower alkyl ester having 18 or more carbon atoms in fatty acid or fatty acid lower alkyl ester is more preferably 80% by mass or more, and further preferably 85% by mass or more. More preferably, it is 90 to 100% by mass. Carbon number of unsaturated fatty acid becomes like this. Preferably it is 18-22, More preferably, it is 18. Specific examples of the unsaturated fatty acid include oleic acid, linoleic acid, and linolenic acid. The content of oleic acid and / or oleic acid lower alkyl ester in the fatty acid and / or fatty acid lower alkyl ester is preferably 60% by mass or more, more preferably 70 to 100% by mass, and still more preferably. It is 75-95 mass%. Here, the fatty acid and / or the lower alkyl ester of the fatty acid is preferably used substantially only of the fatty acid or only of the fatty acid lower alkyl ester. The term “substantially” as used herein means that the content of fatty acid lower alkyl ester mixed with fatty acid or (free) fatty acid mixed with fatty acid lower alkyl ester is preferably 5% by mass or less, more preferably 3% by mass. % Or less, more preferably 0 to 1% by mass. In the present invention, fatty acids are preferably used.
The fatty acid lower alkyl ester is preferably an ester of a fatty acid and an alcohol having 1 to 6 carbon atoms. The alcohol is preferably methanol, ethanol or isopropyl alcohol, more preferably ethanol.

In the step (a), a mixture containing P2FT and a fatty acid and / or a fatty acid lower alkyl ester having a content of unsaturated fatty acid having 18 or more carbon atoms is 70% by mass or more is a triglyceride contained in P2FT. , It is prepared such that the content of palmitic acid in the total amount of fatty acid bonded to the 3-position is 0.15 to 0.65 times before the transesterification after the 1,3-position selective transesterification.
For example,
The proportion of P2FT in the mixture is expressed as Z (%)
The proportion of fatty acid and / or fatty acid lower alkyl ester in the mixture is 100-Z (%)
Before the 1,3-position selective transesterification, the content of palmitic acid in the total amount of fatty acids bound to the 1,3-position of the triglyceride contained in P2FT is defined as BP ₁₃ (%)
The content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of the triglycerides contained in the post-reaction P2FT (P2OL) assumed after the 1,3-position selective transesterification is expressed as AP ₁₃ (%)
age,
The fatty acid and / or fatty acid lower alkyl ester does not include palmitic acid and / or palmitic acid lower alkyl ester,
Then,
Since the portion of P2FT that contributes to the 1,3-position selective transesterification reaction is 2/3 × Z, the portion that contributes to the 1,3-position selective transesterification reaction in the entire reaction system is 2/3 × Z + 100. -Z. And
1,3-position contributes to selective transesterification, parts of palmitic acid and / or palmitic acid lower alkyl _{ester, 2/3 × Z × BP} 13/100 So,
AP ₁₃ of the 1,3-position selective transesterification reaction is
_{2/3 × Z × BP 13} /100
AP ₁₃ = × 100
2/3 × Z + 100-Z
It is represented by
That is,
100 x AP ₁₃
Z =
2/3 × BP ₁₃ + 1/3 × AP ₁₃
And where
AP ₁₃ = 0.15 × BP _{13 to} 0.65 × BP ₁₃
Because
By setting an arbitrary AP ₁₃ between 0.15 × BP _{13 and} 0.65 × BP ₁₃ , Z (%) can be determined.
According to the determined Z (%), the mixture may be prepared by mixing P2FT with a fatty acid and / or a fatty acid lower alkyl ester.
In addition, when the fatty acid and / or fatty acid lower alkyl ester contains a small amount of palmitic acid and / or palmitic acid lower alkyl ester, the 1,3-position selective transesterification reaction in the entire reaction system is performed in the same manner as described above. What is necessary is just to correct | amend the part of palmitic acid and / or a palmitic acid lower alkyl ester which contributes to this.
The above calculation is performed based on mass. There is no practical problem in calculation based on mass.
The ratio of AP ₁₃ after 1,3-position selective transesterification (AP ₁₃ / BP ₁₃ ) to BP ₁₃ (%) before 1,3-position selective transesterification is preferably 0.20 to 0.60. Yes, more preferably 0.25 to 0.55.

Step (b)
Step (b) is a step of transesterifying the mixture using a 1,3-position selective lipase to obtain a transesterification product having a reaction rate of 70% or more.
The 1,3-position selective lipase is not particularly limited as long as it is selective at the 1,3-position of the glyceride and has an activity of transesterifying oil and fat with a fatty acid or a fatty acid lower alkyl ester. Commercially available immobilized lipases, such as Lipozyme RM IM (manufactured by Novozymes, from Rhizomucor miehei), etc. may be used. The 1,3-position selective lipase is preferably derived from Rhizopus delemar or Rhizopus oryzae belonging to the genus Rhizopus. Examples of these lipases include Robin's product: Picantase R8000 and Amano Enzyme's product: Lipase F-AP15. These lipases may be used as a granulated powder lipase granulated and powdered using soybean powder.

The transesterification reaction is controlled so that the reaction rate of the transesterification reaction is 70% or more. The transesterification rate is preferably determined based on the amount of change in the content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of triglycerides contained in P2FT before and after the 1,3-position selective transesterification reaction. (Method 1). That is,
Before the 1,3-position selective transesterification, the content of palmitic acid in the total amount of fatty acids bound to the 1,3-position of the triglyceride contained in P2FT is defined as BP ₁₃ (%)
The content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of the triglycerides contained in the post-reaction P2FT (P2OL) assumed after the 1,3-position selective transesterification is expressed as AP ₁₃ (%)
(As mentioned above, based on the _AP 13 that is set (%), a value of _.AP 13 reaction mixture before being prepared (%) completely when the reaction has been carried out (100% response rate))
age,
The content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of triglycerides contained in P2FT at the end of the transesterification reaction is EP ₁₃ (%)
The reaction rate X (%) is
BP ₁₃ -EP ₁₃
X = × 100
BP ₁₃ -AP ₁₃
It becomes.
The content of palmitic acid (P ₁₃ (%)) in the total amount of fatty acids bound to the 1,3-positions of the triglyceride contained in the oil or fat is:
The content of palmitic acid in the total fatty acid content of triglycerides contained in fats and oils is _Pall (%),
P ₂ (%) is the content of palmitic acid in the total amount of fatty acids bound to the 2-position of triglycerides contained in fats and oils,
Then,
3 × _{P all} -P ₂
P ₁₃ =
2
Calculated by
The composition of all fatty acids (total fatty acid composition) of triglycerides contained in fats and oils is preferably measured according to the standard fat analysis method 2.4.2.3-2013 published by the Japan Oil Chemists' Society. If it is AOCS method, you may measure based on AOCS method Ce1h-05 and Ce1h-07. The composition of the fatty acid that binds to the 2-position of triglycerides contained in fats and oils (2-position fatty acid composition) is preferably 2 positions of the standard oil analysis test method 2.4.5-2016 triacylglycerol published by Japan Oil Chemists' Society Measured according to fatty acid composition (enzyme transesterification method). If it is AOCS method, you may measure based on AOCS method Ch3-91.

The transesterification rate may be determined as described above based on the amount of change in the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-positions of triglycerides contained in P2FT. It may be determined based on the amount of change in the content of palmitic acid and / or palmitic acid lower alkyl ester contained in the fatty acid lower alkyl ester (Method 2).
That is,
The content of palmitic acid and / or palmitic acid lower alkyl ester contained in the fatty acid and / or fatty acid lower alkyl ester before 1,3-selective transesterification is expressed as BP (%)
The content of palmitic acid and / or palmitic acid lower alkyl ester contained in fatty acid and / or fatty acid lower alkyl ester after 1,3-position selective transesterification is expressed as AP (%)
(As described above, since the pre-reaction mixture is prepared based on the set AP ₁₃ (%), AP (%) is calculated based on this information. AP (%) (When it is performed (the reaction rate is 100%))
age,
The content of palmitic acid and / or palmitic acid lower alkyl ester contained in the fatty acid and / or fatty acid lower alkyl ester at the end of the transesterification reaction is EP (%)
The reaction rate X (%) is
BP-EP
X = × 100
BP-AP
It becomes.
The content of palmitic acid and / or palmitic acid lower alkyl ester in the fatty acid and / or fatty acid lower alkyl ester can be measured by a known gas chromatography method.

The transesterification rate can also be determined based on the amount of change in the content of a specific triglyceride as previously reported (Method 3). For example, a triglyceride (hereinafter also referred to as C52) in which the total number of carbon atoms of the constituent fatty acid contained in P2FT is 52 or a triglyceride (hereinafter also referred to as C48) in which the total number of carbon atoms of the constituent fatty acid is 48 may be used as an index. Taking C52 as an example, the content of C52 contained in P2FT before 1,3-position selective transesterification is expressed as BC52 (%)
The content of C52 contained in P2FT (P2OL) after the reaction assumed after 1,3-position selective transesterification is expressed as AC52 (%).
(As described above, the pre-reaction mixture is prepared based on the set AP ₁₃ (%), so these information can be used to determine conventional calculation techniques (eg, review of RJ VANDER WAL ( (See Journal of American Oil Chemist's Society 40, 242-247 (1963)), etc. AC52 (%) is calculated when AC52 (%) is completely reacted (reaction rate (100%))
age,
At the end of the transesterification reaction, the content of triglycerides contained in P2FT (P2OL) and having a total fatty acid number of 52 is EC52 (%)
The reaction rate X (%) is
BC52-EC52
X = × 100
BC52-AC52
It becomes.
However, when a triglyceride having a specific total carbon number is used as an index, a position selection error caused by a 1,3-position selective transesterification reaction by lipase is not reflected. For example, since C52 includes not only UPU but also PUU and UUP, even if UPU isomerizes to UUP during the reaction, it is not reflected in the reaction rate. Moreover, in the reaction of 2 cycles or more, since the change width of the content of triglyceride as an index before and after the transesterification reaction is small, the error is large. Accordingly, the transesterification rate is preferably determined based on Method 1 or Method 2.
In addition, content of the triglyceride contained in fats and oils can be measured by the gas chromatography method (For example, JAOCS, vol70,11,1111-1114 (1993) conformity).
The above U, P, UPU, PUU, and UUP mean the following.
U: Unsaturated fatty acid having 18 carbon atoms P: Palmitic acid UPU: Glycerol UPU is bound to the 1st and 3rd positions, and P is bound to the 2nd position. Triglyceride PUU: P is bound to the 1st position of glycerol. Triglyceride UUP with U bound at the 2nd and 3rd positions: Triglyceride of glycerol with U bound at the 1st and 2nd positions and P bound at the 3rd position

In the step (b), by controlling the 1,3-position selective transesterification reaction so that the reaction rate becomes 70% or more, 2 of triglycerides efficiently accounting for the total amount of palmitic acid contained in the constituent fatty acids. An oil having a palmitic acid content of 50% by mass or more bonded to the position can be produced. The transesterification rate is preferably controlled in the range of 80% or more, more preferably 85 to 98%.
The transesterification reaction can be applied to any conventionally known batch system using a tank or continuous system using a column. The transesterification reaction rate may be adjusted as appropriate according to the reaction mode, such as the amount of lipase per substrate, the reaction temperature, and the reaction time. In the case of a batch reaction, for example, 0.01 to 10 parts by mass (preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass) of lipase preparation per 100 parts by mass of the raw material mixture. (Such as the above granulated powder lipase) is added, and the temperature is 30 to 100 ° C. (preferably 35 to 80 ° C., more preferably 40 to 60 ° C.) for 0.1 to 50 hours (preferably 0.5 to 30). The transesterification reaction may be carried out by stirring for a period of time, more preferably 1 to 20 hours. The transesterification performed in a continuous manner is preferred because it is easy to prevent overreaction. In the case of continuous reaction, for example, 0.5 to 50 parts by mass (preferably 3 to 30 parts by mass, more preferably 5 to 5 parts by mass) per hour with respect to 1 part by mass of the lipase preparation (such as the granulated powder lipase). The transesterification reaction may be carried out by passing a raw material mixture of 25 parts by mass at a temperature of 30 to 100 ° C. (preferably 35 to 80 ° C., more preferably 40 to 60 ° C.).

Step (c)
Step (c) is a step of removing fatty acid and / or fatty acid lower alkyl ester from the transesterification reaction product.
The method for removing the fatty acid and / or fatty acid lower alkyl ester from the transesterification product is not particularly limited. However, fatty acids and / or fatty acid lower alkyl esters are preferably removed by distillation. The distillation method is not particularly limited, and conventionally known thin film distillation, molecular distillation, short process distillation, and the like can be appropriately applied. The distillation is preferably performed at a temperature of 160 to 260 ° C, more preferably 180 to 240 ° C, more preferably 190 to 220 ° C, and preferably 10 to 2000 Pa, more preferably 50 to 1000 Pa, still more preferably 100 to 500 Pa. It may be performed under the condition of pressure.
By removing fatty acid and / or fatty acid lower alkyl ester from the transesterification product, the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the fatty acid of the triglyceride contained in the oil and fat is increased. Oil and fat which is 50 mass% or more is obtained.

The content (β-palmitoyl ratio) of palmitic acid that binds to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acid of triglyceride contained in the oil is as follows:
Total amount of palmitic acid bound to position 2 of triglyceride
× 100
The total amount of palmitic acid bound to positions 1, 2 and 3 of the triglyceride,
The content of palmitic acid in the fatty acids that bind to position 2 of triglycerides
× 100
Palmitic acid content x 3 in the total amount of triglycerides
It can be calculated with

The fats and oils obtained through the group of steps including the above steps (a), (b) and (c) are separated by triglycerides (particularly by solvent fractionation) of triglycerides in the total amount of palmitic acid contained in the constituent fatty acids of the triglycerides. Oils and fats with a further increased content of palmitic acid bonded to the 2-position can be recovered in the liquid part. However, a solid part is generated as a by-product.
On the other hand, the fats and oils obtained through the group of steps including the above steps (a), (b) and (c) are again subjected to the group of steps including the steps (a), (b) and (c). May be applied. A group of steps including steps (a), (b) and (c) is defined as one cycle, and the obtained fats and oils are applied as a plurality of cycles as raw oils and fats, thereby occupying the total amount of palmitic acid contained in the fatty acids constituting triglycerides. Oils and fats in which the content of palmitic acid bonded to the 2-position of triglyceride is further increased can be produced without applying solvent fractionation. Since there is no need for solvent fractionation, there is no generation of a valuable solid part. And all the P2FT supplied as a raw material can be recovered as valuable oils and fats rich in palmitic acid at the 2-position of triglycerides. In a typical production example of the present invention, an oil having a β-palmitoyl ratio of 50 to 65 (mass%) is obtained in the first cycle, and a β-palmitoyl ratio is 70 to 85 (mass%) in the second cycle. Is obtained.
The fats and oils obtained through a group of steps including the steps (a), (b) and (c) described above are used for the purification of ordinary edible fats and oils for deeding, decoloring and deodorizing. Such a purification treatment may be applied.

In the manufacturing method of the present invention, when a group of steps including steps (a), (b) and (c) is applied a plurality of times, the following step (c) ′ is applied instead of step (c). May be.
Step (c) '
Step (c) ′ is a step of selectively removing palmitic acid and / or lower alkyl ester of palmitic acid from the transesterification product by distillation.
The content of palmitic acid and / or palmitic acid lower alkyl ester in the fatty acid and / or fatty acid lower alkyl ester contained in the distillation residue is preferably 5% by mass or less, more preferably 0 to 3% by mass. . The distillation residue can be used as all or part of the mixture when repeating step (a).

One of the preferable embodiments of the present invention is a production method including the following steps (a1), (b1) and (c1).
(A1) Palm stearin having a palmitic acid content of 15 to 35 parts by mass and an iodine value of 9 to 19 and an unsaturated fatty acid content of 85 to 65 parts by mass is 15 to 35 parts by mass. A step (b1) of obtaining a mixture by mixing 80 to 95% by mass (the content of oleic acid is 60 to 85% by mass) and the fatty acid having a palmitic acid content of 0 to 5% by mass. (1) Transesterification using a 1,3-position selective lipase to obtain a transesterification product in which the content of palmitic acid in the total amount of (free) fatty acid is 15 to 30% by mass (c1) The fatty acid is removed from the product, and the total content of palmitic acid contained in the constituent fatty acid of the triglyceride is 35 to 45% by mass, and the palmitic acid binds to two positions of the triglyceride in the total amount of the palmitic acid. Process content of phosphate to obtain a fat and oil is 50 to 65 wt%

Another preferred embodiment of the present invention includes the following steps (a2), (b2) and (c2).
(A2) The total content of palmitic acid contained in 15 to 35 parts by mass of the constituent fatty acid of triglyceride is 25 to 40% by mass, and the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid Is an oil and fat whose weight is 60 to 75% by mass, 85 to 65 parts by mass, the content of unsaturated fatty acid is 80 to 95% by mass (the content of oleic acid is 60 to 85% by mass), and the content of palmitic acid Step (b2) of mixing a fatty acid having an amount of 0 to 5% by mass to obtain a mixture, the mixture is subjected to a transesterification reaction using a 1,3-position selective lipase, and palmitic acid accounts for the total amount of (free) fatty acid Step (c2) for obtaining a transesterification product having an acid content of 5 to 15% by mass The fatty acid is removed from the transesterification product, and the total content of palmitic acid contained in the constituent fatty acid is 2 A 35 wt%, the step of the content of palmitic acid attached to the 2 position of the triglycerides occupied in the palmitate total amount to obtain a fat and oil is 70 to 85 wt%

The production method of the present invention may also include the following step (d).
Step (d)
Step (d) is a step of removing palmitic acid and / or lower alkyl ester of palmitic acid from the fatty acid and / or fatty acid lower alkyl ester removed in step (c).
The method for removing palmitic acid and / or lower alkyl ester of palmitic acid from the fatty acid and / or fatty acid lower alkyl ester removed in step (c) is not particularly limited. However, the removal is preferably distillation by distillation or separation as a solid part by fractionation, more preferably distillation by distillation. In a liquid part where palmitic acid and / or lower alkyl ester of palmitic acid is distilled away, fatty acid or fatty acid lower alkyl ester, or palmitic acid and / or lower alkyl ester of palmitic acid is separated as a solid part. Certain fatty acids or fatty acid lower alkyl esters may be reused in step (a).

The fat and oil obtained by the production method of the present invention, wherein the content of palmitic acid bound to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of triglyceride is 50% by mass or more, has 16 or more carbon atoms The content of trisaturated triglycerides (hereinafter also referred to as HHH) composed of saturated fatty acids is low. The HHH content of the fat obtained by the production method of the present invention is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, and most preferably 0 to 3%. % By mass. Further, the content of tripalmitin (hereinafter also referred to as PPP) in the fat obtained by the production method of the present invention is preferably 7% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass. % Or less, and most preferably 0 to 2% by mass.
Since the fats and oils obtained by the production method of the present invention have a high β-palmitoyl ratio and a low HHH content, they can be suitably used, for example, as a raw material for infant milk powder.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereby.

Preparation of lipase preparation / Lipase preparation 1
An aqueous solution containing 10% by mass of soybean powder was prepared. The aqueous soybean powder solution was autoclaved (121 ° C., 15 minutes) and then cooled to about room temperature. To 1 part by mass of lipase solution (Amano Enzyme's product: Lipase DF “Amano” 15-K, derived from Rhizopus oryzae, 150,000 U / ml), 3 parts by mass of soy flour aqueous solution was added with stirring, and mixed solution Got. The mixture was adjusted to pH 7.8 using 0.5N NaOH solution. Thereafter, the mixed solution was spray-dried to obtain a powdered lipase preparation 1.

Transesterification Reaction Raw Materials The following raw materials were prepared as raw materials for the transesterification reaction.
・ P2FT-1
Palm stearin having an iodine number of 14 (content of palmitic acid in the total amount of constituent fatty acids of triglyceride is 82.6% by mass, content of palmitic acid in fatty acid binding to the 2-position of triglyceride is 72.8% by mass, β-palmitoyl Rate 29.4%) was used as P2FT-1.
・ Fatty acid-1
Mixed fatty acid containing 2.4% by weight lauric acid, 4.6% by weight palmitic acid, 1.7% by weight stearic acid, 78.6% by weight oleic acid, 11.4% by weight linoleic acid Was used as fatty acid-1.

Production of fats and oils rich in triglycerides with palmitic acid at the 2nd position (1)
[Reference Example 1]
10 parts by mass of P2FT-1 and 90 parts by mass of fatty acid-1 were mixed and used as a substrate for transesterification. In the substrate, the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-position of the triglyceride contained in P2FT-1 by selective transesterification at 1,3-position is from 87.5% by mass before the reaction. After the reaction at a reaction rate of 100%, the content is set to be 0.12 times 10.2% by mass.
0.6 parts by mass of lipase preparation 1 was added to 100 parts by mass of the substrate maintained at 50 ° C. in the container. Thereafter, the transesterification reaction was continued for 20 hours by stirring. After 20 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-1). The analysis results are shown in Table 1.
[Example 1]
(First cycle)
20 parts by mass of P2FT-1 and 80 parts by mass of fatty acid-1 were mixed and used as a substrate for transesterification. In the substrate, the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-position of the triglyceride contained in P2FT-1 by selective transesterification at 1,3-position is from 87.5% by mass before the reaction. The reaction rate is set to be 16.4% by mass, which is 0.19 times after the reaction of 100%.
0.6 parts by mass of lipase preparation 1 was added to 100 parts by mass of the substrate maintained at 50 ° C. in the container. Thereafter, the transesterification reaction was continued for 21 hours by stirring. After 21 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-1). The analysis results are shown in Table 1.
(Second cycle)
The reaction fat / oil-1 obtained in 20 parts by mass of the first cycle and 80 parts by mass of fatty acid-1 were mixed to obtain a substrate for the transesterification reaction. In the substrate, the content of palmitic acid in the total amount of the constituent fatty acids bound to the 1,3-positions of the triglycerides contained in the reaction fat-1 by the 1,3-position selective transesterification is 19.7% by mass before the reaction. Thus, after the reaction at a reaction rate of 100%, it is set to be 6.8% by mass, 0.35 times.
0.3 parts by mass of lipase preparation 1 was added to 100 parts by mass of the substrate maintained at 50 ° C. in the container. Thereafter, the transesterification reaction was continued for 22 hours by stirring. After 22 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-2). The analysis results are shown in Table 1.

In addition, * 1, * 2, * 3, * 4, * 5, * 6, and * 7 described in the following tables respectively mean the following.
* 1: Ester exchange reaction rate determined based on the amount of palmitic acid content in the total amount of constituent fatty acids bound to the 1,3-position of triglycerides before and after the 1,3-selective transesterification reaction ( Method 1).
* 2: Transesterification rate determined based on the amount of change in palmitic acid content in the total amount of free fatty acids before and after the 1,3-position selective transesterification (Method 2)
* 3: Transesterification rate determined based on the amount of change in the content of triglycerides (hereinafter also referred to as C52) in which the total number of carbon atoms of the constituent fatty acids is 52 (Method 3)
* 4: Palmitic acid content in all triglyceride fatty acids * 5; Palmitic acid content in triglyceride-binding fatty acid * 6; Triglyceride palmitic acid in 1,3-position fatty acid palmitin Acid content * 7: Palmitic acid content in the total amount of free fatty acids in the substrate mixture before the 1,3-position selective transesterification reaction or the reaction mixture after the 1,3-position selective transesterification reaction

表１の結果から明らかなように、Ｐ２ＦＴ−１に含まれるトリグリセリドの１，３位に結合する構成脂肪酸全量に占めるパルミチン酸の含有量が、反応前の０．１２倍に設定された参考例１の反応を２回行うより、０．１９倍に設定された実施例１の繰り返し反応の方が、同じ収率で、β−パルミトイル率のより高い油脂が得られる。

As is clear from the results in Table 1, a reference example in which the content of palmitic acid in the total amount of constituent fatty acids bound to positions 1 and 3 of the triglyceride contained in P2FT-1 was set to 0.12 times before the reaction. Rather than performing the reaction of 1 twice, the repeated reaction of Example 1 set to 0.19 times yields an oil with a higher β-palmitoyl ratio in the same yield.

Production of fats and oils rich in triglycerides with palmitic acid at position 2 (2)
[Example 2]
(First cycle)
30 parts by mass of P2FT-1 and 70 parts by mass of fatty acid-1 were mixed and used as a substrate for transesterification. In the substrate, the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-position of the triglyceride contained in P2FT-1 by selective transesterification at 1,3-position is from 87.5% by mass before the reaction. The reaction rate is set to be 0.26 times 23.0% by mass after the reaction rate of 100%.
0.6 parts by weight of lipase formulation 1 was added to 100 parts by weight of the substrate maintained at 55 ° C. in the container. Thereafter, the transesterification reaction was continued for 20 hours by stirring. After 20 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-1). The analysis results are shown in Table 2.
(Second cycle)
The reaction fat / oil-1 obtained in the first cycle of 30 parts by mass and 70 parts by mass of fatty acid-1 were mixed to obtain a substrate for the transesterification reaction. In the substrate, the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-positions of the triglycerides contained in the reaction fat-1 by the 1,3-position selective transesterification is 24.5% by mass before the reaction. Thus, after the reaction at a reaction rate of 100%, it is set to be 0.37 times 9.0 mass%.
0.3 parts by mass of lipase preparation 1 was added to 100 parts by mass of the substrate maintained at 50 ° C. in the container. Thereafter, the transesterification reaction was continued for 28 hours by stirring. After 28 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-2). The analysis results are shown in Table 2.
(3rd cycle)
The post-reaction fat (reacted fat-2) obtained in the second cycle of 30 parts by mass and 70 parts by mass of fatty acid-1 were mixed to form a substrate for the transesterification reaction. In the substrate, the content of palmitic acid in the total amount of the constituent fatty acids bound to the 1,3-positions of the triglycerides contained in the reaction fats and oils 2 by selective transesterification at the 1,3-position is 12.8% by mass before the reaction. Thus, after the reaction at a reaction rate of 100%, it is set to be 0.50 times 6.4% by mass.
0.3 parts by mass of lipase preparation 1 was added to 100 parts by mass of the substrate maintained at 50 ° C. in the container. Thereafter, the transesterification reaction was continued for 20 hours by stirring. After 20 hours, the transesterification reaction was completed by removing lipase formulation 1 from the reaction substrate by filtration.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction oil (reaction oil 3). The analysis results are shown in Table 2.

Production of fats and oils rich in triglycerides having palmitic acid at position 2-3
Example 3
(First cycle)
30 parts by mass of P2FT-1 and 70 parts by mass of fatty acid-1 were mixed and used as a substrate for transesterification. In the substrate, the content of palmitic acid in the total amount of constituent fatty acids bound to the 1,3-position of the triglyceride contained in P2FT-1 by selective transesterification at 1,3-position is from 87.5% by mass before the reaction. The reaction rate is set to be 0.26 times 23.0% by mass after the reaction rate of 100%.
0.6 grams of lipase formulation 1 was packed into the column and held at 55 ° C. Transesterification was performed by passing the substrate through the column at a flow rate of 5 grams / hour. After passing for 200 hours, the reaction was completed.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-1). The analysis results are shown in Table 3.
(Second cycle)
The reaction fat / oil-1 obtained in the first cycle of 30 parts by mass and 70 parts by mass of fatty acid-1 were mixed and used as a substrate for the transesterification reaction. In the substrate, the content of palmitic acid in the total amount of the constituent fatty acids bound to the 1,3-positions of the triglycerides contained in the reaction fat-1 by the 1,3-position selective transesterification is 25.1% by mass before the reaction. Thus, after the reaction at a reaction rate of 100%, it is set to be 9.2% by mass, 0.37 times.
0.6 grams of lipase formulation 1 was packed into the column and held at 50 ° C. Transesterification was performed by passing the substrate through the column at a flow rate of 5 grams / hour. The reaction was terminated after 100 hours.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction fat (reaction fat-2). The analysis results are shown in Table 3.
(3rd cycle)
The post-reaction fat (reacted fat-2) obtained in the second cycle of 30 parts by mass and 70 parts by mass of fatty acid-1 were mixed to form a substrate for the transesterification reaction. In the substrate, the content of palmitic acid in the total amount of the constituent fatty acids bound to the 1,3-positions of the triglycerides contained in the reaction fat-and-oil-2 by selective transesterification at the 1,3-position is 11.6% by mass before the reaction. Therefore, after the reaction at a reaction rate of 100%, it is set to be 0.54 times 6.2% by mass.
0.6 grams of lipase formulation 1 was packed into the column and held at 50 ° C. Transesterification was performed by passing the substrate through the column at a flow rate of 10 grams / hour. After passing for 40 hours, the reaction was completed.
From the substrate after the transesterification reaction, the fatty acid was completely distilled off under the conditions of 200 ° C. and 133 Pa to obtain a post-reaction oil (reaction oil 3). The analysis results are shown in Table 3.

表２、表３に記載の結果から明らかなように、1,3位のＰ基準での反応率が高い、連続式反応である実施例３は、得られる油脂のβ−パルミトイル率が高い（品質がよい）。

As is clear from the results shown in Tables 2 and 3, Example 3, which is a continuous reaction with a high reaction rate on the P basis at the 1 and 3 positions, has a high β-palmitoyl ratio of the resulting fat ( Quality is good).

Claims (4)

By transesterifying a mixture containing a raw fat / oil containing palmitic acid as a constituent fatty acid and an unsaturated fatty acid and / or an unsaturated fatty acid lower alkyl ester with a lipase having 1,3-position selectivity, It is the manufacturing method of the said fats and oils which obtain the fats and oils whose content of the palmitic acid couple | bonded with 2-position of the triglyceride which occupies for the whole quantity of the palmitic acid contained in a constituent fatty acid is 50 mass% or more, Comprising:
(A) The content of palmitic acid in the total amount of fatty acids bonded to the 2-position of triglyceride is 30 to 100% by mass, and the content of unsaturated fatty acids having 18 or more carbon atoms is 70% by mass or more. A fatty acid or a fatty acid lower alkyl ester,
In a ratio that the content of palmitic acid in the total amount of fatty acids bound to the 1,3-positions of the triglycerides of the raw fats and oils is 0.15-0.65 times before the transesterification after the 1,3-position selective transesterification Containing, obtaining a mixture,
(B) a step of transesterifying the mixture using a 1,3-position selective lipase to obtain a transesterification product having a reaction rate of 70% or more;
The manufacturing method of the said fats and oils containing. In addition, the following steps:
(C) removing fatty acid or fatty acid lower alkyl ester from the transesterification product,
The manufacturing method of the fats and oils of Claim 1 containing this.   The method for producing fats and oils according to claim 2, wherein a group of steps including the steps (a), (b) and (c) is defined as one cycle, and the obtained fats and oils are repeated as two or more cycles.   The content of palmitic acid that binds to the 2-position of triglyceride in the total amount of palmitic acid contained in the constituent fatty acids of the triglyceride of the fat and oil obtained in the first cycle is 50 to 65% by mass, and in the second cycle The manufacturing method of the fats and oils of Claim 3 whose content of the palmitic acid couple | bonded with two positions of the triglyceride which occupies for the whole quantity of the palmitic acid contained in the fatty acid of the triglyceride of the obtained fats and oils is 70-85 mass%. .