JP2018172517A - Production method of fat and oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the generation of partial glyceride while using a fatty acid having an oleic acid content of 70 to 80% by mass in a method for producing an oil or fat having palmitic acid at the β-position. To do. In order to solve the above problems, 5 to 60% by mass of a fat and oil raw material containing palm-derived fat and oil and 40 to 95% by mass of an oleic acid-containing fatty acid having an oleic acid content of 70 to 80% by mass. A method for producing a fat or oil having palmitic acid at the β-position, comprising a blending step of adjusting the blended fat and oil containing, and a lipase reaction step of reacting the blended fat and oil with a lipase that specifically acts on the α-position. provide. [Selection diagram] None

Description

  The present invention relates to a method for producing fats and oils.

  A method of transesterifying fats and oils (triglycerides) and fatty acids with lipase or the like is called acidolysis, and is used when producing triglycerides having a characteristic structure typified by cacao-like fats used in chocolate.

  Similar to cacao-like fats, fats having a characteristic structure include human breast milk fat. In human breast milk fat, about 70 to 85% of palmitic acid is present in the β-position of triglyceride, and the α-position has a structure in which oleic acid is mainly bound. On the other hand, in normal vegetable oils and fats, most of palmitic acid is bonded to the α-position.

  When an infant ingests fats and oils, pancreatic lipase hydrolyzes the α-position fatty acid of triglyceride and breaks it down into two molecules of free fatty acid and one molecule of 2-monoglyceride. Monoglycerides are absorbed regardless of the fatty acid species bound. As for free fatty acids, monounsaturated fatty acids and polyunsaturated fatty acids, saturated fatty acids having a chain length of 12 or less have good absorbability, but compared with them, the absorbability of long chain saturated fatty acids is poor. That is, the absorbability of palmitic acid monoglyceride is good, but the absorbability of palmitic acid alone is bad. Therefore, the absorbability of triglyceride in which palmitic acid is bonded to the β-position is good, and it is considered that the fat and oil having a structure like human breast milk fat is high in digestibility.

  The only fat that exhibits triglycerides with a structure similar to human breast milk fat is lard (pig fat). The palmitic acid content in lard is about 25%, and about 70 to 80% is bound to the β-position of triglyceride. However, there is a problem that the use of lard causes a peculiar animal odor and the use of lard is religiously avoided. Therefore, it is necessary to develop an oil / fat composition comprising triglycerides having a structure similar to human breast milk fat based on vegetable oil / fat.

  Production of an oil and fat composition based on vegetable oil and fat and similar to human breast milk fat includes an oil and fat composition obtained by transesterification of palm oil and a fatty acid. For example, in Patent Document 1, after oil and fat are subjected to chemical random transesterification to introduce palmitic acid at the β-position, oleic acid is introduced at the α-position using a lipase that specifically acts on the α-position. A method is disclosed. Moreover, as a specific production example in Patent Document 1, oleic acid having a purity of 95% is obtained by using lipase that specifically acts on the α-position after random transesterification of palm oil or palm high melting point fractionated oil. Is described.

Japanese Patent Laid-Open No. 6-70786

The method described in Patent Document 1 has a problem that the raw material cost is high because high-purity oleic acid is used. Therefore, the use of a fatty acid having an oleic acid content of 70 to 80% by mass as an inexpensive fatty acid obtained from palm oil or the like was examined.
As a new problem, the occurrence of partial glycerides consisting of monoglycerides and diglycerides was observed during transesterification with lipase.

  This invention makes it a subject to suppress generation | occurrence | production of a partial glyceride, using the fatty acid whose content of oleic acid is 70-80 mass% in the manufacturing method of the fats and oils which have palmitic acid in (beta) -position.

As a result of intensive research in order to solve the above-mentioned problems, the present inventors have reacted a fat raw material containing palm-derived fat and oil with an oleic acid-containing fatty acid having an oleic acid content of 70 to 80% by mass by lipase. In doing so, it was found that the generation of partial glycerides was suppressed by setting the blending amount of the oleic acid-containing fatty acid to 40 to 95% by mass, and the present invention was completed.
That is, the present invention includes the following [1], [2] and [3].

[1] A blended oil and fat containing 5 to 60% by mass of an oil and fat raw material containing oil derived from palm and 40 to 95% by mass of an oleic acid-containing fatty acid having an oleic acid content of 70 to 80% by mass is prepared. Compounding process, and
The manufacturing method of the fats and oils which have a lipase reaction process which makes the said mixing | blending fats and oils react with the lipase which acts on (alpha) -position specifically, and has a palmitic acid in (beta) -position.
[2] The method for producing fats and oils having palmitic acid at the β-position according to [1], comprising a transesterification step of performing random transesterification of the fat and oil raw material containing the palm-derived fats and oils.
[3] The method for producing fats and oils containing palmitic acid at the β-position according to [1] or [2], wherein the fat and oil raw material containing palm-derived fats and oils contains soybean oil.

According to the first aspect of the present invention, the β-position bond ratio of palmitic acid in the triglyceride can be increased, and the generation of partial triglyceride can be suppressed. Thereby, the manufacturing method of fats and oils which can suppress the production | generation of chloropropanols and its fatty acid ester, glycidol, and its fatty acid ester in subsequent refinement | purification and a process can be provided.
According to the second aspect of the present invention, the β-position bond ratio of palmitic acid in triglyceride can be further increased, and chloropropanols and fatty acid esters, glycidol and fatty acid esters in oil and fat raw materials are reduced. The manufacturing method of fats and oils which can be made can be provided.
According to 3rd invention in this invention, the manufacturing method of fats and oils nearer to the fatty acid composition of breast milk fat can be provided.

Hereinafter, embodiments for carrying out the present invention will be described.
The manufacturing method of the fats and oils of this invention is as follows.
A blending step of adjusting a blended fat containing 5 to 60% by mass of a fat and oil raw material containing oil derived from palm and 40 to 95% by mass of an oleic acid-containing fatty acid having a content of oleic acid of 70 to 80% by mass, and ,
The manufacturing method of the fats and oils which have a lipase reaction process with which the said mixing | blending fats and oils are made to react with the lipase which acts on the (alpha) -position specifically, has a palmitic acid in the (beta) -position.

[Oil raw materials]
As the fat and oil raw material before the lipase reaction in the present invention, a fat and oil containing a large amount of palmitic acid and which can be stably obtained is desirable, and therefore, palm-based fats and oils are suitable. The palm oil and fat used as a raw material may be not only raw palm oil but also a fractionated oil or an extremely hardened oil. Moreover, you may replace a part of said palm oil with palm kernel oil, its fractionation oil, and its extremely hardened oil within the range of the target fatty acid composition.

  It is desirable that palm-derived fats and oils which are raw materials for fats and oils in the present invention do not contain chloropropanols and their fatty acid esters, glycidol and their fatty acid esters before lipase treatment with fatty acids. Therefore, it is preferable to use palm-derived fats and oils obtained by neutralization purification instead of physical purification that is usually performed on palm-derived fats and oils. Physical refining is a refining method that is performed in a deodorization step in which free fatty acids contained therein are distilled while blowing steam under vacuum and high temperature to palm crude oil after oil extraction. On the other hand, neutralization purification is a purification method in which free fatty acids contained in crude oil are neutralized with an alkali and removed.

(Random transesterification)
It is more preferable that the palm-derived fat and oil that is the fat and oil raw material in the present invention is a random transesterified oil of palm-derived fat and oil. By palm transesterification of palm-derived oils and fats, palmitic acid, which is bound to many α-positions of triglycerides, is randomly arranged in α- and β-positions. The palmitic acid binding ratio to can be increased more efficiently.

  Random transesterification can be performed by a method using an alkali catalyst such as sodium methylate or a method using an enzyme catalyst such as a lipase preparation. Random transesterification with an alkali catalyst is more preferable in removing 3-MCPD fatty acid ester and glycidol fatty acid ester contained in the oil and fat raw material.

  Furthermore, the following fats and oils can be blended as other vegetable fats and oils for transesterification. Other vegetable oils and fats include, for example, palm oil, canola oil, corn oil, soybean oil, rice oil, rice bran oil, sunflower oil, high oleic sunflower oil, safflower oil, high oleic safflower oil, olive oil, cottonseed oil , Medium chain fat (MCT), fractionated oils thereof or the like, and one or more of them can be selected.

  The blending amount of the oil and fat derived from palm in the random transesterification is preferably 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more.

  Moreover, it is preferable that the random transesterification oil of the said palm-derived fats and oils carries out random transesterification by mix | blending soybean oil as other vegetable fats and oils. Thereby, essential fatty acids etc. can be strengthened without reducing the β-position bond ratio of palmitic acid in fats and oils, and fats and oils close to the fatty acid composition of breast milk fat can be obtained.

  The blending amount of soybean oil in the random transesterification is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass.

[fatty acid]
The fatty acid in the present invention is a fatty acid having an oleic acid content of 70 to 80% by mass. When the oleic acid content is 70% by mass or less, the substitution with palmitic acid bonded to the α-position becomes insufficient, so that the β-position binding ratio of palmitic acid in the obtained fat becomes low. In addition, when the oleic acid content is 80% by mass or more, the cost of the fatty acid increases, so that it is economically impractical when assuming actual production.
Moreover, there exists an effect of suppressing generation | occurrence | production of a partial glyceride by using a fatty acid with an oleic acid content of 70-80 mass%.

  Examples of raw materials for fatty acids that are high in oleic acid include palm oil, high oleic sunflower oil, high oleic safflower oil, high oleic rapeseed oil, olive oil, lard, and beef tallow. A fatty acid derived from palm oil is preferred.

(Combination of oil raw material and fatty acid)
In the blending of fat and oil raw material and fatty acid in the present invention, the fat and oil raw material containing palm-derived fat and oil is 5 to 60% by mass, and the oleic acid-containing fatty acid is 40 to 95% by mass.
When the fat and oil raw material is less than 5% by mass and the oleic acid is more than 95% by mass, the resulting triglyceride is extremely small, which makes the production inefficient. When the raw material fat exceeds 60% by mass and the oleic acid is less than 40% by mass, the β-position bond ratio of palmitic acid does not sufficiently increase, and some partial glycerides may remain.

[Lipase reaction]
(Lipase)
The lipase in the present invention is a lipase having specificity at the α-position of triglyceride with respect to a mixture of various fats and oils and various fatty acids. Specific examples include lipases derived from microorganisms such as Alkaligenes, Geothorium, Chromobacterium, Rhizopus, Aspergillus, Penicillium, Candida, Pseudomonas, Mucor, and Geotricum. These lipases may be lipases themselves or may be adsorbed and bound to an immobilization carrier. However, it is preferable to adsorb and bond to the immobilization support because the reaction period of the lipase can be extended even when the reaction is performed at a high temperature, and the reaction can be continuously carried out by filling the column container. Specific examples of the immobilization support include activated charcoal, white clay, silica gel, diatomaceous earth, calcium carbonate, celite, cellulose and derivatives thereof, chitosan and derivatives thereof, materials such as glass and resin, and porous adsorption type supports. Can be mentioned. Further, in order to make the immobilized lipase into a certain particle system, it may be granulated using an excipient or the like. In the present invention, those having an arbitrary particle size can be used as the immobilized enzyme. In general, it is preferable to use one having a particle size of 50 to 1000 μm, particularly 500 to 1000 μm.

(Free fatty acid in the reaction product after lipase treatment)
When the oil-and-fat raw material derived from palm and the fatty acid are transesterified by lipase treatment, free fatty acid is contained in the obtained fat and oil. From the viewpoint of obtaining a state suitable for edible use, it is preferable to remove this free fatty acid, and distillation is particularly preferred as the removal method. Examples of the distillation method include thin film distillation, molecular distillation, steam distillation and the like, and it is preferable to perform the process once or twice or more. Furthermore, the free fatty acid contained in trace amount in the fats and oils after reaction can be removed to the state suitable for edible by performing the normal deoxidation process of fats and oils. As the deoxidation step, either neutralization purification or physical purification described above may be selected.
It is preferable that the fats and oils from which free fatty acids have been removed by the above-described method are further edible by performing a degumming step, a decoloring step, and a deodorizing step.

  The fats and oils obtained through the above steps can be used alone as an edible fat or oil, or can be used by mixing with other fats and oils. In this case, the fats and oils to be mixed are the same as the fats and oils shown above, but it is preferable to select fats and oils having a low content of chloropropanols and their fatty acid esters, glycidol and their fatty acid esters.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
Table 1 shows an example of analysis of the constituent fatty acid composition of the oil and fat component used and the constituent fatty acid composition of the raw fatty acid in Examples and Comparative Examples. The fatty acid composition of each fat and oil component and raw material fatty acid was analyzed by “standard fat and oil analysis test method 2.4.2.2-2013”.

[Production Examples A to F: Palm-based fats and oils as raw materials]
In the present invention, the following production examples A to F were prepared as oils and fats derived from palm as a raw material. Moreover, random transesterification was performed by the following method. Table 2 shows the fats and oils used in Production Examples A to F and their blends. In the “Random transesterification” section at the bottom of Table 2, “O” indicates that random transesterification has been performed, and “X” indicates that random transesterification has not been performed.
Production Example A: Palm Oil Production Example B: Palm Oil Fractionated High Melting Point Production Example C: Palm Oil Random Transesterified Oil Production Example D: Palm Oil Fractionated High Melting Point Random Transesterified Oil Production Example E: Palm Oil Fractionated high melting point part, palm kernel oil, random transesterified oil of soybean oil Production Example F: Palm oil fractionated high melting point part, palm kernel oil, soybean oil, canola oil random transesterified oil

(Random transesterification method)
The reaction method and conditions for random transesterification are shown below. The raw material mixed oil was charged into the reaction vessel and heated with stirring in a nitrogen stream. This state was maintained for 3 hours or more in a state of 100 ° C. to 120 ° C., and dehydration was performed until the water content in the fats and oils became 100 ppm or less. Thereafter, the oil and fat was cooled to 80 ° C., 0.1 to 0.2 parts by mass of an alkali catalyst (sodium methylate) was added, and the mixture was reacted for 30 minutes in a nitrogen stream with stirring. In order to remove the catalyst, hot water at 70 ° C. was added to the reaction solution, stirred and washed, and then allowed to stand to separate an oil layer and an aqueous layer. Washing with hot water was repeated until the pH of the separated aqueous layer was 8 or less, and then heating was performed in a nitrogen stream while stirring, and dehydration was performed until water no longer evaporated at 100 ° C to 120 ° C. Next, 3 parts by mass of activated clay was added and decolorized for 15 minutes, followed by filtration.

[Raw fatty acid]
In the present invention, the following two fatty acids were used.
Fatty acid I: oleic acid content 74.3% by mass, derived from palm oil Fatty acid II: oleic acid content 95.4% by mass, derived from high oleic sunflower oil

[Examples 1-8]
The fats and oils raw material (triglyceride) and fatty acid I obtained by said manufacture example AF were mix | blended in the ratio of Table 3, transesterification by the lipase process was performed by the following method, and the mixture of fats and oils and a free fatty acid was obtained. The free fatty acid part was removed from the mixture and the composition was analyzed. Moreover, the partial triglyceride content was analyzed about the fats and oils after free fatty acid removal.
The partial triglyceride was analyzed based on “AOCS Official Method Cd11b-91”. The lower limit of quantification was set to 0.05% by mass.

(Transesterification by lipase treatment)
The reaction method and conditions for transesterification by lipase treatment are shown below. Transesterification while passing the raw materials of Examples 1 to 8 above at a flow rate of 15 to 50 g oil / hour through a column packed with 35 g of “Novozym 40086” (Rhizomucor miehei origin / immobilized lipase) at 60 to 70 ° C. Went. The reaction flow rate was adjusted so that the reaction rate was 90% or more. The reaction rate was confirmed by the reaction rate in palmitic acid calculated based on the theoretical value and the measured value.

(Method for removing free fatty acid from reaction product)
The method and conditions for removing free fatty acids from the reaction product obtained by transesterification with the lipase are shown below. In the present invention, thin film distillation was performed. First, the reaction product was distilled through the reaction at 100 to 200 mL / h under the conditions of a temperature of 220 to 230 ° C. and a degree of vacuum of 8 to 12 Pa. The obtained fat was distilled again under the same conditions.

(Deoxidation method)
The oil and fat after distillation was subjected to deoxidation treatment by neutralization purification. The obtained fats and oils were charged into a reaction vessel, heated to 60 to 70 ° C., and an aqueous sodium hydroxide solution was dropped according to the acid value to neutralize free fatty acids. The formed and precipitated fatty acid soap was removed by centrifugation.

(Analysis of β-linked fatty acid composition)
Furthermore, the fatty acid composition of the fats and oils obtained by the above method and the fatty acid composition bonded to the β-position were analyzed. The analysis of fatty acid composition is carried out by “reference oil analysis test method 2.4.2.2-2013”, and the fatty acid composition analysis of β-position bond is carried out by “reference oil analysis method 2.4.5-2016”. went. Based on these analysis results, the binding ratio of palmitic acid to the β-position was determined from the following calculation formula.
Binding ratio of palmitic acid to β-position (%) =
(Content of palmitic acid bonded to β-position / palmitic acid content in the whole × 3) × 100

[Comparative Examples 1-6]
After blending the fat and oil raw materials obtained in the above Production Examples A to F and the fatty acid I or the fatty acid II in the ratio of Table 4, transesterification by lipase and fatty acid removal by the above methods, Comparative Examples 1 to 6 oils were obtained. Moreover, the composition of the free fatty acid removed according to the above method, and the fatty acid composition of the obtained fat and oil and the fatty acid composition of the β-position bond were analyzed. And the beta-position bond ratio of palmitic acid of fats and oils was calculated | required from said calculation formula.

Looking at Tables 3 and 4, oleic acid-containing fatty acids (fatty acids I) containing 5 to 60% by mass of fat and oil raw materials (Production Examples A to F) containing palm-derived fats and oils and a content of oleic acid of 70 to 80% by mass ) Was inhibited by lipase reaction, and generation of partial glycerides was observed.
In addition, when the comparative examples 1, 2, 5, and 6 are seen, the tendency that generation | occurrence | production of a partial glyceride will increase when the fats and oils raw material increases is recognized. On the other hand, when Examples 3 and 4 are compared with Comparative Examples 3 and 4, Examples 3 and 4 contain a large amount of oil and fat raw material, but the partial glyceride content is low. That is, it can be said that generation of partial glycerides is suppressed by using an oleic acid-containing fatty acid (fatty acid I) having an oleic acid content of 70 to 80% by mass.

Claims (3)

A blending step of adjusting a blended fat containing 5 to 60% by mass of a fat and oil raw material containing oil derived from palm and 40 to 95% by mass of an oleic acid-containing fatty acid having a content of oleic acid of 70 to 80% by mass, and ,
The manufacturing method of the fats and oils which have a lipase reaction process with which the said mixing | blending fats and oils are made to react with the lipase which acts on the (alpha) -position specifically, has a palmitic acid in the (beta) -position.   Furthermore, the manufacturing method of the fats and oils which have a palmitic acid in the (beta) -position of Claim 1 provided with the transesterification process of carrying out random transesterification of the fats and oils raw material containing the said palm-derived fats and oils. The method for producing fats and oils containing palmitic acid at the β-position according to claim 1 or 2, wherein the fat and oil raw material containing fats and oils derived from palm contains soybean oil.