JPH0811798B2 - Method for producing modified fats and oils retaining aroma - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for reforming fats and oils, and more particularly to a method for reforming fats and oils without damaging the unique aroma of the raw fats and oils.

[Prior art]

The modification of fats and oils has been conventionally performed for the purpose of imparting physical properties suitable for their use to fats and oils.

By the way, some fats and oils have a unique fragrance that has no alternative. For example, cocoa butter, milk fat, nut oil and the like.

These fats and oils have a unique fragrance and at the same time have certain physical properties. For example, cocoa butter exhibits extreme hardness behavior at room temperature. As a result, it is convenient to apply to solid food products such as chocolate. However, on the other hand, its use in margarines and creams, which require softness, is limited.

That is, the addition of cocoa butter to margarine or the like is possible only in a very small amount within the range that does not adversely affect the physical properties of margarine or the like. After all, conventionally, margarine and the like could not fully utilize the aroma of cocoa butter. Also,
So far, there has not been provided anything that can impart a savory aroma similar to that of cocoa butter to foods.

Therefore, the advent of a technique for modifying cocoa butter to have physical properties that can be freely applied to foods having various different physical properties without impairing its unique aroma has long been desired. .

Such circumstances existed not only in cocoa butter, but also in milk fat and nut oil having other aromas.

However, none of the conventional methods for modifying fats and oils can satisfy the above-mentioned requirements.

Conventional fat and oil reforming methods are roughly classified into hydrogenation, fractionation and transesterification, and a method combining these is used.

That is, in the hydrogenation carried out with a catalyst such as nickel at a temperature of 150 to 200 ° C. and the reforming method by “chemical” transesterification carried out with a catalyst such as sodium methylate, the reaction pretreatment and the post treatment are performed. Since the treatment, especially the deodorizing process under high vacuum and high temperature, was performed, the aroma of the raw material fat and oil could not be retained, and only a substantially tasteless and odorless modified fat and oil could be obtained.

In addition, the reforming by fractionation consists of solvent fractionation and solvent-free fractionation.
Although it can be divided into species, in the former case, a so-called top fragrance component, which is particularly important among fragrance components, is volatilized when the solvent is removed from the fractionated oil and fat. On the other hand, in the latter case, it is possible to obtain a separated oil and fat that retains the aroma of the raw oil and fat, but there is a limit to the oil and fat that can be separated and applied to all oils and oils with an aroma. I couldn't. Furthermore, the products obtained by fractionation are limited to three types at most, a high-melting point part and a low-melting point part, or an intermediate-melting point part by multi-stage fractionation. Therefore, it is not possible to produce various fats and oils having desired physical properties by fractional modification. It is impossible at all, and it is inconvenient to treat a separated oil or fat having physical properties other than those desired.

In recent years, attention has been paid to transesterification using lipase as an alternative to the "chemical" transesterification method. But,
The transesterification method using lipase has to be carried out especially in the case of transesterification of solid fat in the presence of a solvent, or the solvent has to be used for recovery of fats and oils after transesterification. (For example, JP-A-52-104506 and JP-A-57-19879.
7). This is because it is necessary to carry out the ester conversion reaction at a relatively low temperature in order to maintain the activity of lipase. However, when a solvent is used, post-treatment under high vacuum heating is required to completely remove the residual solvent, and as a result, the aroma component on the top volatilizes to obtain a modified oil or fat with an aroma. I couldn't.

In short, among the various methods for modifying fats and oils that have been known and practiced in the past, fats and oils having physical properties suitable for foods while retaining the unique aroma of raw fats and oils are included. There was no way that it could be modified.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to improve an oil and fat having physical properties that can be freely applied to foods having various different physical properties without impairing the unique aroma of the raw oil and fat. To provide a way to do quality.

[Structure of Invention]

That is, the present invention provides at least one kind of oil and fat having an aroma selected from the group consisting of milk fat, cacao butter, sesame oil and nut oil, or a mixture of at least one kind of oil and fat having the aroma and at least one kind of compounded oil and fat. The raw material oil and fat consisting of is heated to a temperature of 65 to 80 ° C. under an organic solvent to be melted, and then a saturated amount of water is melted in the melted raw material oil and fat, under an organic solvent, 65 to 80 ° C. Characterized in that the raw fats and oils are brought into contact with an immobilized lipase obtained by immobilizing a lipase derived from Mucor and Mihai on a carrier at a temperature of 3 to carry out a transesterification reaction, and the obtained fats and oils are not deodorized. Provided is a method for producing a modified fat or oil that retains the aroma.

First, in the present invention, the fat and oil raw material to be subjected to transesterification is (i) at least one of fats and oils having an aroma selected from the group consisting of milk fat, cocoa butter, sesame oil and nut oil.
Or (ii) a mixture of at least one kind of oil and fat having the aroma and at least one kind of compounded oil and fat.

Further, the above-mentioned “compounded oil and fat” used in the present invention is a substantially tasteless and odorless oil and fat. That is, in addition to unprocessed vegetable and animal liquid oils and solid fats, liquid oils and solid fats obtained by hydrogenation, transesterification, fractionation or a combination of these processes are deodorized after undergoing a purification process. Was
It can be an oil or fat that can be used as it is as it is. Such oils and fats include soybean oil, cottonseed oil, rapeseed oil, corn oil, safflower oil, rice oil, sunflower oil,
Palm oil etc. can be mentioned. Further, cocoa butter and the like exemplified as the oil and fat having the aroma described above and deodorized in the duplication step can also be used as a compounded oil and fat.

In the production method of the present invention, an immobilized lipase prepared by immobilizing a lipase derived from Mucor mihi on a carrier is used. This is because the use of this lipase can suppress the production of trisaturated fatty acid glyceride, which adversely affects the melting of fats and oils, for example, in the modification of cocoa butter.

Examples of such immobilized lipase include NOVO manufactured by Novo
3A-immobilized lipase can be mentioned.

This is a lipase having 1,3-specificity derived from Mucor Miehei, which is immobilized using an ion exchange resin as a carrier.

It should be noted that as the immobilization carrier, one that adversely affects the aroma of the oil or fat or one that adsorbs and reduces the aroma of the oil or fat is not desirable.

Further, the optimum temperature of the immobilized lipase used in the present invention is about 70 ° C, which is extremely high considering that the conventionally used one is at most around 40 ° C.

This means that when the transesterification reaction is carried out in the vicinity of the optimum temperature, the reaction can be completed at a high reaction rate which could not be carried out by the conventionally known method, and the equilibrium point is formed by the production system ( High reaction efficiency).

Further, in the conventional enzyme catalyst, when the reaction temperature was raised, the reaction treatment was certainly increased, but the possibility of thermal denaturation (inactivation) of the enzyme (protein) was not unavoidable. However, in the present invention. That is not the case.

Therefore, the transesterification reaction of the present invention is carried out at 65 to 80 ° C.
Perform at around 70 ° C.

In order to increase the reaction (transesterification) rate, it is common sense that the temperature is high. However, if it is too high, the problem of inactivation of lipase occurs. Therefore, it is preferable to carry out the reaction in the above temperature range close to the optimum temperature of the immobilized lipase.

In the transesterification reaction of the present invention, it is not necessary to use a different organic solvent since the raw material oil and fat. On the contrary, since the organic solvent is unnecessary, it is possible to prevent disappearance of the aroma component which may occur during the removal.

This is the first time that the transesterification reaction can be realized by being able to be carried out at a relatively high temperature of 65 to 80 ° C. at which the raw fat and oil becomes liquid.

The transesterification reaction of the present invention may be carried out in the presence of an inert gas or an antioxidant so as not to impair the aroma component.

In the present invention, the raw fat / oil also dissolves saturated water at the reaction temperature.

By doing so, the content of free fatty acids by-produced during the reaction can be suppressed to a low level. In addition, the odor originally possessed by the starting material is not lost, and the activity of the immobilized lipase can be maintained for an extremely long time.

Further, the transesterification used in the present invention can be carried out in a batch system or a continuous system. However, the continuous system using a column packed with immobilized lipase is better from the viewpoint of equipment and efficiency.

That is, in the batch system, since the reaction proceeds sufficiently, it is necessary to heat the solid fat at a relatively high temperature for a long time, in particular, so that the alteration of the aroma component cannot be avoided. Furthermore, in the batch method, the amount of free fatty acids produced by hydrolysis that occurs as an axial reaction increases. On the other hand, in the continuous method, the heating time is short and the amount of by-produced fatty acid can be suppressed to a low level. Therefore, the continuous method is preferably used in the present invention.

In the present invention, the modified product thus produced is used as it is without being deodorized.

If necessary, treatment may be carried out by a conventional method within a range in which the scent is not spoiled. For example, it can be applied only to the extent of adsorption and removal of trace amounts of water remaining in the product, and can be filtered with a filter medium that does not reduce the fragrance or impart a different odor or taste, or can be dried under mild conditions. is there.

By the production method of the present invention described above, it is possible to produce an oil or fat with improved physical properties without impairing the aroma of the raw oil or fat.For example, an oil or fat modified from cacao butter must be added satisfactorily in the past. Margarine, shortening,
It can be added to spreads or creams to impart a rich scent of cocoa butter without impairing their physical properties.

Further, in order to prevent the bloom occurrence of chocolate conventionally, there was only a method of blending a tasteless and odorless cocoa substitute fat produced from palm oil etc. into chocolate, but according to the production method of the present invention, bloom occurrence It is possible to provide a modified cocoa butter which has a physical property of preventing the above-mentioned effect and also has an aroma by itself.

Also for milk fat having a unique fragrance, it is possible to obtain a modified milk fat having a wide variety of physical properties as compared with the conventional fractionation method, and retain the fragrance, and oils and fats having other fragrances, for example, cocoa butter, By mixing with a nut oil or the like and transesterifying, a complex aroma of the mixture can be retained, and an oil or fat having improved physical properties, for example, rich in emulsion stability can be provided.

The modified fats and oils produced by the production method of the present invention are pulverized by themselves or by using another coated base material, or W / O type or O / W type or double emulsion using an additive. It can be emulsified into a mold, kneaded with a kneading machine for kneading, or used as a food material or food together with other food materials.

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 6 g of 1,3-specific solidified lipase 3A from Novo Co. was packed in a column having an inner diameter of 1.5 cm. 50% cocoa butter with high scent of cocoa obtained by pressing from cocoa mass and 50% of melting point fraction in deodorant tasteless palm oil obtained by acetone fractionation are blended, 65
Saturated by heating and melting at ℃ (water content 0.19% by weight)
After that, the liquid was passed through the column at the same temperature and a flow rate of 12 g per hour. Approximately 1 kg of transesterified oil after 72 hours from the start of liquid passage,
The sample was subjected to the next test without post-treatment.

With respect to the blended oil before transesterification and the obtained transesterified oil, the sensory evaluation panel 10 persons compared and evaluated the difference in flavor. As a result, the difference was 8 persons, the difference was 2 persons, and the difference was 2 in the difference. There was one person who assumed that the blended oil had a higher fragrance and one person who assumed that the transesterified oil had a higher fragrance. No flavor difference was observed between the two, and the aroma component was retained even after transesterification. It was

The blended oil before transesterification and the transesterified oil were examined for the composition of the three main components of palmito oleo palmitin (POP), barmit oleo stearin (POS), and stearo oleo stearin SOS by high performance liquid chromatography. The results were as follows, and it was confirmed that transesterification was carried out.

(Application) Using the blended oil and the transesterified oil used in Example 1, chocolate was trial-produced with the following formulation.

Cocoa mass 35 parts Blended oil or transesterified oil 22 parts Powdered sugar 43 parts Lecithin 0.4 parts After tempering these chocolates at 20 ° C for 1 week, cycle the temperature from 20 ° to 30 ° C every 12 hours in a cycle thermostatic bath. When subjected to a bloom resistance test, bloom was generated at the third time when the compounded oil was used and at the seventh time when the transesterified oil was used.

Example 2 Peanut oil having a pleasant aroma that has not been deodorized and refined
70% and refined palm oil 30% were mixed and heated and melted at 70 ° C to saturate the water (water content 0.19% by weight). This compounded oil was passed through the same column as in Example 1 at 12 g / hr at 70 ° C. to obtain about 1 kg of transesterified oil after 72 hours and subjected to the next test without post-treatment.

The flavor difference of the blended oil and the transesterified oil before transesterification was examined by 10 sensory evaluation panels, and it was found that there were 9 people with no difference and 1 person with difference. Was not observed, and the aroma component was retained even after transesterification.

The softening points of the compounded oil and the transesterified oil before transesterification were 18 and 6 ° C., respectively, and it was confirmed that transesterification was clearly performed.

(Application) An attempt was made to make a dressing using the compounded oil used in Example 2 and the obtained transesterified oil, but the compounded oil could not be prepared because a large amount of solid fat was deposited at room temperature. Regarding the transesterified oil, a little solid fat was observed at room temperature, but separate type and emulsified type dressings could be prepared, and it became a live dressing with the flavor of peanut oil.

Example 3 A column similar to that of Example 1 was prepared, and 50% of cocoa butter used in Example 1 and 50% of milk fat obtained by melting the commercially available butter and filtering the supernatant fat were mixed, and the mixture was heated to 65 ° C. It was heated to saturate the water (water content 0.23% by weight). The column was passed through at a flow rate of 10 g / hour at this temperature. About 2k of transesterified oil after 96 hours
g was obtained and subjected to the next test without post-treatment.

Regarding the blended oil before transesterification and the transesterified oil, the sensory evaluation panel examined 10 flavor differences between them, and found that there were 7 people with no difference and 3 people with difference.
The number of people who said that the blended oil had a richer flavor among the names and differences 2
It was found that the transesterified oil had a richer flavor, and the flavor difference between the two was not recognized, and the flavor component was retained even after transesterification.

When the glyceride composition of the total carbon number of the blended oil before transesterification and the transesterified oil was compared, the chromatograms of both were clearly different, and it was confirmed that the transesterification was performed.

(Application) Using the compounded oil used in Example 3 and the obtained transesterified oil, an oil-in-water type cream having the following formulation was trial-produced.

Oil phase Blended oil or transesterified oil 40 parts Coconut hardened oil 6 parts Emulsifier (lecithin, monoglyceride, sorbitan ester) 1.4 parts Water phase Degreased milk powder 4 parts Sodium hexametaphosphate 0.1 part Water 48.5 parts Procedure 70 ℃ pre-emulsification → 50kg / cm ² Homogenize at 75 ℃ 15
Minute sterilization → rapid cooling to 10 ° C or lower → test after 24 hours The viscosity, emulsion stability, shape retention and end point width ^* of the creams obtained are compared and shown in the table below.

The cream using the transesterified oil obtained by the production method of the present invention has a low viscosity, is excellent in emulsion stability and shape retention, and has a wide end point width ^* at the time of whipping, and has very good workability. Met.

* It is the interval between the best whipping time and the over whipping time during the whipping.

Comparative Example 1 The blended oil of 50% cocoa butter and 50% middle melting point fraction of palm oil used in Example 1 was transesterified by using the solvent specifically described in Example 2 of JP-A-56-154951. Was applied. That is, 1 kg of compounded oil is converted to petroleum ether (boiling point 100 to 12
After melting at 0.degree. C.) 2.73 and saturating the water at 40.degree. C., it was passed through a lipase packed column prepared in the same manner as in Example 1 at a flow rate of 4 g / h. About 2 kg of a transesterified oil solution was obtained after about 200 hours from the beginning of liquid passage, and the solvent was distilled off at 60 to 70 ° C. using a rotary evaporator under reduced pressure of an aspirator.
However, the smell of petroleum ether remained strong. Deodorization of oils and fats (steam distillation under high temperature and high vacuum) is required in order to completely remove the solvent, but it is recommended to select mild conditions as much as 100 ° C.
Was steam distilled under high vacuum for 30 minutes.

The obtained transesterified oil did not have the odor of petroleum ether, but most of the original aroma of cocoa butter had disappeared.

〔The invention's effect〕

 The effects of the present invention are listed below.

(I) Reaction (transesterification reaction) is fast.

(Ii) The aroma originally possessed by the raw material itself is not impaired.
Therefore, it can be effectively used for producing margarine, shortening, spread, cream and the like.

(Iii) The specific pretreatment or posttreatment is substantially unnecessary, and the transesterification reaction can be continuously performed. That is, the equipment cost can be significantly reduced.

Claims (4)

[Claims] 1. At least one of fats and oils having an aroma selected from the group consisting of milk fat, cocoa butter, sesame oil and nut oil.
Or a raw material oil / fat consisting of a mixture of at least one kind of oil / fat having the aroma and at least one kind of compounded oil / fat is melted by heating at a temperature of 65 to 80 ° C. under an organic-free solvent, and then melted. After dissolving a saturated amount of water in the raw fat or oil, at a temperature of 65 to 80 ° C. in an organic-free solvent, the raw fat or oil is contacted with an immobilized lipase obtained by fixing a lipase derived from Mucor-Miehai on a carrier. A method for producing a modified oil / fat that retains an aroma, characterized in that a transesterification reaction is carried out, and the obtained oil / fat is not deodorized. 2. The method according to claim 1, wherein the transesterification reaction is carried out in the absence of the mixed fat and oil. 3. The method according to claim 1 or 2, wherein the oil or fat having an aroma is selected from the group consisting of milk fat, cocoa butter and nut oil. 4. The method according to claim 1, wherein the blended fat is a fat that is substantially tasteless and odorless.