JPS59172596A - Purified fish oil and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a refined fish oil and a method for producing the same, and its purpose is to produce eicosapentaenoic acid (20 carbon atoms, 5 unsaturated double bonds).
and/or to provide a novel refined fish oil containing a high concentration of docosahexaenoic acid (prime number 22, number of unsaturated double bonds 6) as a fatty acid group and hardly giving off a fishy odor, and a method for producing the same.

Eicosaintaenoic acid (hereinafter abbreviated as "EPAJ") and/
It is also known that docosahexaenoic acid (hereinafter abbreviated as "DHA") is effective in the prevention or treatment of thrombotic diseases because it adjusts the cholesterol content in the blood of living organisms and has the effect of preventing thrombotic disorders.

However, fish oil containing EPA and/or DHA is made from fish such as sardines, mackerel, saury, and pollack, and is extracted by boiling, squeezing, and other methods to produce fishmeal and fish meal with a low fat and oil content. To manufacture products of 9
It is obtained as a by-product. Therefore, with regard to fish oil, the method of extracting the oil from the fish body is crude, resulting in a loss of freshness by the time the oil is extracted.Furthermore, during the oil extraction, the protein components of the fish meat are decomposed to produce low-molecular amines, and these amines are contained in the fish oil. It is unavoidable to mix it up. Also, there is EP in fish oil.
In addition to A and/or DHA, a large amount of highly unsaturated fatty acids are included, but these highly unsaturated fatty acids are oxidized and decomposed during storage of fish oil to form low-molecular acids, low-molecular ketones, or This will generate aldehydes. Therefore, fish oil does not have a distinct odor when freshly extracted from the fish body, but the low molecular weight amines contained in the fish oil react with the low molecular weight ketones and aldehydes produced during storage, resulting in the formation of aerosol components. This produces an acrid odor that reduces the commercial value of fish oil products.

In order to prevent the occurrence of such a fish oil odor, conventional methods have been used to remove impurities by subjecting the fish oil obtained by oil extraction to purification treatments such as deacidification and deodorization.

However, although conventional purification methods can remove odorous components, they cannot completely remove imines and ketones, which are precursors of odorous components. Therefore, the obtained refined fish oil has almost no odor immediately after its purification, but odorous components are generated over time during storage, thus giving rise to a fish oil odor. Therefore, to date, no fish oil is commercially available that does not generate odor even after long-term storage.

The inventor of the present invention sought to provide a refined fish oil that does not generate an odor and a method for producing the same, and as a result of various studies, he found that salad oil obtained from plant seeds is almost pure triglyceride, and does not generate an odor even after long-term storage. The present invention was completed based on the finding that even fish oil can be pretreated to a certain extent, deodorized, and then subjected to molecular distillation to obtain purified fish oil similar to salad oil. The refined fish oil of the present invention is characterized in that it contains 5 weight or more, preferably 15 weight or more, of EPA and/or DHA as fatty acid groups, and contains almost no fishy odor components, and the method for producing it includes ester group-exchanged fish oil. Add polyhydric alcohol and monoglyceride to the mixture, heat it under vacuum to deodorize it, and then perform molecular distillation to collect the evaporated components as essential oil, or use molecular distillation to remove odorous components and remove remaining components. These fine oils are collected as essential oils and are characterized in that they are used as refined fish oil products as the object of the present invention. The present invention will be explained in detail below.

In the present invention, oils and fats obtained by extracting oil from the bodies of fish such as sardines, mackerel, and saury using conventional methods for extracting fish oil, oils and fats obtained by extracting oil from the internal organs of pollock, sharks, etc., as well as oils and fats obtained by extracting oil from molluscs such as squid and octopus, are used. It also includes oils and fats obtained by

The fish oil used as a raw material in the present invention may be crude fish oil obtained by extracting oil from fish bodies, but it is preferable to use a pre-purified product of crude fish oil in order to increase the efficiency of deodorization or molecular distillation that will be carried out later. Therefore, the crude fish oil is subjected to preliminary purification such as alkaline purification using phosphoric acid or sulfuric acid in an acid tank or caustic alkali, as well as deoxidation, decolorization, dewaxing, and deodorization by heating and steam distillation, to obtain triglycerides. It is desirable to use a finished oil with a high content as a raw material oil.

In the present invention, first, an ester group conversion reaction catalyst such as sodium alcoholade is added to fish oil according to a conventional method, and the ester group conversion reaction is caused to occur in the presence of an inert gas to obtain an ester group conversion reaction fish oil.

To give an example of one method for the ester group exchange reaction, sodium alcoholade is added to 0.02~0, s weight Ji% of fish oil with an acid value of 0.5% or less and a water content of 0.2% by weight or less, and 5~ 30
The reaction is carried out with stirring in a nitrogen atmosphere at ℃, and when the cloud point of the reactant is 7 to 25 ℃ higher than the cloud point of the raw fish oil, an acid such as phosphoric acid is added as a neutralizing agent in an amount equivalent to the neutralization equivalent. In addition, the reaction is stopped and a transesterified oil is obtained. The time required for the reaction varies depending on the type of fish oil and the reaction temperature, but is in the range of 6 to 36 hours. The reason for converting ester groups here is to adjust most of the glycerides contained in the fish oil to saturated triglycerides so that the glycerides can be recovered in high yield during the subsequent molecular distillation. In addition, if the fish oil used as a raw material is not pre-purified, or if pre-purification is performed but decolorization is omitted, secondary ester potatoes can be effectively decolorized by decolorizing the transesterified oil. Polyhydric alcohols and monoglycerides are added to the exchanged fish oil. The polyhydric alcohol is not particularly limited as long as it is non-toxic, but divalent or trivalent alcohols such as glycerin or zoderopyrene glycol are preferably used. In particular, it is preferable to use glycerin, which is approved as a food additive. The reason for using polyhydric alcohol in the present invention is as follows. In other words, since the amines contained in fish oil have strong hydration properties, a polyhydric alcohol with a boiling point similar to that of the amines is added to the fish oil, and the amines are made to have an affinity for the hydroxyl groups of the polyhydric alcohol, thereby making it possible to absorb polyhydric alcohols during deodorization later. The distillation of amines is facilitated as the alcohol is distilled off, and in this way the amines are removed from the fish oil. However, since polyhydric alcohol is insoluble in fish oil, it is not possible to uniformly disperse it in fish oil simply by adding polyhydric alcohol. Therefore, in the present invention, a monoglyceride compatible with a polyhydric alcohol is added to fish oil together with the polyhydric alcohol, and the polyhydric alcohol is uniformly dispersed in the fish oil using this as a medium. Monoglycerides include monooxyglyceride obtained from vegetable oils such as soybean oil or coconut oil, monooleyl glycerineptide, etc., and any type of glycerin as long as one hydroxyl group has an ester bond with one fatty acid. can be used. As monoglycerides, crude ones separated from fats and oils may be used, but they can be distilled to 1
Since distilled monoglyceride has no odor, it is desirable to use distilled monoglyceride P. Furthermore, since monoglyceride has almost the same boiling point as cholesterol, cholesterol-A is extracted from fish oil in the subsequent molecular distillation.
t- also has the role of effective removal. The amount of polyhydric alcohol and monoglyceride added is approximately 1 to 20 parts by weight per 100 parts by weight of transesterified fish oil.If both are stirred and mixed at room temperature or a temperature below 50°C, a transparent mixed oil will be obtained. can get.

Next, this mixed oil is heated under vacuum to deodorize it.

For deodorization, a continuous flow deodorization device or a molecular distillation machine is used to heat the fish oil under vacuum to remove volatile odorous components. The degree of vacuum and heating conditions for oil and fat are vacuum degree 10 to 100μ.
Hgs temperature is 30 to 100℃, and in this case, the oil and fat feeding rate is 20 to 150 4/h/m2
It is desirable to do so. Note that it is desirable that deodorization be carried out in as short a time as possible in order to prevent deterioration of εPA and/or DHA in the fish oil.

This deodorizing process removes volatile odorous components such as amines, aldehydes, ketones, and organic acids contained in the transesterified fish oil, so the deodorized fish oil, which has almost no fish oil odor, is converted into an ester group. 90~ for exchange reaction fish oil
It can be obtained with a yield of 98% by weight. In addition, during deodorization, polyhydric alcohols that have an affinity for amines are distilled off.
This facilitates the removal of amines, so deodorized fish oil that contains almost no amines is used with EP^ and/or
or D) can be obtained in a short time without deteriorating IA.

In the present invention, the deodorized fish oil thus obtained is further subjected to molecular distillation to condense the evaporated components resulting from the molecular distillation, thereby obtaining the oil, that is, the product for the purpose of the present invention. For molecular distillation, it is preferable to use a centrifugal thin film distiller.

Even if molecular distillation is performed only once, it is possible to obtain the desired unrefined fish oil.

First, the deodorized oil is subjected to a first distillation at a vacuum If of 5 to 30 μHg% and a thin film crystallinity of 100 to 260°C to distill off monoglyceride and cholesterin fatty acid ester (cholesterol), and convert the pure glyceride oil into a transesterified oil. It is obtained in a yield of 80 to 98 parts per 100 parts. This first distillation removes cholesterol along with monoglycerides having similar boiling points, and also completely removes trace amounts of odor components remaining.

Next, the pure glyceride oil obtained in the first distillation was subjected to a second distillation at a vacuum degree of 0.1 to 50 μHq% and a membrane temperature of 150 to 500°C to obtain total saturated fatty acid glyceride with a saturated fatty acid content of 35% by weight or more, 2 Solid fat components such as saturated 1-monoene unsaturated fatty acid glycerides are distilled off, and liquid glyceride is obtained at a concentration of 35 to 65% per 100 parts of transesterification oil.
It is obtained in a yield of . ,...5 When the film τ crystallinity exceeds 300°C, EPA and/or DHA contained in the form of ester groups in fish oil undergoes a thermal decomposition reaction, resulting in ketones, which are one of the components of the precursor of fish oil odor. This is undesirable because it tends to cause similar problems.

Finally, regarding the liquid glyceride obtained in the second distillation, the degree of vacuum is 0.1 to 50 μHg, and the thin film temperature is 200 to 300.
EPA and/or D
The refined oil which is the object of the present invention and which contains HA in a high degree is obtained at a yield of 20 to 60 parts per 100 parts of the ester group conversion reaction oil. It should be noted that a small amount of protein contained in the liquid glyceride or a nitrogen compound which is a decomposition product thereof has a boiling point different from that of the evaporated components of the third distillation, and therefore remains in the residual oil. In addition, the economical charging speed for each distillation process varies depending on the type of molecular distillation machine used, but it is 20 to 150 Ky/hour.
2 is appropriate. If molecular distillation is to be completed only once, the degree of vacuum is 0.1 to 30 μHg, and the thin film temperature is 20 μHg.
0-300℃, preparation speed 20-150 Ky/h
/~2 conditions are appropriate. The yield in this case is about 20 to 60% by weight. In addition, molecular distillation
When performing the first distillation twice, the vacuum level is 5 to 30 rtm.
Hg, carried out at a thin film temperature of 100 to 260°C to distill off trace amounts of odorous components, and then second distillation at a vacuum degree of 0.1 to 3.
It is preferable to conduct the process at 0 μHg and a thin film temperature of 200 to 300° C. to condense and collect the evaporated components. The refined fish oil thus obtained as a condensate of evaporated components contains EPA or DH in its fatty acids.
When molecular distillation is performed once, the content of A is at least 5% by weight for either one, and if it goes well, it is 5% by weight or more for both, and if molecular distillation is performed three times, the content of A is 30% by weight or more. It was also confirmed that the weight was - or more.

The process sequence according to the present invention when performing up to the fifth distillation is as follows: Preliminary 1f4 made demon? ) 11 → Fustel Kichu reaction → Reactive oil extraction! Mata → Cooling of polyhydric alcohol and monoglycium →, 4 (More distillation machine As described above, according to the present invention, the transesterification reaction oil is molecularly distilled, so the content of glyceride and E P
A: You can also use citrus citron, which has a high content of &/or DHA. Moreover, in the despecialization step, the amines are almost completely distilled off due to the action of the polyalcohol.
In addition, in the molecular distillation process, proteins or nitrogen compounds that are decomposition products thereof are not mixed into the so-called lily citrus, so it is possible to eliminate the precursor components of fish oil odor. Therefore, according to the present invention, EPA and/or D
It is possible to provide a novel ``raw oil'' that hardly produces a fish oil odor even when stored for long periods of time, despite having a high content of highly unsaturated fatty acids called HA.

Example acid value 22, saponification ll1i 192, iodine value 178, C
,P.

Using 11℃ sardine oil as raw material, deoxidize and de-
and the acid value is 0, 15. Reserve PIW with 0.1% moisture
0.2 parts by weight of sodium methylate was added to 100 parts by weight of the pre-produced sardine oil, and the transesterification reaction was carried out for 12 hours at a reaction temperature of 20 to 22°C with stirring in nitrogen gas, resulting in a cloudy state. After confirming that the temperature reached 20° C., the mixture was neutralized by adding an equivalent amount of phosphoric acid, and then 3 parts by weight of activated clay was added for decolorization to obtain 95 parts by weight of transesterification oil. The properties of this oil are acid value 1.2 and saponification value 192. Iodine 1lIf+177
, 8. The cutting point was 20°C.

To 100 parts by weight of this transesterified oil, 5 parts by weight of diglobylene glycol and 2 parts by weight of distilled monooleyl glyceride.
parts by weight were added, and the mixture was heated and stirred at 40°C to obtain a transparent mixed oil.

This mixed oil was continuously charged into a thin film deodorizing machine using a heat medium heating method and having an evaporation area of 2 to 2.
8~43℃, degree of vacuum 50~55μHq, thin film temperature 65~
Deodorization was carried out under the conditions of 75° C. and a feeding rate of 130 kg/h, yielding 100.7 parts by weight of deodorized oil.

Next, this deprocessed oil was continuously charged into a high vacuum flow F-type thin film distillation machine using a heat medium heating method with an evaporation area of 2rn2, and the temperature of the charged oil was 120 to 125°C, the degree of vacuum was 15 to 20 μHg, and the temperature was 120 to 125°C.
1 membrane d degree 240-250℃, preparation floor temperature 125 kg/
hr / rn2 (D, ? Distillation conditions f ig -M Distillation was performed to obtain 93.3 parts of residual oil. This residual oil was continuously charged into a heated centrifugal molecular distillation machine with an evaporation area of 1 m2. Oil rl! Anti-2 CI 0-210℃, Ingredients qq$ 9-11 μHg, Preparation 4 degrees 50 /cg/
A second distillation was performed under distillation conditions of hr/~2 to obtain a residual oil of 50.1 type. Furthermore, this residual oil is evaporated over an evaporation area of 1r.
Continuously feed oil crystals into IL2 thermal medium heating centrifugal molecular distillation machine] Sae 230~265℃, A space 8~
9μHg, thin film temperature 260-265℃, preparation speed 35
Distillation was carried out under the third distillation conditions of /C9/hr/m2, and the evaporated matter was condensed, resulting in a refined fish oil of 31.4%.
One part per serving was obtained.

The properties of the obtained refined fish oil are shown in Table 1.

Table 1 (Properties of Refined Fish Oil) Test Example The refined fish oil obtained in the Eioke example was used as the test product, and separately, crude sardine oil was deoxidized, decolorized, and deodorized by conventional methods, and the obtained Hashira Shoura was used as a control. Each product contains 0.1% by weight as an antioxidant.
100 m of each
Fill 989 bottles into 1-volume bottles, seal and store at room temperature (20℃)
The results of observing the occurrence of fish oil odor after storage were as shown in Table 132.

Table 2 (occurrence status of fish oil odor)

Claims (7)

[Claims] (1) Eicosapentaenoic acid and/or fatty acid groups
Or refined fish oil that contains docosahexaenoic acid by weight of 5 or more and contains almost no fishy odor components. (2) Polyhydric alcohol and monoglyceride are added to fish oil that has undergone ester exchange, and this is heated under vacuum to deodorize it, and then molecularly distilled to condense the evaporated components and collect a refined fish oil product as essential oil. A method for producing refined fish oil. (3) A method for producing charred oil according to claim 2, wherein the polyhydric alcohol is glycerin. (4) The method for producing f-made fish oil according to claim g2 or 3, which involves molecular distillation using a centrifugal thin film distiller. (5) Polyhydric alcohol and -monoglyceride are added to the transesterified fish oil, which is heated under vacuum to deodorize it, and then subjected to molecular distillation to remove the component on the far right, leaving -1--1 remaining. A method for producing refined fish oil, which comprises collecting evaporated components as an essential oil, that is, a refined fish oil product. (6) The method for producing purified fish oil according to claim 5, which involves molecular distillation using a centrifugal thin film distiller. (7) Molecular distillation is divided into three steps, first with a vacuum degree of 5 to 50.
The first distillation was carried out at a pH of 100-260'C and a film temperature of 100-260'C, followed by a vacuum of 0.1-50 µHg. The refined fish oil according to claim 5 or 6, wherein the second distillation is carried out at a thin film temperature of 150 to 300°C, and finally the third distillation is carried out at a vacuum degree of 0.1 to 30 μHg and a thin film temperature of 200 to 300°C. Manufacturing method.