JPS59113099A - Highly unsaturated oil composition - 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 highly unsaturated group-containing oil products or highly unsaturated oil compositions obtained by deodorizing aquatic animal oils, especially fish oils that have an unpleasant odor under normal conditions. The present invention relates to products and their production methods, and also relates to compositions containing highly unsaturated oils obtained by blending them with other oil products such as vegetable oils or their analogues, or other substances.

More specifically, the present invention applies specific reaction conditions, deodorization conditions, and distillation conditions to a combination of processes of fish oil and small fish oil transesterification reaction, continuous vacuum deodorization, continuous high-vacuum distillation, and continuous centrifugal molecular distillation. It relates to distilled edible fats and oils obtained by distillation, distilled alcohol ester oils, highly unsaturated oils as residual oils, and their production methods.

Fish oils such as sardine oil, mackerel oil, and saury oil, and small fish oils such as walleye liver oil and squid oil, which are extracted as products, are made from land animal fats such as pork fat, beef tallow, and vegetable oils such as soybean oil, cottonseed oil, and corn oil. Compared to industrially produced land oils such as sunflower oil, safflower oil, and coconut oil, it has a so-called fish oil odor that is unpleasant to humans.
A distinctive feature is that it contains highly unsaturated acids with 20 and 22 carbon atoms with S and Otsu unsaturated double bonds, which are not present in the above-mentioned land-produced oils and fats. Because of these properties, fish oil and miscellaneous fish oil are used industrially after being deoxidized, decolorized and purified, and then hydrogenated to eliminate the fish oil odor. Its use is limited to margarine and shortening; some of it is used as raw material for low-grade paints, and some is used as raw material for laundry soap after being converted into hydrogenated oil.

The present invention uses eicosapentaenoic acid (hereinafter referred to as IPA), which has 0 carbon atoms and 3 unsaturated double bonds, and is contained in the above fish oil.
Intake of appropriate amounts of docosahexaenoic acid (hereinafter referred to as DHA), which has 2.2 carbon atoms and 6 unsaturated double bonds, is effective in controlling blood cholesterol content and preventing thrombotic disorders. The effects of eating fish meat on the prevention and treatment of heart disease have been recognized through the action of these acids, and the effects of eating fish meat on the intake of appropriate amounts of fish meat containing highly unsaturated acids such as these. Focusing on reports that it reduces heart disease and extends lifespan in people who regularly eat foods whose main protein source is raw meat, fish oil Valuable edible fats, edible oils, distilled alcohol ester oils and highly unsaturated oils can be obtained by processing edible oils and small fish oils, and thrombosis can be obtained by blending edible oils with vegetable edible oils. The object of the present invention is to provide an edible oil composition that is effective against heart disease and prolongs life.

The details of the present invention will be described below.

It has been reported that it is possible to remove the so-called pre-oil odor characteristic of fish oil by vacuum steam distillation or vacuum thin film distillation, but these methods only enable temporary deodorization. Immediately after the deodorization process, the fish oil becomes almost odorless, but as time passes, the fish oil odor returns, or the deodorized product becomes unsuitable for food or other uses.
Alternatively, even if deodorization is almost complete, it is currently not economically viable because the cost of deodorization is too high.

In the present invention, the main components of fish oil odor are low molecular weight abans which are enzymatic decomposition products of proteins, lower ketones which are oxidation products of highly unsaturated acids, lower aldehydes, lower acids and their amines and aldehydes, It became clear that the main products were reaction products with ketones, so the fish oil and zoni oil were subjected to acid purification using phosphoric acid, sulfuric acid, etc. using conventional methods, and alkali purification using caustic alkali was performed. Later, in order to increase the value of the distilled glyceride obtained by molecular distillation, a transesterification reaction is performed using an alkali catalyst under the conditions described below, followed by decolorization and purification using activated clay to obtain a purified transesterification oil.

Although a considerable amount of the above-mentioned odorous components such as amines, aldehydes, ketones, acids, and their reaction products are removed through the above purification, the odor removal is insufficient and the fish oil odor remains. In order to completely remove these substances, the purified transesterified oil 7 is purified by the method newly discovered in the present invention.
00 parts to 30 to 100 parts, which is the deodorizing temperature condition of the present invention.
, the vapor pressure is 003'0. / Torr and non-toxic covalent or trihydric alcohol, such as dipropylene glycol or glycerin, which has a good affinity with the above-mentioned odorous components, and a covalent or trivalent alcohol that is compatible with this covalent or trivalent alcohol and has a high cholesterol content. Phosphorus and cholesterin fatty acid esters and monoglycerides having similar distillation temperatures, such as distilled monooleyl glyceride, distilled soybean oil monoglyceride, and distilled coconut oil monoglyceride, are added in amounts of ~20 parts each and mixed with stirring at room temperature or a temperature below SOC. to obtain a clear mixed oil. This mixed oil is continuously charged into a falling type or centrifugal type thin film vacuum deodorizer while thoroughly degassing, and the vacuum level is 10~10%.
Under the deodorizing conditions of 00 μTorr, thin film temperature of 30 to 10 OC, and charging speed of 0 to 100 ℃, it is possible to denature highly unsaturated acids such as eicosapentaenoic acid and docosahexaenoic acid in a short time and economically. Distillation is carried out without any problem, and a purified deodorized product having no fish oil odor and almost odorless is obtained in a yield of 9O-9f% based on the reaction oil.

This deodorization is an extremely important operational part in the present invention, and after simultaneously adding covalent or trihydric alcohol and monoglycerides to the above-mentioned reaction oil and completely mixing and dissolving them, continuous thin film deodorization is carried out under vacuum. This is based on the fact discovered by the present inventor that, depending on the process, odorous substances can be distilled off together with the added covalent or trihydric alcohol in a short period of time.

From the deodorized oil obtained in this way, cholesterin or cholesterin fatty acid ester, which is undesirable as a component of edible fats and oils, is distilled off, and trace amounts of odorous components that remain and cause the return of the fish oil odor are completely removed. In order to distill it off, this deodorized oil is continuously fed into a high-vacuum falling film type or centrifugal thin film distillation machine, and the vacuum level is reduced. i ~30 p Torr, thin film temperature 100 ~. 1AOC.

Distillation is carried out under distillation conditions at a feeding rate of 30~/left θKg/hr/m2, and the product is light in color and contains unpleasant odors, including monoglycerides, alcohol esters of cholesterin fatty acid esters, low molecular weight glycerides, and trace amounts of odorous components. A yield of 2-20% of the distillate, based on the reaction oil, is obtained.

By carrying out the above process, most of the cholesterin and cholesterin fatty acid ester contained in fish oil are distilled out together with the monoglyceride whose distillation temperature is similar to the one added, leaving a very small amount of odor. This distillation completely removes the fish oil odor and eliminates the return of the fish oil odor, which is based on the fact discovered by the present inventor.

For the above-mentioned continuous deodorizing machine and distillation machine, it is appropriate that the economical charging rate is SO to 5oooK4 per 7 hours, and as a thin film surface heating device, steam heating is suitable for the deodorizing machine. In distillers, heat medium heating or electromagnetic induction heating is economical and appropriate.

The portion consisting of almost pure glyceride obtained by distilling off components other than triglyceride such as cholesterin fatty acid ester obtained as described above is continuously charged into a centrifugal molecular distillation machine, and the vacuum is 0. ~! ;OTorr
, thin film temperature/! ;0~30θC1 Preparation speed 30~/!
; Molecular distillation was carried out under the conditions of OKg/hr/m2, and the melting point was 20.
-DaOC1 Total saturated fatty acid glyceride with saturated fatty acid content of 35% or less, Usaturated/monoene unsaturated fatty acid glyceride, /Saturated comononin unsaturated fatty acid glyceride, /
A pale yellow, odorless distilled solid fat containing saturated/monoene unsaturated/polyunsaturated glycerides as a main component is added to the reaction oil using 3S.
- Obtained with a yield of 6S%. A particularly important point in this molecular distillation is not to raise the temperature of the thin film heating element above 300C; if the temperature is raised too high, IPA contained in the distillate and residue will be removed.

Highly unsaturated acids such as DHA undergo thermal decomposition, albeit in a small amount, even if the residence time on the heating surface is extremely short, 7 seconds or less, as in this centrifugal molecular distillation, and the decomposition products generate a pungent odor. It is. Based on this, it was discovered that an odorless, light-colored distilled solid fat could be obtained by relying on fist and centrifugal molecular distillation, for which down-flow molecular distillation was inappropriate for the present distillation process.

A heating medium heating method or an electromagnetic induction heating method is appropriate as a heating method to prevent the heating surface from rising above 310C, and in particular, the electromagnetic induction heating method provides good thermal efficiency and temperature control. It turned out to be optimal.

As the final manufacturing step in the present invention, the liquid glyceride from which the solid fat has been distilled off is continuously charged into a centrifugal molecular distillation machine, vacuum degree θ/~30 Torr, thin film temperature = 00~3
0! SC, preparation speed Sθ~750Kg/hr
Molecularly distilled in 7m2, cloud point below 5C, IPA 10%
Above, mainly /7nonine unsaturated copolyunsaturated fatty acid glycerides, yumonoene unsaturated / having DH^7 or more
A light-colored odorless distilled liquid glyceride consisting of polyunsaturated fatty acid glyceride is obtained with a yield of 20 to 20% based on the reaction oil, and a dark-colored and unpleasant odor-free IPA/θ% or more, DH
A highly unsaturated residual oil consisting mainly of polyunsaturated/monoene unsaturated fatty acid glycerides containing more than 3% AI is obtained in a yield of 5 to 20% based on the reaction oil.

What is particularly important in the above production process is the useful lPA contained in the fish oil by carrying out the deodorization and distillation processes under the above-mentioned deodorization and distillation conditions.

It was discovered that DHA can be processed without undergoing chemical changes such as decomposition and oxidation.

The above ester group exchange reaction is carried out by dehydration after alkali purification to give an acid value of aS or less and a water content of 0. ．． Add an alkaline catalyst such as sodium methylate to less than 2% refined oil at 0.0Z to LI and conduct the reaction at 3 to 30C with stirring in an inert gas such as N2 gas until the cloud point of the reaction product reaches The cloud point of refined oil is 7~
/ At the point where C rises to the left, an acid such as phosphoric acid is added as a neutralizing agent in an amount equivalent to neutralizing the alkali to stop the reaction, thus obtaining a transesterified oil. The time required for this reaction varies depending on the type of fish oil and the reaction temperature, but is within the range of 3 to 36 hours.

The production method of the present invention as detailed above consists of (1) producing refined oil by producing acid sugar from fish oil or miscellaneous fish oil in a conventional manner and refining it with an alkali to have an acid value of θS or less and a water content of 0.2% or less; After carrying out the transesterification reaction at S to 30C in an inert gas using a catalyst for 3 to 36 hours, an equivalent amount of acid is added to neutralize it, and then activated clay is added to decolorize and purify it before the reaction. Step of obtaining purified transesterified oil with a temperature higher than the cloud point of the oil by 7 to 25 C; υ) 100 parts of this reaction oil, a non-toxic covalent or trihydric alcohol such as dipropylene glycol or glycerin, and oleyl monoglyceride. A step of continuously deodorizing under the above deodorizing conditions after adding and uniformly mixing 20 parts of each with distilled monoglyceride; (3)
A high-vacuum distillation process in which a fraction mainly consisting of alcohol fatty acid esters and monoglycerides is continuously distilled under the above distillation conditions for this deodorized oil; A process of continuously distilling solid fat under the above distillation conditions using a molecular distillation machine; (8) Finally, the glyceride oil from which the solid fat has been distilled off is further distilled under the above distillation conditions using a centrifugal molecular distillation machine. The combination of step S of continuous distillation to obtain distilled liquid glyceride oil and residual highly unsaturated oil produces highly nutritious distilled edible oil, residual highly unsaturated oil; and cholesterin fatty acid ester, monoglyceride P. It consists of a combination of each process to obtain distilled ester oil mainly composed of.

The standard operating conditions in the present invention are summarized as shown in Table 7.

The distilled solid fat, distilled liquid oil, highly unsaturated residual oil, and distilled alcohol ester oil thus obtained are all produced by the method of the present invention and have no fish oil odor and are odorless or have a slight, non-offensive smell. It has an odor,
Distilled edible fats and distilled edible oils, either as they are or with the addition of natural antioxidants such as vitamin E, can be used as edible and natural foods, and residual highly unsaturated oils and distilled alcohol ester oils can be used as raw materials for pharmaceuticals and cosmetics. It is offered to 70-30 parts each of distilled liquid oil with added natural antioxidants and vegetable oil containing at least 50% linoleic acid! It is clear that the edible oil composition blended in a ratio of 0 to 90 parts is more effective in maintaining the appropriate cholesterol content in the blood than the so-called linole salad oil made from conventional safflower oil and corn oil. became.

The present invention also relates to an edible oil composition obtained by blending the above-mentioned distilled fat, residual highly unsaturated oil, distilled alcohol ester oil, and distilled liquid oil with a linoleic acid-rich vegetable oil.

The distilled solid fat obtained by the production method of the present invention has (1) a lower saturated fatty acid content of 3 parts % or less; Low content of tocosenoic acid with 20 carbon atoms and unsaturated bonds, which is considered to be nutritionally and physiologically undesirable;
(Jl) It is characterized by a low content of cholesterin, which is said to increase blood pressure, less than 0.7%, and is light-colored, almost odorless, and has a melting point of 20 to 4 toc, and is often used for this purpose. It is possible to make 30-35C.

From the above, this distilled solid fat contains almost no cholesterin, and can therefore be used in place of hydrogenated vegetable oil. It has been shown that when saturated fatty acids in edible fats are ingested, they become starting materials for the production of cholesterin and its derivatives in the body, so it is desired that the content of saturated fatty acids in edible fats be as low as possible.

The distilled liquid oil according to the present invention contains (1) no vegetable edible oil at all compared to currently commonly used vegetable edible oils;11. /''11 Contains PA in an amount of 10% or more and DHA in an amount of 7% or more; (To) Since it is a distilled oil, it is a pure glyceride and is a proteolytic product that contains N compounds that cause the reproduction of fish oil odor. It is characterized by the fact that it does not contain any unsaponifiable components, and it is light-colored and odorless, and can be used as an edible oil by adding natural antioxidants such as vitamin E θ/~0.3T. , sunflower oil, safflower oil, etc., which have a high linoleic acid content of 30% or more, preferably 7.!;-g,!
part and main distilled solid fat 10 to SO parts, preferably 75 to SO parts,
If the edible oil obtained by blending 25 parts with 25 parts is used as an edible oil such as salad oil or tempura oil, it will be extremely effective for nutritional health. It can be expected to last longer than using oil.

Since it has hardly undergone oxidation, it is suitable as a raw material for medicinal IPA that is effective for heart diseases, and it is an economical IPA.
It is hoped that a formulation will be produced.

The distilled alcohol ester oil according to the present invention has a high cholesterin content and does not contain impurities, so it can be used as a raw material for cholesterin production because the cholesterin contained in fish oil is concentrated in the form of cholesterin fatty acid ester. This distillate contains most of the monoglyceride added in advance to efficiently distill cholesterin ester, so it contains a large amount of cholesterin fatty acid ester and monoglyceride, and moreover, it contains distilled glyceride as a component. Therefore, it is expected to be useful as an oily base for cosmetics.

Examples of the present invention will be described below.

Example I Acid value λ1.2, saponification value/92, iodine value/g%c, p
.

The sardine oil of //C was used as a raw material and subjected to phosphoric acid purification and alkali purification by conventional methods to obtain purified sardine oil having an acid value θ/S1 and a water content θ/%. 700 parts of this refined oil and sodium methylate) 0. ．． After adding 2 parts of phosphoric acid and carrying out the transesterification reaction in N2 gas at a reaction temperature of θ~22C for 72 hours with stirring, it was confirmed that the cloud point had become 20C. After mixing, 3 parts of activated clay was added to perform decolorization and purification to obtain q3 parts of purified ester group exchange reaction oil.

The properties of this reaction oil are acid value/2, saponification value/12, iodine value/7
7, g:ζ cloud point, 2OC. To 100 parts of this purified transesterified oil were added 3 parts of dipropylene glycol and 1 part of distilled monooleyl glyceride, and the mixture was heated and stirred to 1 loc to obtain a transparent mixed oil.

This mixed oil is continuously charged into a vacuum flow-type thin film deodorizer with an evaporation area of 2m2 and a heat medium heating method, and the temperature of the charged oil is 3g-13c.
, vacuum degree 30”!; !; μTorr, thin film temperature B,
t~7. tc, preparation speed/30 Ky/hr/m
Deodorization was carried out under the conditions of 2, and 31 g of odorous matter and 10θ7 of deodorized material were obtained.
I got the part. Next, this deodorized product was continuously charged into a high vacuum falling-type thin film distillation machine with an evaporation area of 2.12 and a heating medium heating method, and the temperature of the feed oil was /20 to /2 IC, and the degree of vacuum was /j -z2.
0 tt Torr, thin film temperature, 2tio-, iso”
r;:, Preparation speed K/2! f K9/hr/m
Distillation was carried out under the distillation conditions of 2 to obtain 7.7 parts of an almost odorless, pale yellow distillate containing cholesterin fatty acid ester and monoglyceride, and 93.3 parts of residual oil. This residual oil is continuously charged into a heating type centrifugal molecular distillation machine with an evaporation area of /, +2, a feed oil temperature of 200~2/QC, and a degree of vacuum of 7~/.
A single distillation was carried out under the distillation conditions of /μTorr and charging rate //f/hr/m2 to obtain 3 parts of distilled solid fat containing almost no N compounds and consisting mostly of glyceride and 307 parts of residual oil. Furthermore, the residual oil after distilling off the solid fat is continuously charged into a thermal medium heating type centrifugal molecular distillation machine with an evaporation area/m2, and the temperature of the charged oil is 230~no&! ;C, degree of vacuum g-deμTorr,
Thin film temperature θ~21. ! ;C, Preparation speed/10
Kg/hr/m2 (distillation was carried out under DK distillation conditions to obtain 311 parts of a pale yellow odorless liquid oil glyceride as a distillate, and 31 parts of a residue/g.

In order to increase the yield of edible liquid oil and to increase the IPAM degree of residual highly unsaturated oil, the residual oil obtained from liquid oil glyceride distillation was continuously charged into a molecular distillation machine similar to the above, and the temperature of the charged oil was adjusted. , 2g 0~211, tC1 degree of vacuum 7~
g tt' Torr, thin film temperature 27θ~27jtC,
Distillation was carried out under distillation conditions of 10 K9/hr/m2, and the distillate and pale yellow odorless liquid oil glyceride/
A portion of iQ and 7.2 parts of a dark-colored highly unsaturated oil with no unpleasant odor and a slight odor were obtained as a residue.

Each of the distillate oils and residual oils obtained as described above are useful, and their properties are as described in Section 2.

In the examples, the distilled liquid oil is a mixture of 1 part of 31' and 1 part of /i'.

The distilled liquid oil obtained as described above does not become cloudy at room temperature, but becomes cloudy when it is cold.

Example■ The results shown in Table 3 were obtained by performing the same operations as in the previous example.

Example I 30 parts of distilled liquid oil obtained in the previous example and 70 parts of refined sunflower oil
The edible oil prepared by mixing the above is pale color and odorless, has a saturated acid content of 2%, and contains several points of C, o+-+A and IPA of 3% and 3.7%, respectively. The taste is good. If an adult consumes 25 to 30 g of this oil per serving, it is expected that the cholesterin content in the blood will be maintained at an appropriate level and that they will be able to maintain a long life similar to that of people who eat a lot of fish meat.

Claims (1)

[Scope of Claims] (c. Unsaturated oil, especially aquatic animal oil, fish oil, miscellaneous fish oil, or refined oil thereof, is used as a raw material, and a catalyst for transesterification such as sodium alcoholade is added to kernel oil in the presence of an inert gas. After carrying out transesterification reaction and decolorizing and purifying the reaction product as necessary, a non-toxic polyhydric alcohol and distilled monoglyceride are added to the transesterification reaction oil, and a continuous thin film is formed in vacuum at elevated temperature. The deodorized oil is deodorized by distillation, and this deodorized oil is dewaxed if necessary, and the deodorized oil or deodorized dewaxed oil is subjected to a vacuum degree of S ~ 30 μTorr r% and a thin film temperature of 100 to 2 AOC as the first distillation step. The distilled alcohol ester oil containing alcohol esters such as cholesterin fatty acid ester and monoglycerides is removed by continuous thin film distillation of
The solid fat is removed by centrifugal molecular distillation at /~SOμTo r r, thin film temperature/SO~300C, and the liquid glyceride obtained as a residue is subjected to vacuum degree θ/ as the third distillation step. ~30 ttTorr, thin film temperature 200
Pale color odorless distilled liquid oil containing 70% or more of eicosapentaenoic acid, 7% or more of docosahexaenoic acid, and eicosapene, 70% or more of citric acid, docosahexaenoic acid, characterized by a combination of various steps subjected to molecular distillation at ~300C. acid 7
A method for producing a highly unsaturated oil composition, which obtains a residual oil having a content of 2% or more and having no unpleasant odor. (2) Add an alkaline catalyst such as 0.02 to 65% sodium alcolade to fish oil or miscellaneous fish oil or refined oil thereof with a water content of 0.02% or less and a water content of less than 0. After carrying out the transesterification reaction for 3 to 36 hours while stirring at 5 to 30 C, an equivalent amount of a neutralizing agent such as phosphoric acid is added to stop the reaction, and then activated clay is added to the reaction product to perform decolorization, dehydration, and purification. 7 from the cloud point of the refined refined oil
Obtain a refined transesterified oil with a cloud point of 7 to 4L2C or higher; Add a non-toxic dihydric or trihydric alcohol such as dipropylene glycol or glycerin to this transesterified oil and distillate such as oleyl monoglyceride. Add monoglycerides to the reaction oil at a ratio of ~20%, mix and make uniform, then continuously charge into a vacuum flow type or centrifugal thin film deodorizer, vacuum degree 10 to 100μ TOrrs, thin film temperature 30 to 100R, and charge. Speed 50-730'j/
Deodorization was performed under the conditions of hr/m2 to obtain a deodorized oil of 90 to 9 g% based on the charged ester group exchange reaction oil (hereinafter referred to as reaction oil); then, this deodorized oil was dewaxed by a conventional method. The obtained dewaxed product or undewaxed product is continuously charged into a high vacuum flowing down type or centrifugal thin film distillation machine, and the vacuum degree is S~3.
Distillation is carried out under the conditions of 0 μ Torrs thin film temperature 100-2 OC 1 feeding rate SO ~ 130 Kq/hr/m2, and a light-colored distilled alcohol ester oil containing cholesteryl fatty acid esters, monoglycerides, etc. is reacted. 12 to 1 for oil
Obtained with a yield of 0%; the pure glyceride from which the alcohol ester oils have been distilled off is charged into a centrifugal molecular distillation machine as a second distillation step and the degree of vacuum is 0%. /~SOμTOrr% thin film temperature/SO~300
Distillation is carried out under the conditions of a charging rate Sθ~/left 0'f/hr/m2, and a distilled solid fat with a melting point of 20-1 IOC, light color and odorless, and a saturated content of 33% or less is added to the reaction oil at a rate of 35-20%. Obtained with a yield of 5%; Furthermore, the liquid glyceride from which the solid fat was distilled off was charged into a centrifugal molecular distillation machine and the vacuum degree was 0. /~30μTorr, thin film temperature θ0~300C, preparation speed 50~/50
Distillation was carried out under the conditions of Ky/hr/m2, and the cloud point was 2. tC
Hereinafter, a light-colored odorless distilled liquid oil containing 10% or more of eicosapentaenoic acid and 7% or more of docosahexaenoic acid will be produced at a yield of 20 to 10% based on the reaction oil, and the residual oil will be dark-colored and odorless eicosa 4. The claimed invention consists of a combination of the above steps to obtain a highly unsaturated oil containing 70% or more of tantaenoic acid and 3% or more of docosahexaenoic acid with a yield of 5-20% based on the reaction oil. A method for producing a highly unsaturated oil composition according to scope 1. (3) Highly unsaturated oil composition obtained by the method according to claim 1 or 2, i.e. eicosapentaenoic acid 1
50 parts of edible vegetable oil such as corn oil, sunflower oil, safflower oil containing 50% or more of linoleic acid in 10 to 50 parts of distilled liquid oil containing 0.0% or more of docosahexaenoic acid and 7% or more of docosahexaenoic acid.
A highly unsaturated oil-containing edible oil composition, characterized in that it contains 90 parts of a highly unsaturated oil.