JPH0516478B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to highly unsaturated group-containing oil products (highly unsaturated oils) or highly unsaturated oil composition products obtained by deodorizing aquatic animal oils, especially fish oils that normally have an unpleasant odor, and methods for preparing the same. It also relates to highly unsaturated oil-blended compositions obtained by blending this with other oil products, such as vegetable oils or analogs thereof, or other substances.
More specifically, the present invention involves transesterification of fish oil and small fish oil, continuous vacuum deodorization, high vacuum continuous distillation,
Distilled edible fats and oils, distilled alcohol ester oils, which are obtained by applying specific reaction conditions, deodorization conditions, and distillation conditions through a combination of continuous centrifugal molecular distillation processes, respectively.
It concerns highly unsaturated oils as residual oils and their production methods. Sardine oil, mackerel oil, which are extracted as commercial products,
Fish oil such as saury oil, pollock cod liver oil, and small fish oil such as squid oil include land animal fats such as lard, beef tallow, and vegetable oils such as soybean oil, cottonseed oil, corn oil, sunflower oil, safflower oil, and coconut oil. Compared to industrially produced land-produced oils and fats, such as terrestrial oils and fats, there is a so-called fish oil odor that is unpleasant to humans, and the above land-produced resins contain 5 and 6 unsaturated double bonds. Its distinguishing feature is that it contains highly unsaturated acids with 20 and 22 carbon atoms. Because of these properties, industrial use of fish oil and miscellaneous fish oil requires deacidification, decolorization, and purification, followed by hydrogenation to eliminate the fish oil odor, and then removing the hydrogenated oil odor as a special odor. Its use is limited to margarine and shot toning, and only a small portion is used as raw material for lower grade paints, and a portion is converted into hydrogenated oil and then selected and used as raw material for selected soaps. The present invention is based on the above-mentioned fish oil containing 20 carbon atoms.
KE, Intake of appropriate amounts of eicosapentaenoic acid (hereinafter referred to as EPA), which has 5 unsaturated double bonds, and docosahexaenoic acid (hereinafter referred to as DHA), which has 22 carbon atoms and 6 unsaturated double bonds, will increase the blood concentration. It is said that fish meat containing polyunsaturated acids such as these is suitable for controlling the cholesterol content and is effective in preventing thrombotic disorders, and has been recognized to be effective in preventing and treating heart diseases due to the effects of these. Focusing on reports that the intake of a large amount of meat can reduce heart disease and extend lifespan in people who regularly eat foods whose main protein source is animal meat, which does not consume much fish meat, the following Valuable edible fats, edible oils, distilled alcohol ester oils and highly unsaturated oils can be obtained by processing fish oils and miscellaneous fish oils by the newly discovered inventive method detailed in . The object of the present invention is to provide an edible oil composition that is effective in treating heart disease caused by thrombosis and extending life when combined with a sterile edible oil. The details of the present invention will be described below. It has been reported that it is possible to remove the so-called fish oil odor characteristic of fish oil by vacuum steam distillation or vacuum thin film distillation, but these methods only enable temporary deodorization. Immediately after deodorizing treatment, the fish oil odor returns, or the deodorized product becomes edible and has properties that make it unsuitable for other uses. 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 amines which are oxygen decomposition products of proteins, lower ketones which are oxidation products of highly unsaturated acids, lower aldehydes, lower acids, and these amines, aldehydes, and ketones. It became clear that the main reaction products were the reaction products with In order to increase the value of the distilled glyceride, 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 various purification procedures described above, the odor removal is still insufficient and the fish oil odor remains. In order to completely remove these substances, 100 parts of the above-mentioned purified transesterified oil was subjected to the deodorizing temperature conditions of the present invention of 30 to 100°C and a vapor pressure of 100 parts by the method newly discovered in the present invention.
0.03 to 0.1 Torr and non-toxic dipropylene glycol or glycerin, which has good affinity with the above-mentioned odorous components, and is compatible with this dihydric or trihydric alcohol. Moreover, 1 to 20 parts of each of cholesteri and cholesterin fatty acid ester and a monoglyceride having a similar distillation temperature, such as distilled monooleyl glyceride, distilled soybean oil monoglyceride, or distilled coconut oil monoglyceride, are added and stirred at room temperature or at a temperature below 50°C. Mix to get a clear mixed oil. In this case, the oil is continuously charged into a falling-type or centrifugal thin film vacuum deodorizer while fully degassing, and deodorized at a vacuum degree of 10 to 100μTorr, a thin film temperature of 30 to 100℃, and a charging rate of 50 to 150Kg/hr/ ^m2 . Distillation is carried out in a short time and economically under the conditions, and without deteriorating highly unsaturated acids such as eicosapentaenoic acid and docosahexaenoic acid, to produce an almost odorless purified deodorized product with no fish oil odor.
% yield. This deodorization is an extremely important operational part in the present invention. Monoglycerides of dihydric or trihydric alcohols are simultaneously added to the above-mentioned reaction oil, and after completely mixing and dissolving, continuous thin film deodorization is performed under vacuum. This is based on the fact discovered by the present inventor that by carrying out this process, odorous substances can be distilled off together with the added dihydric 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 off the deodorized oil, this deodorized oil is continuously charged into a high-vacuum falling film type or centrifugal thin film distillation machine, with a vacuum degree of 5 to 30 μTorr, a thin film temperature of 100 to 260°C, and a charging rate of 50 to 150 kg/hr/hr. Distillation is carried out under distillation conditions of ² m2, and a light-colored, unpleasant-odor-free distillate containing monoglycerides, alcohol esters such as cholesterin fatty acid ester, low molecular weight glycerides, and a trace amount of odorous components is obtained from the reaction oil. Obtain ~20% yield. By carrying out the above process, most of the cholesterin and cholesterin fatty acid esters contained in fish oil are distilled out together with the added monoglyceride, which has a similar distillation temperature, and a very small amount of odor is removed. The substance is completely removed by this distillation,
The return of fish oil odor is eliminated, and this is based on a fact discovered by the present inventor. The continuous deodorizing machine and distillation machine mentioned above have an economical feeding rate of 50 to 50 ml per hour.
2000 kg is appropriate, and as a thin film surface heating device, steam heating is economical and appropriate for a deodorizing machine, and heating medium heating or electromagnetic induction heating is suitable for a distilling machine. 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 level is
Molecular distillation is performed under the conditions of 0.1 to 50μTorr, thin film temperature of 150 to 300℃, and feeding rate of 50 to 150Kg/hr/ ^m2 to obtain a total saturated fatty acid glyceride with a melting point of 20 to 40℃ and a saturated fatty acid content of 35% or less, 2 saturated 1 A pale yellow, odorless distilled solid fat containing mainly monoene unsaturated fatty acid glycerides, 1 saturated 2 monoene unsaturated fatty acid glycerides, 1 saturated 1 monoene unsaturated, and 1 polyunsaturated glycerides was added in an amount of 35 to 65% based on the reaction oil. Obtained in yield. A particularly important point in this molecular distillation is not to raise the temperature of the thin film heating element above 300℃. Highly unsaturated acids undergo thermal decomposition, albeit in a small amount, even if the residence time on the heated surface is extremely short, 1 second or less, as in the present centrifugal molecular distillation, and an irritating odor is produced by the decomposed products. As a result, we discovered that flowing-down molecular distillation is inappropriate for this distillation process, and that odorless, light-colored distilled solid fat can only be obtained by centrifugal molecular distillation. In order to prevent the heating surface from rising above 310°C as mentioned above, a thermal medium heating method or an electromagnetic induction heating method is appropriate as a heating method.In particular, the electromagnetic induction heating method has good thermal efficiency and temperature control. It became clear that this was the best option. As the final manufacturing process of the present invention, the liquid glyceride from which the solid fat has been distilled off is continuously charged into a centrifugal molecular distillation machine, at a vacuum degree of 0.1 to 30μTorr, a thin film temperature of 200 to 305℃, and a charging rate of 50 to 150Kg/ hr/ ^m2
Perform molecular distillation with cloud point below 25℃, EPA above 10%,
Pale color odorless distilled liquid glyceride consisting mainly of 1-monoene unsaturated 2-polyunsaturated fatty acid glyceride and 2-monoene unsaturated 1-polyunsaturated fatty acid glyceride containing 7% or more of DHA is added to the reaction oil at 20 to 20% of the reaction oil.
Obtained with 60% yield, dark color and no unpleasant odor
Add a highly unsaturated residual oil consisting mainly of mono-mono-unsaturated di-polyunsaturated fatty acid glycerides containing 10% or more of EPA and 13% or more of DHA to the reaction oil.
Obtained in ~20% yield. What is particularly important in the above production process is that by performing the deodorization and distillation processes under the above-mentioned deodorization and distillation conditions, the useful substances contained in the fish oil can be removed.
It was discovered that EPA and DHA can be processed without undergoing chemical changes such as decomposition and oxidation. The above transesterification reaction is carried out by applying an alkali catalyst such as sodium methylate to purified oil that is dehydrated after alkali purification and has an acid value of 0.5 or less and a water content of 0.2% or less.
0.5% and react at 5 to 30°C with stirring in an inert gas such as _N2 gas, and when the quantitative point of the reactant rises 7 to 15°C above the cloud point of the refined oil, remove the neutralizing agent. The reaction is stopped by adding an acid such as phosphoric acid in an amount equivalent to neutralizing the alkali, thus obtaining a transesterified oil. The time required for this reaction varies depending on the type of fish oil and 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) using an alkali catalyst to obtain refined oil by acid refining fish oil or miscellaneous fish oil in a conventional manner and alkali refining to obtain an acid value of 0.5 or less and a water content of 0.2% or less; After carrying out an ester group exchange reaction at 5 to 30°C in an inert gas for 3 to 36 hours, an equivalent amount of acid is added to neutralize, and activated clay is then added to decolorize and purify the refined oil before the reaction. Step of obtaining purified transesterified reaction oil whose cloud point is 7 to 25 degrees Celsius; (2) Distillation of 100 parts of this reaction oil, a non-toxic dihydric or trihydric alcohol such as dipropylene glycol or glycerin, and oleyl monoglyceride. A step of continuously deodorizing the deodorized oil under the above deodorizing conditions after adding 1 to 20 parts of each monoglyceride and uniformly mixing; (3) Continuously deodorizing the deodorized oil under the above distillation conditions. , a high-vacuum distillation process that distills a fraction mainly consisting of monoglycerides; (4) The pure glyceride obtained by distilling off the alcohol esters is continuously distilled under the above distillation conditions using a centrifugal molecular distillation machine. (5) Finally, the glyceride oil from which the solid fat has been distilled off is further distilled continuously under the above distillation conditions using a centrifugal molecular distillation machine to obtain distilled liquid glyceride oil and residual high It consists of a combination of five steps to obtain a highly nutritious distilled edible oil, residual highly unsaturated oil, and a distilled ester oil mainly consisting of cholesterin fatty acid ester and monoglyceride. The standard operating conditions in the present invention are summarized as shown in Table 1.

[Table] The distilled solid fat, distilled liquid oil, highly unsaturated residual oil, and distilled alcohol ester oil obtained in this way are all produced by the method of the present invention and have no fish oil odor, and have no oil odor or odor. Distilled edible fats and distilled edible oils have a slight odor that is not unpleasant, and can be used as such or with the addition of natural antioxidants such as vitamin E. Ester oil is used as a raw material for pharmaceuticals and cosmetics. The edible oil composition contains 10 to 50 parts and 50 to 90 parts of distilled liquid oil with added natural antioxidants and vegetable oil containing 50% or more linoleic acid, respectively, and is made from conventional safflower oil and corn oil. It has become clear that the so-called linole salad oil is more effective in maintaining an appropriate level of cholesterol in the blood. The present invention provides the above-mentioned distilled fats and oils, residual highly unsaturated oils,
The present invention also relates to an edible oil composition obtained by blending a distilled alcohol ester oil or a distilled liquid oil with a linoleic acid-rich vegetable oil. The distilled solid fat obtained by the production method of the present invention has a lower saturated fatty acid content than fish oil, and a lower saturated fatty acid content than the edible hydrogenated oil produced as a raw material for margarine.
(2) The content of docosenoic acid, which has 20 carbon atoms and 1 unsaturated bond, which is considered to be nutritionally and physiologically unfavorable; (3) It is said to increase blood pressure. It is characterized by having a low cholesterin content of 0.1% or less, and can be made with a light color, almost odorless, and a melting point of 20 to 40°C, compared to the 30 to 35°C cholesterin that is often used for this purpose. You can make it. From the above, this distilled solid fat contains almost no cholesterin, and can therefore be used in place of hydrogenated vegetable oil. It is known 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) 10% or more EPA and 7% or more DHA, which are not contained in vegetable edible oils at all, compared to vegetable edible oils currently in general use; (2) Since it is a distilled oil, it is pure glyceride and contains protein degradation products such as lower aldehydes, lower ketones, and N, which are responsible for reproducing the fish oil odor.
Corn oil is characterized by the fact that it does not contain any unsaponifiable components such as chemical compounds, and is light in color and odorless, and can be used as an edible oil by adding 0.1 to 0.3% of natural antioxidants such as vitamin E. , himalary oil,
Linoleic acid content such as safflower oil and sesame oil
Edible products obtained by blending 50 to 90 parts, preferably 75 to 85 parts, of a vegetable oil containing high linoleic acid content of 50% or more or a mixture thereof with 10 to 50 parts, preferably 15 to 25 parts of this distilled edible oil. If the oil is used as an edible oil such as salad oil or tempura oil, it is extremely effective for nutrition and health, and if used regularly at a rate of 25 to 30 g per day, it can be expected to last longer than using ordinary vegetable edible oil. The residual highly unsaturated oil according to the present invention contains 10% or more of EPA and 13% or more of DHA, and can be thermally polymerized.
Since it has undergone almost no oxidation, it is suitable as a raw material for pharmaceutical EPA that is effective for heart diseases, and it is expected that EPA preparations can be made more economically. 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 a large amount of cholesterin fatty acid ester and monoglyceride, which is useful and contains most of the monoglyceride added in advance in order to efficiently distill cholesterin ester.
Moreover, since it contains distilled glyceride as a component, it is expected to be effective as an oily base for cosmetics. Examples of the present invention will be described below. Example Using sardine oil as a raw material with an acid value of 2.2, a saponification value of 192, an iodine value of 178, and a cp of 11°C, purified sardine oil with an acid value of 0.15 and a water content of 0.1% was obtained after performing phosphoric acid purification and alkali purification by conventional methods. Add 0.2 parts of sodium methylate to 100 parts of this refined oil and add N ₂ at a reaction temperature of 20 to 22°C.
The transesterification reaction was carried out in gas for 12 hours with stirring, and it was confirmed that the cloud point had reached 20°C. After neutralization by adding an equivalent amount of phosphoric acid, 3 parts of activated clay was added for decolorization and purification. Refined ester group exchange reaction oil 95
I got the department. The properties of this reaction oil are acid value 1.2, saponification value 192, and iodine value.
The temperature was 177.8, and the cloud point was 20°C. 3 parts of dipropylene glycol and 2 parts of distilled monorail glyceride were added to 100 parts of this purified transesterified oil and heated to 40°C.
The mixture was heated and stirred to obtain a transparent mixed oil. This mixed oil is continuously charged into a vacuum falling thin film deodorizer with an evaporation area of ^{2m2 and} a thermal contact heating method.The feed oil temperature is 38 to 43℃, the degree of vacuum is 50 to 55μTorr, the thin film temperature is 65 to 75℃, and the preparation speed is
Deodorization was performed under the conditions of 130 Kg/hr/m ² to obtain 3.8 parts of odorous matter and 100.7 parts of deodorized material. Next, this deodorized product was continuously charged into a high vacuum falling film distillation machine with an evaporation area of 2 m ² and a heating medium heating method, with a feeding oil temperature of 120 to 125°C, a degree of vacuum of 15 to 20 μTorr, a thin film temperature of 240 to 250°C, and a feeding rate of 125 kg. Distillation was carried out under distillation conditions of /hr/m ² to produce 7.1 parts of an almost odorless, pale yellow distillate containing cholesterin fatty acid esters and monoglycerides, and residual oil.
93.3 copies were obtained. This residual oil was continuously charged into a heated centrifugal molecular distillation machine with an evaporation area of 1 m ² and distilled under the following distillation conditions: oil temperature 200 to 210°C, degree of vacuum 9 to 11 μTorr, and feeding rate 116 kg/hr/m ² . 43 parts of distilled solid fat consisting mostly of glycerides and residual oil containing no lower aldehydes, lower ketones, or N compounds
50.1 copies were obtained. Furthermore, the residual oil from which the solid fat has been distilled off is continuously charged into a heating medium heating type centrifugal molecular distillation machine with an evaporation area of 1 m ² , and the charged oil temperature is 230 to 235°C, the degree of vacuum is 8 to 9 μTorr, and the thin film temperature is 260 to 265°C. Distillation was carried out at a feed rate of 110 Kg/hr/m ² to obtain 31.4 parts of a pale yellow odorless liquid oil glyceride as a distillate and 18.6 parts of a residue. In order to increase the yield of edible liquid oil and increase the EPA concentration 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. 240-245
℃, vacuum level 7~8μTorr, thin film temperature 270~275℃,
Distillation was carried out under distillation conditions at a charging rate of 110 Kg/hr/ ^m2 , and the distillate and pale yellow odorless liquid oil glyceride were extracted.
There were obtained 11.4 parts and 7.2 parts of a dark-colored highly unsaturated oil with no unpleasant odor and a slight odor as a residue. The distillate oils and residual oils obtained as described above are all useful, and their properties are shown in Table 2.

【table】

[Table] Note that the distilled liquid oil in the examples is a mixture of 31.4 parts of distilled liquid oil and 11.4 parts of distilled liquid oil. 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 operating in the same manner as in the previous example.

[Table] Reference example The edible oil prepared by mixing 30 parts of the distilled liquid oil obtained in the previous example and 70 parts of refined sunflower oil is light-colored and odorless, has a saturated acid content of 12%, a cloud point of ~11°C, and a low content of DHA and EPA. The content is 4.3% and 3.1%, respectively, and the taste is good. Adults consume 25-30g of this oil at a time.
It is expected that if ingested, the cholesterin content in the blood will be maintained at an appropriate level, allowing people to live as long as people who eat a lot of fish. Reference example 10 parts of distilled liquid oil obtained in the previous example and refined corn oil
The edible oil prepared by mixing 70 parts of deodorized purified sesame oil with 20 parts of deodorized refined sesame oil is light-colored and odorless, has a saturated acid content of 14%, and a cloud point of -8.
℃The content of DHA and EPA is 1.6% and 1.6%, respectively.
At 1.4%, the taste is good and the oxidation stability is 40℃.
In an oven test, the stability of flavor and POV increase rate after 3 weeks was similar to that of commercially available edible salad oil, and this modified oil can be used not only as salad oil, but also as frying oil and when heated. Practical tests have shown that it can be used equally well without emitting unpleasant odors.

Claims (1)

[Claims] 1. An unsaturated oil consisting of at least one of aquatic animal oil, fish oil, miscellaneous fish oil, or their refined oil is used as a raw material, and an ester group is added to the oil using an alkali catalyst in the presence of an inert gas. After carrying out the exchange reaction and decolorizing and purifying the reaction product if necessary, non-toxic polyhydric alcohol and higher fatty acid monoglyceride are added to the transesterified oil and continuous thin film distillation is carried out in vacuum at elevated temperature. The deodorized residual oil is subjected to continuous thin film distillation at a vacuum degree of 5 to 30 μTorr and a film temperature of 100 to 260°C as the first distillation step to obtain cholesterin fatty acid esters. The distilled alcohol ester oil containing alcohol esters and monoglycerides is removed, and the pure glyceride residue is distilled into a second distillation process at a vacuum level of 0.1 to 50 μTorr and a thin film temperature of 150 to 100 μTorr.
The solid fat is removed by centrifugal molecular distillation at 300℃, and the liquid glyceride obtained as a residue is subjected to a third distillation process at a vacuum degree of 0.1 to 3.0 μTorr and a thin film temperature of 200 to 300℃. A light-colored, odorless distilled liquid oil containing at least 10% eicosapentaenoic acid and 7% docosaxaenoic acid after molecular distillation at A method for producing a highly unsaturated oil composition, characterized by obtaining an oil.