KR20070002910A - Edible oil containing high content of tocopherol produced by using super critical fluid from pre-treated crude materials and process for production thereof - Google Patents

Abstract

A method of producing edible fats and oils with a high content of tocopherol from raw material for edible fats and oils by using supercritical carbon dioxide and ethanol are provided to remarkably increase the tocopherol content and to reduce the bitter taste of edible oil while enhancing the flavor as compared with conventional manufacturing methods. Raw material for edible fats and oils is pretreated, introduced into an extractor and extracted in the extractor containing 90 to 95% by weight of supercritical carbon dioxide and 5 to 10% by weight of ethanol at 35 to 80deg.C and 100 to 900bar. Then the supercritical carbon dioxide is separated from the edible oil mixture in a vacuum separator to give separated edible fats and oils and recycled after pressurization with a pump. The pretreatment process contains any one process selected from the group consisting of ultraviolet irradiation, heat treatment, drying, peeling, grinding and far-infrared irradiation. The edible fats and oils are any one separated from the group consisting of sesame oil, perilla oil, rape oil, rice bran oil, safflower oil, sunflower oil, cotton seed oil, peanut oil, olive oil, palm oil, coconut oil and red pepper seed oil.

Description

Edible oil containing high content of tocopherol produced by using super critical fluid from pre-treated crude materials and process for production according to edible oils prepared from edible fats and oils preprocessed using supercritical fluids

1 is a schematic diagram showing a process for producing an edible fat containing a large amount of tocopherol from a maintenance material using supercritical carbon dioxide.

2 is a graph depicting HPLC analysis chromatograph of tocopherol.

<Description of the symbols for the main parts of the drawings>

1: extractor 2: heat exchanger

3, 4: pump 5: co-solvent storage tank

6: carbon dioxide storage tank 7: co-solvent separator

8: pressure reducer 9: pressure reducing valve

10, 11 discharge valve 12, 13 supply valve

The present invention relates to a tocopherol-containing edible fat prepared from edible fats and oils pretreated using a supercritical fluid, and more particularly, to tocopherols from edible fats and fats pretreated using supercritical carbon dioxide. The present invention relates to a method for mass-producing edible oils containing as much as possible and improved flavor and tocopherol-containing edible oils produced by the method.

According to the definition of the Food Code, edible oils and fats are soybean oil, corn oil, rapeseed oil, rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil manufactured and processed from raw milk obtained from a vegetable (including crushed powder) or animal containing fat or oil. Cotton seed oil, peanut oil, olive oil, palm oil, palm oil, mixed cooking oil, refined common oil, shortening, margarine, red pepper seed oil, other edible oils and fats (excluding cod liver oil). Edible oils and fats are generally a general term for edible oil (liquid at room temperature) and fat (solid at room temperature). Vegetable edible oil is generally called edible oil. Edible oils and fats are applied to bread (butter, margarine) and dressing (vegetable oil) in addition to cooking such as tempura (vegetable oil, lard, shortening), stir-fry (various oils).

Edible oils and fats are classified into vegetable oils and animal oils according to raw materials. Processed fats and oils made from new fats and oils are called processed fats (margarine, shortening, powder fat, etc.). Vegetable oil is divided into fried oil and salad oil according to the degree of refinement, and may be divided into two kinds of refined oil and salad oil, depending on the type such as safflower and corn. Refined oil is usually refined edible oil one more time, salad oil does not harden to oil state for a certain period of time in cold test, and there are prescribed standards such as acid value and color tone in each type and stage.

Vegetable oils are classified according to the drying rate, which is one of chemical characteristics, from fast drying to dry oils (those having an iodine value of 130 or higher; linseed oil, safflower oil, safflower oil, etc.), semi-dry oils (from iodine value of 130 to 100; cottonseed oil, rapeseed oil, soybean oil, rice bran oil, sesame oil, etc., and undried oil (with iodine value of 100 or less; peanut oil, olive oil, camellia oil, etc.). Among vegetable fats and oils, solids at room temperature are classified as solid fats (palm oil, palm oil, cacao fat, etc.). The vegetable oil has a taste that has its own characteristics depending on the raw materials. Sesame oil is squeezed from sesame seeds. It has a strong aroma and tastes good. It contains a lot of antioxidants called sesamoline and vitamin E (tocopherol). When cooking, no tablets are added to add aroma, leaving a distinctive taste and color tone. Soybean oil is derived from soybeans, also known as soybean oil. It is a raw material of salad oil, fried oil and margarine. There are many other varieties, including peanut oil, corn oil, corn oil, rice bran oil, sunflower oil, and safflower oil. Fried oil is made by mixing two or three vegetable edible oils to taste good when fried. Animal edible oils include refined lard, butter and liver oil. In addition, fish oil, light oil (whale oil), and general vegetable fats and oils are hydrogenated hydrogenated oils, and are used as raw materials for processed fats such as shortening and margarine.

The main component of edible oils and fats is fat. Many fats consist of glycerin and fatty acids and are characterized by these fatty acids. In general, vegetable fats and oils contain many unsaturated fatty acids (including double-bonded carbon), and animal fats and oils contain many saturated fatty acids. But fish oil is high in unsaturated fatty acids. Fats and oils vary depending on the nature and amount of these fatty acids.

Edible oils and fats are used as energy sources in the body. It has about twice as much energy as protein or carbohydrates. As nutrients, essential fatty acids (linoleic acid, linolenic acid, arachidonic acid, etc.) and vitamin E are supplied and mainly contained in vegetable oils and fats. Animal fats, on the other hand, contain cholesterol and saturated fatty acids, and excessive intake causes arteriosclerosis and hypercholesterolemia. Although fat is nutritionally important, increasing fat intake, especially animal fat intake, is a problem these days. It is important to take the right amount in balance without biasing the animal. Linoleic acid is attracting attention in order to prevent and improve arteriosclerosis and hypercholesterolemia, a major cause of adult disease. For this reason, sesame oil, rice bran oil, safflower oil, etc., are particularly treated as health foods high in linoleic acid. Recently, eicosapentaenoic acid (EPA), an unsaturated fatty acid contained in fish oil, is known to prevent blood clots and improve hyperlipidemia. This is why blue fish such as sardines, mackerel, horse mackerel, and saury are among the healthy foods. Fish oils are naturally rich in unsaturated fatty acids, and because of the action of EPA, are treated like nutritious vegetable oils and fats, including linoleic acid.

Sesame is a perennial herbaceous plant ( Sesamun indicum) belonging to Sesamum in the Pedaliaceae . Seeds are used as food. Sesame seeds have been recognized as a valuable flow food (유량 食品), especially among the flow plant (品 食品), which is not known for some time, but is known as a healthy food with a variety of medicinal effects. In the 3rd century BC, China's intentional book, "Nongxunbyeon," sesame seeds are a food that restores the function of the kidneys to vitalize the body. It is written to make good.

Tocopherol is the main bioactive substance present in sesame seeds. In particular, tocopherol not only has vitality as vitamin E, but also has an antioxidant effect. The biochemical function of tocopherol as vitamin E is known to be anti-cancer effect, immune enhancing effect, thrombosis and inflammatory response control effect, and affects nucleic acid and protein fat metabolism. Above all, tocopherol's biggest function is to protect damaged cells caused by free radicals and peroxides as antioxidants in biological membranes. Free radicals or free radicals generated during metabolic processes in vivo decrease and decrease the function of living organisms. Since the theory that oxidative stress caused by free radicals is the cause of aging, cancer, arteriosclerosis, and diabetes is recognized, it is possible to suppress oxidative stress such as free radicals and free radicals for a long time, that is, a bioactive substance having an antioxidant function Much attention has been paid to. There is also research showing that the antioxidant effects of tocopherols synergize with sesamol present in sesame seeds (H. Yoshida and S. Takagi, Journal of the Science of Food and Agriculture , vol 79, 220--226, 1999). .

Perilla is a perennial plant of the moss family of nectar and is native to Southeast Asia, about 1m tall, with long hairs, squares, straight branches, and has a peculiar smell. The leaves are opposite each other, broad oval-shaped, pointed at the end, rounded at the bottom, and have dull teeth at the edges. The flowers are inflorescences, many white and small lips bloom. Fruits are four small branches perched under calyx, almost ball-shaped, with smooth net surface. It is divided into several species according to the morphological characteristics of the fruit. In Korea, almost brown berries are grown. Seeds are roasted with sesame salt or with oil. Other uses include paints, varnishes, linoleum, printing inks, pomades and soaps. It is widely distributed in Korea, China, India, and Japan.

Perilla helps heal viral bronchitis, stomach ulcers, and colds. In addition, it contains a lot of vitamin E, which helps to improve fertility, vision recovery, prostate treatment, hair loss control, gout prevention, gallstone dissolution. Perilla has a coughing effect and is known to quench thirst and strengthen the cranial nerves. In addition, there is a function to clear the hair was used by the ancient scholars.

Tocopherol, a mouse's anti-fertility factor, means 'bearing children' in Greek. Tocopherol is contained in vegetable oils such as soybean oil, rapeseed oil, sesame oil, perilla oil, cottonseed oil, and palm oil. It is a vitamin that is insoluble in water and nontoxic. Tocopherol is a representative antioxidant that exists in nature. This is because eight homologues are present in nature, but a large amount of α, β, γ, and δ homologues are present in normal vegetable fats and oils (see Table 1).

Tocopherol content in edible oil and fat (unit: mg / 100g) Edible oils and fats α-tocopherol β-tocopherol γ-tocopherol δ-tocopherol Sum Soybean oil 7.19 1.24 59.16 18.84 86.43 Cottonseed oil 28.32 0.32 27.13 0.42 56.19 Corn oil 17.08 0.75 59.95 2.53 80.31 Rapeseed oil 15.21 0.32 37.78 1.01 48.33 Sunflower seed oil 38.66 0.84 1.98 0.36 41.84 Rice Bran Oil 25.54 1.52 3.43 0.36 30.85 Safflower oil 27.10 0.58 2.34 0.30 30.32 palm oil 8.58 0.40 1.26 0.19 10.43 Sesame oil 0.36 Tr. 43.36 0.66 44.68

In the conventional manufacturing method of edible oils and fats, the organic solvent extraction method is mainly used when the oil content is about 20% based on the oil content in the raw material, and when it contains more than that, the compression method is mainly used. Therefore, the sesame oil content is 51.9% and the olive fruit contains about 25% of the oil, so extraction by pressing is carried out a lot, while soybean and safflower contain about 20% and 1519.0% of lipid, respectively. I use it. However, this conventional crimping production method includes several problems. First, all the components present in the raw material cannot be extracted evenly and evenly through physical crimping, so that the yield is not high. Second, in the pretreatment process, Third, the intrinsic scent of raw materials is increased and disappeared. Third, the extraction content of the main bioactive substances other than oils and fats is low, and it is destroyed and deteriorated by high heat. Chemical extraction using organic solvents would also be desirable as a method of producing edible fats and oils in high yields, but the use of organic solvents causes environmental problems, and in particular, large negative consumer reactions to the use of organic solvents in food manufacturing are expected. There is a problem.

Therefore, the present inventors have developed a method for producing edible oils with improved flavor in a high yield in the state of high content of tocopherol, which is an effective physiologically active substance contained in the raw materials, without using organic solvents directly, to complete the present invention. Reached.

It is an object of the present invention to provide a method for producing edible oil containing a large amount of tocopherol from a raw material pretreated using supercritical carbon dioxide in high yield.

An object of the present invention is to optimize the optimum temperature, the optimum pressure, the concentration of the co-solvent in the production and extraction of tocopherol-containing edible oil by using supercritical carbon dioxide and using ethanol as a co-solvent from the pretreated raw material This was achieved by evaluating the properties of the resulting edible oils and fats.

Specific technical configuration of the present invention comprises the steps of pre-processing edible fat and oil raw material; Filling the extractor with pretreated raw material; Extracting edible oil and fat by adding supercritical carbon dioxide to an extractor filled with raw materials; Decompressing the supercritical carbon dioxide and the edible fat and oil mixture in a decompressor to separate them; Recirculating by pressurizing the supercritical carbon dioxide separated in the step with a pump.

As a raw material to which the edible oil and fat extraction method of the present invention can be applied, any raw material capable of extracting edible fat and oil known in the art may be used. Specific examples of edible oil which can be produced by applying the method of the present invention include sesame oil, perilla oil, soybean oil, corn oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil, red pepper seed oil, and the like. There is this.

However, except for the case of sesame oil and perilla oil, a purification process may be further performed in order to meet the food standards after the extraction process using the supercritical carbon dioxide of the present invention. Purifying the edible oil and fat may be carried out according to the general method in the art as follows.

The degumming process is a purification step to remove phospholipids, viscous substances, carbohydrates, proteins, pigments and trace metals and the like to increase the stability of the oil and improve the color improvement yield. After heating the edible oil to 70 ℃ usually for 7 minutes with the addition of 0.15% of 95% phosphoric acid, and then reacted for 3 minutes with the addition of 1% purified water and centrifugation to separate the gums can be prepared degum oil.

The deoxidation or alkali purification process is a purification step to remove free fatty acids and remove pigments, phospholipids, trace metals, and oxidation products. Usually, edible oil is heated to 70 ~ 80 ℃, NaOH is added as a neutralizing agent, reacted for 1 minute while mixing with a high speed mixer, and centrifuged to remove foots (precipitated by adsorbing impurities such as pigments with soap). The edible oil thus obtained is washed with hot water, washed with water and dried under reduced pressure to obtain deoxidized oil.

Decolorization is a purification step to remove pigments, trace metals, and oxidation products (peroxides). Usually, edible oils and fats are heated to 105-110 ° C., followed by reaction for 20 minutes by adding 2 to 3% of clay, activated carbon, etc. as a bleaching agent, and filtering at 50-80 ° C. to remove the bleaching oil. Xanthophyll and chlorophyll are adsorbed by white clay and discolored. Carotene is a nonpolar substance, so it is difficult to discolor by adsorption and decomposes by heat. In the decolorizing process, not only the pigment but also the remaining soap and gum, the curing nickel catalyst, and some oxidized fats and oils are removed at the same time.

The deodorization process is already a purification step to remove odors, remove free fatty acids, destroy pigment material and destroy oxidation products. Usually, edible oil is heated to 240 to 260 ° C, stripped steam is added, deodorized for 40 to 90 minutes, and cooled to obtain decolorized oil. Important factors in the deodorization process are temperature, vacuum and time of stripping steam. A common deodorization method is a vacuum steam distillation introduced by David Wesson of Cotton Oil in 1900. Oil triglycerides are not leaked in this operation, but the hobby is relatively volatile and is removed. The peroxide, which is an oxidation product, is destroyed by heating, and carotene is also decomposed and discolored by heat. Deodorization is performed under a high vacuum of about 2 to 6 mmHg, so that even if the fat or oil is heated to a high temperature, the fat or oil does not burn.

The pretreatment step of the edible oil and fat raw material, the treatment for removing harmful substances such as microorganisms, residual pesticides and preservatives on the surface of the raw material, the treatment for increasing the contact area with supercritical carbon dioxide, the treatment for increasing the extraction efficiency And a treatment for increasing the sensuality of the edible oil and fat.

As a treatment for removing harmful substances, methods such as ultraviolet irradiation, heat treatment, and peeling can be used, and as a treatment for increasing the contact area, a grinding method can be used. In order to increase the extraction efficiency, sesame seeds and perilla can be heat-treated to remove 5 ~ 10% of moisture to increase the extraction efficiency of oils and fats. In this case, the extraction efficiency can be increased by going through a drying process. As a treatment for increasing the functional beauty of the edible oil and fat, methods such as heat treatment and far-infrared irradiation can be used.

In the present invention, UV irradiation may be performed for 1 hour or more, but preferably performed for 1 to 3 hours, and heat treatment may be performed at 80 ° C. or more for 30 minutes or more in terms of removing harmful substances or functionalities, and preferably at 180 to 220 ° C. It is preferable to perform 15 to 40 minutes, more preferably 15 minutes at 220 ℃. Soybean, olive, safflower seed drying process is preferably carried out at 100 ~ 120 ℃ until the water content reaches 0.1-0.2%, most preferably at 110 ℃ until the water content reaches 0.18%. . Moisture content can be measured with a commercially available moisture meter. In addition, the peeling is different for each raw material, but may be performed by using a friction force or the like so that a weight reduction of about 2 to 6% occurs with respect to the total weight. In the case of sesame seeds, it is best to carry out a weight loss of about 3 to 4% of the total weight.

The smaller the powder degree used in the present invention, the better, but generally, the particle size is preferably 1.25 mm or less.

In the present invention, in order to overcome the disadvantage that the inherent scent of the raw material is increased by the loss in the process of heat treatment at a high temperature can be irradiated with far infrared rays during the heat treatment.

In the present invention, the far-infrared irradiation can be used any method known in the art, the emissivity (5 ~ 20㎛) is 0.8 ~ 0.9, the radiation energy (W / ㎡) is preferably about 3.5 × 10 ² ~ 3.8 × 10 ² Most preferably, the emissivity (5-20 μm) is 0.913, and the radiation energy (W / m 2) is about 3.68 × 10 ² .

The supercritical carbon dioxide used in the present invention is characterized in that the input temperature is 35 ~ 100 ℃, the input pressure is 100 ~ 900bar.

In addition, in the step of adding the supercritical carbon dioxide, ethanol is further added as a co-solvent, wherein the concentration of the co-solvent is characterized in that 5 to 10%.

On the other hand, the method using the supercritical carbon dioxide of the present invention is one of the technologies using the advantages of the fluid of the supercritical state, since the principle of distillation (extraction) and extraction (extraction) has the characteristics of a complex technology applied at the same time It has several unique advantages. That is, since supercritical carbon dioxide can be set to any condition of high density to low density by manipulation of the pressure and temperature, it is excellent in selectivity such as fractionation and separation, so that a high purity product can be obtained, and the extraction solvent is almost completely lost. It can be easily recovered, and there is an advantage in that a purified product having no residual solvent can be obtained. In addition, the viscosity of supercritical carbon dioxide is small, so it penetrates into the sample, and the extraction efficiency is high. Also, the diffusion coefficient is large, so the extraction speed is high. Since the density difference between the sample and the supercritical carbon dioxide is large and the viscosity of the supercritical carbon dioxide is low, it has many advantages such as the separation of the extraction residue and the solvent. However, the edible oil and fat extraction means using supercritical carbon dioxide has to use a high pressure device, so the cost of facility and maintenance is high.

Carbon dioxide in supercritical fluids is most preferred because its critical pressure is 73.8 bar and its critical temperature is 31 ° C., which is why it is generally easy to create supercritical conditions, because it is nontoxic and inexpensive to carbon dioxide itself. In addition, supercritical carbon dioxide is a nonpolar solvent and is preferable for extraction of substances having low polarity, such as fats and oils. In addition, by adding a polar substance such as alcohol to some of the carbon dioxide to induce a change in the polarity of the supercritical fluid, that is, it can significantly change the dissolving power, there is an advantage that can be utilized in the extraction of oil and fat components other than triglycerides.

Although studies using supercritical fluid clean technology have been actively conducted, studies on producing tocopherol derived from edible fat and oil using supercritical fluid with high efficiency have not been reported. Therefore, the present invention has been invented a method for producing an edible oil and fat containing a large amount of tocopherol component from the raw material by using a supercritical fluid extraction method that is currently spotlighted as a clean technology.

The present invention is characterized in that the supercritical carbon dioxide is brought into contact with the raw material to extract various oils and fats and tocopherols present in the raw material with high efficiency, and the edible fat and oil in the supercritical carbon dioxide is separated under reduced pressure after extraction. The depressurization separation consists of a circulator that decompresses the supercritical fluid from the extractor through a depressurizer to obtain high purity edible oil, and recovers the supercritical fluid solvent separated from the depressurizer and supplies it to the extractor for reuse. .

1 is a schematic diagram schematically showing an apparatus for extracting edible oil and fat from raw materials using supercritical carbon dioxide.

Looking at the edible oil and fat extraction system in more detail in the present invention, as shown in Figure 1, two or more extractors 1 is filled with pre-treated raw material, the supercritical carbon dioxide through the heat exchanger (2) extractor (1) Supply at the bottom of the At this time, the supply valve 12, 13 controls the supply of supercritical carbon dioxide supplied to each extractor (1).

The supercritical carbon dioxide supplied is contacted with the packed raw material to extract the edible oil and then rises and is released out of the extractor. At this time, the mixture of the released carbon dioxide and the edible oil is controlled by the discharge valves 10 and 11, and the extraction is performed. The mixture of the supercritical carbon dioxide and the edible oil and fat is transferred to the decompressor 8 under reduced pressure via the decompression valve 9.

In the decompressor (8), the extracted edible oil and carbon dioxide are separated, and the separated carbon dioxide is recycled to the storage tank (6) and reused, and the edible oil separated in the decompressor (8) is passed through the co-solvent separator (7). Collected as final product.

The carbon dioxide storage tank 6 is supplemented with carbon dioxide from the outside so as to compensate for some losses generated in the entire process in addition to the carbon dioxide supplied through the circulation.

The carbon dioxide stored in the reservoir 6 is pressurized through the pump 3 and supplied to the extractor through the heat exchanger 2 in a supercritical state.

This series of systems proceeds continuously until the target yield of edible oil and fat is extracted. For continuous operation, the extractor 1 is provided with two or more feed valves 12, 13 And a plurality of discharge valves (10) and (11) to adjust and use alternately, in the extractor is not used to remove the residue after the extraction and fill the new raw material to prepare for the next extraction.

Therefore, the supply of raw materials and the production of edible oil and fat products continue to occur.

In this regard, a method for extracting edible oil and fat using supercritical carbon dioxide according to the present invention will be described.

The edible oil extraction method using supercritical carbon dioxide according to the present invention basically pre-processes the raw material, fills the pretreated raw material into the extractor, and inputs the supercritical carbon dioxide to the extractor filled with the raw material to extract the edible oil and fat, thus extracted The mixture of supercritical carbon dioxide and edible oil is separated under reduced pressure, and the separated carbon dioxide is pressurized by a pump to recycle.

At this time, in order to remove the harmful substances such as microorganisms, residual pesticides and preservatives on the surface of the raw material to improve the hygienic aspect of the edible oil, ultraviolet irradiation, heat treatment, peeling treatment may be performed before filling the raw material into the extractor. .

In order to improve the extraction efficiency, the particle size of the raw material is preferably included in the pre-treatment step of crushing into fine particles having a particle diameter of 1.25mm or less for the maintenance and extraction efficiency of bioactive substances. Extraction efficiency is low in the form of particles larger than 1.25mm, and the extraction efficiency is rapidly increased in the fine particles smaller than 1.25mm.

Furthermore, heat treatment or far-infrared treatment may be performed in advance before filling the raw material into the extractor in order to improve the taste and flavor of the edible oil and fat.

The supercritical fluid may be used in various ways, but it is most preferable to use carbon dioxide. The supercritical carbon dioxide supplied to the extractor increases the extraction efficiency at higher temperature and higher pressure, in particular, the temperature is less than 100 ℃ The extraction efficiency is best when the pressure is preferably 35 to 80 ° C., the pressure is 900 bar or less, and preferably 100 to 500 bar.

In addition, when the supercritical carbon dioxide is supplied to the extractor when the co-solvent is supplied together, the extraction efficiency is greatly increased. In the present invention, ethanol is used, and the concentration is preferably 15% or less, and most preferably. 5-10%.

Hereinafter, the excellence of the extraction method and process of the present invention was verified through actual experiments, and the results are shown in the following tables.

Experimental Example 1 Pretreatment Process of Raw Materials to Improve Edible Oil Extraction Efficiency

Sesame, soybean and olive were used to measure the extraction efficiency of the edible oil and oil while changing the properties of the raw materials in the process. The raw materials were extracted in supercritical carbon dioxide at 60 ° C. and 450 bar for 3 hours in the form of seeds, flakes, and crushed particles, respectively, and the extraction efficiency was measured. With the exception of sesame seeds, soybeans and olives were subjected to supercritical extraction and further refined to produce final soybean oil and olive oil. The average seed shape of the sesame seeds was 2.3 mm in diameter, the average seed shape of the soybean was 7.0 mm in diameter, and the oval olive fruit was 2.5 cm long and 1.5 cm in diameter. Extraction efficiency was compared by converting the yield of sesame oil, soybean oil and olive oil, respectively, in terms of yield. At this time, sesame oil was measured after the supercritical extraction, and soybean and olive oil were measured after the supercritical extraction. Yield was calculated as a percentage of the total weight of the edible oil contained in each raw material and the weight of extracted edible oil, that is, sesame oil, soybean oil and olive oil. The results are shown in Table 2 below.

Extraction efficiency of edible oils and fats according to the type of raw material Raw material form Yield (%) Sesame Big head olive Seed form 26.7 10.2 2.9 Flake 34.1 15.3 10.1 Particle type (diameter 1.25mm or more) 96.3 89.3 90.2 Fine particle form (diameter 1.25mm or less) 99.8 99.7 99.3

As shown in Table 2, the extraction efficiency was greatly affected by the form of the raw material. In particular, the extraction efficiency was excellent when the size of the particle size was below a certain size, that is, the particle diameter was 1.25 mm or less.

Experimental Example 2: Edible fat and oil extraction efficiency according to temperature and pressure change of supercritical carbon dioxide

In the extraction process as shown in Figure 1 was measured the extraction efficiency of edible oil and fat while changing the temperature and pressure of supercritical carbon dioxide. Raw materials used were sesame seeds, soybeans and olives. Using the crushed microparticles as raw materials, the extraction temperature is changed to 35, 40, 50, 60, 70, 80, 90 and 100 ° C, and the pressure is 100, 150, 200, 250, 300, 350, 400, 450, Yield was calculated by measuring the weight of the edible oil extracted for 2.5 hours with 2.5kg of raw material 25kg of supercritical carbon dioxide per hour while changing to 500 and 900 bar. With the exception of sesame seeds, soybeans and olives were subjected to supercritical extraction and further refined to produce final soybean oil and olive oil. In the yield calculation, sesame oil was calculated by the amount obtained after supercritical extraction, and soybean and olive oil were calculated by the amount obtained after the purification process after supercritical extraction. As a result, as shown in Tables 3 to 5, the higher the pressure, the higher the extraction efficiency, but the optimum value was shown at 70 ° C at 350 bar (each extraction efficiency is the arithmetic mean value of the results of three replicates.

Sesame Oil Extraction Efficiency According to Temperature and Pressure Change of Supercritical Fluids Extraction pressure: 350 bar Temperature (℃) 35 40 50 60 70 80 90 100 Extraction efficiency (%) 79.5 91.6 93.5 97.2 99.5 98.5 98.2 98.1  Extraction temperature: 70 ℃ Pressure (bar) 100 150 200 250 300 350 400 450 500 900 Extraction efficiency (%) 6.8 12.5 30.2 46.5 84.7 99.5 99.5 99.6 99.8 99.8

Soybean Oil Extraction Efficiency with Temperature and Pressure Changes in Supercritical Fluids Extraction pressure: 350 bar Temperature (℃) 35 40 50 60 70 80 90 100 Extraction efficiency (%) 78.3 89.2 90.2 95.4 98.7 98.4 98.1 97.9  Extraction temperature: 70 ℃ Pressure (bar) 100 150 200 250 300 350 400 450 500 900 Extraction efficiency (%) 5.4 8.9 26.3 40.8 80.1 98.7 98.0 99.1 99.4 99.6

Olive Oil Extraction Efficiency with Temperature and Pressure Changes of Supercritical Fluids Extraction pressure: 350 bar Temperature (℃) 35 40 50 60 70 80 90 100 Extraction efficiency (%) 77.4 90.3 95.5 97.2 99.8 99.4 98.7 98.4  Extraction temperature: 70 ℃ Pressure (bar) 100 150 200 250 300 350 400 450 500 900 Extraction efficiency (%) 7.9 15.5 35.4 50.3 88.3 99.8 99.3 99.5 99.7 99.8

Experimental Example 3: Tocopherol Extraction with Temperature Change of Supercritical Carbon Dioxide

In order to investigate the extraction efficiency of tocopherol according to the temperature change of supercritical carbon dioxide, the temperature of supercritical carbon dioxide was changed to 25, 30, 35, 40, 50, 60, 70 and 80 ° C. in the extraction process as shown in FIG. Tocopherol extraction efficiency was measured for 3 hours at 350 bar. Raw materials used were sesame seeds, soybeans and olives. With the exception of sesame seeds, soybeans and olives were subjected to supercritical extraction and further refined to produce final soybean oil and olive oil. In the yield calculation, sesame oil was calculated by the amount obtained after supercritical extraction, and soybean and olive oil were calculated by the amount obtained after the purification process after supercritical extraction.

The extracted components were analyzed by high performance liquid chromatography (HPLC). Silica columns (Zorbax RX-Sil 5 ° C., 250 × 4.6 mm, and 12.5 mm guard columns) were used as stationary phases. Hexane and isopropanol (99: 1, v / v) were used as the mobile phase at an elution rate of 1.0 mL / min. The sample was saponified with 11% (w / v) potassium hydroxide-ethanol at 80 ° C. for 3 hours, cooled, dissolved in hexane through layer separation, filtered, and then injected into 20 μl. At this time, an antioxidant of 25 ppm BHT was administered to prevent oxidation of tocopherol during sample processing. The detector was measured at excitation 295 nm and emission 325 nm using a fluorescence detector. 2 is an HPLC analysis chromatography of tocopherol.

As a result, γ-type tocopherol was mainly present in sesame oil extracted with supercritical carbon dioxide, and neither α or β type was detected. The tocopherol content of sesame oil extracted with supercritical carbon dioxide and sesame oil produced by conventional compression was compared in Table 6. The effect of extraction temperature on tocopherol content was also compared. Extraction efficiency was expressed as a percentage of the extracted tocopherols compared to the total amount of tocopherols present in the feed. The total amount of tocopherol present in the raw material was quantified by HPLC using organic solvent (ethanol) extraction.

As shown in Table 6, the extracted tocopherol content increased as the temperature of supercritical carbon dioxide increased, but did not increase above 70 ° C. Above 70 ° C the extraction efficiency was 95% or more. This is significantly higher than about 65% of the conventional sesame oil production method, the supercritical fluid extraction method was found to be the only method to extract tocopherol with high efficiency.

Tocopherol Extraction Efficiency with Temperature Change of Supercritical Fluids Extraction form Tocopherol Content (mg / L) efficiency (%) Conventional crimping 311.8 64.7 The present invention 25 ℃ 394.4 81.8 30 ℃ 413.2 85.7 35 ℃ 413.0 85.7 40 ℃ 419.2 87.0 50 ℃ 429.7 89.2 60 ℃ 456.6 94.7 70 ℃ 459.1 95.3 80 ℃ 458.6 95.2

In addition, as a result of the experiment, more tocopherol was detected in soybean oil and olive oil as compared with the conventional compression type, and increased as the temperature of supercritical carbon dioxide increased, but did not increase any more than 70 ° C. Above 70 ° C the extraction efficiency was 95% or more. This may be a result of suggesting that the supercritical fluid extraction method of the present invention can extract tocopherol with high efficiency as compared to conventional edible oil production methods in soybean oil or olive oil as well as sesame oil.

Experimental Example 4: extracting edible oils and fats from raw material powder in supercritical carbon dioxide extraction process using ethanol as cosolvent

The edible oil and fat was extracted from the raw powder by using ethanol as a co-solvent in a process including high efficiency extraction conditions designed through the above experimental example. In FIG. 1, the ethanol of the co-solvent reservoir 5 is supplied through the pump 4, mixed with supercritical carbon dioxide, and then supplied to the extractor through the heat exchanger 2. Since the fats and oils separated from the pressure reducer 8 contain co-solvents, they are separated from the co-solvent separator 7 and then recovered to the co-solvent storage tank 5.

The edible oil and fat was extracted from the raw material microparticles by increasing the co-solvent up to 10% in the extraction which changes the extraction temperature to 30 to 80 ° C. and the pressure to 100 to 900 bar. The use of a co-solvent improved the extraction speed than without the co-solvent.

In the present invention, the extraction efficiency is improved with increasing the extraction speed, the higher the concentration of ethanol appeared, the higher the extraction efficiency was increased at a lower pressure than the high pressure. Table 7 compares the extraction efficiency of sesame oil when ethanol is used as a co-solvent at 150 bar and 35 ° C. and when the co-solvent is not used.

Change of Sesame Oil Extraction Efficiency at 35 ℃, 150bar and 70 ℃, 350bar Cosolvent concentration (%) Sesame oil extraction efficiency (%) Tocopherol Extraction Efficiency (%) 35 ℃ / 150 bar 0 7.2 12.1 5 98 97.8 10 99.5 99.5 15 99.9 99.5 70 ℃ / 350 bar 0 89.1 95.3 5 99.5 98.5 10 99.9 99.5 15 99.9 99.5

In the case of soybean oil and olive oil, as in the case of sesame oil, the extraction speed was increased, and the extraction efficiency was increased with increasing ethanol concentration, and the extraction efficiency was increased at a lower pressure than at high pressure. Larger.

Table 8 is a comparison of the present invention (experimental) and the conventional crimping method for producing sesame oil, the yield of sesame oil 33.1%, tocopherol content is 47.2% to show the superiority of the present invention, respectively.

In the production of sesame oil, the results of the present invention compared with the existing method Conventional Crimping Method of the Invention Increase Yield (%) 75 99.8 33.1% Tocopherol Content 311.8 mg / L 459.1 mg / L 47.2%

Experimental Example 5: Sensory evaluation of the edible oil and fat prepared by the method of the present invention

Using the raw powder prepared by different pretreatment as shown in Table 9, extracting the edible oil with supercritical carbon dioxide at 65 ℃, 450 bar for 3 hours, respectively, and then carried out the sensory evaluation using the edible oil prepared by conventional compression extraction method as a control. It was. Sesame seeds, beans and olives were used as raw materials. In this case, except for sesame seeds, soybeans and olives were subjected to a supercritical extraction, followed by further purification to prepare final soybean oil and olive oil, and used for sensory evaluation.

The evaluation method was a random sampling of 10 men and women aged 20 to 50 years, and the taste, flavor, and color preference were evaluated by a nine-point grading system (9 = best; 8 = very good; 7 = usually good; 6 = slightly good; 5 = good or not hate; 4 = slightly disliked; 3 = normally disliked; 2 = very disliked; 1 = disliked most.

The results were as shown in Tables 10 to 12 below.

division Raw material Heat treatment Far Infrared Minutes Temperature (℃) Sesame oil 1 Sesame 0 - No treatment Sesame oil 2 Sesame 0 - process Sesame oil 3 Sesame 30 220 No treatment Sesame oil 4 Sesame 30 220 process Sesame oil 5 Sesame 90 180 No treatment Sesame oil 6 Sesame 90 180 process Soybean oil 1 Big head 0 - No treatment Soybean oil 2 Big head 0 - process Soybean Oil 3 Big head 30 120 No treatment Soybean oil 4 Big head 30 120 process Soybean Oil 5 Big head 90 100 No treatment Soybean oil 6 Big head 90 100 process Olive oil 1 olive 0 - No treatment Olive oil 2 olive 0 - process Olive oil 3 olive 30 120 No treatment Olive oil 4 olive 30 120 process Olive oil 5 olive 90 100 No treatment Olive oil 6 olive 90 100 process Note: Far-infrared ray treatment is the treatment of far-infrared rays with emissivity (5 ~ 20㎛) 0.913 and radiation energy (W / ㎡) of about 3.68 × 10 ² for 20 minutes.

Sesame Oil Panel Test Results Comprehensive sensory incense Savory taste bitter color Control 3 2 3 5 4 Sesame oil 1 6 6 5 No bitter taste 6 Sesame oil 2 8 8 8 No bitter taste 8 Sesame oil 3 8 6 9 6 7 Sesame oil 4 9 9 9 7 9 Sesame oil 5 8 6 9 7 8 Sesame oil 6 9 9 9 8 8

Soybean Oil Panel Test Results Comprehensive sensory incense color Control 4 3 5 Soybean oil 1 6 7 6 Soybean oil 2 8 8 8 Soybean Oil 3 7 6 6 Soybean oil 4 9 9 8 Soybean Oil 5 7 6 6 Soybean oil 6 8 9 7

Olive Oil Panel Test Results Comprehensive sensory incense color Control 4 2 5 Olive oil 1 6 7 6 Olive oil 2 8 9 8 Olive oil 3 7 6 7 Olive oil 4 9 9 9 Olive oil 5 7 6 6 Olive oil 6 9 9 9

Through the above table it was confirmed that the edible oil and fat by the method of the present invention is significantly superior to the crimp in the functional aspect. In addition, when the far-infrared ray was irradiated, it was found that the fragrance loss problem during heat treatment was greatly reduced.

As described above, the present invention relates to a method for producing an edible oil containing a high content of tocopherol from a edible oil raw material that has undergone pretreatment such as UV, heat treatment, drying, peeling, grinding, and far infrared using supercritical carbon dioxide and a cosolvent. In particular, the edible oil and fat extraction efficiency is increased, as well as the effect of significantly increasing the content of tocopherol compared to the conventional edible oil and fat manufacturing method. Moreover, the product of the present invention is more excellent in flavor and bitter taste than the product manufactured by the conventional crimping method through pretreatment as well as the product prepared using supercritical carbon dioxide and co-solvent without pretreatment. It is a very useful invention.

Claims (2)

A method for producing edible oil and fat containing tocopherol at a high concentration using carbon dioxide as an extract from an edible oil and fat raw material, the method comprising: Pretreatment of the edible fat and oil raw material by at least one pretreatment method selected from the group consisting of ultraviolet irradiation, heat treatment, drying, peeling, grinding and far infrared irradiation; Filling the pretreated raw material into an extractor; Extracting edible oil and fat by adding 90-95% of supercritical carbon dioxide and 5-10% of ethanol having a temperature of 35-80 ° C. and a pressure of 100-900 bar through a heat exchanger to a raw material-filled extractor; Separating the supercritical carbon dioxide and the edible fat and oil mixture by decompressing the pressure reducing valve through a pressure reducing valve in a pressure reduction separator; And The separated supercritical carbon dioxide is circulated in a storage tank and then recycled by pressurizing with a supercritical carbon dioxide supplemented by a pump and collecting the separated edible oil, characterized in that it comprises a step of sequentially collecting edible oil and fat . Prepared by the method of claim 1, selected from the group consisting of sesame oil, perilla oil, soybean oil, corn oil, rapeseed oil, rice bran oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, field free, pepper seed oil Tocopherol-containing edible oil, characterized in that any one.

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