KR20200013875A - Method for extracting functional oil from skate liver and functional oil of skate liver manufactured therefrom - Google Patents

Abstract

The present invention relates to functional oil having high unsaturated fatty acids using skate liver discarded through a method for extracting the functional oil from the skate liver. The method for extracting the functional oil from the skate liver according to the present invention comprises: a first step of trimming an edible part in the skate and separating the skate liver; a second step of extracting skate oil from the separated skate liver; and a third step of purifying the skate oil extracted from the skate liver.

Description

TECHNICAL FOR EXTRACTING FUNCTIONAL OIL FROM SKATE LIVER AND FUNCTIONAL OIL OF SKATE LIVER MANUFACTURED THEREFROM}

The present invention relates to a method for extracting functional fats, and more particularly, to a method for extracting functional fats and oils from skates and the functional fats of the skates prepared therefrom.

Skates are benthic fish and cartilage that inhabit deep waters in most of the world's waters up to 3000 m deep. Skate sashimi, one of the traditional local fish foods, has a unique taste and contains a lot of health-friendly functions such as enhancing digestion and appetite, improving immunity, anti-aging, improving arthritis and maintaining skin elasticity. Skates contain a large amount of urea and urea precursors in the body to control osmotic pressure during growth, thus producing unique flavors through the production of nitrogen compounds, ammonia and trimethylamic acid, during fermentation, and a large amount of Photobacterium sp. It promotes ripening of skates. In addition, there are a large amount of functional peptides having antihypertensive effect on skates, and the antibacterial peptides isolated from mature skates have bacteriostatic control effects of Bacillus subtilis, Escherichia coli, and Saccharomyces cerevisiae. Taurine, which increases production during skate fermentation, has the effect of preventing the accumulation of cholesterol. Especially in skate oil, omegas such as EPA and DHA have the effect of reducing LDL-cholesterol, increasing HDL-cholesterol, and lowering triglycerides. It contains a large amount of trifatty acid, which is effective in preventing coronary artery disease.

Many of these skates are consumed as mature skates. After selecting fish meat or larvae in the process of ripening skates, by-products corresponding to about 40% of the raw skates are generated. These by-products are composed of shells and cartilage, but most of them are disposed of without any additional treatment, resulting in environmental pollution such as odor generation and pest breeding, as well as incurring disposal costs.

The edible part of matured skates is wing and body flesh, and only 60 to 65% of the original weight is used as an edible part before processing, and the remaining 35 to 40% is composed of bone, skin, and intestine, which are non-edible parts. More than 500 tons are thrown away every year. Busan buckwheat is mostly composed of shells, chicks, bones, etc. As mentioned above, chicks contain a large amount of functional fats and fats. But they are also classified as by-products and can only be discarded or used as feed. The government has introduced a plan to zero land waste marine dumping in 2012 and a 2014 landfill and incineration burden, inducing the recycling of waste resources. Therefore, there is a need for a study on the utilization of the non-edible by-products of the skate, which are being used or disposed of in the production, distribution, processing and sales stages.

Skates (liver) contain about 40% lipids, fatty acids account for about 90% of the lipids and the fatty acid and saturated fatty acid ratio of 20:70. Among fatty acids, EPA contains 5% of oil and DHA contains 20% of oil. Unsaturated fatty acids increase HDL cholesterol levels when absorbed into the blood, which cleans blood vessels and promotes arteriosclerosis in the blood. It acts to move the substance to the liver, which protects the heart. However, these highly nutritious skatefish are discarded after being removed due to processing problems in the process of producing large-scale ripened skatefish.

Republic of Korea Patent Publication No. 10-2005-0007020 discloses a technique for extracting gelatin from the skin of the skates by-products. However, the patent only specifies the use of the shell of the by-products, it does not provide a way to use the skatefish containing a large amount of unsaturated fatty acid.

Republic of Korea Patent Publication No. 10-2005-0007020

The present invention has been made to solve the above problems, an object of the present invention is to provide a method for extracting a functional oil having a high nutritional value from the skate.

These and other objects and advantages of the present invention will become more apparent from the following description of preferred embodiments.

The purpose of the present invention includes trimming a edible part from a skate, a first step of separating the skates, a second step of extracting the skates from the separated skates, and a third step of purifying the skates extracted from the skates. It is achieved by a method of extracting functional oils from skates.

Preferably, the second step is the step of slicing the separated skates to a size of 1 to 3mm, steaming the sliced skates at 95 ~ 100 ℃ 40 ~ 90 minutes in the steamer and steaming the liquid generated in the steaming step To remove the residue.

Preferably, the second step is the step of slicing the separated skates to a size of 1 to 3mm, the step of immersing 22 ~ 25 hours in a mixture of chloroform and methanol in the sliced skates, 10 Washing with% aqueous sodium chloride (NaCL) solution, dewatering the washed skatefish using sodium sulfate anhydrous and filter paper, and rotating evaporator in the dewatered skatefish It may include the step of removing the organic solvent using.

Preferably, the third step may include separating and degumming phospholipids and gums from the extracted skate oil, deoxidizing free fatty acid from the degreased skate oil, and decolorizing the pigment from the dehydrated skate oil. .

Preferably, the step of degumming is adding a 60-65 ℃ citric acid (citric acid) aqueous solution to the extracted skate oil, stirring for 20 to 25 minutes at 300 to 320rpm at 60 ~ 65 ℃ and 1,500 ~ 1,800rpm Centrifugation for 15 to 20 minutes at may include removing lecithin, gums, phospholipids and proteins.

Preferably, the step of deoxidation is the step of adding an aqueous alkali solution to the degreased skate oil, the reaction by stirring for 20-25 minutes at 200 ~ 250rpm at 60 ~ 65 ℃, centrifugation at 3,000 ~ 3,500rpm 15-20 minutes Step to remove free fatty acid salt, and then mix the water of 4 ~ 10 ℃ in the skates oil free fatty acid removed, put into the fractional filter and left for 5-10 minutes and the lower layer of Repeating the process of removing the liquid may include the step of filtering to remove the residual free fatty acid salt and alkali components.

Preferably, the decolorizing may include adding a decolorizing agent to the deoxidized skate oil, depressurizing for 20 to 30 minutes at 60 to 65 ° C, and passing the filter through decompression filtration to remove the decolorizing agent. have.

Preferably, the step of purifying the extracted skate oil is crystallized by mixing n-hexane to decolorized skate oil and left for 12 to 18 hours at -70 to -65 ℃, and then filtering the crystal using a suction filter Separation, and further comprising a cold immersion step of removing n-hexane with a rotary vacuum concentrator.

In addition, the above object can be achieved by the functional oil of the skates prepared by the method for extracting the functional oils from the above-described skate.

In addition, the above object can be achieved by the matured skates prepared by immersing the functional oils of the skates prepared by the method of extracting the functional oils from the above-described skate.

Functional fats may be prepared by extracting functional fats and oils from skates according to the present invention to prepare functional fats rich in unsaturated fatty acids. In addition, when producing a matured skate product using the functional oil of the skate prepared by the method of extracting the functional oil from the skate, according to the present invention can produce a mature skate with a higher unsaturated fatty acid content than the normal mature skate have.

In addition, by recycling the skate, it is possible to reduce the amount of waste, and to increase the income of maintaining the functionality of the skate.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a flowchart of a method for extracting functional oils from a skatefish according to an embodiment of the present invention.
2 is a flow chart of the extraction step using the steaming compression method of the method for extracting the functional oil from the skates according to an embodiment of the present invention.
Figure 3 is a flow chart of the extraction step using the organic solvent extraction method of the method for extracting functional oils from skates according to an embodiment of the present invention.
Figure 4 is a flow chart of the purification step of the method for extracting functional oils from skates according to an embodiment of the present invention.
Figure 5 is a flow chart of the degumming step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.
Figure 6 is a flow chart of the deoxidation step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.
7 is a flow chart of the decolorizing step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.
8 is a view showing the results of measuring the chromaticity according to each purification process of Example 4.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Also, although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

1 is a flowchart of a method for extracting functional oils from a skatefish according to an embodiment of the present invention.

2 is a flow chart of the extraction step using the steaming compression method of the method for extracting the functional oil from the skates according to an embodiment of the present invention.

Figure 3 is a flow chart of the extraction step using the organic solvent extraction method of the method for extracting functional oils from skates according to an embodiment of the present invention.

Figure 4 is a flow chart of the purification step of the method for extracting functional oils from skates according to an embodiment of the present invention.

Figure 5 is a flow chart of the degumming step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.

Figure 6 is a flow chart of the deoxidation step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.

7 is a flow chart of the decolorizing step of the purification step of the functional fat manufacturing method according to an embodiment of the present invention.

1 to 7, a method of extracting functional oils from a skatefish according to an embodiment of the present invention will be described.

Method for extracting the functional oil from the skates according to an embodiment of the present invention is the first step (S100) to largely trim the edible portion from the skates and to isolate the skates, the second step of extracting the skates from the separated skates (S200) and a third step (S300) for purifying the extracted skate oil.

First, the trimming unit is trimmed from skates and a first step of separating the skates is performed (S100). Skates are sorted by trimming the edibles during the processing of ripened skates. At this time, the edible portion of matured skates is 60-65% of the original weight of the wings and body meat before processing, the remaining 35-40% is classified as an unedible portion. At this time, the skatefish is separated from the parts classified as non-planting site. Skatefish (skate liver) is about 40% lipids, fatty acids account for about 90% of the lipids. In the fatty acid of skatefish, the ratio of saturated fatty acid and unsaturated fatty acid is 2: 7. Fatty acids are 5% EPA and 20% DHA, and they are very good oils. Unsaturated fatty acids increase HDL cholesterol levels in the blood to clean blood vessels and transport substances that promote atherosclerosis to the liver. Role to protect the heart.

At this time, the isolated skate can be further subjected to the aging process before extracting the skate. The separated skates may be aged for 10 to 15 days at a temperature of 3-7 ° C. to improve the quality of the extracted skates. Alternatively, after aging 20 to 30 days before separating the edible portion and skate in the skate, it can be used to separate the skate from mature skate.

When the skates are separated from the skate, a second step of extracting the maintenance of the skate from the separated skates (S200). The following two extraction methods can be used to extract the skate oil from the separated skate.

The first method of extracting the skate oil is first cut the separated skates (S201). When extracting the skate oil from the isolated skate, it is preferable to cut the separated skate into 1 to 3 mm in order to reduce the extraction time and increase the extraction amount. When the skates are sliced, the sliced skates are boiled in a steamer (S202). After cutting the skates, boil the water at 95 ~ 100 ℃ and boil it in the steamer for 40 ~ 90 minutes, more preferably steam for 1 hour. After steaming the shredded red ice in the steamer, the liquid generated in the steaming step is vacuum filtered to remove the residue (S203). When boiled sliced skates are steamed in a steamer, liquid is generated from skates. At this time, the liquid generated from the skate can be vacuum filtered (pressure reduction manganese) to remove residues and impurities in the liquid.

The second method of extracting the skate oil is first cut the separated skates (S211). When extracting the skate oil from the isolated skate, it is preferable to cut the separated skate into 1 to 3 mm in order to reduce the extraction time and increase the extraction amount. When the skates are chopped, the chopped skates are immersed in a mixture of chloroform and methanol (S212). In this case, the mixing ratio of chloroform and methanol is preferably 2: 1, and the mixed solution of chloroform and methanol is preferably 3 to 4 times the volume of the sliced redfish. Moreover, it is preferable that immersion time is 22-25 hours. In step S212, when the shredded redfish is sufficiently immersed in the mixed solution, put the aqueous solution of sodium chloride (Nacl) of 10% concentration in the dipped skates and washes (S213). The submerged skatefish can be washed clean with an aqueous sodium chloride solution. As an example, after dipping sap and an aqueous sodium chloride solution, an aqueous sodium chloride solution may be removed using a separatory funnel. Next, the washed skate is dehydrated using sodium sulfate anhydrous and filter paper (S214). Then, the organic solvent is removed using a rotary evaporator in the dewatered skated fish (S215).

When the skate oil is extracted (S200) by any one of the first and second methods, the extracted skate oil is purified (S300). The process of purifying the extracted skate oil is to separate the phospholipids and gums from the extracted skate oil (S310), the step of deoxidizing the free fatty acid from the degreased skate oil (S320) and decolorized pigment in deoxidized skate oil It includes the step (S330).

Separation of phospholipids and gums from the extracted skate oil (S310) is a process of removing gums and phospholipids, including lecithin present in skate oil. The gums and phospholipids, including lecithin present in fats and oils, have emulsification, which makes it difficult to separate the free fatty acid salts generated in the deoxidation process (S320) and adversely affects browning. You should remove it. In addition, the protein is also removed through the degumming step S310.

The detailed process of separating and degumming phospholipids and gums from the extracted skate oil (S310) includes adding a citric acid aqueous solution to the extracted skate oil (S311), and stirring the skate oil to which the citric acid aqueous solution is added. Step S312 and centrifugation of the stirred skate oil to remove lecithin, gum, phospholipids and proteins (S313).

First, the detailed process of the degumming step S310 is performed by adding an aqueous citric acid solution to the extracted skate oil (S311). The aqueous citric acid solution added is a weak organic acid, a natural preservative, and a food additive used to give the taste or sour taste of food or carbonated drinks. At this time, the citric acid aqueous solution added to the extracted skate oil to remove the phospholipids in the skate oil and to remove the adverse effects such as browning, the temperature is preferably 60 ~ 65 ℃.

After the aqueous citric acid solution is added to the skate oil, a step of stirring the skate oil to which the citric acid aqueous solution is added is performed (S312). When stirring, the temperature is preferably maintained at 60 ~ 65 ℃, the stirring speed is preferably 300 ~ 320rpm. When the skate oil to which the citric acid solution is added is sufficiently stirred, the stirred skate oil is centrifuged to remove lecithin, gum, phospholipid and protein (S313). At this time, the rotation speed of the centrifuge is preferably 1,500 ~ 1,800rpm. In addition, the rotation time of the centrifuge is preferably 15 to 20 minutes. When rotating less than 15 minutes in the centrifuge, the lecithin, gum, phospholipids and proteins are not sufficiently separated, when rotating for more than 20 minutes, there is a problem that unnecessarily long process time.

A step of deoxidizing the free fatty acid in the degreased skate maintains (S320). This removes the free fatty acids produced by rancidity. Free fatty acids are produced according to the rancidity of skate oil, and the value is the acid value. If the acid value is high, it is unsuitable for food, so it is reacted with an alkaline aqueous solution to form a free fatty acid in the form of free earth salt, followed by a deoxidation process.

The step of deoxidizing the free fatty acid in the degreased skate oil (S320) is a step of adding an alkaline aqueous solution to the degreased skate oil (S321), a step of stirring the skate oil oil to which the alkaline aqueous solution is added (S322), the stirred skate oil Step of removing free fatty acid salt by centrifugation (S323), mixing water in the free fatty acid salted skate oil and then leaving it in the fractional filter space (S324), the lower layer liquid in the oil remaining oil fraction Repeating the process to remove the water and then filtered to remove the residual free fatty acid salt and alkali component (S3250).

First, an alkaline aqueous solution is added to the degreased skate oil (S321). At this time, the aqueous alkali solution is added to react with the free fatty acid to change into free fatty acid form. The aqueous alkali solution may be freely used as an aqueous solution of an alkaline component capable of reacting with free fatty acid, and sodium hydroxide is preferably used as an example.

Next, a step of stirring the skate oil oil to which the alkaline aqueous solution is added (S322). After the aqueous alkali solution is added to the skate oil, the aqueous alkali solution is stirred to sufficiently react with the free fatty acid contained in the skate oil. At this time, the stirring temperature is preferably 60 ~ 65 ℃, the stirring speed is 200 ~ 250rpm, the stirring time is preferably 20 to 25 minutes.

Next, centrifugation of the stirred skate oil is carried out to remove the free fatty acid salt (S323). After stirring the alkali aqueous solution sufficiently with free fatty acid of the skate oil, and then centrifuged through a centrifuge to remove the fat of the upper layer separated free fatty acid. At this time, the rotation speed of the centrifuge is preferably 3,000 to 3,500 rpm, and the rotation time is preferably 15 to 20 minutes.

Next, water is mixed with the skates from which free fatty acid salts have been removed, and then placed in a fractional filter, leaving a predetermined time (S324). When free fatty acid salt is removed from the skate oil through centrifugation, 4 ~ 10 ℃ water is mixed with the skate oil, and then left for a predetermined time in the fractional filter. Fractional filter refers to a device that shows layer separation when mixed solution and other solution are added.When 4 ~ 10 ℃ water is added to skate oil in the process of deoxidation, the washed oil floats on the top, and roughness and residual free fatty acid on the bottom. It sinks and is removed. At this time, leave time is 5 ~ 10 minutes Is preferably. Next, after repeating the process of removing the liquid of the lower layer is filtered to perform the step of removing the residual free fatty acid salt and alkali component (S325). The mixture of skate oil and water left in the fractional filterhead is separated into upper and lower layers over time. Then, the process of removing the separated lower layer solution is repeated, followed by filtration to completely remove residual free fatty acid salts and alkali components.

After the step S320, the step of discoloring the pigment in the deoxidized skate oil (S330) is a process for removing heavy metals such as pigment and lead contained in the fat and oil. Stain oil is also decolorized, so the acid value and peroxide decreases with the adsorption of pigments.

This decolorizing step (S330) is a step of adding a decolorizing agent to the deoxidized skate oil (S331), the step of depressurizing to a predetermined pressure (S332) and the step of removing the decolorant by passing the filtration filter through a reduced pressure filtration (S333) ).

First, a step of adding a bleaching agent to deoxidized skate oil is carried out (S331). In this case, the added bleaching agent may include any one or a combination of two or more of activated carbon, magnesium silicate, and activated clay. Next, a step of depressurizing the skate oil to which the decolorant is added to a predetermined pressure is performed (S332). At this time, it is preferable that the temperature at the time of decompression is 60-65 degreeC, and it is preferable that the decompression time is 20-30 minutes. And passing through the filter by filtration under reduced pressure to perform a step of removing the decolorant (S333). This manufactures the functional oils of skates from skates.

In the method of extracting the functional oil from the skate oil according to an embodiment of the present invention, the step of purifying the oil oil (S300) may include deodorization, cold acupuncture, and desorption (S310), deoxidation (S320), and decolorization (S330). It may further comprise an antioxidant treatment process.

Deodorization process is to remove odor causing substances contained in skate oil. Substances such as ammonia and trimethylamine are representative odor causing substances that cause pain, vomiting, allergies, dizziness, difficulty breathing, and stress in body organs and remove these odor components through a deodorizing process.

Cold soaking is performed by low temperature crystallization to reduce saturated fatty acids and increase omega-3 fatty acid composition. In the cold soaking process, 10-fold n-hexane was mixed with oil, and then crystallized by leaving it at -70 to -65 ° C for 12 to 18 hours. The crystal was quickly filtered by suction filtration using a suction filter (buchner funnel). After proceeding to remove the n-hexane with a rotary vacuum concentrator.

The antioxidant treatment process adds antioxidants to maintain and improve the quality of the skate. After the deodorization process, add the green tea extract catechin (catechin), which is a natural flavoring agent, and soak it in a constant temperature water bath at 100 ° C.

Functional maintenance of the skate oil prepared according to the method for extracting the functional oil from the skate oil according to an embodiment of the present invention can be various applications. As an example, ripened skates can be prepared using the functional oils of the prepared skates. After immersing the trimmed portion of the mandarin in the functional oil of the skates and then aged for 3 hours to 24 hours at a temperature condition of 20 ~ 23 ℃ can be prepared aging skates with the addition of functional fats and oils. Matured skates added with such functional fats and fats have higher unsaturated fatty acid contents such as EPA and DHA, compared to general matured skates, which may help lower blood cholesterol content and suppress thrombus formation.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

EXAMPLE

Example 1

After removing the skates frozen at -25 ℃, boil the water at 100 ℃ and put it in the steamer for 1 hour. After steaming the solution, the residue is removed by vacuum filtration. Next, an aqueous 6% citric acid solution heated to 60 ° C. was added to the extracted skate oil, and then stirred at 300 rpm at 60 ° C. for 20 minutes, followed by centrifugation at 1,500 rpm for 15 minutes to degumming. After adding 4% sodium hydroxide aqueous solution to the degreased skate oil, the reaction was stirred at 60 rpm at 200 ° C. for 20 minutes and then centrifuged at 3,000 rpm for 15 minutes to remove the fatty acid from the free fatty acid. After adding water at 4 ° C. and mixing, the mixture is left in a fractional filter, and the process of removing the lower layer is washed repeatedly with water and filtered to remove residual free fatty acid salt and sodium hydroxide and deoxidized. Next, 5% aqueous activated carbon solution was added to the deoxidized skate oil, followed by decolorization under reduced pressure at 60 ° C. for 20 minutes, and activated charcoal was removed through reduced pressure filtration to prepare functional oils of the skate.

Example 2

In Example 1, the boiled water at 100 ° C. was boiled in a steamer and steamed for 1 hour, and the resulting solution was vacuum filtered to remove the residue to extract the remaining oil, which was then divided into 4 times the amount of chloroform and methanol of the skate. After immersion in a mixed solution (2: 1 ratio), an aqueous 10% sodium chloride solution was added, followed by washing with a separatory funnel, followed by dewatering using sodium sulfate anhydrous and filter paper. Functional oils of the skatefish were prepared in the same manner as in Example 1 except that the organic solvent was removed by using a rotary evaporator to extract the skate oil.

Example 3

Functional oils of the skatefish were prepared in the same manner as in Example 2 except that the deodorizing process for the pigmented skate oil was carried out using 7% concentration of bamboo vinegar solution.

Example 4

After n-hexane was mixed with the functional oil of the skate oil prepared in Example 2, the mixture was left to crystallize at 70 ° C. for 12 hours, and then crystallized by suction filtration using a suction filter. Functional oils of the skatefish was prepared in the same manner as in Example 2 except that the chilling step of removing n-hexane was further performed.

Example 5

Functional oils of the skatefish was prepared in the same manner as in Example 2 except that the natural oxidizing agent catechin was added to the functional oils prepared in Example 1 and then immersed in a constant temperature water bath at 100 ° C. do.

Example 6

Functional oil of the skates prepared in Example 1 was immersed in the edible portion of the groomed skates and then aged for 3 hours at a temperature of 20 ℃ to prepare a mature skate.

Example 7

A matured skate was prepared in the same manner as in Example 6 except that the functional oil of the skate prepared in Example 2 was used.

Comparative Example 1

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that a 2% aqueous citric acid solution was used.

Comparative Example 2

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that an aqueous 4% citric acid solution was used.

Comparative Example 3

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that 8% aqueous citric acid solution was used.

[Comparative Example 4]

Functional oils and fats of a skatefish were prepared in the same manner as in Example 2 except that an aqueous 1% sodium hydroxide solution was used.

[Comparative Example 5]

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that a 2% sodium hydroxide aqueous solution was used.

Comparative Example 6

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that an aqueous 3% sodium hydroxide solution was used.

Comparative Example 7

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that a 5% aqueous sodium hydroxide solution was used.

Comparative Example 8

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that an aqueous 1% activated carbon solution was used.

Comparative Example 9

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that 10% aqueous activated carbon solution was used.

Comparative Example 10

A functional oil of a skatefish was prepared in the same manner as in Example 2 except that 15% aqueous activated carbon solution was used.

Comparative Example 11

Functional oils of the skatefish were prepared in the same manner as in Example 2 except that the deodorization process for the pigmented skate oil was performed using 1% concentration of bamboo vinegar solution.

Comparative Example 12

Functional oils of the skatefish were prepared in the same manner as in Example 2 except that the deodorizing process for the pigmented skate oil was performed using 3% concentration of bamboo vinegar solution.

Comparative Example 13

Functional oils of the skatefish were prepared in the same manner as in Example 2 except that the deodorizing process for the pigmented skate oil was performed using 5% concentration of bamboo vinegar solution.

Comparative Example 14

A matured skate was prepared in the same manner as in Example 6 except that the functional oil of the skate was not used.

Components 1 to 7 and Comparative Examples 1 to 14 prepared as described above were measured and evaluated according to the following experimental example.

Experimental Example

(1) determination of phosphorus content

20 g of the functional oil of the prepared skate was taken in a crucible, and preliminarily carbonized and dry-painted at 500 to 550 ° C. in an induction furnace. After incineration, 0.5N nitric acid was added, warmed, dissolved, filtered, and the phosphorus content was analyzed by inductively coupled plasma (ICP). The analysis conditions are shown in Table 1. Standard Reference Material (SRM) 384 was used to ensure the reliability of the phosphorus content analysis results.

Inductively Coupled Plasma (ICP) equipment Perkin Elmer OPTIMA 3300XL RF power (W) 1200 Pump (mL / min) 1500 Gas flow
(L / min) Plasma 15 Auxiliary 0.5 Nebulizer 0.7

(2) Acid value measurement

The acid value is the number of mg of KOH needed to neutralize the free fatty acids contained in 1 g, which measures the amount of free fatty acids that are not in the form of glycerides. 3 g of the functional oil of the prepared skate was taken in a 250 ml Erlenmeyer flask, mixed with 100 ml of a solution of 2: 1 of ethyl-ether and ethanol, and completely dissolved. After titrating until the light pink color lasts for 30 seconds, the acid value was measured by substituting Equation 1.

AV: Sanga

a: 0.1N KOH-ethanol consumption (ml)

b: sampling amount (g)

F: Titer of 0.1N KOH-ethanol

(3) Peroxide value measurement

Peroxide value is the number of mg equivalent of peroxide contained in 1 kg of fats and fats, which increases with oxidation of fats and fats, and eventually breaks down to carbonyl compounds, and eventually decreases. When it is 20 ~ 40 meq / kg, it is considered as the time of rancidity.

3 g of the functional oils of the prepared skate oil were mixed with 30 ml of a solution containing 3: 2 of acetic acid and chloroform to dissolve the fats and oils, and 1 ml of saturated potassium iodine solution was added. 1 ml of 30 ml of distilled water and 1% starch solution were added and then titrated until the colorless purple color was maintained for 30 seconds with 0.01 N sodium thiosulfate (Na ₂ S ₂ O ₃ ) solution.

POV: Peroxide

a: 0.01N Na ₂ S ₂ O ₃ consumption (ml)

b: 0.01N Na ₂ S ₂ O ₃ consumption of blank (ml)

c: sampling amount (g)

F: Titer of 0.01 N Na ₂ S ₂ O ₃

(4) thiobarbitulic acid (TAB) measurement

As a principle of measuring the concentration of malonaldehyde, a fatty acid secondary product produced as fats and fats are lost, add benzene, dissolve it sufficiently, add thiobarbitulic acid reagent, and leave it in a separatory funnel. Subsequently, the lower layer was transferred to a screw cap tube, and heated in a 95 ° C. water bath for 30 minutes to develop a solution of reddish violet. The solution was cooled in running water, and the absorbance was measured.

S = absorbance at 530 nm in this test

B = absorbance at 530 nm in ball test

W = weight of fat (g)

(5) yield measurement

Yield is expressed as the ratio of the volume of each purified sample and the sample before passing through.

(6) fatty acid composition analysis

After immersing for 24 hours in a solution mixed with chlorform and methanol at 2: 1 (v / v), the separatory funnel was washed with a 10% aqueous sodium chloride solution and dehydrated using sodium sulfate anhydrous and a filter paper. The organic solvent was removed using a rotary evaporator and then analyzed. To 0.1 g of the functional oil of prepared skates, 2 ml of 0.5 N-NaOH and methanol mixtures were added, heated at 100 ° C. for 10 minutes, cooled to room temperature, 4 ml of BF ₃ solution was added thereto, and then heated at 100 ° C. for 40 minutes to room temperature. After cooling, 2 ml of n-hexane was added, and a vortex was made for 20 seconds. 5 ml of saturated sodium chloride was added to form a vortex, and the supernatant was passed through a 0.45 μm syringe filter, followed by gas chromatography. In addition, docosahexaenoic methyl ester and eicosapentaenoic methyl ester were prepared at concentrations of 0.1, 0.5, 1, 5, 7.5, and 10 ppm, respectively. The same conditions were analyzed to compare the DHA and EPA contents of the skates, which were processed through raw material maintenance, degumming, deoxidation, and decolorization. Analysis conditions of the fatty acid composition analysis are shown in Table 2.

DHA, EPA Fatty Acid Analysis Conditions Items state Column SP-2560
(100m * 0.25m * 0.2㎛) Carrier gas helium Oven temperature 100 ° C (5min) → 4 ° C (1min)
→ 240 ° C (20min) Detecting temperature 260 ℃ Inject temperature 250 ℃ Split temperature 10: 1 Injection volume 1 uL

(7) Measurement of Volatile Base Compounds

The reduction effect was analyzed by measuring the ammonia content for functional fats and oils which had been deodorized using bamboo vinegar. 5ml of bamboo vinegar solution with different amounts was added to each of the empty bottles, and the stopper was closed and left for 1 hour at 60 ° C. The odor was concentrated using a vacuum apparatus and measured using an automatic thermal desorption system and GC-MS.

(8) chromaticity analysis

The chromaticity change of the purification process was analyzed by measuring the chromaticity immediately after performing the raw material, degumming, deacidification, and decolorization steps, respectively.

(9) Antioxidant Effect Analysis

Antioxidant effect was analyzed by measuring the amount of change of acid value and peroxide value according to antioxidant treatment time.

Experimental results carried out on the functional maintenance of the skatefish according to the above experimental example are as follows.

Table 3 shows the result of comparing the yield of Example 1 and Example 2.

Yield comparison result yield(%) Example 1 Example 2 Before degumming 43.6% 26.2% After Degumming (6%) 42% 23% After deoxidation (4%) 35% 17% After bleaching (5%) 13% 4%

Example 1 showed a yield of 262g on the basis of 1kg of raw material, and Example 2 showed a yield of 436g on the average of 1kg of raw material, and Example 2 showed about 1.7 times higher yield. In addition, after all the purification process, 130g purified oil was obtained in the case of Example 2, 40g purified oil was obtained in the case of Example 1, and as a result, Example 2 obtained about 3.25 times higher purified oil. Appeared to be.

Table 4 shows the results of measuring the change in phosphorus content for each citric acid concentration in Example 2 and Comparative Examples 1 to 3.

Measurement result of change in phosphorus content by citric acid concentration Citric acid Unrefined Comparative Example 1 Comparative Example 2 Example 2 Comparative Example 3 Phosphorus content
(mg / Kg) 89.78 ± 0.76 33.34 ± 0.16 0.51 ± 0.03 0.24 ± 0.03 0.4 ± 0.04

Phosphorus content of crude oil, which is an initial raw material maintenance, was 89.78 mg / kg, which was considerably high. mg / kg, Comparative Example 3 was shown to gradually decrease to 0.4 mg / kg, the optimum degumming conditions 6% citric acid aqueous solution of Example 2 showed the lowest value of 0.24 mg / kg.

The acid value, peroxide value, and yield change according to the content of sodium hydroxide in the deoxidation step are shown in Table 5.

Acid value, peroxide value, and yield measurement results according to sodium hydroxide content Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 2 Comparative Example 7 Acid
(mg KOH / g) 2.4 ± 0.04 1.87 ± 0.04 0.36 ± 0.07 0.18 ± 0.02 0.4 ± 0.12 Peroxide value
(meq / kg) 3.37 ± 0.07 3.01 ± 0.11 2.46 ± 0.09 1.37 ± 0.07 2.71 ± 0.04 yield
(%) 72 ± 0.01 76 ± 0.02 85 ± 0.02 83 ± 0.01 81 ± 0.01

Table 5 shows the acid value, the peroxide value, and the yield result by varying the concentration of the aqueous sodium hydroxide solution. When the concentration of 1% was treated in Comparative Example 4, the acid value was 2.4 mg KOH / g, the peroxide value was 3.37 meq / kg, and the yield was 72%. In Comparative Example 5, the acid value was 1.87 mg KOH / g. , Peroxide was 3.01 meq / kg, yield 76%, the acid value 0.36 mg KOH / g, peroxide value 2.46 meq / kg, yield 85% when treated at a concentration of 3% in Comparative Example 6. In Example 2, the acid value was 0.18 mg KOH / g, the peroxide value was 1.37 meq / kg, and the yield was 83%. In Comparative Example 7, the acid value was 0.4 mg KOH / g and the peroxide value was 2.71. meq / kg, yield 81%. As the optimum deoxidation condition, the acid and peroxide values were the lowest in 4% aqueous sodium hydroxide solution, and the yield was also good.

Table 6 shows the results of measuring acid value, peroxide value, and yield by varying the concentration of the activated carbon aqueous solution.

Acid value, peroxide value and yield measurement results according to activated carbon content Comparative Example 8 Example 2 Comparative Example 9 Comparative Example 10 Acid
(mg KOH / g) 0.24 ± 0.02 0.05 ± 0.02 0.33 ± 0.06 0.38 ± 0.05 Peroxide value
(meq / kg) 2.59 ± 0.04 1.21 ± 0.06 1.14 ± 0.06 1.16 ± 0.04 yield
(%) 37 ± 0.01 37 ± 0.02 32 ± 0.01 27 ± 0.01

According to Table 6, an acid value of 0.24 mg KOH / g, a peroxide value of 2.59 meq / kg and a yield of 37% were obtained when the concentration of 1% was treated in Comparative Example 8, and the acid value when the concentration of 5% was treated in Example 2 0.05 mg KOH / g, peroxide is 1.21 meq / kg, yield 37%, when treated with a concentration of 10% in Comparative Example 9, the acid value is 0.33 mg KOH / g, peroxide is 1.14 meq / kg, yield 32%. And when treated in a concentration of 15% in Comparative Example 10, the acid value 0.38mg KOH / g, peroxide 1.16meq / kg, yield 27%. As the optimum decolorization conditions, the acid value and the peroxide value were the lowest in the 5% activated carbon aqueous solution as in Example 2, it can be seen that the yield is also good.

Table 7 is a result of measuring the fatty acid content of Example 1, Table 8 is a result of measuring the fatty acid content of Example 2.

Fatty Acid Content of Example 1 Concentration (mg / g) EPA and DHA Content (mg / g) EPA and DHA content (%) Before degumming EPA 32.363 219.586 21 DHA 187.223 After degumming EPA 39.508 279.895 27 DHA 234.387 After deoxidation EPA 40.011 276.615 27 DHA 234.604 After bleaching EPA 41.201 282.046 28 DHA 240.845

Fatty Acid Content of Example 2 Concentration (mg / g) EPA and DHA Content (mg / g) EPA and DHA content (%) Before degumming EPA 36.595 235.65 23 DHA 199.055 After degumming EPA 39.176 250.188 25 DHA 211.012 After deoxidation EPA 43.313 281.184 28 DHA 237.871 After bleaching EPA 44.321 291.754 29 DHA 247.433

In the case of Example 1, the EPA and DHA content in the raw material oil and fat was about 21%, and after degumming, 27%, 27% after deoxidation, and 28% after decolorization, finally 282.046mg / g of EPA and DHA. In the case of Example 2, the EPA and DHA content in the raw material oil and fat was about 23%, and after degumming, 25%, 28% after deoxidation, and 29% after decolorization, finally 291.754 mg / g. The EPA and DHA content was higher than the 20% level, which is the standard for maintaining functional levels of the Ministry of Food and Drug Safety.

Table 9 shows the results of measuring the ammonia content according to the concentration of bamboo vinegar solution which is a deodorant.

Ammonia Content Determination Example 2 Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 3 Ammonia content 34.6% 18.9% 5.8% 2.8% 1.3%

In Example 2, which did not undergo the deodorization process using the bamboo vinegar solution, the odor component of the whole liver oil accounted for 34.6% of the ammonia odor component, and 1.3% of Example 3, which performed the deodorization process using the 7% concentration of bamboo vinegar solution, was used. It can be seen that the amount is reduced.

Table 10 shows the results of measuring the content of functional fats and oils before and after cold soaking.

The content of functional fats and oils before and after cold soaking density
(mg / g) EPA and DHA Content (mg / g) EPA and DHA content (%) Example 4 EPA 51.632 316.444 31% DHA 264.812

In Example 2 of Table 8 (without the cooling process), the content of EPA and DHA after bleaching was 291.754 mg / g, whereas Example 4 of Table 10 showed a value of 316.444 mg / g, which was used as a functional fat. It is judged to be excellent in use.

Table 11 is a result of measuring the chromaticity according to the purification process for Example 4.

Chromaticity Measurement by Purification Process Raw material Degum Deoxidation decolorization Cold Example 4 L 40.76 ± 0.03 41.9 ± 3.01 42.74 ± 0.09 45.05 ± 0.04 58.33 ± 0.02 a + 15.69 ± 0.06 + 13.84 ± 0.04 + 0.06 ± 0.03 -2.59 ± 0.01 -3.75 ± 0.03 b + 24.58 ± 3.94 + 24.17 ± 4.38 + 22.79 ± 3.96 + 18.92 ± 0.9 + 8.86 ± 0.06

In Table 11, the L value represents the brightness and becomes whiter as the value increases. The value a is biased toward red or purple if it is positive, and to green when negative. The value b is blue for negative numbers and yellow for positive values. In Example 4, the L value after the purification process (degumming, deoxidation, decolorization, and cold soaking) was 58.33, showing a bright value, a value of -3.75, and b value of +8.86. Such chromaticity change can be more clearly distinguished through FIG. 8. 8 is a diagram illustrating a result of measuring chromaticity according to each purification process of Example 4. FIG. In FIG. 8, the first picture on the left is chromaticity 801 immediately after degumming, the second picture is chromaticity 802 immediately after deoxidation, the third picture is chromaticity 803 immediately after decolorization, and the fourth picture is immediately after cold Chromaticity 804 after all purification. As such, it can be visually confirmed that the functional maintenance of the skatefish gradually clears through each step of the purification process.

Table 12 shows the results of measuring the acid value, peroxide value, and TBA value immediately after soaking / after 24 hours / 48 hours / 72 hours / 96 hours after soaking Example 5 and Comparative Example 1 in a constant temperature water bath at 100 ° C., respectively. .

Acid, Peroxide, and Thiobarbitulic Acid (TBA) Measurement Results According to Antioxidant Treatment Time Processing time 0h 24h 48h 72h 96h Acid Example 5 0.25 0.26 0.48 1.37 1.88 Comparative Example 1 0.05 0.75 3.49 5.08 6.59 Peroxide value Example 5 1.21 1.94 2.76 3.44 5.36 Comparative Example 1 1.21 5.32 10.15 13.29 15.78 TBA Example 5 125.416 137.068 140.534 147.003 162.744 Comparative Example 1 125.416 145.644 167.279 180.295 189.312

The initial acid value of Example 5 was 0.05, the peroxide value was 1.21, the TBA value was 125.416, and after 96h, the acid value was 1.88, the peroxide value was 5.36, and the TBA value was 162.744. On the other hand, in Comparative Example 1 without an antioxidant, the value of the acid value of 6.59, the peroxide value of 15.78, and the TBA of 189.312 showed a significantly low value when the antioxidant was treated.

Table 13 shows the results of measuring the unsaturated fatty acid (EPA, DHA) content of the mature skate.

Unsaturated Fatty Acids (EPA, DHA) Content in Aged Skate Products density
(mg / g) EPA and DHA Content (mg / g) EPA and DHA content (%) Comparative Example 14 EPA 36.956 254.696 25% DHA 217.74 Example 6 EPA 43.452 299.569 29% DHA 256.117 Example 7 EPA 45.597 309.57 30% DHA 263.973

In Comparative Example 14, which is a mature skate that did not use functional oils of skates, the unsaturated fatty acid contained 25% at 254.66 mg / g, but 299.569 mg / of Example 6 in which the functional oils of skates were dipped. g is 29%, and Example 7, which is another example of immersed functional oil of skate, also shows 309.57 mg / g, 30%. As such, by immersing the functional fat of the spearfish prepared according to the present invention to produce mature skates, it is possible to produce mature skates having higher unsaturated fatty acid (EPA, DHA) content.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (10)

A first step of trimming the edible part from the skate, and separating the skate;
A second step of extracting the skate oil from the separated skate; And
A third step of purifying the skate oil extracted from the skate;
Method for extracting a functional fat from a skate. The method of claim 1,
The second step,
Slicing the separated skates to a size of 1 to 3 mm;
Steaming the minced skates at a steamer at 95 to 100 ° C. for 40 to 90 minutes;
Vacuum filtering the liquid generated in the steaming step to remove residues;
Method for extracting a functional fat from a skate. The method of claim 1,
The second step,
Slicing the separated skates to a size of 1 to 3 mm;
Immersing the sliced skate in 22 ~ 25 hours with a chloroform and methanol mixture;
Washing the solution by putting 10% sodium chloride (NaCl) in an aqueous solution;
Dewatering the washed skates using sodium sulfate anhydrous and filter paper; And
Removing the organic solvent from the dewatered skate, using a rotary evaporator;
Method for extracting a functional fat from a skate. The method of claim 1,
The third step,
Separating and degumming phospholipids and gums from the extracted skate oil;
Deoxidizing by removing free fatty acid from the degreased skate; And
Decolorizing the pigment in the deacidified skate;
Method for extracting a functional fat from a skate. The method of claim 4, wherein
The degumming step,
Adding an aqueous solution of citric acid (citric acid) at 60 to 65 ° C. to the extracted skate oil;
A step of stirring for 20 to 25 minutes at 300-320 rpm at 60-65 ° C. in the skate oil to which the citric acid aqueous solution was added; And
Centrifuging the stirred skate oil at 1,500 to 1,800 rpm for 15 to 20 minutes to remove lecithin, gums, phospholipids and proteins;
Method for extracting a functional fat from a skate. The method of claim 4, wherein
The deoxidation step,
Adding an aqueous alkaline solution to the degreased skate oil;
Reacting the skates to which the alkaline aqueous solution is added are stirred for 20 to 25 minutes at 200 to 250 rpm at 60 to 65 ° C .;
Centrifuging the stirred skate oil at 3,000 to 3,500 rpm for 15 to 20 minutes to remove free fatty acid salts;
Mixing 4 ~ 10 ° C. water in the skates from which the free fatty acid salts have been removed, and then placing them in a fractional filter head for 5 to 10 minutes; And
Removing the remaining free fatty acid salt and alkali component by repeating the process of removing the lower layer solution from the skates left in the fractional filter;
Method for extracting a functional fat from a skate. The method of claim 4, wherein
The decolorizing step,
Adding a decolorant to the deacidified skate oil;
Depressurizing the skater to which the bleaching agent is added at 60 to 65 ° C. for 20 to 30 minutes; And
Passing the filter through reduced pressure filtration to remove the decolorant;
Method for extracting a functional fat from a skate. The method of claim 4, wherein
After the n-hexane was mixed with the dehydrated skate oil and left to crystallize at -70 to -65 ° C. for 12 to 18 hours, the crystals were separated by filtration using a suction filter and the n-hexane was removed by a rotary vacuum concentrator. Chilling step;
Method for extracting a functional fat from the skates. Functional oils and fats of a skatefish prepared by the method of extracting functional oils and oils from the skates according to claim 1. Matured skates prepared by immersing the functional oil of the skates prepared according to claim 1.

Images