KR20160040882A - Method for refinement of lipid extracing by-products of aquatic products - Google Patents

Abstract

The present invention relates to a purification method of lipids extracted from byproducts of processing marine products. More particularly, the purification method of lipids extracted from byproducts of processing aquatic products hydrolyzes the byproducts of processing marine products using proteases and simultaneously separates the hydrolysis product into a protein layer and a lipid layer. Further, the purification method uses the protein layer to prepare a liquid fertilizer, and uses the lipid layer to manufacture products such as a capsule containing high degree of unsaturated fatty acids, or the like. Therefore, the purification method of the present invention does not discard the lipid layer which is additionally generated in the process of the purification method, and recovers the lipid layer, thereby enhancing an effective use of raw materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for purifying lipids extracted from a by-

The present invention relates to a method for purifying lipids extracted from fish processing by-products. More specifically, the byproducts of fish processing are hydrolyzed by proteolytic enzymes and then separated into protein and lipid layers. The protein layer is used to make liquid fertilizers. The lipid layer is purified through a purification process Capsules or the like, thereby improving the effective utilization of the lipid layer by recycling without discarding the lipid layer, which is generated additionally.

Generally, aquatic products contain a large amount of functional ingredients. Among the functional components, EPA (eicosapentanoic acid) and DHA (didocosahexanoic acid), which are n-3 polyunsaturated fatty acids, act on blood vessels or atherosclerosis and are useful for physiological actions such as vasodilation, platelet aggregation, blood TG and cholesterol lowering, It is known to affect.

In particular, mammals are the essential fatty acids that must be obtained from the outside through diets because the precursors of EPA and DHA, a-linolenic acid and linoleic acid, are not synthesized in the body. In addition, a-linolenic acid and linoleic acid are effective in converting EPA and DHA in the body to about 10 ~ 15% in adults and 3 ~ 6% in children, so the efficacy of EPA and DHA In order to function in the body, direct intake of DHA and EPA-containing foods is more effective than consumption of precursors such as a-linolenic acid and linoleic acid.

Foods that contain a lot of DHA and EPA are mackerel. Mackerel is a turbulent extraterrestrial fish species distributed in tropical and temperate waters. It has the highest lipid content in mackerel, saury, sardine and mackerel, and has the most abundant polyunsaturated fatty acids (PUFA) such as EPA and DHA.

Accordingly, various purification processes for purifying fish oil for use in foods using fish oil or in the form of capsules for commercialization have been disclosed.

Korean Patent Publication No. 2002-0048912 (2002.6.24) discloses a method for isolating DHA and EPA using proteolytic enzymes in seafood embryos, which comprises hydrolyzing the intestines of fish and shellfish into a fermentation tank with a protease, The binding force between the phospholipid and the protein is lowered in the hydrolysis step, and the separation is performed using the difference in the specific gravity of the phospholipid and the protein.

However, the prior art describes only the separation process between lipid and protein, and there is no detailed description of purification process after separation.

DISCLOSURE Technical Problem The present invention has been devised to solve the problems as described above, and it is an object of the present invention to provide a method for separating a protein layer and a lipid layer from each other after decomposition using a proteolytic enzyme during hydrolysis in a hydrolysis process, It is an object of the present invention to provide a method for purifying lipids extracted from a by-product of aquatic products which can be reused without being disposed of by disposing the lipid layer in the form of capsules containing polyunsaturated fatty acids.

In order to accomplish the above object, the present invention provides a method for purifying lipids extracted from a by-product of aquatic products processing, comprising the steps of: (a) hydrolyzing a byproduct of a fish product using proteolytic enzymes, separating the protein and lipid layers, Extracting the obtained lipid layer; (b) a step of removing gum, which is a colloidal impurity including a phospholipid, by mixing a citric acid aqueous solution of 3% concentration with the result of step (a); (c) a deoxidation step of removing the acid value and the peroxide value by treating the resultant product of step (b) with an alkali aqueous solution at least once, followed by rinsing with water; (d) a discoloring step of removing coloring matter and heavy metals by using an adsorbent containing activated carbon, magnesium silicate, and activated clay to the result of step (c); And (e) a cold-freezing step of cooling the crystallized saturated fatty acid by filtration to cool the saturated fatty acid contained in the result of the step (d) at a predetermined temperature or lower in order to crystallize the saturated fatty acid.

After the addition of a citric acid aqueous solution having a concentration of 3% to the resultant product of step (a), the mixture was stirred at a rate of 300 rpm at 60 DEG C for 20 minutes, and the resultant mixture was centrifuged at 1,500 rpm for 15 minutes, Only the liquid can be taken, and the ginseng containing phospholipids as the lower layer can be removed.

Further, in the deoxidation step, an aqueous 8% alkaline solution was added to the resultant product of step (b), stirred at 60 ° C for 20 minutes at 200 rpm in a reactor, and centrifuged at a speed of 3,000 rpm for 15 minutes, The process of only taking up the raw material is repeated a plurality of times and centrifugation is carried out at a speed of 100 rpm for 10 minutes to remove the impurities including the fatty acid salt component remaining in the supernatant.

According to the present invention, the byproducts of fish processing are hydrolyzed by proteolytic enzymes and then separated into protein layer and lipid layer, and the protein layer is used to make liquid fertilizer. The lipid layer is purified through a purification process to contain polyunsaturated fatty acid The present invention has the effect of increasing the effective utilization by recycling the added lipid layer without discarding the generated lipid layer.

In addition, according to the present invention, when extracting a by-product of aquatic products, the protein layer and the lipid layer are separated into a protein layer and a lipid layer by using a proteolytic enzyme without heat treatment.

FIG. 1 is a flowchart illustrating a method for purifying lipids extracted from a by-product of processing aquatic products according to a preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to designate the same or similar components throughout the drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, the preferred embodiments of the present invention will be described below, but it is needless to say that the technical idea of the present invention is not limited thereto and can be variously modified by those skilled in the art.

Prior to the present invention, the present applicant filed a "Method for manufacturing high-speed fermentation environmentally friendly amino acid fertilizer using marine processing by-products" (Korean Patent Application No. 10-2013-0135113, filed on November 11, 2013, hereinafter referred to as " There is one. According to the above-mentioned invention, a by-product of aquatic products is pulverized and a protein layer hydrolyzed with a low molecular weight by using a proteolytic enzyme is fermented as a microorganism to be produced as an environmentally friendly amino acid fertilizer. The present invention provides an advantageous effect that the effective utilization of the raw materials can be enhanced by making the lipid layer to be discarded recyclable by making it possible to produce the product through the purification method according to the method of purifying the lipid extracted from the byproducts of fisheries processing according to the preferred embodiment of the present invention.

FIG. 1 is a flowchart illustrating a method for purifying lipids extracted from a by-product of processing aquatic products according to a preferred embodiment of the present invention.

The method for purifying lipids extracted from fishery processing by-products according to a preferred embodiment of the present invention includes an extraction process (P100), a de-sludging process (P200), a deoxidation process (P300), a decoloring process (P400), and a cold- .

The extraction process (P100) is a process of hydrolyzing a byproduct of aquatic products using a proteolytic enzyme, separating the protein layer and the lipid layer, and extracting only the lipid layer.

When the byproducts of fisheries processing are separated into a protein layer and a lipid layer, it is decomposed using proteolytic enzymes, so that denaturation of the resultant product due to heat treatment can be prevented, and the molecular weight of the degraded product can be minutely increased, There is an effect.

The ratio of polyunsaturated fatty acids in saturated fatty acids was higher than that of saturated fatty acids. Especially DHA (C22: 6n3 fatty acids) was found to be highly unsaturated fatty acids .

The deoxidation process (P200) is a process for removing gum quality which is a colloidal impurity including a phospholipid contained in the raw material retention as a result of the P100 process.

Particularly, the phospholipid contained in the fat is emulsifiable, which makes it difficult to separate the fatty acid generated in the next process, deoxidation process, and causes browning, so it is removed through the P200 process.

The organic acid containing citric acid may be used as a substance for removing the phospholipid in the elimination step P200, but it is not limited to citric acid because citric acid, citric acid, and the like can be used.

Hereinafter, the table shows the results of testing the optimal concentration of citric acid, which has a high separation efficiency of the gum in the deionization step (P200).

Citric acid concentration One% 2% 3% 4% 5% yield 78% 80% 68% 69% 76%

Referring to Tables 1 to 2, when the citric acid aqueous solution was added at a concentration of 3%, the yield of 68% was obtained, and it was found that the gum containing the phospholipid was most removed. When the citric acid aqueous solution was added at a concentration of 4% And 69%, respectively. However, the addition of a higher concentration (4%, 5%) results in a decrease in the amount of the separated gum, which is considered to be the most preferable setting condition. Here, the yield indicates the yield after separation of the gum from the raw material holding, and the lower the yield value, the more the gum is removed.

In the deionization step (P200), citric acid aqueous solution of 3% concentration at 3% concentration was stirred (300 rpm) in a reactor at 60 ° C for 20 minutes, centrifuged at a speed of 1500 rpm for 15 minutes, Remove the gum vagina.

The deoxidation process (P300) is a process for treating the result of the P200 process with an alkaline aqueous solution at least once and then washing with water to maintain the neutral state.

The P300 process is referred to as 'free fatty acid' when the raw material is exposed to the air and is bound to oxygen and is then shrouded. The amount of free fatty acid measured is called 'acid value'. The higher the acid value, the more inadequate the food is consumed. Since it affects the subsequent decolorization process (P400), it reacts with the aqueous alkaline solution to form a fatty acid salt A process for removing the acid value is necessary.

In measuring the acid value of the result of the P200 process, the acid value is 18, so that the alkali value is lowered by treating the alkali aqueous solution. When the alkali aqueous solution is treated at the concentration of 8%, the acid value is reduced to 1. In the alkali aqueous solution having the concentration of 8% or more, it is difficult to wash the aqueous solution at a concentration of 8%. For example, the aqueous alkaline solution may be NaOH, but is not limited to an aqueous alkaline solution.

Even in the case of the peroxide value, the higher the concentration of the alkali aqueous solution, the larger the decrease rate of the peroxide value, but the aqueous alkali solution of 8% concentration is preferable.

For example, an aqueous 8% alkali solution can be treated at 20% of the raw material retention.

More specifically, in the P300 process, an alkali aqueous solution of 8% concentration is added to the result of the P200 process, followed by stirring at a speed of 200 rpm for 20 minutes at 60 DEG C, followed by centrifugation at a speed of 3,000 rpm for 15 minutes to obtain an supernatant . Thereafter, water at 60 캜 is added and mixed, and the process of removing the lower layer liquid is repeated until it becomes a neutral state. After centrifugation at 100 rpm for 10 minutes, the supernatant is removed to remove residual fatty acid salts and peroxide.

The decolorization process (P400) is a process for reducing the acid value and the peroxide value by removing pigments and heavy metals by using an adsorbent containing activated carbon, magnesium silicate, and activated clay to the result of the P300 process. For example, the treatment of the adsorbent comprising magnesium silicate and active clay is preferably 10%. When 10% is exceeded, the decolorization process (P400) is not performed smoothly due to the absence of the decrease in chromaticity, and the peroxide value is increased at 10% or less. Therefore, 10% treatment is the most desirable condition.

More specifically, an adsorbent containing activated charcoal, magnesium silicate and activated clay is added to the raw material washed by the deoxidation process (P300), the reaction is carried out at 60 DEG C for 20 minutes under reduced pressure, a 0.45um filter paper is placed, and filtration under reduced pressure is performed. As a result, the adsorbent adsorbing the pigment and the heavy metal and the purified raw material oil are separated and filtered.

Cooling process (P500) is a process that is performed to reduce saturated fatty acids and increase omega-3 fatty acids. The P500 process was allowed to stand in the temperature range of 4 ° C to -20 ° C for 12 hours, filtered through a 0.45-μm filter, filtered, mixed with 10-fold nucleic acid, left at -70 ° C for 12 hours, do. Since the saturated fatty acid crystallizes below the predetermined temperature, the saturated fatty acid contained in the raw material retention is crystallized by filtration through the filter, so that the saturated fatty acid content can be reduced through the P500 process.

Hereinafter, examples of methods for measuring acid value, peroxide value, and fatty acid in a method for purifying lipids extracted from a by-product of fish processing according to a preferred embodiment of the present invention will be described. Here, the method of measuring acid value, peroxide value, and fatty acid is not limited to the following examples.

Acid value is the amount of alkali aqueous solution necessary to neutralize the free fatty acid contained in the raw material holding sugar, and the amount of the free fatty acid which is not the glycride binding type is measured. Usually, the feedstock retention after the refining process is less than 1.0.

1. Acid value measurement method

The mixture was mixed with 100 ml of the mixed solution of ethyl-ether: ethanol = 2: 1, and then 3 drops of phenolphtalein indicator was added. The pale pink color lasted for 30 seconds with 0.1N KOH-ethanol Titrate until time.

AV = 5.611 * a * F / b

a: consumption of 0.1 N KOH-ethanol (ml)

b: sample amount (g)

F: Potency of 0.1N KOH-ethanol

The peroxide value is an equivalent number of the peroxide contained in the raw material oil, which increases as the oxidation of the raw material oil progresses, and decomposes into carbonyl compounds and decreases.

As the peroxide value is higher, it is not suitable for commercialization. Therefore, the peroxide value is selected to select an appropriate peroxide value.

2. Method of measuring peroxide value

Mix the raw material with 30 ml of mixed solution of acetic acid: chloroform = 3: 2 to dissolve the raw material, add 1 ml of KI saturated solution, and shake vigorously for 5 minutes. After adding 30 ml of water and shaking, add 1 ml of 1% strength starch solution and titrate until the purple color becomes dark with 0.01 N Na ₂ S ₂ O ₃ solution and lasts for 30 seconds.

POV = (a-b) * F * 0.01 * 1000 / c

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

b: Potency of 0.1 N Na ₂ S ₂ O ₃

0.01269: g number of I ₂ corresponding to 1 ml of 0.1 N Na ₂ S ₂ O ₃

3. Fatty acid measurement

After dissolving the fatty acids, filter with anhydrous sodium sulphate and 0.45uM filter pater and remove the solvent with a rotary evaporator. Then, the extracted lipids are mixed with a 0.5N NaOH-Methanol aqueous solution, hydrolyzed at 75 ° C for 60 minutes, and subjected to BF ₃ complex and methyl esterification at 75 ° C for 15 minutes. Then, 3 ml of hexane is added and the supernatant is taken and analyzed by GC (Gas Chromatograph).

After the deoxidation process (P200), the raw material is retained by neutralization and washing with acid-catalyzed esterification without passing through a deoxidation process (P300), a decoloring process (P400), and a cold-rolling process (P500) Biodiesel can be produced through esterification, and a gum which has not undergone the deoxidation process (P200) can be added to liquid fertilizer.

It will be apparent to those skilled in the art that various modifications, substitutions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. will be. Therefore, the embodiments disclosed in the present invention and the accompanying drawings are intended to illustrate and not to limit the technical spirit of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments and the accompanying drawings . The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

P100 - Extraction process P200 -
P300 - Deoxidation process P400 - Discoloration process
P500 - Cooling process

Claims (3)

(a) hydrolyzing a byproduct of a fishery product using proteolytic enzymes, separating the product into a protein layer and a lipid layer, and extracting the obtained lipid layer in the supernatant;
(b) a step of removing gum, which is a colloidal impurity including a phospholipid, by mixing a citric acid aqueous solution of 3% concentration with the result of step (a);
(c) a deoxidation step of removing the acid value and the peroxide value by treating the resultant product of step (b) with an alkali aqueous solution at least once, followed by rinsing with water;
(d) a discoloring step of removing coloring matter and heavy metals by using an adsorbent containing activated carbon, magnesium silicate, and activated clay to the result of step (c); And
(e) a cold-pressing step of cooling the crystallized saturated fatty acid by filtration to cool the saturated fatty acid contained in the result of step (d)
By-product of aquatic product processing. The method according to claim 1,
In the deionization step, citric acid aqueous solution of 3% concentration was added to the resultant product of step (a), and the mixture was stirred at 60 ° C and 300 rpm for 20 minutes. The resultant mixture was centrifuged at 1,500 rpm for 15 minutes, And removing the gum containing the phospholipid, which is the lower layer, from the by-product of the processing of aquatic products. The method according to claim 1,
In the deoxidation step, an aqueous 8% alkaline solution was added to the resultant product of step (b), stirred at 60 rpm for 20 minutes at 200 rpm in the reactor, and centrifuged at a speed of 3,000 rpm for 15 minutes to retain the raw material Is subjected to centrifugation at a speed of 100 rpm for 10 minutes to remove the impurities including the fatty acid component remaining in the supernatant by taking the supernatant and purifying the lipid extracted from a by-product of aquatic products processing.

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