KR102015987B1 - Method eliminating fish smell from salmon oil - Google Patents

Abstract

The present invention relates to a method for removing a fish smell of a salmon oil, which comprises the steps of: (S10) cooling a salmon oil, which is liquid at room temperature, and solidifying the same; (S20) decreasing a pressure around the solidified oil to 0 to 1 torr; (S30) removing gas generated in a pressure range of 0.3 to 5 torr, which is a pressure range in which a fish smell is generated, while increasing a temperature of the solidified oil; and (S40) removing the fish smell by eluting the oil, at a mixing ratio of 4 : 1 (v/v) of a mixing solvent of hexane and ethylacetate, from a column filled with a porous silica gel prepared by stirring a silica precursor having a 1,3-bis(triethoxysilyl)benzene group, hexamethyldisilane, and 3-aminopropyltriemethoxysilane in the presence of a surfactant.

Description

How to remove odor of salmon oil {Method eliminating fish smell from salmon oil}

The present invention relates to a method for removing odor of salmon oil, and more particularly, to provide a method capable of removing odor of salmon oil by only one continuous process.

Salmon oil is known to be rich in unsaturated fatty acids such as EPA (Eicosapentaenoic Acid) and DHA (Docosahexaenoic Acid). EPA and DHA are unsaturated fatty acids (omega 3 fatty acids) that must be consumed through foods such as fish oil, and are effective in preventing various diseases such as lowering cholesterol and promoting brain function.

As a technique for removing the odor of the conventional fish oil, Patent No. 10-0822059 is a step of solidifying by cooling the raw fish oil raw material at room temperature; Lowering the pressure around the solidified fish oil raw material; And while raising the temperature of the solidified fish oil raw material, there is disclosed a fish oil odor removal method comprising the step of removing the gas generated in the odor generating pressure range that is the pressure range in which odor occurs (see Fig. 1). . However, the prior art document, as can be seen in the apparatus of Figure 1, the process is complicated in that the odor can be substantially removed only by repeating the process two to three or more times to reduce the process efficiency It has a problem that causes it.

Accordingly, it is required to develop a method for removing fish odor that can increase process efficiency with a simple process by allowing fish to be removed in one continuous process without repeating the process without changing the chemical properties of the useful nutrients of salmon oil. have.

Republic of Korea Patent No. 10-0822059 (2008.04.07)

Therefore, it is an object of the present invention to provide a method capable of removing fish odor of salmon oil by only one continuous process in order to increase process efficiency with a simple process.

Salmon oil odor removal method according to an embodiment of the present invention for achieving the above object, the step of solidifying by cooling the salmon oil liquid at room temperature (S10); Lowering the pressure around the solidified oil to a pressure of 0 torr to 1 torr (S20); Removing the gas generated in a pressure range of 0.3 torr to 5 torr, which is a pressure range in which odor is generated while raising the temperature of the solidified oil (S30); And a silica precursor, hexamethyldisilane and 3-aminopropyltrimethoxysilane having a 1,3-bis (triethoxysilyl) benzene} group in the presence of a surfactant In the column filled with porous silica gel, the oil may be eluted at a mixing ratio of 4: 1 (v / v) of a mixed solvent of hexane: ethyl acetate to remove odor (S40).

In addition, in the method for removing fish odor of salmon oil according to the present invention, a silica precursor having 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene} group, hexamethyldisilane, and 3 The weight ratio of aminopropyltrimethoxysilane is characterized by being 2: 5: 3.

In addition, in the method for removing fish odor of salmon oil according to the present invention, the step of removing the fish odor (S40), the mixing ratio of the mixed solvent of hexane: ethyl acetate: butanol in the oil filled column 4 It is characterized in that it removes the odor by eluting at 1: 1 (v / v).

According to the present invention, the process of removing fish odor from the conventional fish oil is capable of removing fish odor only when repeated two or more times cyclically, which has a problem that the process is complicated and causes a decrease in process efficiency. Bar, the present invention can increase the process efficiency in a simple process by allowing the removal of fish in one continuous process without repeating the process.

1 is a photograph showing a device for removing the fish odor of the conventional fish oil.
2 is a view showing a gas collecting container according to an embodiment of the present invention.
Figure 3 is a graph showing the concentration change of the odor generating gas according to the odor removal process according to an embodiment of the present invention.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

Salmon oil odor removal method according to the present invention, cooling the solid salmon oil at room temperature to solidify (S10); Lowering the pressure around the solidified oil to a pressure of 0 torr to 1 torr (S20); Removing the gas generated in a pressure range of 0.3 torr to 5 torr, which is a pressure range in which odor is generated while raising the temperature of the solidified oil (S30); And a silica precursor, hexamethyldisilane and 3-aminopropyltrimethoxysilane having a 1,3-bis (triethoxysilyl) benzene} group in the presence of a surfactant In the column filled with porous silica gel, the oil may be eluted at a mixing ratio of 4: 1 (v / v) of a mixed solvent of hexane: ethyl acetate to remove odor (S40).

Wherein the step of solidifying (S10) is to solidify by cooling the salmon oil liquid at room temperature. At this time, the raw material of salmon oil can be put into the container and cooled, but the container is not particularly limited, but it is preferable to use a container made of a material capable of maintaining durability even at cryogenic temperatures. Alternatively, instead of cooling in the vessel, it may be cooled in a refrigeration system to solidify and then transferred to a separate vessel.

The method of lowering the temperature of the salmon oil to cryogenic temperature to solidify the salmon oil may be lowered using liquid nitrogen, liquefied air, dry ice, or the like. That is, when these liquid nitrogen, liquefied air, dry ice, etc. change into gas, the temperature of the salmon oil can be lowered to cryogenic temperature using the heat of vaporization. As such, the configuration of the device for lowering the temperature of salmon oil using liquid nitrogen or the like is well known to those skilled in the art, and thus detailed description thereof will be omitted.

Through this, the temperature of the salmon oil can be lowered to cryogenic temperature so that the salmon oil can be physically solidified by changing below the freezing point.

The pressure lowering step (S20) is to lower the pressure around the solidified oil to a pressure of 0 torr to 1 torr. The method of lowering the pressure may be achieved by placing the solidified salmon oil raw material in the same space as the container and removing the gas inside the container. The method of removing the gas inside the container can be removed using, for example, a vacuum pump, and the detailed configuration of the device is well known to those skilled in the art, and thus detailed description thereof is omitted here. When removing the gas in the container, it is preferable to use the refrigerant so that the salmon oil component in the container does not phase change and maintains the solid phase. For this purpose, it is preferable to carry out the removal of the gas slowly. The pressure around the solidified salmon oil raw material is preferably a pressure of 1 torr or less. If the pressure exceeds 1 torr, sublimation of the salmon oil raw material may not occur smoothly in a subsequent process.

The step of removing the gas (S30) is to remove the gas generated in the pressure range of 0.3 torr to 5 torr, which is a pressure range in which odor occurs while raising the temperature of the solidified oil. While raising the temperature of the solidified salmon oil raw material, the gas generated in the odor generating pressure range which is the pressure range in which odor is generated is removed. When the temperature of the solidified salmon oil raw material is gradually raised, since the inside of the container is low pressure, the boiling point is sequentially sublimed to change into gas. As the temperature inside the vessel gradually rises, the ingredients having a higher boiling point gradually sublimate. Sublimed gas may be separated to the outside using a vacuum pump or the like and recycled to the salmon oil raw material. At this time, since the pressure inside the container is almost equal to the vapor pressure of the raw salmon oil, the temperature of the salmon oil and the pressure inside the container can be regarded as directly proportional.

When a certain pressure range is reached, the gas generated in the odor generating pressure range, which is the temperature at which the component causing odor occurrence, sublimes, is selectively removed. The odor generating pressure range may be different depending on the fish species used in the production of salmon oil, a method of producing oil, and the like, and may have a range of about 0.3 torr to 5 torr.

It is preferable that the increase of the temperature proceeds very slowly, preferably at a temperature increase rate of about 0.1 ° C. to about 10 ° C. per minute, and more preferably at a temperature increase rate of about 0.3 ° C./min to 3 ° C./min. .

The removal method of the component which generate | occur | produces in a odor generating pressure range can use various methods, It does not specifically limit. For example, the gas generated in the pressure range may be separated and removed by cooling again using a refrigerant, or the gas generated in the pressure range may be removed by being adsorbed on a high surface area adsorbent such as activated carbon. In addition, since the odor generating material generally has a slightly negative functional group such as an amine group or a sulfone group, the odor generating gas component may be selectively used by making the gas collecting container have a positive charge. Can be removed. The gas collecting container is not limited in shape, and may be provided with a device capable of applying a positive voltage or a negative voltage.

One embodiment of the gas collecting container is shown in FIG. Referring to FIG. 2, the gas collection container 110 may have a U-shaped tube, and valves 120a and 120b may be provided at both ends to block gas from entering and exiting. In addition, as shown in FIG. 2, an electrode may be provided to apply a voltage of −100 V to +100 V between the electrodes. When an electrode is applied in such a gas collection container, a charged gas component is induced near the electrode, thereby making it possible to collect it.

Removing the odor (S40) is a silica precursor having 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene} group, hexamethyldisilane and 3-aminopropyltrimethoxy In the column filled with porous silica gel prepared by stirring the silane in the presence of a surfactant, the oil is eluted at a mixing ratio of 4: 1 (v / v) of a mixed solvent of hexane: ethyl acetate to remove odor. In the conventional case, the odor can be removed only when the solidification step, the pressure drop step, and the step of removing the gas generated in the odor generating pressure range are repeated two or more times in a cyclic manner, but in this case, the process is complicated. In order to solve this problem, the present invention is characterized by adopting this step in order to solve the problem and to remove the fish in one continuous process without repeating the process.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

<Example 1> Determination of the odor generating pressure range

Fish oil extracted from salmon was placed in a container and solidified with liquid nitrogen. Then, the gas inside the vessel was removed using a vacuum pump connected to the top of the vessel and the pressure inside the vessel was lowered to 0.03 torr. The temperature and pressure were increased while gradually removing the refrigerant, and the gas produced by sublimation was extracted to the outside and smelled snorting in turn to confirm that smell was generated. As a result, the first pressure was detected in the fish odor was 0.5 torr, it was detected that the odor occurs until 12 torr. In addition, a gas sample was taken from the pressure range, and gas chromatographic analysis was performed to confirm the position at which the main peak appeared.

Example 2 Degassing

In the same manner as in Example 1, the fish oil extracted from salmon was examined whether odor was detected and samples were taken to measure the concentrations of DHA and EPA. In addition, gas chromatography analysis was performed on the sample. It was then placed in a container and solidified with liquid nitrogen. Then, a vacuum pump connected to the top of the vessel was used to remove the gas inside and lower the pressure inside the vessel to 0.03 torr.

While slowly removing the refrigerant, the sublimated gas is taken out, cooled by using a refrigerant, recycled to a vessel containing fish oil, and gas close to the gas collection vessel until the pressure reaches 0.5 torr to 12 torr. Was collected by removal. At this time, the temperature increase rate was 0.5 degreeC / min. In addition, the method of removing gas used the method of cooling a gas collection container with liquid nitrogen, and liquefying the collected gas, and removing. At the time of gas collection, the voltage applied to the electrode of the gas collection container was + 100V. When the pressure in the vessel exceeded 12 torr and exceeded the odor generating pressure range, the sublimed gas was raised to room temperature without discharged to the outside. Odor was examined whether fish odor occurred in salmon oil whose temperature rose to room temperature. In addition, samples of fish oil were taken to measure the concentrations of DHA and EPA and subjected to gas chromatography analysis.

<Example 3> Fish odor removal

In order to remove the odor from the salmon oil obtained in Example 2, in order to prepare a porous silica gel of step S40 of the present invention, as a surfactant as a template material for forming pores, poly (ethylene oxide) -b-poly (propylene oxide 40 g of) -b-poly (ethylene oxide) was added to a polyethylene vessel with 1500 mL of 1.6 M HCl, and the mixture was dissolved by stirring at room temperature. Then, 20 g of 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene}, 50 g of hexamethyldisilane and 30 g of 3-aminopropyltrimethoxysilane were added thereto and maintained at 40 ° C. Stir for 24 hours. After aging for 24 hours in an autoclave maintained at 100 ℃, the resulting porous material was filtered and dried at 40 ℃, vacuum. Dispersed in 200 mL of ethanol per 1 g of the porous material prepared to remove the surfactant, refluxed for 8 hours, filtered and washed with ethanol, and vacuum-dried for 24 hours at 80 ℃.

Salmon oil was eluted at a mixing ratio of 4: 1 (v / v) of a mixed solvent of hexane: ethyl acetate in a column filled with porous silica gel prepared by stirring in the presence of the surfactant to remove odor.

<Example 4> Fish odor removal

The same procedure as in Example 3 was carried out, but the fish odor was removed by allowing the mixed solvent of hexane: ethyl acetate: butanol to be eluted at a mixing ratio of 4: 1: 9 (v / v) instead of the mixed solvent of Example 3.

<Sensory test result>

The first salmon oil, salmon oil according to the conventional method of performing the step S10 to S30 once, salmon fish obtained after the fish removal process (steps S10 to S40) according to the present invention 20 testers fish odor on a five-point scale The occurrence was examined.

Further, instead of using the porous silica gel of Example 3, 20 g of 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene}, 1,2-bis (triethoxysilyl) ethane {1,2-bis (triethoxysilyl) ethane 80g (Comparative Example 1), 1,3-bis (triethoxysilyl) benzene} 5g 1,2-bis (triethoxy The odor was removed in the same manner using a silica gel column prepared by adding 95 g of silyl) ethane {1,2-bis (triethoxysilyl) ethane (Comparative Example 2).

In addition, instead of using the mixed solvent of Example 3, hexane (comparative example 3), ethyl acetate (comparative example 4), butanol (comparative example 5), a mixed solvent of hexane: butanol having a mixing ratio of 4: 1 (comparative example) 6) The odor was removed in the same manner using a mixed solvent of ethyl acetate: butanol having a mixing ratio of 1: 9 (Comparative Example 7) as a solvent.

The score was 1 point for clarity, 2 points for slightly odor, 3 points for odor, 4 points for no odor, and 5 points for no odor. Ranked. As a result, the same results as in Table 1 were obtained.

division 1 point 2 points 3 points 4 points 5 points First salmon oil (raw material) 19 people 1 person 0 0 0 Perform the conventional method once
(S10 to S30 step once) 0 12 people 8 people 0 0 Example 3 of the present invention (perform step S10 to step S40)
In the case of the mixing ratio of 4: 1 (v / v) of the mixed solvent of hexane: ethyl acetate 0 0 0 1 person 19 people Example 4 of the present invention (perform step S10 to step S40)
Mixing ratio of hexane: ethyl acetate: butanol mixed solvent 4: 1: 9 (v / v) 0 0 0 0 20 people Comparative Example 1 0 9 persons 11 people 0 0 Comparative Example 2 0 7 people 13 people 0 0 Comparative Example 3 0 5 people 15 people 0 0 Comparative Example 4 0 10 people 10 people 0 0 Comparative Example 5 0 13 people 7 people 0 0 Comparative Example 6 0 8 people 11 people 1 person 0 Comparative Example 7 0 8 people 12 people 0 0

<Fouling gas concentration analysis result>

Salmon oil obtained after the first salmon oil (A), the salmon oil (B) according to the conventional method of performing the steps S10 to S30 once, the fish odor removal process (steps S10 to S40) according to the third embodiment of the present invention ( C), comparing the results of analysis by using gas chromatography on the gas collected from the salmon oil (D) obtained after the odor removal process (steps S10 to S40) according to Example 4 of the present invention, and the results 3 is shown.

As shown in Figure 3, when repeating the conventional method (B) once, the odor generated gas content is reduced by only about 50% compared to the initial content, while Example 3 (C) and Example 4 (D) of the present invention Was significantly reduced to 6% and 4%, respectively, compared to the initial content, from which it can be seen that the present invention can completely remove the odor with only one process.

<Concentration of active ingredient>

Salmon oil obtained after the first salmon oil (A), the salmon oil (B) according to the conventional method of performing the steps S10 to S30 once, the fish odor removal process (steps S10 to S40) according to the third embodiment of the present invention ( C), the concentration change of the active ingredient of the salmon oil (D) obtained after the odor removal process (steps S10 to S40) according to Example 4 of the present invention was measured. Active ingredients were limited to DHA and EPA. As a result of the measurement, the concentrations of these active ingredients hardly changed, and it can be seen that the fish odor removing method of the present invention can remove fish odor efficiently without loss of the active ingredient.

On the other hand, the above detailed description should not be construed as limited in every respect and should be considered as illustrative. The scope of the invention should be determined by reasonable interpretation of the appended claims, and all changes within the equivalent scope of the invention are included in the scope of the invention.

Claims (3)

Cooling the solid salmon oil to solid at room temperature (S10);
Lowering the pressure around the solidified oil to a pressure of 0 torr to 1 torr (S20);
Removing the gas generated in a pressure range of 0.3 torr to 5 torr, which is a pressure range in which odor is generated while raising the temperature of the solidified oil (S30); And
Prepared by stirring a silica precursor, hexamethyldisilane, and 3-aminopropyltrimethoxysilane having a 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene} group in the presence of a surfactant And removing the odor by allowing the oil to elute at a mixing ratio of 4: 1 (v / v) of a mixed solvent of hexane: ethyl acetate in a column filled with porous silica gel (S40).
The weight ratio of the silica precursor, hexamethyldisilane and 3-aminopropyltrimethoxysilane having the 1,3-bis (triethoxysilyl) benzene {1,3-bis (triethoxysilyl) benzene} group is 2: 5: 3 The odor removal method of salmon oil characterized by the above-mentioned.
delete The method of claim 1,
The step of removing the odor (S40), the odor is obtained by allowing the oil to be eluted at a mixing ratio of 4: 1: 9 (v / v) of the mixed solvent of hexane: ethyl acetate: butanol in the column filled with the porous silica gel. The fish oil removal method of salmon oil characterized by the above-mentioned.

Images