KR20220067714A - High purity purification apparatus and purification method of docosahexaenoic acid or eicosapentaenoic acid - Google Patents

Abstract

An apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid according to the present invention are capable of extracting and purifying docosahexaenoic acid or eicosapentaenoic acid from a raw material containing a fatty acid compound with high purity and on a large scale, while minimizing the time and cost required for purifying the same. Furthermore, the apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid minimize the pressure increase due to the differential pressure generated by reflux during distillation, thereby being effective in preventing the formation of impurities due to thermal denaturation.

Description

High purity purification apparatus and purification method of docosahexaenoic acid or eicosapentaenoic acid

The present invention provides an apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid

It relates to an apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid with high purity, in particular.

Unsaturated fatty acids have long been a necessary component to prevent circulatory diseases such as arteriosclerosis, cerebral hemorrhage, and myocardial infarction. In particular, as an unsaturated fatty acid, docosahexaenoic acid (DHA) is an FDA-approved treatment for secondary prevention after hypertriglyceridemia and myocardial infarction. have. In addition, as an unsaturated fatty acid, eicosapentanoic acid (EPA) inhibits platelet aggregation in the human body, lowers the level of triglyceride in plasma, and lowers low density lipoprotein (LDL) cholesterol. It exhibits various physiological activities such as raising high-density lipoprotein (HDL) cholesterol, lowering blood viscosity and blood pressure, and acting as an anti-inflammatory and anti-tumor. In addition, eicosapentaenoic acid having a purity of 95% or more has been approved by the Food and Drug Administration (FDA) of the United States as a treatment for hyperlipidemia.

Such docosahexaenoic acid or eicosapentaenoic acid can be mainly purified from fish oil, but in general, crude oil collected from animals and plants contains various impurities. , pigments, viscous substances, fatty acids, etc. This process of removing undesirable impurities in advance is generally referred to as refining. Therefore, in order to use docosahexaenoic acid or eicosapentaenoic acid having the above-described effects, a technology capable of purifying them with high purity from raw materials is required, and it is possible to minimize the time and cost required for purification. Of course, it should be able to be purified in large quantities.

Conventionally, as a technique for purifying docosahexaenoic acid or eicosapentaenoic acid, a method of increasing purification purity through chromatography has been mainly used, but in this method, docosahexaenoic acid or eicosapentaene It is difficult to mass-purify acid with high purity, and therefore, a technology capable of producing more purified products with higher purity is required.

Korean Patent Registration No. 10-2085775 (2020.03.02)

An object of the present invention is to provide an apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid capable of purifying docosahexaenoic acid or eicosapentaenoic acid with high purity from a fatty acid compound-containing raw material.

Another object of the present invention is that docosahexaenoic acid or eicosapentaenoic acid can be purified in large quantities from fatty acid compound-containing raw materials, and the time and cost required for purification can be minimized, docosahexaenoic acid or eico To provide a sapentaenoic acid purification apparatus and purification method.

Another object of the present invention is to provide an apparatus and method for purifying docosahexaenoic acid or eicosapentaenoic acid, which can prevent the formation of impurities due to thermal denaturation by minimizing pressure increase due to differential pressure generation due to reflux during distillation will do

The apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid according to the present invention is an apparatus for purifying fatty acid compound-containing raw materials, wherein the raw materials are introduced, primary distillation removes moisture in the raw materials, and stagnation at the bottom a precipitation unit to separate the sediment; and a first distillation column in which the first obtained product from which moisture and sediment are removed from the precipitation unit is introduced, and the low boiling point impurities in the first obtained product are removed by secondary distillation.

In an example of the present invention, docosahexaenoic acid may be obtained from the lower portion of the first distillation column.

In an example of the present invention, a second distillation column in which the secondary obtained product from which the low boiling point impurities are removed is introduced, and the high boiling point impurities are removed in the secondary obtained product by third distillation may be further included.

In an example of the present invention, eicosapentaenoic acid may be obtained from the upper portion of the second distillation column.

The purification apparatus according to an embodiment of the present invention may further include a first control unit, the first control unit may allow the sediment to be removed after the raw material is stagnated in the settling unit for 45 minutes or more.

In an example of the present invention, the first control unit may allow the primary distillation in the precipitation unit to be performed at 300 to 500 torr and less than 120 °C.

The purification apparatus according to an embodiment of the present invention may further include a second control unit, and the second control unit may be performed at 0.7 torr or less and 120 to 200° C. in the second distillation column.

The purification apparatus according to an embodiment of the present invention may further include a third control unit, and the third control unit may be performed at 0.54 torr or less and 120 to 200° C. in the third distillation column.

The purification apparatus according to an embodiment of the present invention includes: a retention part located at a lower portion of the distillation column and into which a distillate descending from the distillation column is introduced; and a falling film type heat exchange unit for re-introducing a portion of the distillate in the retention unit to the distillation column by re-distilling it.

In an example of the present invention, the retention unit may include: a first space positioned at a lower side facing the lower portion of the distillation column to introduce a distillate and discharge the distillate to the heat exchange unit; a second space located adjacent to one side of the first space without facing the lower part of the distillation column; and a barrier rib located between the first space and the second space, and spaced apart the lower portions of each space so that the distillate of the first space does not flow directly into the second space; may include, in the first space The distillate discharged may be introduced into the heat exchange unit, the distillate discharged from the heat exchange unit may be introduced into the second space, and upper portions of the first space and the second space may be in communication with each other, and the heat exchange unit The re-distilled vapor discharged from may be re-introduced into the distillation column through the second space and the first space.

In an example of the present invention, the inside of the distillation column may be provided with a packing portion having a network structure so that the internal temperature does not exceed 200° C. by reducing the differential pressure due to the pressure loss while the distillate is refluxed.

The purification method of docosahexaenoic acid or eicosapentaenoic acid according to the present invention is a method of purifying from a fatty acid compound-containing raw material, comprising: a) removing moisture by primary distillation of the raw material; And b) removing the low-boiling point impurities by second distilling the obtained product from which the moisture has been removed under a condition higher than the pressure of the first distillation; It may include the step of removing.

In an example of the present invention, docosahexaenoic acid may be obtained in step b).

In the purification method of docosahexaenoic acid or eicosapentaenoic acid according to the present invention, c) high boiling point impurities are removed by thirdly distilling the obtained product from which the low boiling point impurities are removed under a condition higher than the pressure of the second distillation It may further include the step of, eicosapentaenoic acid can be obtained in step c).

In an example of the present invention, in step a), the precipitate may be removed after the raw material is stagnated for 45 minutes or more.

In an example of the present invention, in step a), the primary distillation may be performed at 300 to 500 torr and less than 120°C.

In an example of the present invention, in step b), the secondary distillation may be performed at 0.7 torr or less and 120 to 200°C.

In an example of the present invention, in step c), the tertiary distillation may be performed at 0.54 torr or less and 120 to 200°C.

The docosahexaenoic acid or eicosapentaenoic acid purification apparatus and purification method according to the present invention has the effect of purifying docosahexaenoic acid or eicosapentaenoic acid with high purity from a fatty acid compound-containing raw material.

In addition, the docosahexaenoic acid or eicosapentaenoic acid purification apparatus and purification method according to the present invention can purify docosahexaenoic acid or eicosapentaenoic acid in large quantities from a fatty acid compound-containing raw material, There is an effect that can minimize time and cost.

In addition, the docosahexaenoic acid or eicosapentaenoic acid purification apparatus and purification method according to the present invention minimizes the pressure increase due to the differential pressure generated by reflux during distillation, thereby preventing the formation of impurities due to thermal denaturation. .

1 shows a process diagram of a docosahexaenoic acid or eicosapentaenoic acid purification apparatus in an example of the present invention, and is a process chart for the purpose of docosahexaenoic acid purification.
2 is a flowchart showing a process diagram of a docosahexaenoic acid or eicosapentaenoic acid purification apparatus in an example of the present invention, and is a process chart for the purpose of purifying eicosapentaenoic acid.
3 is a process diagram showing a part including a distillation column and a retention part of a docosahexaenoic acid or eicosapentaenoic acid purification apparatus in an embodiment of the present invention, the blue line is the flow path of the distillate, and the red line is the distillation It is the path of movement of vapor in liquid.

Hereinafter, a high-purity purification apparatus and purification method of docosahexaenoic acid or eicosapentaenoic acid according to the present invention will be described in detail with reference to the accompanying drawings.

The drawings described in this specification are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the drawings presented and may be embodied in other forms, and the drawings may be exaggerated to clarify the spirit of the present invention.

Unless otherwise defined in technical terms and scientific terms used in this specification, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood, and in the following description and accompanying drawings, the subject matter of the present invention Descriptions of known functions and configurations that may unnecessarily obscure will be omitted.

A singular form of a term used herein may be construed to include a plural form as well unless otherwise indicated.

s1, s2, s3, ... as referred to herein; a1, a2, a3, ...; b1, b2, b3, ...; a, b, c, ...; The term itself referring to each step, such as etc., is only used to refer to a certain step, means, etc., and should not be construed as meaning an order relationship between the respective objects referred to by the terms.

Unless otherwise specified, the unit of % used in the present specification means % by weight unless otherwise specified.

The purification apparatus of docosahexaenoic acid (DHA) or eicosapentanoic acid (EPA) according to the present invention relates to an apparatus and method for purifying from a raw material containing a fatty acid compound, and the present invention relates to an apparatus and method for purifying docosahexaenoic acid (DHA) or eicosapentanoic acid (EPA) A first aspect for purifying hexaenoic acid with high purity and a second aspect for purifying eicosapentaenoic acid with high purity are provided.

The raw material used in the present invention is a fatty acid compound containing docosahexaenoic acid or eicosapentaenoic acid or a mixture containing the same, and the present invention provides docosahexaenoic acid or eicosapentaenoic acid from such a fatty acid compound-containing raw material. The purpose is to minimize the time and cost required for purification, as well as to purify to high purity. As a specific example, as the raw material, various things such as saury, anchovies (anchovy), sardines, mackerel, fish such as tuna, macadamia, and plants such as sea buckthorn berry may be exemplified, and intermediates processed therefrom, for example, Of course, an esterified reaction product through treatment such as ethanolysis from fish or plants containing docosahexaenoic acid or eicosapentaenoic acid may also be used. Here, for the esterification method, specifically, the ethanolysis method, reference may be made to various publicly known documents such as Korean Patent Publication No. 10-1815110.

As an apparatus for purifying docosahexaenoic acid with high purity, the first aspect according to the present invention is a needle in which a fatty acid compound-containing raw material is introduced, and the moisture in the raw material is removed by primary distillation and at the same time stagnant at the bottom to separate the precipitate all (100); and a first distillation column 200 in which the first obtained product from which moisture and sediment are removed from the precipitation unit 100 is introduced, and the low boiling point impurities in the first obtained product are removed by secondary distillation.

In the precipitation unit 100, a holding vessel (still vessel), etc. is provided, so that stagnation and distillation for a predetermined time are simultaneously performed, so that sediment and moisture, including ultra-low boiling point impurities, are effectively removed. That is, separation and removal of ultra-low-boiling point impurities and precipitates and dehydration are simultaneously performed, so that docosahexaenoic acid of high purity can be produced through a distillation column in which secondary distillation is performed thereafter. At this time, a heating device and a vacuum device may be provided so that the distillation can be performed.

The first distillation column 200 allows secondary distillation of the distillate obtained from the precipitation unit 100 , and low-boiling impurities are discharged as steam to the upper portion of the first distillation column 200 , A distillate containing docosahexaenoic acid is discharged to the bottom.

A first aspect according to an embodiment of the present invention is located at the lower portion of the distillation column, the retention unit 400 into which the distillate descending from the distillation column is introduced; and a falling film type heat exchange unit (500, 510) for re-distilling a portion of the distillate in the retention unit 400 and re-introducing it into the distillation column. If this is satisfied, docosahexaenoic acid may be purified with higher purity. Specifically, the retention unit 400 is located at a lower side facing the lower portion of the distillation column, a first space 410 into which the distillate is introduced and the distillate is discharged to the heat exchange units 500 and 510; a second space 420 located adjacent to one side of the first space 410 without facing the lower portion of the distillation column; and a partition wall positioned between the first space 410 and the second space 420 and spaced apart the lower portions of the spaces so that the distillate of the first space 410 does not flow directly into the second space 420 . (430); may include. At this time, the distillate discharged from the first space 410 may flow into the heat exchange units 500 and 510 , and the distillate discharged from the heat exchange units 500 and 510 may flow into the second space 420 . can be imported. In addition, the partition wall 430 partitions the first space 410 and the second space 420, but does not block and partition all the areas where the first space 410 and the second space 420 come into contact with each other. The first space 410 and a portion of the second space 420, that is, the upper part are formed to communicate with each other, so that the re-distilled steam discharged from the heat exchange units 500 and 510 is separated from the second space 420 and the second space 420 . It may be re-introduced into the distillation column through the first space 410 . The positions of the heat exchange units 500 and 510 are not particularly limited, and may be provided, for example, at the upper portion of the retaining unit 400 , and steam (distillate) passing through the heat exchange unit flows in from the upper portion of the retaining unit 400 . can be When it has such a structure, docosahexaenoic acid can be purified with a higher purity.

The retention unit 400 will be described in terms of the movement path of the vapor or distillate as follows, but this is only an example and the present invention is not limited thereto. In FIG. 3, the blue path is the movement path of the liquid phase, the red path is the movement path of the gas phase, and as shown in FIG. 3, the distillate containing vapor from the distillation towers 200 and 300 is It falls into the first space 410 located at the lower side, and the distillate is introduced into the heat exchange unit 500 through a pump or the like. The distillate containing the vapor introduced into the heat exchange unit 500 falls into the second space 420 located below the heat exchange unit 500 and is collected in the boot. At this time, the liquid phase flows into the docosahexaenoic acid storage tank 910 or the high boiling point impurity storage tank 830, and the gaseous phase (steam) passes through the portion where the first space 410 and the second space 420 communicate. It flows into the distillation column 200 and is refluxed.

As described above, docosahexaenoic acid may be obtained from the bottom of the distillation column. However, of course, the purified product may include eicosapentaenoic acid in addition to only docosahexaenoic acid.

The purity of docosahexaenoic acid of the obtained product purified according to the first aspect of the present invention may be 60% or more, preferably 65% or more, more preferably 70% or more.

As an apparatus for purifying eicosapentaenoic acid with high purity, the second aspect according to the present invention is the secondary obtained product from which the low-boiling point impurities have been removed along with the configuration of the first aspect described above, followed by third distillation It further includes a second distillation column 300 for removing the high boiling point impurities in the secondary harvest. That is, in the second aspect, the fatty acid compound-containing raw material is introduced, the precipitation unit 100 for removing the moisture in the raw material by primary distillation and stagnating at the bottom to separate the sediment; a first distillation column 200 in which the first obtained product from which moisture and sediment are removed from the precipitation unit 100 is introduced, and the low boiling point impurities in the first obtained product are removed by secondary distillation; and a second distillation column 300 in which the secondary obtained product from which the low boiling point impurities are removed is introduced, and the high boiling point impurities in the secondary obtained product are removed by third distillation. As shown in FIG. 2 , since eicosapentaenoic acid is a relatively high boiling point material, eicosapentaenoic acid is obtained from the upper part of the second distillation column 300 , and high boiling point impurities are transferred to the lower part of the second distillation column 300 . is emitted Although the second aspect has been described as a means for purifying eicosapentaenoic acid with high purity, of course, it can also be used for purification of docosahexaenoic acid.

In an example of the present invention, the second aspect may further include the retention unit 400 and the heat exchange units 500 and 520 described above in the first aspect. That is, in some cases, the second aspect may also include the retention unit 400 and the heat exchange units 500 and 520 having the same configuration as the first aspect, and if this is satisfied, a higher purity of docosahexaenoic acid or Eicosapentaenoic acid can be obtained.

The purification apparatus according to an embodiment of the present invention, that is, the first aspect or the second aspect may further include a first control unit for allowing the distillate to stand still for a predetermined time in the precipitation unit 100 . As described above, in the precipitation unit 100, stagnation and distillation for a predetermined time are simultaneously performed, and sediment and moisture, including ultra-low boiling point impurities, are effectively removed. to 300 minutes. That is, the first control unit may allow the sediment to be removed after the raw material is stagnated in the sedimentation part 100 for 45 minutes or more.

In addition, the apparatus according to an embodiment of the present invention may further include a heating unit 700 for allowing the vapor liquid discharged from the precipitation unit 100 to easily flow into the first distillation column 200 .

The first control unit may allow the primary distillation in the precipitation unit 100 to be performed at 300 to 500 torr and less than 120°C. When distillation is performed under this condition, the effect of separation and removal of ultra-low boiling point impurities and precipitates together with moisture is further improved. In particular, when the distillate is sent to the first distillation column 200 after being distilled at 300 to 500 torr and less than 120° C. in the precipitation unit 100 and at the same time stagnating for 45 minutes or more, 2 of the second distillation column 300 Higher docosahexaenoic acid or eicosapentaenoic acid can be purified through secondary distillation.

The purification apparatus according to an embodiment of the present invention, that is, the first or second aspect may further include a second control unit, wherein the second control unit is 0.7 torr or less and 120 to 200 in the first distillation column 200 . ℃, specifically, 0.001 to 0.7 torr or less and 120 to 200 ℃ can be carried out. If it exceeds 200 ℃, since heat denaturation may occur among the raw material components, it is preferable not to exceed 200 ℃. If this is satisfied, the first aspect can purify higher docosahexaenoic acid, and the second aspect is then higher docosahexaenoic acid or eicosapentaene through the secondary distillation of the second distillation column 300 . The acid can be purified.

The purification apparatus according to an example of the present invention, that is, the second aspect may further include a third control unit, wherein the third control unit operates the second distillation column 300 under ultra-low vacuum conditions lower than the pressure of the first distillation column 200 . ) may be to control the pressure, and specifically, 0.54 torr or less and 120 to 200 ° C., more specifically, 0.001 to 0.54 torr or less and 120 to 200 ° C. in the second distillation column 300. . If it exceeds 200 ℃, since heat denaturation may occur among the raw material components, it is preferable not to exceed 200 ℃. If this is satisfied, higher docosahexaenoic acid or eicosapentaenoic acid may be purified through the above-described precipitation unit 100 and the first distillation column 200 .

In an example of the present invention, the inside of the distillation column may be provided with a packing portion having a network structure so that the internal temperature does not exceed 200° C. by reducing the differential pressure due to the pressure loss while the distillate is refluxed. As the distillate is refluxed, a pressure loss may occur in the distillation column and a differential pressure may occur, thereby increasing the pressure at the bottom of the distillation column, making it difficult to maintain a temperature of 200° C. or less. When the temperature at the bottom of the distillation column exceeds 200° C., the components in the raw material are thermally decomposed to generate impurities, and in this case, docosahexaenoic acid or eicosapentaenoic acid cannot be purified with high purity. In the case of a packing that can reduce the differential pressure inside the distillation column, specifically, the wire is made in the form of a mesh gauze, and the differential pressure is minimized, the phenomenon of exceeding 200℃ due to pressure change is prevented. can do.

The purification apparatus according to an example of the present invention, that is, the first or second aspect is a condenser 600 condensing water separated from the settling unit 100, a water storage tank in which the condensed water is introduced and stored ( 810) may be further included. In an example of the present invention, the apparatus may further include a low-boiling-point impurity storage tank 820 in which the low-boiling-point impurities discharged from the upper portion of the first distillation column 200 are introduced and stored. In one example of the present invention, the apparatus may further include a high boiling point impurity storage tank 830 in which the high boiling point impurities discharged from the lower portion of the second distillation column 300 are introduced and stored. In an example of the present invention, the apparatus may further include a docosahexaenoic acid storage tank 910 into which the purified water containing docosahexaenoic acid discharged from the lower portion of the first distillation column 200 is introduced. have. In an example of the present invention, the apparatus may further include an eicosapentaenoic acid storage tank 920 into which the purified water containing eicosapentaenoic acid discharged from the upper part of the second distillation column 300 is introduced. have.

The purity of eicosapentaenoic acid of the obtained product purified according to the second aspect of the present invention may be 90% or more, preferably 95% or more, more preferably 99% or more.

As a method for purifying docosahexaenoic acid with high purity, a first aspect according to the present invention is a method of purifying from a raw material containing a fatty acid compound, comprising: a) removing moisture by primary distillation of the raw material; And b) removing the low-boiling point impurities by second distilling the obtained product from which the moisture has been removed under a condition higher than the pressure of the first distillation; removing it. Therefore, it is possible to produce high-purity docosahexaenoic acid through step a) in which separation and removal of ultra-low-boiling-point impurities and precipitates and dehydration are performed simultaneously and step b) in which secondary distillation is performed thereafter.

In step a), the primary distillation may be preferably performed at 300 to 500 torr and less than 120° C., and in step b), the secondary distillation is 0.7 torr or less and 120 to 200° C., specifically 0.001 to It may be preferable to be carried out at 0.7 torr or less and at 120 to 200°C. If it exceeds 200 ℃, since thermal denaturation may occur in the raw material components, it is preferable not to exceed 200 ℃, and when it is satisfied, docosahexaenoic acid of high purity can be produced.

As a method for purifying eicosapentaenoic acid with high purity, the second aspect according to the present invention is a method for purifying from a fatty acid compound-containing raw material, along with the configuration of the first aspect, c) the low boiling point impurities are removed The method may further include the step of removing high boiling point impurities by thirdly distilling the obtained product under conditions higher than the pressure of the second distillation. That is, the second aspect comprises the steps of: a) removing moisture by primary distillation of the raw material; b) removing the low boiling point impurities by second distilling the obtained product from which the moisture has been removed under a condition higher than the pressure of the first distillation; and c) thirdly distilling the obtained product from which the low boiling point impurities have been removed under a condition higher than the pressure of the second distillation to remove the high boiling point impurities.

In step c), the tertiary distillation may be performed at a pressure lower than that of the secondary distillation, specifically, 0.54 torr or less and 120 to 200 ° C., more specifically 0.001 to 0.54 torr or less and 120 to 200 ° C. It may be desirable to be If this is satisfied, docosahexaenoic acid or eicosapentaenoic acid of high purity can be produced.

Hereinafter, the present invention will be described in detail with reference to Examples, but these are for describing the present invention in more detail, and the scope of the present invention is not limited by the Examples below.

<Purification of docosahexaenoic acid>

Docosahexaenoic acid was purified from a fatty acid mixture raw material from fish oil through a process system as shown in FIG. 1 .

1. Moisture and sediment removal process

The raw material was supplied to the settling unit 100, which is a still vessel, and the still vessel is a jacket, and a heating device capable of heating it, a condenser 600 for condensing and liquefying moisture, and a vacuum device required for vacuum operation are provided. provided in the system. When the raw material is supplied to the Still Vessel, it is heated to a vacuum of 400 torr to evaporate moisture at less than 120°C. In this process, ultra-low-boiling-point impurities are evaporated, and moisture and ultra-low-boiling point impurities are condensed and liquefied and removed in the condenser 600 located above. At this time, some sediment is generated, and the sediment is sufficiently separated and removed by properly sizing the size of the container so that the residence time is at least 45 minutes or more.

2. Low-boiling point impurity removal process

Since docosahexaenoic acid can be seen as the component having the highest boiling point among the components in the raw material, from the obtained product obtained in the water and sediment removal process, through fractional distillation through the first distillation column 200, docosahexaenoic acid is better than docosahexaenoic acid. By separating and removing low boiling point impurities with a low boiling point, docosahexaenoic acid can be purified and commercialized with high purity.

In order to produce high-purity docosahexaenoic acid, the temperature of the lower part of the distillation column 200 is continuously maintained at 200° C. or less, thereby preventing the problem of generating impurities due to thermal decomposition of components in the raw material by exceeding 200° C. Therefore, the inside of the distillation column 200 is made of a special packing so that the temperature of the lower part of the distillation column 200 can be maintained below 200 °C. As the distillate is refluxed, a pressure loss may occur in the distillation column 200 to generate a differential pressure, thereby increasing the pressure in the lower portion of the distillation column 200, making it difficult to maintain a temperature of 200° C. or less. Accordingly, the packing capable of reducing the differential pressure, specifically, the packing made in the form of a mesh-type gauze of wire, can be used to minimize the differential pressure, thereby solving the above problem. At this time, the pressure of the first distillation column was set to 0.6 torr.

Retention parts 400 and 410 are provided in the lower part of the distillation column 200, and a boot is installed in the retention parts 400 and 410 so that the liquid level can be kept to a minimum. If the liquid in the lower part of the distillation column 200 is stagnant for a long time, the components may be decomposed by heat to generate impurities. Make sure it doesn't stagnate.

In addition, a forced circulation RE-BOILER device including a falling film type heat exchange unit (500, 510) is provided at the lower part of the distillation column 200, and a distributor is installed at the upper part so that a certain amount of liquid is evenly distributed in each tube. inlet to allow sufficient heat exchange. At this time, a partition wall 430, which is a partition, is installed inside the retention units 400 and 410, so that the liquid that comes down from the distillation column 200 is directly pumped through the heat exchange units 500 and 510, and a portion is evaporated and returned to the distillation column 200. The liquid that has gone and is not evaporated is collected in the boot and obtained as a final purified product while maintaining a minimum liquid level.

A heat medium supply temperature automatic control valve is installed in the heat exchange units 500 and 510 to maintain the temperature of the lower part of the distillation column 200, and a separate temperature control unit (TCU) is installed to maintain a constant heat medium temperature. ) including a temperature control system is designed so that the temperature can be stably maintained constant.

In addition, in the case of the upper condenser provided in the distillation column, an internal cooling method that is directly connected to the upper part of the distillation column so that the vapor can be liquefied as soon as it rises was adopted. It is refluxed, and an automatic flow control valve capable of controlling the content of purified water is provided so that the remainder is refluxed directly to the distillation column.

As a result of the above-described process, a raw material of 27 kg per hour was input to produce a purified product of 17 kg per hour, and the mass fractions of the raw material and the purified material are shown in Table 1 below.

wt. SAC OAC LAC LNAC EAC EPA DPA DHA Raw material (27 kg/h) 0.0721 0.1303 0.0139 0.0157 0.0339 0.1082 0.0245 0.4710 Purified material (17 kg/h) 0.0212 0.0806 0.0056 0.0109 0.0006 0.1250 0.0383 0.7177 SAC: Stearic acid
OAC: Oleic acid
LAC: Linoleic acid
LNAC: Linolenic acid
EAC: Ecosatrienoic and Ecosatertaenoic acid)
EPA: Eicosapentanoic acid
DPA: Clupanodonic acid
DHA: docosahexaenoic acid

<Purification of eicosapentaenoic acid>

Eicosapentaenoic acid was purified from a fatty acid mixture raw material from fish oil through a process system as shown in FIG. 2 .

1. Moisture and sediment removal process

The raw material was supplied to the settling unit 100, which is a still vessel, and the still vessel is a jacket, and a heating device capable of heating it, a condenser 600 for condensing and liquefying moisture, and a vacuum device required for vacuum operation are provided. provided in the system. When the raw material is supplied to the Still Vessel, it is heated to a vacuum of 400 torr to evaporate moisture at less than 120°C. In this process, ultra-low-boiling-point impurities are evaporated, and moisture and ultra-low-boiling point impurities are condensed and liquefied and removed in the condenser 600 located above. At this time, some sediment is generated, and the sediment is sufficiently separated and removed by properly sizing the size of the container so that the residence time is at least 45 minutes or more.

2. Low-boiling point impurity removal process

Low-boiling-point impurities were separated and removed through fractional distillation through the first distillation column 200 from the obtained product in the water and sediment removal process.

Specifically, in order to produce high-purity eicosapentaenoic acid, the temperature of the lower part of the distillation column 200 is continuously maintained at 200° C. or less, thereby preventing the problem of generating impurities by thermal decomposition of components in the raw material by exceeding 200° C. can Therefore, the inside of the distillation column 200 is made of a special packing so that the temperature of the lower part of the distillation column 200 can be maintained below 200 °C. As the distillate is refluxed, a pressure loss may occur in the distillation column 200 to generate a differential pressure, thereby increasing the pressure in the lower portion of the distillation column 200, making it difficult to maintain a temperature of 200° C. or less. Accordingly, the packing capable of reducing the differential pressure, specifically, the packing made in the form of a mesh-type gauze of wire, can be used to minimize the differential pressure, thereby solving the above problem. At this time, the pressure of the first distillation column was set to 0.6 torr.

Retention parts 400 and 420 are provided in the lower part of the distillation column 200, and a boot is installed in the retention parts 400 and 420 so that the liquid level can be kept to a minimum. If the liquid in the lower part of the distillation column 200 is stagnant for a long time, the components may be decomposed by heat to generate impurities. Make sure it doesn't stagnate.

In addition, a forced circulation type RE-BOILER device including a falling film type heat exchange unit (500, 520) is provided at the lower part of the distillation column 200, and a distributor is installed at the upper part so that a certain amount of liquid is evenly distributed in each tube inlet to allow sufficient heat exchange.

A partition wall 430 is installed inside the retention parts 400 and 420 so that the liquid descended from the distillation column 200 directly flows into the heat exchange units 500 and 520 through the pump, and a portion is evaporated to the distillation column 200. The liquid that is returned and is not evaporated is collected in the boot to obtain the final purified product while maintaining the minimum liquid level. Since eicosapentaenoic acid belongs to the lowest boiling point among the raw material components, eicosapentaenoic acid, which is a low boiling point, can also be removed together with low boiling point impurities by conventional simple fractional distillation. . However, in the present invention, since the retention parts 410 and 420 having a specific structure as shown in FIG. 3 are provided, it can be purified from low boiling point impurities to a high concentration even by using eicosapentaenoic acid, which belongs to the lowest boiling point among the raw material components, as the obtained material. Specifically, the retaining parts 410 and 420 are positioned to face the lower part of the distillation column, a first space into which the distillate is introduced, and the distillate is discharged to the heat exchange part; a second space located adjacent to one side of the first space without facing the lower part of the distillation column; and a barrier rib located between the first space and the second space, and spaced apart the lower portions of each space so that the distillate of the first space does not flow directly into the second space. In particular, the distillate discharged from the first space flows into the heat exchange unit, and the distillate heated and discharged from the heat exchange unit flows into the second space. At this time, the first space and the upper portion of the second space are in communication with each other, so that the re-distilled steam heated and discharged from the heat exchange unit is re-introduced into the distillation column through the second space and the first space, and this circulation The intermediate purified product containing docosahexaenoic acid and high concentration eicosapentaenoic acid is discharged to the lower part of the second space through the retention part of the formula structure and the distillation column structure.

A heat medium supply temperature automatic control valve is installed in the heat exchange units 500 and 520 to maintain the temperature of the lower part of the distillation column 200, and a separate temperature control unit (TCU) is installed to maintain a constant heat medium temperature. ) including a temperature control system is designed so that the temperature can be stably maintained constant. In addition, in the case of the upper condenser provided in the distillation column 200, an internal cooling method that is directly connected to the upper part of the distillation column so that the vapor can be liquefied as soon as it rises was adopted, and this liquid is liquefied at the same time It is refluxed directly to the distillation column, and an automatic flow control valve capable of controlling the content of purified water is provided, so that the remainder is refluxed directly to the distillation column.

As a result of the above-described process, an intermediate purified product of 27 kg per hour was produced by injecting 60 kg of raw material per hour, and the mass fractions of the raw material and the intermediate purified product are shown in Table 2 below.

wt. SAC OAC LAC LNAC EAC EPA DPA DHA Raw material (60 kg/h) 0.0621 0.1081 0.0170 0.0380 0.0320 0.2703 0.0400 0.1722 Medium purification (27 kg/h) 0 0 0 0 0 0.5287 0.0890 0.3823 SAC: Stearic acid
OAC: Oleic acid
LAC: Linoleic acid
LNAC: Linolenic acid
EAC: Ecosatrienoic and Ecosatertaenoic acid)
EPA: Eicosapentanoic acid
DPA: Clupanodonic acid
DHA: docosahexaenoic acid

3. High boiling point impurity removal and EPA concentration process

High boiling point impurities were separated and removed from the intermediate purified product obtained in the low boiling point impurity removal process through fractional distillation through the second distillation column 300 . At this time, as shown in FIG. 2 , the second distillation column 300 had the same structure as that of the first distillation column 200 , and the same conditions were used except that the pressure was 0.5 torr in the second distillation column 300 . The process was carried out.

As a result of the above-described process, a final purified product of 13 kg per hour was produced by introducing an intermediate purified product of 27 kg per hour, and the mass fractions of the intermediate purified product and the final purified product are shown in Table 3 below.

wt. SAC OAC LAC LNAC EAC EPA DPA DHA Medium purification (27 kg/h) 0 0 0 0 0 0.5287 0.0890 0.3823 Final purified product (27 kg/h) 0 0 0 0 0 0.9991 0 0.0009 SAC: Stearic acid
OAC: Oleic acid
LAC: Linoleic acid
LNAC: Linolenic acid
EAC: Ecosatrienoic and Ecosatertaenoic acid)
EPA: Eicosapentanoic acid
DPA: Clupanodonic acid
DHA: docosahexaenoic acid

From Table 3, it can be confirmed that the purity of eicosapentaenoic acid (EPA) of the final purified product can be produced to 99.9% or more.

The same as in Example 2, except that the retention part connected to the first distillation column 200 and the retention part connected to the second distillation column 300 are excluded, and the final containing eicosapentaenoic acid is performed in the same process as in Example 2 A purified product was produced. As a result, it was confirmed that the purity of Example 3 was lower than that of Example 2.

100: precipitation unit, 200: first distillation column,
300: second distillation column, 400: retention unit,
410: first space, 420: second space;
430: bulkhead, 500: heat exchange unit,
510: a first heat exchange unit; 520: second heat exchange unit
600: condenser, 700: heating unit,
810: water storage tank, 820: low boiling point impurity storage tank;
830: high boiling point impurity storage tank, 910: docosahexaenoic acid storage tank,
920: eicosapentaenoic acid storage tank

Claims (17)

An apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid from a fatty acid compound-containing raw material,
a precipitation unit in which the raw material is introduced, primary distillation removes moisture in the raw material and stagnates at the bottom to separate the sediment; and
Docosahexaenoic acid or eicosapentaenoic acid comprising a; a first distillation column in which the first yield from which moisture and sediment are removed from the precipitation unit is introduced, and the low boiling point impurities in the first yield are removed by secondary distillation of refining device. According to claim 1,
An apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid in which docosahexaenoic acid is obtained from the lower portion of the first distillation column. According to claim 1,
A second distillation column in which the secondary obtained product from which the low boiling point impurities are removed is introduced, and the high boiling point impurities in the secondary obtained product are removed by third distillation,
An apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid in which eicosapentaenoic acid is obtained from the upper part of the second distillation column. According to claim 1,
The purification apparatus further comprises a first control unit,
The first control unit is a purification apparatus of docosahexaenoic acid or eicosapentaenoic acid so that the precipitate is removed after the raw material is stagnated in the precipitation unit for 45 minutes or more. According to claim 1,
The purification apparatus further comprises a first control unit,
The first control unit is an apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid such that the primary distillation is performed at 300 to 500 torr and less than 120° C. in the precipitation unit. According to claim 1,
The purification apparatus further comprises a second control unit,
The second control unit is an apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid to be performed at 0.7 torr or less and 120 to 200° C. in the first distillation column. 4. The method of claim 3,
The purification apparatus further comprises a third control unit,
The third control unit is an apparatus for purifying docosahexaenoic acid or eicosapentaenoic acid to be performed at 0.54 torr or less and 120 to 200° C. in the second distillation column. 4. The method of claim 3,
a retention unit located at a lower portion of the distillation column and into which the distillate descending from the distillation column is introduced; and
A purifying apparatus for docosahexaenoic acid or eicosapentaenoic acid further comprising a; a falling film type heat exchange unit for re-distilling a portion of the distillate in the retention unit and re-introducing it into the distillation column. 9. The method of claim 8,
The staying unit,
a first space positioned at a lower side opposite to the lower portion of the distillation column, into which a distillate is introduced, and through which the distillate is discharged to the heat exchange unit;
a second space located adjacent to one side of the first space without facing the lower part of the distillation column; and
and a partition wall positioned between the first space and the second space, and spaced apart from the lower part of each space so that the distillate of the first space does not flow directly into the second space; and
The distillate discharged from the first space flows into the heat exchange unit, and the distillate discharged from the heat exchange unit flows into the second space,
Docosahexaenoic acid or Eico in which the first space and the upper part of the second space communicate with each other and the re-distilled steam discharged from the heat exchange unit is re-introduced into the distillation column through the second space and the first space A purification apparatus for sapentaenoic acid. According to claim 1,
The inside of the distillation column is a docosahexaenoic acid or eicosapentaenoic acid purification apparatus having a network-shaped packing part that reduces the differential pressure due to pressure loss while the distillate is refluxed so that the internal temperature does not exceed 200 °C. A method for purifying docosahexaenoic acid or eicosapentaenoic acid from a fatty acid compound-containing raw material, comprising:
a) removing moisture by primary distillation of the raw material; and
b) removing the low-boiling-point impurities by secondary distilling the obtained product from which the moisture has been removed under a condition higher than the pressure of the primary distillation;
The step a) is a purification method of docosahexaenoic acid or eicosapentaenoic acid comprising the step of removing the precipitate by stagnating the raw material at the same time as distillation. 12. The method of claim 11,
The purification method of docosahexaenoic acid or eicosapentaenoic acid in which docosahexaenoic acid is obtained in step b). 12. The method of claim 11,
c) further comprising the step of removing the high-boiling-point impurities by thirdly distilling the obtained product from which the low-boiling point impurities have been removed under a condition higher than the pressure of the second distillation;
A method of purifying docosahexaenoic acid or eicosapentaenoic acid in which eicosapentaenoic acid is obtained in step c). 12. The method of claim 11,
In step a), a method of purifying docosahexaenoic acid or eicosapentaenoic acid in which the precipitate is removed after the raw material is stagnated for 45 minutes or more. 12. The method of claim 11,
In step a), the primary distillation is a purification method of docosahexaenoic acid or eicosapentaenoic acid that is performed at 300 to 500 torr and less than 120 °C. 12. The method of claim 11,
In step b), the secondary distillation is a purification method of docosahexaenoic acid or eicosapentaenoic acid performed at 0.7 torr or less and 120 to 200°C. 17. The method of claim 16,
In step c), the third distillation is a purification method of docosahexaenoic acid or eicosapentaenoic acid that is carried out at 0.54 torr or less and 120 to 200°C.

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