KR100903270B1 - Extraction Process Of Functional Pigments using Supercritical Carbon Dioxide and Sub-ingredientsfrom Natural Materials - Google Patents

Abstract

The present invention is a method for extracting a pigment-like substance such as Fucoxanthin or Chlorophylla from seaweeds such as seaweed, in particular not only the seaweed, but also shellfish and vegetables as raw materials, the raw material of rice bran or wheat germ, or rice bran and wheat germ The present invention relates to a method for extracting a pigment material, comprising adding and mixing any one or more selected from a processed product and a by-product as a submaterial, and extracting a high purity pigment material from the mixture.

According to the present invention, by adopting a method of mixing and extracting an appropriate subsidiary material into a raw material, a higher pigment component can be secured in a high yield, and in particular, the raw material is composed of carbon dioxide, an extraction solvent, ethanol and water, in the extraction step. The salt component contained in can be effectively removed in the extraction step, there is an advantage that does not need a separate washing treatment in the processing.

Seaweed, seaweed, vegetables, cereals, grain processing by-products, supercritical carbon dioxide, functional substances

Description

Extraction process of functional pigments using supercritical carbon dioxide and sub-ingredients from natural materials

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of extracting a pigment component from seaweed such as seaweed, and relates to a method of extracting a functional substance which adds and blends grains and the like as a subsidiary material to a natural raw material and extracts a high purity functional pigment substance from the mixture.

In general, the functional materials are obtained from natural raw materials such as seaweed, crustaceans, and vegetables. Such functional materials include pigments and essential oils. It is developed with various products.

In particular, algae and crustaceans are known to be rich in pigments and essential oils, which are the functional substances. And grains or grain processing by-products such as rice bran, wheat germ, rice bran, and bran are present in a large amount of vegetable oil, which is mixed with the functional materials and used in various products and industries.

However, natural raw materials such as seaweed, crustaceans, vegetables, and the like have not been actively used as food materials due to a decrease in the recognition of the available ingredients and the limitation of the use range.

Accordingly, various methods for effectively extracting functional materials from the natural raw materials have been proposed. Proposed extraction methods include hot water extraction, distillation, compression, and solvent extraction, but these have complicated problems, require a long time in the production process, and low purity of the extracted solvent. .

In addition to the above methods, there are organic solvent extraction methods and neutral salt extraction methods. When the functional material is extracted by using the organic solvent extraction method, there is a problem about the quality of the extract due to the incorporation of impurities and the inability to recover harmful solvents. In addition, there is a problem in that the process is complex, and thus useful components may be lost in this process. In addition, the above extraction methods may be mixed with foreign substances by chemicals, so that the purity of the functional extract may be lowered.

In order to solve the above disadvantages, the applicant has proposed a 'method extraction method using cereals or seeds' in Patent Application No. 10-2004-0106733.

This method uses an extraction method called supercritical or subcritical extraction method. A supercritical extraction method is a technique for separating a substance by using a supercritical fluid in a state above a critical point as a solvent. The properties allow the selective extraction of specific substances of interest in the mixed components. Due to these characteristics, supercritical extraction is widely used in the chemical, pharmaceutical, and biochemical fields.

However, 'the method of extracting functional substances using cereals or seeds' proposed by the applicant has the advantage of extracting functional substances such as natural fragrance components contained in raw fruits or plants with higher purity, but the raw materials include salinity. When separating substances such as functional pigments from algae, crustaceans, and vegetables, the salt, aroma, taste, and shelf life are deteriorated by the salts included above. There was a disadvantage that it was necessary.

The present invention has been made in order to solve the above problems, by adopting a method of extracting by mixing the appropriate subsidiary materials with the appropriate natural materials to ensure a higher yield of pigment components in a high yield, the extraction solvent carbon dioxide, It is an object of the present invention to provide a method for extracting a pigment substance which is composed of co-solvent, ethanol and water, which can effectively remove the salt component contained in the raw material in the extraction step.

The present invention comprises the steps of preparing any one or more selected from seaweeds, shellfish, vegetables as raw materials; Preparing at least one selected from rice bran or wheat germ, processed products or by-products of rice bran and wheat germ, and adding and mixing the raw materials; Extraction step of extracting the pigment material from the mixed raw materials and subsidiary materials, wherein the extraction step is 20g / min ~ 40g / min carbon dioxide, supercritical or subcritical fluid as an extraction solvent, 1ml / min ~ 3ml co-solvent continuously charged at / min and set at a temperature of 30 ° C. to 60 ° C. and a pressure in the range of 80 bar to 500 bar; It provides a pigment extraction method from the natural raw material using a supercritical carbon dioxide and the subsidiary material; characterized in that the separation step of separating the extraction solvent and the co-solvent with the pigment material.

In addition, the co-solvent is a mixture of ethanol and water, the mixing ratio of the ethanol and water is a supercritical carbon dioxide and subsidiary material, characterized in that the ratio consisting of any one selected from weight ratio 7: 3, 8: 2, 9: 1. It provides a method of extracting pigments from natural raw materials using.

In addition, the separating step provides a method for extracting a pigment from a natural raw material using supercritical carbon dioxide and a subsidiary material, characterized in that the separator (separator) comprising a spray nozzle.

In addition, the raw material provides a method for extracting pigments from natural raw materials using supercritical carbon dioxide and subsidiary materials, characterized in that mixed in a relative proportion to each other in the range of 1 to 99% by weight.

The pigment material extraction method according to the present invention can be obtained by mixing and extracting a subsidiary material containing a large amount of suitable vegetable oil in natural materials to secure a pigment component in a higher yield, as well as carbon dioxide, co-solvent which is an extraction solvent in the extraction step The salt component contained in the raw material to be composed of ethanol and water can be effectively removed in the extraction step, there is an effect that does not require a separate washing process in the processing.

In addition, since the salt is removed from the pigment extracted by the pigment material extraction method according to the present invention, the aroma, taste and shelf life are improved.

In addition, the present invention does not require a separate mixing step to ensure homogeneity in the extracted pigment material, there is an advantage that the overall process is simplified.

Hereinafter, each preferred embodiment according to the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, a detailed description of related well-known technologies or configurations may unnecessarily obscure the subject matter of the present invention. If so, the detailed description thereof will be omitted.

In addition, in the case where descriptions according to the relationship between the elements of the present invention described above are overlapped, the description thereof will be omitted.

First, Figure 1 is a block diagram of a device for extracting the dye according to the present invention, Figure 2 is an extraction step of the pigment according to the present invention.

As shown in Figure 1, the dye material extraction method according to the present invention, the material preparation step 510, the material mixing step 520, the co-solvent mixing step 530 and the extraction step of the pigment material 540 And a separation step 550.

The material preparation step 510 is a step of preparing a material containing a functional material such as a natural pigment component to be extracted, any one selected from a variety of seaweeds, shellfish or vegetables as the raw material 210 or It is also possible to prepare a mixture of different kinds of raw materials in any ratio.

When each raw material is comprised in several types, it is preferable to comprise the mixing ratio within 1-99 weight%.

On the other hand, the raw material 210 is not limited to seaweeds, crustaceans, vegetables itself, and the processed products or by-products, as well as the form of the raw materials include, of course, in the form of powder or liquid. In the case of powder or liquid, processed products such as juice or extract that have already been processed and sold may be used.

In addition, the subsidiary material 220 is selected as a processed product or by-product of rice bran or wheat germ, or rice bran and wheat germ, among various various grains, and the selected subsidiary materials 220 are cleaned and then sliced to a predetermined size.

In the present invention, the rice bran or wheat germ as the subsidiary material 220 is described as an optimal embodiment, but rice bran, bran, and bran may be used by substituting or mixing the subsidiary material 220, of course.

The subsidiary material 220 plays a role of containing a material that collects and adsorbs the dye material 310 extracted from the raw material 210 of the dye material extraction step 540 which will be described later. That is, when the pigment material is extracted from only the raw material 210, the yield (yield) decreases significantly over time due to the lipid content that is insufficient to capture the fat-soluble pigment due to the characteristics of the extract to be extracted from the raw material 210. The subsidiary material 220 is to be in charge of a function that makes it easy to collect such a dye material.

In addition, in the case of using rice bran or wheat germ as the submaterial 220, polyunsaturated fatty acid (HUFA), vitamin B1, tocopherol, sterol, protein, mineral, fiber, a from rice bran oil (rice bran oil) extracted therefrom When materials such as tocopherol, r-orizanol, and essential amino acids are extracted and mixed with the raw material 210, a more efficient functional pigment material 310 can be produced.

The mixing step 520 is a step of evenly mixing the prepared raw material 210 and the subsidiary material 220 at a predetermined ratio, and if the total amount of the raw material and the subsidiary material is mixed is 100% by weight, each of the raw material and the subsidiary material 50% by weight or raw material It is preferable that it consists of a relative mixing ratio within 1-99 weight% like 70 weight% and 30 weight% of submaterials, or 30 weight% of raw materials, and 70 weight% of submaterials.

In the extraction step 540, the pigment material 310 is extracted from the mixed materials 210 and 220. In extracting the pigment material, the present invention uses a supercritical extraction method to obtain a higher purity extract. It does not exclude organic solvent extraction, hot water extraction, neutral salt extraction, etc. using general heating and concentration.

In particular, as shown in FIG. 1, in order to obtain high solubility and high extraction efficiency, the extraction tower 110 and the extraction tower 200 in which the extraction solvent 110 and the materials 210 and 220 are mixed and extracted are extracted from the extraction tower 200. It is preferable to use a supercritical extraction method comprising a separator 300 for separating the pigment material 310 by rapidly reducing the pressure in the mixture of the extracted extract and the solvent.

Since supercritical or subcritical carbon dioxide has a nonpolar characteristic, it is possible to extract pigment substances such as non-polar natural pigment components contained in each of the raw materials and subsidiary materials, and mix the extracted substances into a single phase to make a highly volatile natural fragrance component. Or materials containing pigments and essential oil components can be maintained in a stable state.

In particular, the extraction step in the pigment material extraction method according to the present invention is made of a supercritical or subcritical fluid carbon dioxide 20g / min ~ 40g / min as the extraction solvent, the co-solvent is 1ml / min ~ 3ml It consists of / min. As described above, the main solvent and the cosolvent are preferably continuously introduced into the extraction column. In addition, the extraction conditions are such that the temperature and pressure are respectively made within the range of 30 ℃ ~ 60 ℃ and 80 bar ~ 500 bar.

The mixing step 530 of the co-solvent, which is a process of mixing the ethanol 120 and the water 130, is performed in advance before the extraction step 540, or by adjusting the discharge amount of the pipe supplied as shown in FIG. It is preferable to make a mixing ratio.

In particular, the weight ratio of the ethanol 120 and water 130 is preferably composed of any one selected from the ratio of 7: 3, 8: 2, 9: 1. Each of the three weight ratios of ethanol and water may be selected optimally according to the type of raw material in the selection thereof, and the following will be described with reference to one embodiment in Experiment 4 described below.

When explaining the embodiment of the present invention by the extraction method of the pigment material according to the supercritical extraction method as follows. First, any one selected from seaweeds, crustaceans, vegetables, and the like is used as the raw material 210, and rice bran or wheat germ is prepared as a subsidiary material 220, and mixed with each other in the extraction tower 200.

In addition, carbon dioxide is introduced into the extraction solvent 110 injected into the extraction tower 200, and in addition, ethanol 120 and water 130 are added as co-solvents.

In particular, the water added in addition to the extraction solvent and the co-solvent to absorb the salt contained in the raw material or subsidiary material to remove the salt contained in the pigment material to be extracted later. In the present invention, unlike the conventional extraction method, the pre-treatment step such as washing and the like may be omitted in order to remove the salt from the raw materials or members, and the water is added to the extraction tower together with the main solvent and the co-solvent. Increased productivity can be expected by eliminating complicated processes.

The heating and pressurizing range in the extraction tower 200 may be changed depending on the raw materials and the materials used, and the extraction solvent, but the temperature and the pressure are preferably in the range of 30 ° C. to 60 ° C. and 80 bar to 500 bar.

When heating and pressurization are performed within an appropriate range, the mixture of the pigment material and the solvent is extracted from the extraction tower 200 to the separator 300.

On the other hand, the separation step 550 is in a pressurized state in the extraction tower 200, when extraction to the separator 300 occurs due to the sudden drop in pressure is dissolved in the supercritical or sub-critical carbon dioxide, volatile and pigment material Among the extracts in which 310 is mixed, the pigment material is separated by reference numeral 310, and the solvent used is separated by reference numeral 320, thereby obtaining a functional substance such as a natural pigment component according to the present invention.

In particular, the separator 300 is to use a separator (separator) including the injection nozzle. The pigment material 310 and the solvent (main solvent and cosolvent) are sprayed by the spray nozzle while the pressure drops below the critical point. And in the injection nozzle to adjust the diameter of the nozzle to ensure the homogeneity of the pigment material (310).

This is because the pigment material 310 is not composed of only a single material, so that various materials are mixed. That is, the dye material 310 is formed by mixing different materials to ensure homogeneity by stirring for homogeneous mixing.

Homogenizers should be used for homogeneity of mixing in conventional mixtures. However, by using the separator in the separation step according to the present invention, there is an advantage that a high homogeneity can be secured without a separate mixing process of the dye material 310 as a mixture.

In this process, grains used as subsidiary materials are refined in the extraction tower 200 and are produced as rice bran oil, wheat germ oil, etc., which are chemically stable and have excellent capturing ability, and are extracted from seaweeds, crustaceans, and vegetables used as raw materials ( It serves as a collector or adsorbent to prevent the loss of 310).

On the other hand, the following experiment was performed to find out the functional substances such as pigments extracted from the raw material by the present invention.

Experiment 1

Seaweed powder and subsidiary materials were filled with wheat germ into the extraction tower as the main raw material, supercritical carbon dioxide (32.2 g / min) and co-solvent (ethanol) (2 ml / min) and water were added as the extraction solvent. The extraction conditions of the extraction tower was set to a temperature of 40 ℃, pressure 200 bar, extraction time 60 min.

3 to 5 each show a graph showing the results of the experiments performed in accordance with the present invention. The analytical instrument used in this experiment was HPLC (Waters 600E) and other analysis conditions were: Column: ZORBAX Eclipse Plus C18, Oven temperature: 40 ° C, Mobile Phase: methanol, ACN (acetonitrile), ethly acetate, Mobile Phase Flow Rate: 1 ml / min, Wave Length: 485 nm and the like.

Figure 3 is a graph recording the extraction amount of the pigment according to the input or not wheat germ as a subsidiary material, more specifically, using a supercritical carbon dioxide and co-solvent and subsidiary materials at a pressure of 200 bar, temperature 40 ℃ conditions This is a chart comparing the case of pigment extraction in seaweed and the case of pigment extraction when exclusion of subsidiary materials is mixed with the change of extraction amount with time.

4 and 5 are diagrams for analyzing the pigment component in the extract after the extraction of the pigment in the seaweed by the pigment component contained in the unprocessed red algae and the extraction method according to the present invention.

As shown in Figure 5, the result of extracting the pigment by the extraction method according to the invention it can be seen that the extract contains Fucoxanthin and chlorophyll Chlorophyll a known as an excellent pigment of the antioxidant carotenoids. In addition, when the wheat germ is mixed with the subsidiary material, it can be seen that the pigment component contained in the seaweed is more reliably extracted than when the wheat germ is extracted without the subsidiary material. This result indicates that the wheat germ used as the subsidiary material collects the pigment component of the seaweed. This is because it functions as a collector.

Experiment 2

The main raw material was crab shell powder and subsidiary materials filled with wheat germ into the extraction tower, supercritical carbon dioxide (32.2g / min), co-solvent (ethanol) (2ml / min) and water was added to the extraction solvent, As extraction conditions of the extraction tower, a temperature of 40 ° C., a pressure of 200 bar, and an extraction time were set to 60 min.

6 to 7 each show a graph showing the results of the experiments performed in accordance with the present invention. Meanwhile, the analysis equipment and other analysis conditions used in this experiment are the same as in Experiment 1 described above.

This experiment is the case of using the crab shell as the main material in the crustacean, Figure 6 is a graph of the analysis of the components of the standard solution of Astxanthin known as a carotenoid pigment, a fat-soluble pigment, Figure 7 is a crab extraction method according to the present invention The result of analyzing the pigment components in the extract after the pigment extraction from the shell is a graph.

As compared to the graph of Figure 6 and Figure 7, it can be seen that the extract extracted by the extraction method according to the present invention contains an extract of a component almost equivalent to Astxanthin contained in the standard solution of FIG.

Experiment 3

As a main raw material, carrot powder and subsidiary materials were filled with wheat germ into the extraction tower, supercritical carbon dioxide (32.2 g / min) was extracted, co-solvent (ethanol) (2 ml / min) and water were added as auxiliary solvents. The extraction conditions of the extraction tower was set to a temperature of 40 ℃, pressure 200 bar, extraction time 60 min.

8 to 9 each show a graph showing the results of the experiments performed in accordance with the present invention. Meanwhile, the analysis equipment and other analysis conditions used in this experiment are the same as in Experiment 1 described above.

This experiment is to detect the extracted components after the extraction of the pigment by the extraction method according to the present invention using the carrot as a vegetable as a main material, Figure 8 is a component of the standard solution of β-carotene, a pigment of the carotenoid-based pigment of fat-soluble pigment As a result, Figure 9 is a graph showing the results of the analysis of the pigment component in the extract after the pigment extraction from carrots as vegetables in the extraction method according to the invention.

As a result of analyzing the components of the pigment extracted in Figure 9, it can be seen that it contains β-carotene, a carotenoid pigment, which is a fat-soluble pigment, and the present invention shows that it is possible to extract pigments from vegetables as well as seaweeds and shellfish. have.

Experiment 4

First, wakame and subsidiary materials are filled with wheat germ into the extraction tower, the extraction solvent is supercritical carbon dioxide (32.2g / min), the auxiliary solvent is co-solvent (ethanol) (2ml / min) and distilled water (water) Input.

However, in this experiment, the weight ratio of the co-solvent and distilled water was three different conditions, and the pressure and temperature extraction conditions were also composed of three different conditions.

More specifically, the weight ratio of cosolvent and water was set to 7: 3, 8: 2, and 9: 1. In addition, the extraction conditions were set to 200bar and 40 ℃, 200bar and 50 ℃, 200bar and 60 ℃

Figure 10 is a graph showing the salt removal rate according to different embodiments according to the present invention, the X-axis shows the pressure and temperature three groups, the Y-axis shows the removal rate of salt (NaCl) in terms of% have.

As shown in Figure 10, it can be seen that the extraction rate of the largest salt (NaCl) (81%) in the extraction conditions of the pressure 200bar, temperature 50 ℃, the co-solvent and distilled water at the weight ratio of 8: 2 It can be seen that the removal rate of the large salt is shown.

As in the present experiment, it can be seen that by mixing ethanol and water in an appropriate ratio as a co-solvent, it is possible to remove salt from seaweed samples that have not been pretreated (washed untreated) and selectively extract the desired functional pigments. Therefore, in the prior art, in order to remove the salt of seaweed, but the water washing process is required in the process, the extraction method according to the present invention has the advantage that it can omit the washing process for removing salt of seaweed.

In the above, but limited to the preferred embodiment according to the present invention described above, it will be apparent to those skilled in the art that the present invention is not limited thereto and can be variously changed or modified.

1 is a block diagram of an apparatus for extracting a pigment according to the present invention.

Figure 2 is an extraction step of the pigment according to the present invention.

Figure 3 is a graph recording the extraction amount of the pigment according to whether or not the input of wheat germ as a subsidiary material.

4 and 5 are graphs of the pigment components contained in the unprocessed red algae and the pigment components in the extract after the pigment extraction in the seaweed by the extraction method according to the present invention.

Figure 6 is a graph of the results of analysis of the components of the standard solution of Astxanthin known as a carotenoid pigment, a fat-soluble pigment.

Figure 7 is a graph of the results of analyzing the pigment components in the extract after the pigment extraction from the crab shell by the extraction method according to the present invention.

8 is a graph analyzing the components of the standard solution of β-carotene which is a carotenoid pigment which is a fat-soluble pigment.

Figure 9 is a graph showing the results of analyzing the pigment components in the extract after the pigment extraction from carrots as vegetables in the extraction method according to the present invention.

10 is a graph showing the salt removal rate by different embodiments according to the present invention.

* Description of the symbols for the main parts of the drawings *

110: extraction solvent 120: ethanol

130: water

200: extraction tower 210: raw materials

220: material 300: separator

310: pigment material 320: co-solvent after separation

510: material preparation step 520: material mixing step

530: mixing step of the cosolvent 540: pigment extraction step

550: separation step

Claims (4)

Preparing at least one selected from seaweeds, shellfish, and vegetables as raw materials; Preparing at least one selected from rice bran or wheat germ, processed products or by-products of rice bran and wheat germ, and adding and mixing the raw materials; Extraction step of extracting the pigment material from the mixed raw materials and subsidiary materials, wherein the extraction step is 20g / min ~ 40g / min carbon dioxide, supercritical or subcritical fluid as an extraction solvent, 1ml / min ~ 3ml co-solvent continuously charged at / min and set at a temperature of 30 ° C. to 60 ° C. and a pressure in the range of 80 bar to 500 bar; Separation step of separating the extraction solvent and the co-solvent with a pigment material; Pigment extraction method from a natural raw material using supercritical carbon dioxide and subsidiary material. The method of claim 1, The co-solvent is a mixture of ethanol and water, the mixing ratio of the ethanol and water is one of the weight ratio of 7: 3, 8: 2, 9: 1 using a supercritical carbon dioxide and using a subsidiary Pigment extraction from natural raw materials. The method of claim 2, The separation step, A method for extracting a pigment from a natural raw material using supercritical carbon dioxide and a subsidiary material, characterized in that the separator comprises a spray nozzle. The method according to any one of claims 1 to 3, The raw material is a method for extracting pigments from natural raw materials using supercritical carbon dioxide and subsidiary materials, characterized in that mixed in a relative proportion to each other within 1 to 99% by weight.

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