JPH04256401A - Device for separating trace volatile effective component - Google Patents

Abstract

PURPOSE:To efficiently separate and recover a volatile effective component by extracting the trace volatile effective component with supercritical or nearly supercritical carbon dioxide and introducing the material to be extracted into an U tube with the inner diameter of the bottom larger than those of the other parts. CONSTITUTION:A material to be extracted is brought into contact with supercritical or nearly supercritical carbon dioxide in an extractor 2, and the trace volatile effective component is extracted by the carbon dioxide. The effective component extracted in an extraction vessel 8 is continuously drawn off along with the carbon dioxide from the top of the vessel 8 through a conduit 7c, cooled by a heat exchanger 6b and then introduced into a collector 3 through an inlet pipe 21. The carbon dioxide introduced into the collector 3 and contg. the effective component is decelerated at the bottom 24 of an U tube 22 and cooled, hence the effective component is collected on the bottom 24, and the carbon dioxide is discharged from an outlet pipe 23.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a method for extracting and separating trace amounts of volatile active ingredients from a material to be extracted containing trace amounts of volatile active ingredients using supercritical carbon dioxide or carbon dioxide in the vicinity of supercritical state. The present invention relates to a device for separating volatile active ingredients.

0002

[Prior art] Flowers, buds, fruits, seeds, branches and leaves of plants,
The bark, stem, rhizome, or cultured cells thereof contain active ingredients such as pharmaceuticals, foods, and fragrances. These active ingredients are volatile and often contained in trace amounts. Conventionally, these volatile active ingredients have been extracted by an extraction method such as a steam distillation method using a steam distillation device or a solvent extraction method using a solvent extraction device.

[0003] However, when volatile active ingredients are extracted by steam distillation, the distillation is carried out at high temperatures, so the heat-labile ingredients change in quality during distillation, and the active ingredients originally contained in plants are There is a problem in that foreign components are extracted. In addition, water-soluble substances dissolve in the aqueous layer, resulting in a decrease in yield, or when recovering components dissolved in the aqueous layer, a recovery operation is required, which is complicated and evaporates during the recovery operation. This results in a decrease in yield due to the escape of active ingredients. Further, after steam distillation, an operation is required to separate the oil layer and the water layer, but even in this separation step, volatile active ingredients are dissipated, resulting in a decrease in yield. Such a decrease in yield makes it difficult to recover trace amounts of volatile active ingredients. Furthermore, separation of volatile active ingredients and solvent requires complicated equipment such as a pressure reduction device.

On the other hand, when volatile active ingredients are extracted using an organic solvent, the volatile active ingredients may be deteriorated by the organic solvent. Furthermore, after extraction, it is necessary to separate the volatile active ingredient and the organic solvent, but this is usually done by adding thermal energy to the boiling point difference between the volatile active ingredient and the organic solvent. Often separated by
A heating device, etc. is required. Further, during separation, there is a problem that thermally unstable volatile active ingredients change in quality, and the yield decreases due to evaporation. As described above, when volatile active ingredients are extracted using an organic solvent, the quality of the volatile active ingredients and the yield of the volatile active ingredients are lowered.

[0005] Among volatile active ingredients, the aromatic components in liquid cultured cells in particular consist of a wide variety of volatile and water-soluble components with different polarities and boiling points, and a mixture of these components gives off a unique aroma. Further, the content of each component is small and coexists with a large amount of water. Since trace amounts of volatile components are easily dissipated at high temperatures, and water-soluble components are dissolved in a large amount of coexisting water, extraction methods using organic solvents are inefficient. Therefore, it is difficult to uniformly extract and separate such aroma components by the above-mentioned steam distillation method or extraction method using an organic solvent without impairing the characteristics of the aroma.

[0006] Furthermore, when searching for trace amounts of volatile active ingredients in a small amount of raw materials, it is important to extract the ingredients without altering their quality and to collect the extract without escaping it. However, the above-mentioned extraction method using the conventional extraction device has the problem that it is difficult to search for the true ingredients contained in the raw material because it causes deterioration and a decrease in yield during the extraction process.

[0007]

[Problems to be Solved by the Invention] In order to solve the above-mentioned problems, it is an object of the present invention to easily extract a trace amount of volatile active ingredients, and to contain a trace amount of volatile active ingredients after extraction. To provide a device for separating a trace amount of volatile active ingredients, which can efficiently separate and recover volatile active ingredients from an extractant using a simple device.

[0008]

[Means for Solving the Problems] The present invention provides the following device for separating trace amounts of volatile active ingredients. (1) An extraction device that extracts trace amounts of volatile active ingredients using supercritical carbon dioxide or carbon dioxide in a near supercritical state; and volatile extraction from carbon dioxide containing trace amounts of volatile active ingredients extracted by this extraction equipment. a collection device that separates and collects the active ingredient; the collection device includes a U-shaped tube having a larger inner diameter at the bottom than the other portions; an inlet tube; and an outlet tube; A trace amount volatile active ingredient separation device, characterized in that one end of the is connected to the extraction device via an inlet pipe, and the other end is connected to an outlet pipe.

(2) In the inlet pipe and outlet pipe of the collection device,
The device for separating a trace amount of volatile active ingredient according to (1) above, in which a constricted portion is formed.

The separation device of the present invention includes an extraction device for extracting trace amounts of volatile active ingredients using supercritical carbon dioxide or near-supercritical carbon dioxide; It consists of a collection device that separates and collects volatile active ingredients from the carbon dioxide contained therein.

[0011] The extraction device has an extraction tank that can be adjusted to a predetermined pressure and temperature, and carbon dioxide is supplied to this extraction tank from a carbon dioxide supply source so that extraction is carried out in a supercritical or near supercritical state. It has become.

[0012] The collection device comprises a U-shaped tube whose inner diameter at the bottom is larger than the inner diameter at other parts, an inlet tube and an outlet tube,
One end of the U-shaped tube communicates with the extraction tank of the extraction device via an inlet tube, and the other end communicates with an outlet tube. The bottom of the U-shaped tube can be cooled from the outside. The ratio of the inner diameter of the bottom/the inner diameter of other parts is usually 1.5 to 4.
, preferably 2 to 3. Preferably, the inlet tube and the outlet tube have a constriction.

[0013]

[Operation] In order to extract and collect a trace amount of volatile active ingredients from a material to be extracted containing a trace amount of volatile active ingredients using the separation device of the present invention, carbon dioxide is added to the extraction device filled with the material to be extracted. Carbon dioxide is supplied from a source and brought to a supercritical or near supercritical state for extraction. Then, the extracted carbon dioxide containing a trace amount of volatile active ingredients is guided from the extraction device to a collection device to separate the volatile active ingredients and carbon dioxide.

[0014] In the extraction device, the material to be extracted is brought into contact with supercritical or near supercritical carbon dioxide, thereby extracting a trace amount of volatile active ingredients with carbon dioxide. The trace amounts of volatile active ingredients extracted in this way are led together with carbon dioxide into the U-shaped pipe through the inlet pipe of the collection device.
Here carbon dioxide and traces of volatile active ingredients are separated.

In the collection device, when the carbon dioxide containing a trace amount of volatile active ingredients introduced into the U-shaped tube reaches the bottom part which is cooled from the outside, the bottom part of the U-shaped tube has an inner diameter different from that of the other one. Since the inner diameter of the part is larger than the inner diameter of the U-shaped tube, the flow rate of the introduced carbon dioxide containing a trace amount of volatile active ingredient is slowed down and cooled, so the trace amount of volatile active ingredient is collected at the bottom of the U-shaped tube. The carbon dioxide is discharged from the outlet tube. In order to prevent the volatile active ingredients separated and collected in this way from escaping, the inlet and outlet pipes are quickly sealed after extraction. If the inlet and outlet pipes have constrictions, these constrictions are sealed.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the separation apparatus of the present invention will be explained with reference to the drawings. FIG. 1 is a configuration diagram showing an example of a separation device according to an embodiment of the present invention, FIG. 2 is a front view of the collection device, and FIG. 3 is a plan view thereof.

In the figure, 1 is a separation device, and this separation device 1 is composed of an extraction device 2 and a collection device 3.

The extraction device 2 includes a carbon dioxide supply source 4, booster pumps 5a, 5b, heat exchangers 6a, 6b, and conduits 7a, 7b.
, 7c, an extraction tank 8, an entrainer storage tank 9, stop valves 10a, 10b, and a capillary 11.

The carbon dioxide supply source 4 and the bottom of the extraction tank 8 are connected by a conduit 7a, and a booster pump 5a and a heat exchanger 6a are arranged between them. Further, the entrainer storage tank 9 and the bottom of the extraction tank 8 are connected by conduits 7a and 7b, and a booster pump 5b and a stop valve 10 are connected between the two.
a and a heat exchanger 6a are arranged. The entrainer supply conduit 7b is connected between the boost pump 5a and the heat exchanger 6a.

The upper part of the extraction tank 8 and the inlet pipe 21 of the collection device 3
are connected by a conduit 7c, and a capillary 11, a heat exchanger 6b, and a stop valve 10b are arranged between the two. The capillary 11 has an inner diameter of 50 to 3
00 μm, preferably 50-200 μm, length 50-5
00 mm, preferably 50 to 300 mm, can be used, and is appropriately selected depending on the extraction pressure. Also, capillary 1
1 can also be replaced by a pressure regulating valve.

The collection device 3 is composed of an inlet pipe 21, a U-shaped pipe 22 and an outlet pipe 23. The bottom part 24 of the U-shaped tube 22 has a larger inner diameter than other parts. The inlet pipe 21 and the outlet pipe 23 have a constriction 25 and face in opposite directions. The bottom portion 24 is cooled in the cooling bath 12 .

In such a separation apparatus 1, carbon dioxide as an extractant supplied from a carbon dioxide supply source 4 is pressurized by a pressure booster pump 5a, heated by a heat exchanger 6a, and made into supercritical or near supercritical state. , and is continuously supplied to the extraction tank 8 through the conduit 7a. The extraction tank 8 can be adjusted to a predetermined pressure and temperature, and volatile active ingredients are extracted by bringing the material to be extracted into contact with carbon dioxide in a supercritical or near-supercritical state. The pressure in the extraction tank 8 is regulated by a capillary 11 and a stop valve 10b. From the entrainer storage tank 9, entrainer (a third component as an extraction aid), which is used as necessary, is supplied to the bottom of the extraction tank 8 from a conduit 7a via a boost pump 5b, a stop valve 10a, and a heat exchanger 6a. be done.

The trace amount of volatile active ingredients extracted in the extraction tank 8 is passed from the upper part of the extraction tank 8 to the conduit 7c together with carbon dioxide.
After being continuously extracted through the heat exchanger 6b and cooled by the heat exchanger 6b, it is led to the collection device 3 via the inlet pipe 21.

The carbon dioxide containing a trace amount of volatile active ingredients introduced into the collection device 3 is collected at the bottom 24 of the U-shaped tube 22.
The flow rate is slowed down and cooled so that traces of volatile active ingredients are collected in the bottom 24 and carbon dioxide is discharged through the outlet tube 23. The emitted carbon dioxide may be recovered and reused. After separation and collection, the constrictions 25 of the inlet pipe 21 and the outlet pipe 23 are sealed. Inlet pipe 21
and the outlet pipe 23 are facing in opposite directions, so
When the constricted portions 25 are welded together, they do not interfere with the welding process.

In order to extract and separate a trace amount of volatile active ingredients from a material to be extracted using the separation apparatus shown in FIG. The volatile active ingredients are extracted by contacting with carbon dioxide. Here, carbon dioxide as an extractant is continuously supplied from the carbon dioxide supply source 4 to the bottom of the extraction tank 8. Further, if necessary, entrainer is continuously supplied from the entrainer storage tank 9 to the bottom of the extraction tank 8. At this time, carbon dioxide is pressurized by a pressure booster pump 5a, heated by a heat exchanger 6a, and brought into a supercritical or near supercritical state and supplied to the extraction tank 8. The entrainer includes a boost pump 5b and a stop valve 10a.
and is continuously supplied via the heat exchanger 6a.

[0026] The carbon dioxide used as an extractant for a trace amount of volatile active ingredients is supercritical carbon dioxide in a state exceeding the critical temperature (31.1°C) and critical pressure (75.3 kgf/cm2) or supercritical carbon dioxide. It is carbon dioxide in a state close to a point. Specifically, the temperature is 20 to 80°C, preferably 31.1 (critical temperature of carbon dioxide) to 70°C, more preferably 35 to 60°C, and the pressure is 70 to 400 kgf/
cm2 gauge, preferably 75.3 (critical pressure of carbon dioxide) to 300 kgf/cm2 gauge supercritical carbon dioxide or carbon dioxide near the supercritical state, temperature and pressure are appropriate depending on the type of volatile active ingredient to be extracted. select.

Examples of the entrainer include methanol, ethanol, water and acetone.

Extractable materials include, for example, plant tissues or cells such as flowers, buds, fruits, seeds, branches and leaves, bark, stems, and rhizomes, or cultured cells, and pharmaceuticals present therein. Extracts small amounts of volatile active ingredients used in the fields of food, fragrances, etc.

Next, the extracted trace amount of volatile active ingredients is extracted from the upper part of the extraction tank 8 together with carbon dioxide, cooled by a heat exchanger 6b, and then led to the collection device 3, where the trace amount of volatile active ingredients are removed. and carbon dioxide, the trace amounts of volatile active ingredients are collected in the bottom 24 of the U-shaped tube 22, and the carbon dioxide is discharged through the outlet tube 23. Note that the collection device 3 is cooled by immersing the bottom portion 24 of the U-shaped tube 22 in a cooling tank 12 filled with dry ice, acetone, or the like. The collection device 3 is preferably made of glass, but is not limited thereto.

After extraction and separation, the constriction 25 is quickly sealed with a gas burner or the like, and the volatile active ingredients are transferred to the collection device 3.
Enclose in. The collection device 3 is preferably one in which the inlet pipe 21 and the outlet pipe 23 are connected to the U-shaped pipe 22 at an angle and in a direction that allows the sealing operation to be performed quickly and easily.

Example 1 Picea spruce (Japanese spruce) emitting a fruit-like aroma that was kept frozen
Weighed 2.3 g (0.34 g after drying and removing the contained moisture after extraction) of the callus of Picea glehnii) and volatilized it using the separation device 1 shown in Figs. 1 to 3. The active ingredients were extracted.

That is, the callus of Picea acanthus was filled into an extraction tank 8 with an internal volume of 15 ml, supercritical carbon dioxide was used as an extractant, and the extraction pressure was 180 kgf/cm2 gauge.
Extraction was performed at an extraction temperature of 40° C. for 1 hour, and the extract was collected. Carbon dioxide was supplied continuously at a flow rate of 20 Nl/h. In the extraction operation, the weight of the charged material to be extracted was determined by weighing it using a balance, and the amount of carbon dioxide used was measured using a gas meter. The bottom 24 of the U-shaped tube 22 was cooled with dry ice/acetone. As the capillary 11, a capillary with an inner diameter of 200 μm and a length of 150 mm was used. As the collection device 3, a U-shaped tube 22 made of glass was used, with the bottom 24 having an inner diameter of 10 mm and the other portions having an inner diameter of 5 mm.

After the extraction was completed, the constriction 25 was quickly sealed with a gas burner to obtain an extract. This extract is extracted as Extract A.
shall be.

[0034] Weighed 24.7 g of the same Picea callus as above while it contained moisture (3.7 g after the moisture content was removed by drying after extraction), and extracted it in the same manner as above. An extract was obtained. This extract is referred to as extract B.

In all of the above cases, the extracts A and B collected by the collection device 3 had a fruit-like aroma exactly the same as the fruit-like aroma emitted by the callus of Scots spruce, which is the extract. Furthermore, the above-mentioned aroma was not observed in the carbon dioxide discharged from the outlet pipe 23 during extraction, and the above-mentioned aroma was not observed at all in the callus of Picea abies taken out from the extraction tank 8 after extraction. These results show that the fruit-like aroma emitted by the callus of Picea acanthus can be completely extracted and separated by extraction using the separation device 1 shown in FIG. 1, and that it does not dissipate along with carbon dioxide.

Extract A was mainly used to analyze lipophilic components. That is, one end of the collection device 3 where the extract A is collected is cut off, and 50 mm is removed from the opening.
0 μl of ether and 500 μl of water were injected using a syringe, and the collection device 3 was rotated to dissolve the extract. The solution was collected in the open part of the collection device 3. The ether layer of the solution in the collection device 3 was transferred to a sample bottle, and the aqueous layer was transferred to a test tube with a stopper. The collection device 3 was mixed with 500 μl of water and 100 μl of water.
The cells were washed with 0 μl of ether and the washings were transferred to a stoppered test tube. This stoppered test tube was stoppered and shaken well to separate the ether layer. After adding 500 μl of ether again to the aqueous layer and shaking well, the ether layer was separated. All the ether layers separated by the above method were collected, dried over anhydrous sodium sulfate, and then analyzed using a gas chromatography/mass spectrometer.

Extract B was used to analyze components with low boiling points and relatively hydrophilic properties. That is, the collection device 3
The aqueous solution extracted with supercritical carbon dioxide was directly analyzed using a gas chromatography/mass spectrometer.

[0038] The above two types of gas chromatography
1 to 3 μl of the sample to be subjected to mass spectrometry was injected into a gas chromatography/mass spectrometer. The conditions of the gas chromatography/mass spectrometer at that time were as follows. M-80B mass spectrometer manufactured by Hitachi, Ltd. Ionization energy: 70 eV Gas chromatography column: Fused silica capillary column UNBON HR
-101,50m x 0.25mmφ (manufactured by Shinwa Chemical Industry Co., Ltd.) Temperature conditions: 60℃ (5 minutes) 60-220℃ (2℃/min)

Ion chromatograms of the ether solution treated with extract A and the aqueous solution coexisting with extract B are shown in FIGS. 4 and 5, respectively.

As a result of structural analysis of peaks A to K components shown in FIG. 4, it was confirmed that they were the following substances. Peak A: Isoamyl alcohol peak B: Fatty acid ethyl ester peak C: Butyric acid peak D: Heptyl butyrate peak E: Fatty acid ethyl ester peak F: Fatty acid propyl ester peak G: Fatty acid ethyl ester peak H: Fatty acid ethyl ester peak I: Fatty acid methyl Ester peak J: Fatty acid ethyl ester peak K: Fatty acid ethyl ester

Further, as a result of structural analysis of peaks A to H components shown in FIG. 5, it was confirmed that they were the following substances. Peak A: Butenal peak B: Acetic acid peak C: Acetoin peak D: Ethylpropionic acid peak E: Fatty acid isobutyl ester peak F: Benzaldehyde peak G: Fatty acid isopropyl ester peak H: 1-
formylnaphthalene

[0042] From the above, it was confirmed that the main components of the fruit-like aroma emitted by the callus of Picea acanthus were the components shown in FIGS. 4 and 5.

Comparative Example 1 100 ml of distilled water was added to 13.4 g of callus of Picea spruce producing the same aroma as the callus used in Example 1, and the mixture was extracted by continuous distillation for 90 minutes with 30 ml of ether. The ether extract was dried over anhydrous sodium sulfate overnight, concentrated under reduced pressure, and then concentrated using a hand warm method, followed by gas chromatography/mass spectrometry. The conditions of the gas chromatography/mass spectrometer at that time were as follows. M-80B mass spectrometer manufactured by Hitachi, Ltd. Ionization energy: 70 eV Gas chromatography column: Silicone OV-101, 50 m x 0.25 mm
φ (manufactured by Shinwa Chemical Industry Co., Ltd.) Temperature conditions: 60°C (5 minutes) 60-220°C (2°C/min)

As a result, pyridine, benzaldehyde,
Aromatic compounds such as ethyl benzoate, vanillin, naphthalene ethyl acetate, ethoxybenzaldehyde, acetic acid, acyl alcohol, various aldehydes with 6 to 10 carbon atoms, alcohol, fatty acids with 12 to 18 carbon atoms and their methyl or ethyl esters, acyl Acetate, carbon number 1
Although 3 to 16 linear hydrocarbons were identified, the extract showed no aroma and failed to capture fruity aromas.

Comparative Example 2 After thawing 102.8 g of liquid cultured cells of Picea acanthus that produce the same aroma as the callus used in Example 1, the cells were soaked in 200 m of water.
1 was added to make the mixture uniformly suspended. Divide this into 4 parts, 7
5 ml portions were dispensed into 500 ml round bottom flasks, rapidly frozen with acetone/dry ice, and then freeze-dried. 295 ml of recovered water (required time: 6 hours) was obtained and extracted with dichloromethane. In addition, the obtained freeze-dried residue is
Furthermore, the water recovered after the dichloromethane extraction was added, and the volatile components were collected by freeze-drying in the same manner as above. The two batches were combined and concentrated using a Guderner-Danish concentrator (manufactured by Shibata Kagaku Kikai Kogyo Co., Ltd.) to obtain 3 mg of a concentrate.

[0046] This concentrate did not exhibit any fruity aroma as observed in Example 1. Moreover, this concentrate was used for gas chromatography/mass spectrometry. The conditions of the gas chromatography/mass spectrometer are as follows. M-80B mass spectrometer manufactured by Hitachi, Ltd. Ionization energy: 70 eV Gas chromatography column: PEG 20M bonded (25 m x 0.25 mm
ID, ) (manufactured by Shinwa Chemical Industry Co., Ltd.) Temperature conditions: 45°C (4 minutes) 45-230°C (3°C/min)

According to the results of gas chromatography/mass spectrometry, acetoin, acetoin alcohol, 1-octen-3-ol, butene-1,4-olide, menthol, methyl carbinol, isopentenol, Low-boiling substances such as 4-methyl-butyric acid were detected, but no components thought to be related to the fruity aroma could be identified.

[0048]

As described above, according to the present invention, it is possible to easily extract a trace amount of volatile active ingredients, and moreover, the volatile active ingredients can be extracted from an extractant containing a trace amount of volatile active ingredients after extraction. A device for separating a trace amount of volatile active ingredients can be obtained, which can efficiently separate and recover a small amount of volatile active ingredients using a simple device.

[Brief explanation of the drawing]

FIG. 1 is a configuration diagram showing a separation apparatus of the present invention.

FIG. 2 is a front view of a collection device used in the separation device of FIG. 1.

FIG. 3 is a plan view of the collection device of FIG. 2;

FIG. 4 is a graph showing the results of Example 1.

FIG. 5 is a graph showing the results of Example 1.

[Explanation of symbols]

1 Separation device 2 Extraction device 3 Collection device 4. Carbon dioxide supply source 5a, 5b Boost pump 6a, 6b Heat exchanger 7a, 7b, 7c conduit 8 Extraction tank 9 Entrainer storage tank 10a, 10b Stop valve 11 Capillary 12 Cooling tank 21 Inlet pipe 22 U-shaped tube 23 Outlet pipe 24 Bottom 25 Neck part

Claims (2)

[Claims] Claim 1: An extraction device for extracting trace amounts of volatile active ingredients using supercritical carbon dioxide or carbon dioxide in a near supercritical state; a collection device for separating and collecting volatile active ingredients; said collection device comprises a U-shaped tube having a larger inner diameter at the bottom than the other portions; an inlet tube; and an outlet tube; An apparatus for separating a trace amount of volatile active ingredient, characterized in that one end of the shaped tube is connected to the extraction device via an inlet pipe, and the other end is connected to an outlet pipe. 2. The device for separating a trace amount of volatile active ingredient according to claim 1, wherein a constriction is formed in the inlet pipe and the outlet pipe of the collection device.