JP2005213327A - Vegetable essential oil, manufacturing method therefor and method for manufacturing thymol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a vegetable essential oil using a carbon dioxide fluid in a supercritical or subcritical state, and other technologies related thereto. <P>SOLUTION: This method for manufacturing a vegetable essential oil comprises a step of preparing a liquid vegetable essential oil sample in which a raw, essential oil-containing vegetable material is extracted with either one of water, a hydrophilic solvent and a mixture thereof followed by preparing the liquid vegetable essential oil sample through concentration, and a carbon dioxide fluid contacting step in which the obtained liquid vegetable essential oil sample contacts with a carbon dioxide fluid in a supercritical or subcritical state. The carbon dioxide fluid contacting step in this method preferably comprises a carbon dioxide gas dissolving step in which the liquid vegetable essential oil sample contacts with the carbon dioxide fluid to dissolve the carbon dioxide gas in the liquid vegetable essential oil sample to the saturation, and a step of treatment with a carbon dioxide gas in a supercritical state in which the liquid vegetable essential oil sample having the carbon dioxide gas dissolved therein is kept and stirred in the carbon dioxide supercritical state. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a plant essential oil using a supercritical or subcritical carbon dioxide fluid, a plant essential oil obtained by the production method, and a method for producing thymol.

Essential oil components, which are volatile oily substances extracted from essential oil-containing plants, are widely used in fragrances, deodorants, fungicides, antibacterial agents, and the like. Examples of the essential oil component extraction method include a supercritical extraction method and a steam distillation method. Since the supercritical extraction method uses high-pressure equipment, there is a drawback that the amount of the plant dry raw material charged per extraction batch is small and a great manufacturing cost is required. The steam distillation method requires a large amount of heat for recovering essential oil components, and is liable to cause enormous energy consumption and quality deterioration such as browning, and is only produced on a small-scale production machine.
For this reason, provision of the extraction method which can manufacture an essential oil component from an essential oil containing plant efficiently and in large quantities at low temperature was strongly calculated | required.

In recent years, as a method for performing low-temperature extraction of essential oil components from a plant body, an apparatus has been proposed in which a carbon dioxide supercritical fluid is microbubbled and mixed and contacted with a liquid material (see Patent Documents 1 and 2, Non-Patent Document 1). ).
However, it is difficult to supercritically extract a large amount of essential oil components, which are volatile oily substances, at low cost and efficiently without losing quality, and further improvements and developments are desired. .

JP 2001-299303 A JP 2001-128652 A No. 4 1995 Yutaka Samejima

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, according to the present invention, by bringing a supercritical or subcritical carbon dioxide fluid fluid into contact with a plant essential oil liquid sample, an essential oil component can be efficiently extracted at a high content from an essential oil-containing plant, and the quality is impaired. It is possible to provide a method for producing a plant essential oil that can be continuously extracted at a low temperature, can be mass-produced, and can achieve a significant cost reduction, a plant essential oil obtained by the production method, and a method for producing thymol. Objective.

As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained. That is, it has been found that the essential oil component can be efficiently extracted by liquid-liquid extraction by bringing the hydrous alcohol extract of an essential oil-containing plant into contact with a carbon dioxide supercritical fluid.
Further, the carbon dioxide supercritical fluid can be microbubbled to reach the saturation concentration of carbon dioxide in a short time. Furthermore, the extraction efficiency is dramatically increased by using a reaction coil, and the extraction raw material is efficiently extracted on a large scale by alcohol extraction without drying and directly extracting the extraction raw material as in the past. It was found that the essential oil components can be extracted efficiently by making the best use of the diffusive and cohesive properties of supercritical fluids by performing critical extraction.
Specifically, in order to extract and purify thymol, an essential oil component contained in Hosoyama Yamajiso, which has strong antibacterial properties, extraction and purification similar to steam distillation can be performed by drying the Hosobayamajiso raw material in the sun and performing supercritical extraction with carbon dioxide gas. Although it was possible, it was difficult to commercialize the product because the drying cost and the supercritical extraction cost, which is a unit operation, became enormous, but it was obtained after a large amount extraction processing of Hosobayamajiso raw material by hydrous alcohol extraction It was discovered that by processing Hosoyama Yamajiso extract using a micro-bubble carbon dioxide supercritical fluid extraction device, continuous extraction processing becomes possible, mass production becomes possible, and significant cost reduction can be achieved.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A plant essential oil liquid sample preparation step in which an essential oil-containing plant material is extracted with water, a hydrophilic solvent, or a mixed solvent thereof to prepare a plant essential oil liquid sample, and the obtained plant essential oil liquid sample And a carbon dioxide fluid contact step of contacting the carbon dioxide fluid in a critical or subcritical state.
<2> The carbon dioxide fluid contact step comprises contacting the plant essential oil liquid sample with the carbon dioxide fluid to dissolve the carbon dioxide gas to a saturated concentration in the plant essential oil liquid sample, and dissolving the carbon dioxide gas. The method for producing plant essential oil according to <1>, further comprising a carbon dioxide gas supercritical treatment step in which the plant essential oil liquid sample is kept in a supercritical state of carbon dioxide gas and stirred.
<3> The method for producing a plant essential oil according to <2>, wherein in the carbon dioxide gas dissolving step, a carbon dioxide fluid that is microbubbled through a mesh filter having a mesh of 100 μm or less is used.
<4> The method for producing a plant essential oil according to any one of <2> to <3>, wherein the carbon dioxide gas dissolving step is performed under a carbon dioxide gas saturated concentration condition of a temperature of 0 to 30 ° C. and a pressure of 10 to 30 MPa.
<5> The plant according to any one of <2> to <4>, wherein the carbon dioxide supercritical treatment step is performed while maintaining carbon dioxide supercritical conditions at a temperature of 31.1 to 50 ° C. and a pressure of 10 to 30 MPa. It is a manufacturing method of essential oil.
<6> The method according to any one of <2> to <5>, further including a carbon dioxide removal step of removing carbon dioxide from the plant essential oil liquid sample by rapidly reducing the pressure applied to the plant essential oil liquid sample to normal pressure. This is a method for producing a plant essential oil.
<7> The method for producing a plant essential oil according to any one of <2> to <6>, wherein the carbon dioxide fluid contact step further includes a recycling step, and the plant essential oil liquid sample is continuously processed.
<8> The method for producing a plant essential oil according to any one of <1> to <7>, wherein the essential oil-containing plant material is at least one selected from Hosoyama Yamajiso, Thyme, Oregano and Rosemary.
<9> The method for producing a plant essential oil according to <8>, wherein the essential oil-containing plant raw material is Hosobayamajiso and the essential oil component is thymol.
<10> A plant essential oil produced by the method for producing a plant essential oil according to any one of <1> to <9>.
<11> A carbon dioxide gas dissolving step in which the ground portion of Hosoyama Yamajiso is extracted with water-containing ethanol and brought into contact with a microbubbled carbon dioxide fluid to dissolve the carbon dioxide gas to a saturated concentration. And a carbon dioxide supercritical treatment step of stirring and maintaining the supercritical state of carbon dioxide in a supercritical state of carbon dioxide gas.

  According to the present invention, various problems in the prior art can be solved, a large amount of plant essential oil liquid sample can be extracted as alcohol extraction, and the liquid-liquid extraction part that becomes supercritical extraction is downsized as continuous extraction and is of high quality at low cost. Essential oil components can be obtained, and a significant cost reduction can be achieved.

(Plant essential oil production method and plant essential oil)
The plant essential oil production method of the present invention comprises a plant essential oil liquid sample preparation step and a carbon dioxide gas fluid contact step. The carbon dioxide fluid contact step comprises a carbon dioxide gas dissolution step, a carbon dioxide gas supercritical treatment step, a reduced pressure. The process further includes other processes as necessary.
The method for producing thymol according to the present invention is to treat Hosoyama Yamajiso extract in a carbon dioxide gas dissolving step and a carbon dioxide supercritical treatment step.
The plant essential oil of the present invention is obtained by the method for producing the plant essential oil of the present invention.
Hereinafter, the details of the method for producing the plant essential oil and thymol of the present invention will be clarified through the description of the method for producing the plant essential oil of the present invention.

-Plant essential oil liquid sample preparation process-
The plant essential oil liquid sample preparation step is a step of preparing a plant essential oil liquid sample by extracting and concentrating an essential oil-containing plant material with water, a hydrophilic solvent, or a mixed solvent thereof.

As said essential oil containing plant raw material, at least 1 sort (s) selected from Hosobayamajiso, thyme, oregano, and rosemary is suitable, for example, Among these, Hosobayamajiso is especially preferable.
Examples of the essential oil component include thymol, carvacrol, linalool, citral, geraniol, menthol, and the like. Among these, thymol is particularly preferable.

  The extraction treatment is not particularly limited and may be appropriately selected from known methods according to the purpose. Examples thereof include extraction treatment with water, hot water, a hydrophilic organic solvent, and the like. As a solvent used for extraction, it is preferable to use water, a hydrophilic organic solvent, or a mixture thereof at room temperature or a temperature not higher than the boiling point of the solvent.

  Examples of the water include pure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, and fresh water, and those obtained by performing various treatments on these. Examples of the treatment applied to water include purification, heating, sterilization, filtration, ion exchange, adjustment of osmotic pressure, buffering, and the like. Therefore, the water that can be used as the extraction solvent in the present invention includes purified water, hot water, ion-exchanged water, physiological saline, phosphate buffer, phosphate buffered saline, and the like.

  Examples of the hydrophilic organic solvent include lower alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propyl alcohol, and isopropyl alcohol; lower aliphatic ketones such as acetone and methyl ethyl ketone; 1,3-butylene glycol, propylene glycol, Examples thereof include polyhydric alcohols having 2 to 5 carbon atoms such as glycerin, and a mixed solvent of these hydrophilic organic solvents and water can be used. In addition, when using the mixed solvent of water and a hydrophilic organic solvent, in the case of the said lower alcohol, 1-90 mass parts of lower alcohol is preferable with respect to 10 mass parts of water. In the case of the lower aliphatic ketone, 1 to 40 parts by mass of the lower aliphatic ketone is preferable with respect to 10 parts by mass of water. In the case of the said polyhydric alcohol, 1-90 mass parts of polyhydric alcohol is preferable with respect to 10 mass parts of water.

  For example, an essential oil-containing plant raw material is put into a treatment tank filled with an extraction solvent, and left to stand for 30 minutes to 2 hours with occasional stirring as necessary to elute soluble components, and then filtered to remove solids. Then, the extraction solvent is distilled off from the obtained extract and dried to obtain an extract. The amount of the extraction solvent is usually 5 to 15 times the mass of the extraction raw material (mass ratio), and the extraction conditions are usually 50 to 95 ° C. and about 1 to 4 hours when water is used as the extraction solvent. Moreover, when using the mixed solvent of water and ethanol as an extraction solvent, it is about 30 minutes-4 hours at 40-80 degreeC normally.

-Carbon dioxide dissolution process-
The carbon dioxide gas dissolving step is a step of bringing a plant essential oil liquid sample into contact with a carbon dioxide gas fluid and dissolving the carbon dioxide gas in the plant essential oil liquid sample to a saturated concentration.
The carbon dioxide gas dissolving step is preferably performed under carbon dioxide saturation conditions of a temperature of 0 to 30 ° C. and a pressure of 10 to 30 MPa.
In the carbon dioxide gas dissolving step, using a carbon dioxide gas fluid that is micro-bubbled through a mesh filter having a mesh of 100 μm or less improves the solubility of carbon dioxide gas in the plant essential oil liquid sample and saturates the carbon dioxide gas. It can be dissolved to a concentration, which is preferable in terms of increasing contact efficiency. It is more preferable to use a mesh filter having a mesh of 20 μm or less.
Note that the contact efficiency between the plant essential oil liquid sample and carbon dioxide can be increased by using a high-speed mixer, an ultrasonic generator, or the like.

-Carbon dioxide supercritical processing-
The carbon dioxide supercritical treatment step is a step in which carbon dioxide dissolved in a plant essential oil liquid sample is kept in a supercritical state and stirred.
The carbon dioxide supercritical treatment step is preferably performed while maintaining carbon dioxide supercritical conditions at a temperature of 31.1 to 50 ° C. (preferably 31.5 to 40 ° C.) and a pressure of 10 to 30 MPa. Under these conditions, carbon dioxide dissolved in the plant essential oil liquid sample quickly changes to a supercritical state. Carbon dioxide in the supercritical state diffuses and aggregates very efficiently, and the extraction efficiency of essential oil components is improved by the permeation of carbon dioxide.

-Decompression step-
The decompression step is a step of removing carbon dioxide by rapidly reducing the pressure applied to the plant essential oil liquid sample to normal pressure.
By rapidly reducing the pressure applied to the plant essential oil liquid sample to normal pressure, the carbon dioxide dissolved in the plant essential oil liquid sample is instantaneously expanded and vaporized.

In the present invention, further comprising a recycling step, the separated carbon dioxide supercritical fluid is separated from the solute extracted in the decompression section, dehydrated with molecular activated carbon after carbon sieve dehydration as carbon dioxide, and pressurized liquefaction treatment It is preferable in that it can be reused through the process and the cost can be reduced.
The plant essential oil production method of the present invention described above can extract a plant essential oil liquid sample very efficiently by connecting the respective steps and performing continuous treatment, whereby a high-content essential oil can be produced.

(Thymol production method)
In the method for producing thymol of the present invention, an extract of Hosoyama Yamajiso obtained by extracting the above-ground portion of Hosobayamajiso with hydrous ethanol is brought into contact with a microbubbled carbon dioxide fluid to dissolve carbon dioxide to a saturated concentration. A carbon dioxide gas dissolving step, and a carbon dioxide gas supercritical treatment step of stirring and maintaining the supercritical state of the carbon dioxide gas dissolved in the supercritical state of carbon dioxide gas. And other steps.
In this case, the carbon dioxide dissolving step, the carbon dioxide supercritical treatment step, and the carbon dioxide removing step are the same as described above.
The obtained essential oil component, thymol, has a stronger bactericidal action than phenol and cresol, and is useful as a fungicide and antiseptic.

  Here, as an apparatus for implementing the manufacturing method of the plant essential oil and the manufacturing method of thymol of this invention, the micro bubble carbon dioxide supercritical processing apparatus shown in FIG. 1 is mentioned suitably, for example. The details of the microbubble carbon dioxide supercritical processing apparatus are described in Japanese Patent Application Laid-Open Nos. 2001-299303 and 2001-128652.

The microbubble carbon dioxide supercritical processing apparatus shown in FIG. 1 continuously supplies a plant essential oil liquid sample from a stock solution supply tank 1 to a dissolution tank 7 by a high-pressure pump 2, and contacts the carbon dioxide gas fluid in the dissolution tank 7.
On the other hand, between the liquid carbon dioxide cylinder 3 and the bottom of the dissolution tank 7, a carbon dioxide gas flow path including a cooler 4, a pump 4, and a heater 6 is provided. Thus, by cooling liquid carbon dioxide gas with a cooler and letting it pass through a pump, the pressure becomes constant, so that a certain amount of carbon dioxide gas can be put into the dissolution tank.

  A mesh filter 9 is provided at the bottom of the dissolution tank 7. The saturated concentration is efficiently reached by contacting and mixing with the liquefied carbon dioxide gas formed into microbubbles through the mesh filter 9 having a mesh of 100 μm or less (preferably a mesh of 20 μm or less). The dissolution tank 7 is maintained at 0 ° C. to 30 ° C., and the pressure is adjusted to 10 Mpa to 30 Mpa, so that the diffusibility reaching the saturated dissolution concentration of carbon dioxide gas is sufficiently exhibited. Then, the contact / mixed solution having reached the saturated concentration is transferred to the reaction coil 8 (holding section) and heated to 31.1 ° C. or higher to bring the carbon dioxide gas into a supercritical state. Extract solutes into Then, a reaction liquid is moved to the gas-liquid separation tank 10, and a plant essential oil extract and a carbon dioxide supercritical fluid are isolate | separated. Since the separation tank is thus provided, the efficiency of the supercritical processing is improved.

Next, the separated carbon dioxide supercritical fluid is separated from the solute extracted in the decompression section, dehydrated with molecular activated carbon after carbon sieve dehydration, and reused through pressure liquefaction treatment. The separated and collected liquid sample is concentrated under reduced pressure and then spray-dried to obtain a powder product.
In FIG. 1, 11 is a gas-liquid separation sensor, 12 is a separation tank, 13 is a trap, and 16 is a processing sample tank.

According to the plant essential oil production method of the present invention, essential oil components can be efficiently extracted from a plant essential oil liquid sample, an excessive amount of heat can be avoided, quality deterioration can be prevented, and continuous extraction processing is possible. Thus, significant cost reduction can be achieved.
The plant essential oil obtained by the method for producing a plant essential oil of the present invention can be widely used for a fragrance, a deodorant, a fungicide, an antibacterial agent and the like.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
-Production of thymol from Hosobayamajiso-
0.9 kg of dried foliage of Hosobayamajiso was extracted in 9 L of 60% by mass ethanol for 2 hours while circulating at room temperature. Subsequently, solid-liquid separation was performed on a 100 mesh screen, 9 L of 60 mass% ethanol was added to the extraction residue, extraction was performed for 1 hour while circulating at room temperature, and solid-liquid separation was performed on a 100 mesh screen.
The obtained extracts were combined and subjected to clarification filtration with a diatomaceous earth precoat to obtain 12 L of Hosoyama Yamajiso extract. The solid concentration of the extract of Hosoyama Yamajiso was 2.1% by mass.

  Next, using the microbubble supercritical processing apparatus shown in FIG. 1 (with a mesh filter having a mesh of 100 μm disposed at the lower part of the dissolution tank 7), the extract of Hosoyama Yamajiso obtained was liquefied carbonic acid at a sample flow rate of 10 mL / min. A liquid flow treatment was performed at a gas flow rate of 20 mL / min, a treatment pressure of 20 Mpa, a dissolution bath temperature of 20 ° C., and a temperature of the reaction coil holding unit of 40 ° C., and extraction was performed for 3 hours. After the gas-liquid separation, the ethanol solution containing thymol obtained in the reduced pressure recovery part was 190 mL, and the ethanol concentration was 93% by mass.

About the obtained extraction sample liquid and microvalve process liquid, thymol content was measured using the high performance liquid chromatography (HPLC) on the following conditions. The results are shown in Table 1.
HPLC conditions were as follows: column: packed with Wakosil added with 5C18HG, carrier: 50% by volume acetonitrile, flow rate: 1.0 mL / min, wavelength: 260 nm, injection volume: 20 mL.

表１の結果から、ミクロバブル超臨界処理を行うことによって、飛躍的にチモールの含有量が高くなることが認められる。

From the results of Table 1, it is recognized that the content of thymol is dramatically increased by performing the microbubble supercritical treatment.

  According to the plant essential oil production method of the present invention, essential oil components can be efficiently extracted from essential oil-containing plant raw materials at a high content, and a continuous extraction process can be performed at a low temperature without impairing the quality. And a significant cost reduction can be achieved. The plant essential oil produced by the method for producing a plant essential oil of the present invention can be widely used for a fragrance, a deodorant, a fungicide, an antibacterial agent and the like.

FIG. 1 is a schematic view showing an example of a microbubble supercritical processing apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stock solution supply tank 2 High pressure pump 3 Liquid carbon dioxide cylinder 4 Cooler 5 Carbon dioxide supply pump 6 Heater 7 Dissolution tank 8 Reaction coil (holding part)
9 Mesh Filter 10 Gas-Liquid Separation Tank 11 Gas-Liquid Separation Sensor 12 Separation Tank 13 Trap 16 Processed Sample Tank 20 Decompression Unit

Claims (11)

  A plant essential oil liquid sample preparation step in which an essential oil-containing plant raw material is extracted with water, a hydrophilic solvent or a mixed solvent thereof to prepare a plant essential oil liquid sample, and the obtained plant essential oil liquid sample is supercritical to sub- And a carbon dioxide fluid contact step for contacting the carbon dioxide fluid in a critical state.   The carbon dioxide fluid contact step includes contacting the plant essential oil liquid sample with the carbon dioxide fluid to dissolve the carbon dioxide gas to a saturated concentration in the plant essential oil liquid sample, and the plant essential oil liquid in which the carbon dioxide gas is dissolved. A method for producing a plant essential oil according to claim 1, comprising a carbon dioxide supercritical treatment step of stirring the sample while maintaining the sample in a supercritical state of carbon dioxide gas.   The method for producing a plant essential oil according to claim 2, wherein in the carbon dioxide gas dissolving step, a carbon dioxide gas fluid that is microbubbled through a mesh filter having a mesh of 100 µm or less is used.   The method for producing a plant essential oil according to any one of claims 2 to 3, wherein the carbon dioxide gas dissolving step is performed under a carbon dioxide saturated concentration condition of a temperature of 0 to 30 ° C and a pressure of 10 to 30 MPa.   The method for producing a plant essential oil according to any one of claims 2 to 4, wherein the carbon dioxide supercritical treatment step is performed while maintaining carbon dioxide supercritical conditions at a temperature of 31.1 to 50 ° C and a pressure of 10 to 30 MPa.   The method for producing a plant essential oil according to any one of claims 2 to 5, further comprising a carbon dioxide removal step of removing carbon dioxide from the plant essential oil liquid sample by rapidly reducing the pressure applied to the plant essential oil liquid sample to normal pressure. .   The method for producing plant essential oil according to any one of claims 2 to 6, wherein the carbon dioxide fluid contact step further includes a recycling step, and the plant essential oil liquid sample is continuously processed.   The method for producing a plant essential oil according to any one of claims 1 to 7, wherein the essential oil-containing plant material is at least one selected from Hosobayamajiso, thyme, oregano and rosemary.   The method for producing a plant essential oil according to claim 8, wherein the essential oil-containing plant raw material is Hosobayamajiso and the essential oil component is thymol.   A plant essential oil produced by the method for producing a plant essential oil according to any one of claims 1 to 9. A carbon dioxide gas dissolving step in which the above-ground portion of Hosoyama Yamajiso is extracted with hydrous ethanol and brought into contact with a microbubbled carbon dioxide fluid to dissolve the carbon dioxide gas to a saturated concentration, and carbon dioxide gas. And a carbon dioxide supercritical treatment step of stirring and maintaining a supercritical state of carbon dioxide in a supercritical state of Hosoyama Yamajiso dissolved in thymol.

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