JPH05345899A - Method for recovering plant component - Google Patents

Abstract

PURPOSE:To industrially and advantageously recover plant components by making the plant components dissolved in water absorbed on a synthetic absorbent, an anion exchange resin, etc., and desorbed by using a solvent. CONSTITUTION:Plant components, containing hinokitiol, phenolic hydroxyl group or carboxyl group, dissolved in water are absorbed on a synthetic absorbent such as styrene-divinylbenzene-based copolymer, an anion exchange resin such as acrylic ester resin or active carbon. When the synthetic absorbent or active carbon is used, the plant components are extracted with an organic solvent such as hexane or ethanol. When the anion exchange resin is used, the plant components are treated with an alkaline agent for regeneration, returned to acidity, extracted with organic solvent and recovered.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for recovering plant components. More specifically, in a method of recovering useful components such as hinokitiol from a plant, a synthetic adsorbent that synthesizes a plant component from an aqueous solution or an aqueous extract produced during steam distillation,
The present invention relates to a method of adsorbing and desorbing using an anion exchange resin or activated carbon for recovery.

[0002]

2. Description of the Related Art There are many useful substances among the plant components contained in various plants. For example, hinokitiol is useful as a highly safe food preservative and antibacterial agent. Conventionally, as a method for extracting oil containing hinokitiol from trees such as Hiba and Taiwan cypress, steam distillation and solvent extraction have been performed from sawdust and chips of these trees. Among them, the steam distillation method which is mainly carried out produces oil containing hinokitiol by separating it from an aqueous solution which is distilled together. However, even though distillate contains the same amount of hinokitiol as oil, this distillate is rarely used and is discarded. The reason is that an effective technique for recovering hinokitiol contained in distilled water has not been discovered yet.

This is not limited to the case of hinokitiol. That is, although there are plant components having a phenolic hydroxyl group or a carboxyl group in the plant body, this is often the case even when these plant components are recovered by steam distillation or boiling. For example, although useful components of plants are dissolved in a large amount of distillate water and other aqueous solutions that are generated, they are often used because they are not used because they are difficult to collect. The amount of these ingredients is
In the case of hinokitiol, it is usually about 50 to 200 ppm in an aqueous solution contained in distillate of Hiba wood steam distillation or a residue, and in the case of a plant component having a phenolic hydroxyl group or a carboxyl group, several tens ppm to several% with respect to the aqueous solution. However, due to the large amount of water, the amount of water-soluble components (plant components) cannot be ignored.

When the plant components contained in such an aqueous solution are extracted with an organic solvent or the like, it is necessary to use a considerable amount of a dangerous organic solvent for a large amount of the aqueous solution, and the extraction and concentration are performed. A large device is also required. There is also a method of recovering a chemical reaction from an aqueous solution using a base or an acid, but it is necessary to use a large amount of extraction solvent, and neutralization wastewater and the like are generated. I won't.

Therefore, as a method for solving these complicated problems, it is ideal to use a simple small-sized apparatus, reduce the amount of solvent used, and make a system in which waste water and the like due to chemical reaction does not occur. .. On the other hand, silica gel, activated clay, etc. have been conventionally known as adsorbents used for adsorbing plant components from an aqueous solution, but both have a low adsorption effect, and there is a problem that activated clay is clogged and difficult to use. ..

Therefore, an object of the present invention is to provide a method for efficiently and industrially recovering plant components from an aqueous solution containing plant components such as hinokitiol.

[0007]

[Means for Solving the Problems] The inventors of the present invention have made various studies to develop a method for recovering plant components that can solve the above problems. As a result, the distilled water of the steam distillation of the plant body containing the plant component and the aqueous solution contained in the residue are passed through a tower filled with a synthetic adsorbent, an anion exchange resin, or activated carbon to adsorb the plant component. Then, a simple and efficient method of recovering a plant component by treating a resin or the like with a solvent or a regenerant was found, and the present invention was completed.

That is, the gist of the present invention is that a plant component dissolved in water is adsorbed to a synthetic adsorbent, an anion exchange resin or activated carbon and desorbed with a solvent to selectively recover the plant component. The present invention relates to a method for recovering a plant component, which comprises:

The method for recovering plant components of the present invention is not particularly limited. For example, in the case of recovering hinokitiol from Hiba as a raw material, phenolic hydroxyl groups and carboxyl groups are selected from water-soluble components of various trees. It is used, for example, when recovering a useful component having

The plants used in the present invention include hiba, cypress, cedar, koyamaki, black pine, pine, and other general tree materials and leaves, and herbaceous plants such as medicinal plants. These are pulverized or cut and steam-distilled or boiled to extract water-soluble components. When the plant component to be recovered is hinokitiol, hiba wood is mainly used, but as the types of the hiba wood, there are Hibaraki, Red cypress, Heinez, Nezuko, Hiba, Aomori Hiba, Hinoki Asunaro, Ate, Taiwan Hinoki, etc. Can be mentioned. When the plant component to be recovered has a phenolic hydroxyl group or a carboxyl group, hiba, cypress, cedar, koyamaki, pine wood, ginkgo biloba, tea leaves and the like are used as the plant body. In the present invention, the distillate water of steam distillation of these plants and / or the aqueous solution contained in the residue is used as a raw material, and the distillate water or the aqueous solution contained in the residue may be used alone, respectively. You may mix and use. Steam distillation is carried out by a conventional method, and the conditions are not particularly limited.

In the present invention, a synthetic adsorbent, an anion exchange resin or activated carbon is used as the adsorbent. As the synthetic adsorbent used, a synthetic resin such as a styrene-divinylbenzene copolymer resin, an acrylic ester resin, or a polystyrene resin is used. For example, resins XAD-2, XAD-4, XAD-7, XAD- manufactured by Organo Corporation.
16, XAD-2000 Further, DIAION HP-10, -20, -21, -30, -4 manufactured by Mitsubishi Kasei Co., Ltd.
0, -50 and Sepers SP-800, SP-90
0, SP-206, SP-207 and the like.

As the anion exchange resin, styrene-divinylbenzene copolymer resin, acrylic ester resin,
Polystyrene resin and methacrylic ester resin are used. For example, IRA-900, I manufactured by Organo Co., Ltd.
RA-35, IRA-21, IRA-94S, and DIAION PA-306 and PA-30 manufactured by Mitsubishi Kasei Co., Ltd.
8, PA-312, PA-316, PA-318 and the like. In each case, a resin made of a styrene-divinylbenzene-based copolymer resin, a polystyrene-based resin, a methacrylic ester resin, and an acrylic ester resin was used, but those manufactured by other companies can be used as well. As the activated carbon, one manufactured by Wako Pure Chemical Industries, Ltd. was used in the examples, but ones manufactured by other companies can also be used.

When a plant component is adsorbed by using the above-mentioned synthetic adsorbent or activated carbon, it is possible to extract by a solvent after adsorption,
Plant components can be recovered. As the solvent used for the extraction here, a wide range of organic solvents such as hexane, benzene, toluene, methanol, ethanol, propanol, acetic acid ester, acetone, methyl ethyl ketone and ethers can be used.

On the other hand, when an anion exchange resin is used,
For example, in the case of desorbing hinokitiol, it is necessary to carry out an operation of treating with a regenerating alkaline agent, for example, acidifying the hinokitiol Na salt transferred to the aqueous solution layer, and then extracting with a solvent. Examples of the alkaline agent for regeneration used here include a 4 to 10% aqueous NaOH solution, and examples of the solvent used for extraction include those similar to the above.

As an advantage of the method of recovering an oil containing a plant component from distilled water and / or an aqueous solution contained in a residue or boiling water according to the present invention, firstly, a small amount of hinokitiol of these resins in an aqueous solution is used. Efficiently adsorbs compounds having a phenolic hydroxyl group or a carboxyl group (adsorption rate of 75% or more), and secondly, in a packed column of resin in which the adsorption is saturated, 2 to 5 times the resin volume If the solvent for extraction is run, most of the adsorbed components are flowed out and extracted, and the resin can recover the adsorbing ability. A high content of recovered oil can be obtained by concentrating from an extract in which components such as hinokitiol and phenols are dissolved. Thirdly, since the resin can be recycled and used 10 times or more by this method, the ratio of the resin to the cost is lower than that of the product. Fourth, since this method can be made compact in terms of equipment, there is an advantage that the amount of equipment investment can be small.

The amount of plant components that the resin adsorbs by one-time solvent extraction is about 0.4 g to 2 g of hinokitiol per 50 cc of resin, taking hinokitiol as an example. Although it depends on the concentration, the resin can usually be recycled 10 to 100 times, so 10 to 4 to 20 g, 100 to 40 to 200
It is possible to recover g of hinokitiol.

Next, in the present invention, an operation method when a synthetic adsorbent is used will be described. First, the resin is packed in a cylindrical packed tower, and an aqueous solution containing a plant component is pumped at an appropriate flow rate to pass through the resin layer of the packed tower. From time to time, take a certain amount of the aqueous solution that has passed through the resin layer, shake it with a certain amount of organic solvent (toluene, chloroform, etc.) for extraction, and perform GC analysis on the extracted liquid to confirm that the adsorption ability of the target substance has not deteriorated. To do.
Also, the UV absorption maximum wavelength of the target substance can be measured, and the saturation state of adsorption can be examined from the difference in absorbance between the undiluted solution and the water passing through the resin layer. For example, in the case of treated water of an aqueous solution of hinokitiol, which is a component of Hiba, an aqueous ferric chloride solution is added to the treated water to develop the color of the hinokitiol-iron complex under UV45.
It can be measured by 8 nm absorbance (a calibration curve of hinokitiol-FeCl ₃ complex is prepared in advance).

The content of plant components in the treated water is usually 10 to 10.
Since it is considered that the adsorption capacity has decreased when it becomes 20 ppm or less, the feeding of the aqueous solution containing the plant component is stopped, and the above-mentioned solvent is slowly flowed in the packed tower in an amount 2 to 3 times as much as the normal packing to elute the target substance. Guide the solvent to the tank. When the plant component is hinokitiol, the content is 40-50p
When it becomes pm, the adsorption capacity is lowered, and the inflow amount of the solvent is 2 to 5 times the filling amount. This restores the adsorption capacity of the resin, so that the aqueous solution can subsequently flow into the packed bed. The amount of distilled water, residual water, and boiling water to be flown for the resin is
It is considered that 300 g / hr to 3 kg / hr per 50 cc of resin is suitable, but a smaller amount or a larger amount may be used depending on the situation.

When an anion exchange resin is used, it is particularly effective for hinokitiol, and when the residual hinokitiol content of the treated water increases, the above-mentioned alkaline agent for regeneration is flushed and the alkaline liquid after the treatment is treated. For example, a hinokitiol-containing oil is obtained by neutralizing hinokitiol, which is dissolved as a soda salt, with dilute sulfuric acid, dilute hydrochloric acid, etc. to make it free and extracting with a solvent. The regenerated resin can be reused as in the case of synthetic adsorbents. The amount of the distilled water and / or the aqueous solution contained in the residue flowing with respect to the resin is the same as in the case of the synthetic adsorbent.

Further, although adsorption by activated carbon and desorption by a solvent can be carried out by a conventional method, both the adsorption and desorption abilities of hinokitiol are generally inferior to those of synthetic adsorbents.
However, it can be used as an effective method in that it adsorbs other plant components well and is inexpensive.

The method for recovering plant components of the present invention is a synthetic adsorbent for synthesizing plant components from distillate water and / or the aqueous solution contained in the residue when recovering the plant component from the aqueous solution contained in the residue. , An anion exchange resin, or activated carbon may be used.
You may carry out combining the method of 2 or more types suitably. For example, the plant component is recovered from the distilled water and / or the aqueous solution contained in the residue with a synthetic adsorbent, and the obtained recovery liquid is further applied to an anion exchange resin to obtain a high-purity plant component recovery liquid. You can Similarly, for example, plant components may be recovered from the distilled water and / or the aqueous solution contained in the residue with a synthetic adsorbent, and then adsorbed and desorbed with activated carbon.

Further, in the present invention, any method may be used as long as it has a step of adsorbing and desorbing plant components by these methods to recover, and further other recovering methods such as solvent extraction of an objective substance from an aqueous solution. It may be carried out by appropriately combining it with a known method.

As a result of conducting an antibacterial test on the plant components recovered by the above method, water-soluble plant components such as cypress, cedar and Koyamaki contain antibacterial components together with hinokitiol which is a component obtained from Hiba. I showed that. Further, the plant component also had acaricidal activity, insecticidal activity, hypotensive action and other physiological activities.

[0024]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples.

Example 1 50 cc of the adsorption resin XAD-7 (manufactured by Organo Corporation) was washed with 100 cc of methanol, and then 3.2 cm in diameter and 6 in height.
It was packed in a cm packed tower, and Hiba steam distillation water was continuously added dropwise with a pump (dropping amount 1.0 kg / 30 min). The amount of hinokitiol in the distilled water is 140 ppm, and the amount of residual hinokitiol in the first treated water of 1 kg is 22 ppm, 6 kg.
The amount of residual hinokitiol in the eyes increased to 27 ppm. Then, 150 cc of methanol was slowly flowed over the resin over 30 minutes to obtain a red methanol solution. The adsorption power of the resin after recovering methanol was recovered, and when the bottom of the distillate droplet was restarted, the remaining hinokitiol was 22.5 pp at the 7th kg.
m and 12 kg were 28 ppm. When such an operation was similarly repeated 18 times, the amount of residual hinokitiol in the 120 kg treated water was 45 ppm. The extracted methanol solution for 20 times was collected and concentrated to obtain 35.54 g of a red oil, and the weight% of hinokitiol was 36%. The recovery rate of hinokitiol from 120 kg of distillate water in this experiment was 7 in terms of the amount of hinokitiol in the recovered oil.
It will be 6%.

The remaining hinokitiol in the treated water was prepared by adding 50 g of methanol to 50 g of treated water and 2.0 g of a 0.02 molar ferric chloride aqueous solution, and then adding Shimadzu spectrophotometric UV-
The absorbance was measured at 240 and 458 nm, and 50 g of methanol and 50 g of water were added to the same high-purity hinokitiol.
It was quantified using a calibration curve prepared by adding a molar ferric chloride aqueous solution. Mixing methanol when making a calibration curve is because it is difficult to dissolve hinokitiol crystals in water. The quantification of hinokitiol in the recovered oil was performed by GC using anisole or diphenyl ether as an internal standard. GC
Conditions: Shimadzu GC-14A: FID, column ULBON-
HR-1701 Capillary column 25m x 0.25m
m, He 2.0 ml / min, split ratio 1:50,
60 to 260 ° C, temperature rise 8 ° C / min, 260 ° C 30 minutes,
Det. , Inj. 280 ° C, H ₂ 0.5 kg / c
m ² , Air 0.5 kg / cm ² .

Examples 2 to 6 Examples 2 to 6 were carried out in the same manner as in Example 1 except that the synthetic adsorbents shown in Table 1 were used. The results are also shown in Table 1.
The resin used was 50 cc, and the amount of hinokitiol in the distilled water of Hiba steam distillation was 140 ppm.

[0028]

[Table 1]

As a result, in each case, 75% or more of the hinokitiol in the distilled water was recovered in the oil, and the resin can be recycled 10 times or more for use.

Examples 7 to 12 Examples 7 to 12 show the results of the same apparatus as in Example 1 using 50 cc of anion exchange resin. The amount of hinokitiol in the distilled water of Hiba steam distillation was 120 ppm.
When applied to the anion exchange resin, a prescribed pretreatment was previously performed using a NaOH aqueous solution or the like. After the adsorption of hinokitiol, the hinokitiol sodium salt transferred to the alkaline water layer after being treated with a regenerant such as a NaOH aqueous solution was treated with 6N-H
_The pH was adjusted to _{2 to 4 with 2} SO ₄ or 6N-HCl aqueous solution, followed by extraction with toluene or ethyl acetate and concentration to obtain a recovered oil. The results are shown in Table 2.

[0031]

[Table 2]

As a result, in each case, about 30% of the hinokitiol in the distilled water could be recovered.

Example 13 and Comparative Examples 1 and 2 Activated carbon (for chromatography: manufactured by Wako Pure Chemical Industries, Ltd.) 50 cc was filled in a cylindrical packed column, and 1.0 kg of distillate water from Hiba steam distillation was added dropwise to Example 1 and Example 1. Similarly, hinokitiol was extracted from the packed material with methanol and concentrated to obtain a recovered oil. Hinokitiol in the distilled water was 120 ppm. Further, in the same manner, instead of activated carbon, silica gel and activated clay (both manufactured by Wako Pure Chemical Industries, Ltd.) were filled in a cylindrical packed column to collect hinokitiol. The results are also shown in Table 3. As a result, activated carbon has a relatively good oil adsorption amount, but the hinokitiol content in the recovered oil is higher than that of synthetic adsorbents.
It was about one-third. On the other hand, when silica gel and activated clay were used, they were about 1/10 and 1/5, respectively.

Example 14 Hinokithiol was recovered in the same manner as in Example 2 by using the synthetic adsorbent XAD-2000 for the aqueous solution remaining with the residue of the steam distillation of Hiba wood. The amount of hinokitiol in the aqueous solution contained in the residue was 80 ppm. The obtained results are also shown in Table 3.

[0035]

[Table 3]

Example 15 20 kg of steam distilled distillate of Hinoki Shavings was used in Example 1.
In the same manner as above, continuous dropping was carried out into a packed column packed with 50 cc of XAD-2000 (dropping amount 1 kg / 30 min).
100 g of treated water and 100 g of raw water (water to be treated) were added, and 100 g of toluene or chloroform was added to each, and the mixture was shaken and extracted in a separating funnel. The extraction solvent was dried over anhydrous sodium sulfate, concentrated and adjusted to a 1 g solution to give a 0.1.
A 2 μl aliquot was taken and a GC analysis was carried out under the conditions of Example 1 to confirm whether the adsorption was saturated. Then, 150 cc of acetone was slowly flowed into the packed tower over 30 minutes to obtain a red acetone solution. The acetone solution was collected and concentrated, and the attached water was separated, dissolved in toluene, dried over anhydrous sodium sulfate, and concentrated again by an evaporator to obtain 1.45 g of a deep red oil. The adsorption power of the resin was recovered after flowing acetone, and the extracted acetone solution for 10 times obtained by repeating the above operation 9 times was collected and concentrated to obtain 15 g of a deep red oil. The composition of this oil is different from the composition of the oil directly obtained by steam distillation of Hinoki sawdust, and as a result of measurement by Shimadzu Gas Chromatograph Mass Spectrometer QP-1000A, monoterpenes such as borneol, casino and sesquiral. The compounds were compounds having a phenolic hydroxyl group such as pen alcohol and hinokiol, and compounds of carboxylic acids.

Example 16 Adsorption resin XA with 11 kg of steam distillate distilled from Sugiogakuzu
When it was poured into a column filled with 50 cc of D-7 and treated in the same manner as in Example 15, 1.56 g of a brown oil was obtained. Example 1
As a result of measurement in the same manner as in 5, it was a sesquiterpene alcohol such as cryptomellidiol and a phenol compound such as sugiol.

Example 17 16 kg of steam distillate of Chromodios typhimurium was passed through a column packed with 50 cc of the adsorption resin Diaion HP-20 and treated in the same manner as in Example 15 to obtain 6.8 g of a brown oil. As a result of measurement in the same manner as in Example 15, monoterpene alcohols such as borneol and carboxylic acids such as decylenic acid were found.

Example 18 4 kg of the steam distillation residue water of Koyamagi sawdust was poured into a column packed with 50 cc of the adsorption resin XAD-2000 and treated in the same manner as in Example 15 to obtain 1.9 g of a brown oil. As a result of measurement in the same manner as in Example 15, sesquiterpene alcohols such as cedrol and phenol compounds such as isoeugenol were found.

Test Example Using the recovered oils obtained in Example 1 and Examples 15 to 18, an antibacterial test was conducted by the paper disc method. Bacteria used were Bacillus subtilis (IFO 3134), E. coli (IF
O 3366) and black mold (IFO 4414). The medium used was Bacillus subtilis normal agar medium, E. coli L medium, and Black mold Potato SUCROSE medium in 20 cc in a sterile petri dish. The paper disc used had a diameter of 8 mm. The recovered oil was dissolved in ethanol to prepare a solution having a concentration of 500 to 10,000 ppm, which was subjected to aseptic filtration, impregnated with 50 μl each of sterilized paper disks, and dried to obtain a sample. Five samples were prepared for each one, and the diameter of the inhibition circle (mm) generated was taken as the average value of five. For Bacillus subtilis and E. coli, after 2 days at 37 ℃, for black mold, 24 ℃
After 3 days, the diameter of the inhibition circle was measured. The results are shown in Table 4.

[0041]

[Table 4]

As a result of the antibacterial test, the hiba oil obtained in Example 1 contained a high concentration of hinokitiol and showed a strong antibacterial property against any bacteria. Japanese cypress, Japanese cedar, Japanese algae,
It was shown that Koyama oil also has antibacterial properties, although to a lesser degree, it is a gram-positive bacterium, Bacillus subtilis.

[0043]

EFFECTS OF THE INVENTION The method of the present invention is an industrially advantageous method because plant components can be easily and efficiently recovered at a high recovery rate from an aqueous solution containing plant components such as hinokitiol. ..

Claims (3)

[Claims] 1. A plant component selectively dissolved by adsorbing a plant component dissolved in water on a synthetic adsorbent, an anion exchange resin or activated carbon, and desorbing it with a solvent. A method for collecting plant components. 2. The recovery method according to claim 1, wherein the plant component is hinokitiol. 3. The method according to claim 1, wherein the plant component is a component having a phenolic hydroxyl group or a carboxyl group.