JP2000072790A - Method of removing residual agrochemical in plant extract - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method that can readily remove residual agrochemicals from plant extracts to be used as food, cosmetic, medicine and the like, when residual agrochemicals of organic chlorine compounds having strong toxicity, for example, BHC or DDT, are detected in the extracts. SOLUTION: A plant extract including residual agrochemicals of organic chlorine compounds is dissolved in a mixture of a lower aliphatic alcohol and water at a volume ratio of 10/90-80/20. Then, the resultant solution is brought into contact with a porous adsorption resin having pores with a modal radius of 30-120 Å thereby adsorbing the residual agrochemicals in the solution into the adsorption resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to remove a plant extract to be used as a component of foods, cosmetics, pharmaceuticals, etc., when an organic chlorine compound-based pesticide residue harmful to the human body is contained. It is about the method.

[0002]

2. Description of the Related Art In recent years, there has been a tendency to use natural products that are superior in safety to chemically synthesized products in various fields, such as food additives, cosmetic components, pharmaceuticals, quasi-drugs, and the like. As a result, research on useful components contained in plants has progressed, and as a result, extracts from various plants have been provided for many uses.

However, harmful pesticides may be detected in plant extracts which should be essentially safe, and countermeasures have become a problem.

There are two reasons why pesticide residues are detected from plant extracts. One is that pesticides used in the cultivation process of raw material plants are attached or absorbed, and the other is that pesticides used in the past have been used. This is the case where the source plant absorbed the pesticides accumulated in the soil without decomposition from the roots. Therefore, the use of organochlorine pesticides, such as BHC and DDT, which have been found to be problematic for safety and are not currently used, has been delayed from being banned in China, India, Southeast Asia and Africa. Nevertheless, there are still many cases detected in plant extracts. BHC and DDT, which have been widely used for a long time due to their excellent medicinal properties, and have been used for a long period of time, and are difficult to decompose in nature, remain in the soil for many months as they are, and are absorbed by plants. It is being spread or taken in the natural food chain.

[0005] Therefore, pesticides may be contained not only in cultivated plants but also in plants that grow naturally in mountainous areas where pesticides have never been used. It is necessary to inspect pesticides, and if pesticides are detected, remove them as much as possible before using them.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for removing pesticide residues when the pesticide residues are detected in a plant extract to be used for any purpose. It is another object of the present invention to provide an effective method for removing organochlorine compounds of high frequency and high toxicity among pesticide residues, for example, BHC and DDT.

[0007]

According to the present invention, there is provided a method for removing pesticide residues, the method comprising removing an organochlorine compound-based pesticide from a plant extract dissolved in a water-containing lower aliphatic alcohol having a specific range of water content to a specific pore size. Based on the finding that it is selectively adsorbed on a porous adsorption resin having
A plant extract containing an organic chlorine compound-based pesticide residue is dissolved in a mixture of lower aliphatic alcohol and water in a volume ratio of 10:90 to 80:20, and the resulting solution is subjected to the most frequent radius of pores. Is contacted with a porous adsorption resin having a temperature of 30 to 120 ° to adsorb residual pesticides in the solution to the adsorption resin, and a plant extract is recovered from the solution after the treatment.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for removing pesticide residues according to the present invention, a plant extract to be treated is first treated with a volume ratio of 10: 9.
It is dissolved at a suitable concentration in a mixture of a lower aliphatic alcohol of 0 to 80:20 and water (hereinafter referred to as a treatment liquid solvent). As the lower aliphatic alcohol used at this time, methanol, ethanol, isopropanol and the like are suitable, but ethanol is most preferable in consideration of safety. Depending on the type of plant extract, it may be difficult to obtain a clear solution using the treatment liquid solvent described above, and a part may be in a dispersed state without being dissolved, but in such a case,
Most of the residual pesticides can be treated because they are dissolved in the above-mentioned aqueous alcohol.

It is important that the ratio of alcohol to water in the solvent of the treatment liquid is within the above range. If the alcohol ratio is less than 10 vol%, not only residual pesticides but also useful components in plant extracts are adsorbed. As a result, processing losses increase. Conversely, if the alcohol ratio exceeds 80 vol%,
Residual agricultural chemicals are less likely to be adsorbed by the adsorption resin, about 90vol
%, It is hardly adsorbed.

The plant extract solution to be brought into contact with the adsorption resin is not limited to a solution prepared by dissolving a solid or liquid plant extract in the above-mentioned solvent for the treatment liquid. If there is, it may be in the state of an extract as obtained from the raw material plant. A solution to be treated may be similarly prepared by adjusting the solvent composition of the extract to the same composition as the solvent of the treatment liquid by concentration, addition of a solvent, or the like.

The porous adsorbent resin used in the treatment is a three-dimensional copolymer of styrene and divinylbenzene or one obtained by replacing a part of hydrogen atoms of the benzene ring with bromine to increase the hydrophobicity. It has no group.
The most frequent radius of the group of pores is 30 to 120 °. If the pore size is smaller than this, the residual pesticide hardly diffuses into the pores in the adsorption resin, and the removal rate of the residual pesticide becomes poor. On the other hand, if the pore diameter is larger than this, the loss of adsorption of useful components is small, but the ability to adsorb and remove residual pesticides is also low.

Specific examples of usable adsorption resins include Diaion HP21, 30, 30, 40, 50, Sepabeads SP207, 825, and 850 (all of which are products of Mitsubishi Chemical Corporation) and Amberlite XAD2. , And 4 and 7 (both are products of Organo Corporation).

The method for bringing the prepared treatment solution into contact with the adsorption resin is not particularly limited. It is most appropriate to flow the processing solution from above or below the column filled with the adsorption resin, but it is also possible to put the processing solution and the adsorption resin in a batch type processing tank and stir. In the case of performing column treatment, it is appropriate that the liquid passing speed is 0.3 to 3.0 / h as SV. It is desirable that the adsorption resin used in the treatment is brought into contact with a solvent having the same composition as the solvent of the treatment liquid in advance and the pores are filled with the solvent.

When the pesticide residue in the treatment solution comes into contact with the adsorption resin, it enters the pores of the adsorption resin and is adsorbed. On the other hand, useful components in plant extracts, such as polyphenols, saponins, vitamins, pigments, terpenoids, etc., have high solubility in the treatment liquid solvent but do not have much affinity for the hydrophobic adsorption resin. It is not adsorbed in pores and stays in solution. Therefore, the extract obtained by concentrating and drying the solution after the treatment is one from which most of the residual pesticide contained in the extract before the treatment has been removed.

The adsorbing resin used in the treatment can be regenerated and reused by washing with 90% or more of lower aliphatic alcohol by passing it through.

The method of the present invention relates to the most commonly detected pesticide residues, BHC, DDT (a similar insecticide, DD).
D, DDE, etc.), and other organic chlorine compound pesticides such as aldrin, dieldrin, endrin, heptachlor, heptachlor epoxide, and the like.

The method for removing pesticide residues according to the present invention is in principle difficult to apply to plant extracts which are completely insoluble and cannot be dispersed in the solvent of the processing solution, but are indispensable in the fields of medicine, cosmetics, foods and the like. Since there is very little such in the plant extracts utilized in the above, it is applicable to virtually all plant extracts. That is, thistle, amateur, opium, aloe-bear, ginkgo, fennel, turmeric, usbnia oyster, vladinki, edibles, elephant grass, prolonged life grass, yellow sperm, maggot, giant gourd, maggot, barley, genus grass,
Persimmon, chamomile, licorice, kidachi aloe, gymnema, cabbage, tamatake, kiraya, gold and silver flower, chrysanthemum flower, wolfberry, red ginseng, bittersweet,
Kumasa, mulberry, bay leaves, Akiko, gentian, wheat,
Rice, Burdock, Sesame, Salvia, Sanza, Shiso, Sanshishi, Sanshu, Sansho, Sanpaku, Shiitake, Shiitake, Shakuyaku, Carabusa, Jujube, Ginger, Birch, Japanese horsetail, Stevia, Senkyu, Senna, Senburi, Japanese radish , Daisies, soybeans,
Tamarind, cod, cock, toki, eucommia, caterpillar, corn, stinging pear, carrot, shin winter, parsley, beach windbreak, hamamelis, himematsutake, bilberry, loquat, boukuro, grape, blueberry, loofah, hematin, bodhi tree, peony, Hops, pine needles, peaches, melissa, yucca, yoquinin, mugwort, rye, lakanka, green tea, apple,
The method can be applied to extracts with various solvents from rooibos, ruscath, reishi, reenzo, rosehip, rosemary and the like.

[0018]

EXAMPLES Example 1 and Comparative Examples 1 and 2 3 kg of Chinese red ginseng was extracted with 30 vol% aqueous ethanol under reflux for 1 hour, and the extraction residue was subjected to the same extraction treatment again to obtain a total of 48 liters. The extract was concentrated under reduced pressure to obtain 3 kg of a concentrate.

This concentrated liquid has a solid content of 362 per kg.
g, 106 g of crude saponin, and BHC 0.6
It contained 0 mg and 0.40 mg of DDT.

The above extract concentrate is divided into 3 parts each for 1 kg, and ethanol and water are added thereto, and three kinds of adsorbing resin treatment liquids having different ethanol concentrations in the solvent (solid concentration 5.5).
% By weight), and the treatment liquid was subjected to the following adsorption resin treatment.

Adsorption resin treatment conditions: 1 liter of a porous adsorption resin, Diaion HP-21 (most frequently 80 μm in diameter) was packed in a column having an inner diameter of 10 cm, and the inside of the column was filled with a solvent having the same composition as the solvent of the processing liquid. deep. The adsorption resin treatment liquid is passed through this column at SV = 0.3 / h, and then the column is washed with 3 liters of a solvent having the same composition as the treatment liquid solvent.

The processing solution passed through the column in the above-mentioned adsorption resin treatment and the washing solution are combined and concentrated until the total amount becomes about 2 kg. The obtained concentrated solution contains solid content, crude saponin, B
HC and DDT were quantified. Table 1 shows the results.

[0023]

Table 1 Comparative Example 1 Example 1 Comparative Example 2 Solvent Ethanol Concentration of Treatment Solution 5 vol% 50 vol% 90 vol% Solids Recovery (%) 79.0 89.8 98.1 Crude Saponin Recovery (%) 49.1 99.1 99.1 BHC removal rate (%) 100 100 11.7 DDT removal rate (%) 100 100 22.5

Example 2 and Comparative Examples 3 and 3 3 kg of Chinese green tea leaves were refluxed and extracted with 50% by volume of aqueous ethanol for 1 hour, and the extraction residue was subjected to the same extraction treatment again to obtain a total of 37 liters. The extract was concentrated under reduced pressure to obtain 3 kg of a concentrate.

This concentrated liquid has a solid content of 354 per kg.
g, 148 g of polyphenol, and BHC
It contained 0.36 mg and 0.20 mg of DDT.

The above extract concentrate is divided into 3 parts each of 1 kg, and ethanol and water are added thereto, and the three kinds of adsorbent resin treatment liquids having different ethanol concentrations in the solvent (solids concentration of 5.5) are added.
% By weight), and the treatment liquid was subjected to the following adsorption resin treatment.

Adsorption resin treatment conditions: 1 liter of porous adsorption resin, Sepabead SP-825 (most frequent pore diameter 57 °) is packed in a column having an inner diameter of 10 cm, and the inside of the column is filled with a solvent having the same composition as the solvent of the processing liquid. . The adsorption resin treatment liquid is passed through this column at SV = 0.5 / h, and then the column is washed with 3 liters of a solvent having the same composition as the treatment liquid solvent.

The treatment liquid passed through the column in the adsorption resin treatment and the washing liquid were combined, concentrated until the total amount became about 2 kg, and the solid content, polyphenol, BHC and DDT of the obtained concentrated liquid were quantified. Table 2 shows the results.

[0029]

Table 2 Comparative Example 3 Example 2 Comparative Example 4 Treatment Solution Solvent Ethanol Concentration 5 vol% 70 vol% 90 vol% Solids Recovery (%) 80.8 94.9 98.3 Polyphenol Recovery (%) 69.6 98 .6 99.3 BHC removal rate (%) 100 100 16.7 DDT removal rate (%) 100 100 0

Comparative Examples 5 to 7 Adsorption resin was used as Diaion HP having a most frequent pore diameter of 260 °.
Table 3 shows the results of the adsorption resin treatment performed in the same manner as in Example 1 except that the value was changed to -20.

[0031]

Table 3 Comparative Example 5 Comparative Example 6 Comparative Example 7 Treatment Solution Solvent Ethanol Concentration 5 vol% 50 vol% 90 vol% Solids Recovery (%) 77.9 91.7 97.8 Crude Saponin Recovery (%) 76.4 97.2 99.1 BHC removal rate (%) 91.7 56.7 0.02 DDT removal rate (%) 95.0 62.5 0.08

[0032]

As described above, according to the present invention, organic chlorine compound-based pesticide residues in a plant extract can be almost completely removed by a simple operation, and the loss of useful components can be minimized.

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Claims (3)

[Claims] 1. A plant extract containing an organic chlorine compound-based pesticide residue is dissolved in a mixed solution of lower aliphatic alcohol and water in a volume ratio of 10:90 to 80:20, and the resulting solution is finely divided. A plant extraction method comprising contacting a porous adsorbent resin having pores with a most frequent radius of 30 to 120 ° to adsorb residual pesticides in the solution to the adsorbent resin, and recovering a plant extract from the treated solution. A method for removing pesticide residues in goods. 2. The method according to claim 1, wherein ethanol is used as the lower aliphatic alcohol. 3. The method according to claim 1, wherein the pesticide residue is BHC or (and) DD.
The method of claim 1, wherein T is T.