A method for removing propamocarb in a plant extract

Abstract

The application discloses a method for removing propamocarb in plant extracts, and belongs to the technical field of pesticide residue removal, which comprises the following steps: S1. adjusting the pH of the dissolved solution of the dissolved extract to 8-12, and then performing cation exchange resin chromatography to collect an eluate; and S2. adjusting the pH of the eluate to 4-6, and then concentrating to obtain a removal product. The application is used for overcoming the technical problems that the existing technology cannot completely remove propamocarb or damages effective components, and therefore provides a method for removing propamocarb in plant extracts. The application uses the existence state difference of effective components and propamocarb in plant extracts under different pH environments and the method of ion exchange selective adsorption to efficiently remove propamocarb, while ensuring the recovery of the effective components, and improves the safety of the plant extracts.

Description

Technical Field

[0001] This invention belongs to the field of pesticide residue removal technology, specifically a method for removing cymoxanil from plant extracts. Background Technology

[0002] Plant extracts (such as monk fruit extract, ginseng extract, grape skin extract, and ginkgo leaf extract) are widely used in food, pharmaceuticals, and health products due to their significant pharmacological activities or health benefits from active ingredients such as mogrosides, ginsenosides, resveratrol, and ginkgo flavonoids. During plant cultivation, fungicides like propiconazole are often used to control diseases such as downy mildew, leading to residues in the plant. During subsequent extraction, these residual propiconazoles can enter the extract along with the active ingredients, affecting its purity and quality and potentially posing health risks. Therefore, it is necessary to remove propiconazole from plant extracts.

[0003] However, existing technologies for removing cymoxanil from plant extracts are incomplete, failing to reduce its content to below the stringent standard of 0.01 ppm, thus failing to meet the high-quality requirements of the food and pharmaceutical industries. Some methods, in an effort to improve cymoxanil removal, employ strong acid / alkali conditions or complex separation steps, leading to hydrolysis, decomposition, or over-adsorption of active ingredients such as mogroside and resveratrol, significantly reducing the recovery rate of these active ingredients and impacting the economics of the process. Most existing methods are designed only for single types of plant extracts or single active ingredients, failing to consider the differences in properties among different types of active ingredients such as glycosides, polyphenols, and flavonoids, making it difficult to achieve efficient removal of cymoxanil from multiple plant extracts and limiting their applicability. Summary of the Invention

[0004] This invention overcomes the technical problems of incomplete removal of propamocarb or damage to active ingredients in existing technologies, and therefore provides a method for removing propamocarb from plant extracts. This invention utilizes the differences in the existence states of active ingredients and propamocarb under different pH conditions in plant extracts, and employs ion exchange selective adsorption to efficiently remove propamocarb while ensuring the recovery of active ingredients, thus improving the safety of plant extracts.

[0005] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0006] This invention discloses a method for removing cymoxanil from plant extracts, comprising the following steps: S1. Adjust the pH of the solution after dissolving the extract to 8-12, then pass it through cation exchange resin chromatography and collect the eluent; S2. Adjust the pH of the eluent to 4-6, concentrate it to obtain the removed product.

[0007] According to some embodiments of the present invention, the extract contains >0.1 ppm of cymoxanil, preferably >0.5 ppm, for example 0.9~5 ppm.

[0008] According to some embodiments of the present invention, the solvent used for dissolution is at least one of water, ethanol or methanol.

[0009] According to some embodiments of the present invention, the mass-to-volume ratio of the extract to the solvent in the solution is 1:1 to 10 g / mL.

[0010] According to some embodiments of the present invention, the cation exchange resin is selected from at least one of 001×7 cation exchange resin, 732 cation exchange resin, 110 cation exchange resin, D113 cation exchange resin, and LX-50 cation exchange resin.

[0011] According to some embodiments of the present invention, the active ingredients in the extract are one or more of glycosides, polyphenols and flavonoids.

[0012] According to some embodiments of the present invention, the solution can also undergo a pretreatment process for macroporous resin adsorption.

[0013] Furthermore, the macroporous adsorption resin is of type D101, LX-T28, or DM131.

[0014] According to some embodiments of the present invention, the pH adjustment is performed using an alkaline solution or anion exchange resin.

[0015] According to some embodiments of the present invention, the alkaline solution is at least one selected from sodium hydroxide aqueous solution, calcium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and sodium carbonate aqueous solution; According to some embodiments of the present invention, the mass concentration of the alkaline solution is 0.5% to 5%; According to some embodiments of the present invention, the anion exchange resin is of type LX-T2, LX-762, LX-94, D941, D285 or 330.

[0016] According to some embodiments of the present invention, the concentration temperature is 40~68°C and the concentration pressure is -0.06~-0.09 MPa; According to some embodiments of the present invention, the concentration may further include a drying process, wherein the drying process is vacuum freeze drying or spray drying.

[0017] According to some embodiments of the present invention, the content of cymoxanil in the removal product is ≤0.01ppm.

[0018] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0019] Compared with the prior art, the beneficial effects of the present invention are: This invention utilizes the difference in chemical states between the target active ingredient and the pesticide residue propamocarb under different pH conditions to efficiently remove propamocarb without damaging the active ingredient. Under alkaline conditions, propamocarb molecules are in an ionic state, making them more easily adsorbed by the subsequent cation exchange resin; while the target ingredient usually exists stably in a molecular state under these conditions, with weak interaction with the resin, thus achieving selective separation of propamocarb and the active ingredient through resin adsorption.

[0020] The process route of this invention is simple, requiring no strong acid or alkali conditions or complex multi-step separation, making it convenient to operate and easy to scale up for production. It also exhibits good compatibility with systems containing common active ingredients such as glycosides, polyphenols, and flavonoids.

[0021] The method of this invention can significantly reduce the residue of cymoxanil in plant extracts to below 0.01 ppm, with a removal rate of over 95%, and ≥99% in some preferred embodiments; this meets the requirements for pesticide residues in the food, pharmaceutical, and other fields. While achieving deep removal of pesticide residues, the recovery rate of the target active ingredient is ≥85%, and ≥90% in some preferred embodiments, and its purity is not adversely affected; in some embodiments, the purity is even slightly improved. Detailed Implementation

[0022] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0023] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0024] The "range" disclosed in this invention is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for specific parameters, it is understood that ranges of 60-110 and 80-120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and if maximum range values ​​3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this invention, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed herein; "0-5" is merely a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer greater than or equal to 2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0025] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0026] Unless otherwise specified, all technical features and optional technical features of this invention can be combined to form new technical solutions.

[0027] Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0028] Unless otherwise specified, the terms "comprising" and "including" as used in this invention can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0029] Unless otherwise specified, the term "or" is inclusive in this invention. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0030] In some preferred embodiments, the extract may be monk fruit extract, grape skin extract, ginseng extract, ginkgo leaf extract, stevia extract, and sweet tea extract, etc.

[0031] Example 1 S1. Extract 1 kg of monk fruit raw material with water to obtain 2 kg of aqueous extract. Add cymoxanil aqueous solution to the extract (simulating a raw material system with high cymoxanil content). Load the mixture onto a D101 macroporous adsorption resin chromatography column (column volume 1 L). After loading, first wash the chromatography column with 2 BV of water, then wash with 2 BV of 1% hydrochloric acid aqueous solution, and then continue washing with water until the pH of the effluent is 5. Next, desorption was performed using 2 BV 60% ethanol aqueous solution, and the eluent (i.e., the solution) was recovered. The pH of the solution was adjusted to 10 using 1% sodium hydroxide aqueous solution. The pH-adjusted solution was then loaded onto a 200 mL 001×7 cation exchange resin chromatography column, the column was rinsed with 200 mL of water, and the eluent was collected.

[0032] S2. Add 1% sodium hydroxide aqueous solution to the eluent collected in S1 to adjust the pH of the eluent to 6; concentrate the adjusted solution at -0.09 MPa and 45°C, and spray dry to obtain the powdered removal product.

[0033] Example 2 S1 Dissolve 100g of monk fruit extract in 1kg of water; adjust the pH of the solution to 12 with 1% calcium hydroxide aqueous solution, then load the adjusted solution onto a 732 cation exchange resin chromatography column (column volume 200mL), rinse the column with 200mL of water, and collect the eluent.

[0034] S2: The eluent collected from S1 was adjusted to pH 6 with 1% sodium hydroxide aqueous solution; the adjusted eluent was concentrated at -0.09 MPa and 45°C, and then spray-dried to obtain a powdered removal product.

[0035] Example 3 S1. Dissolve 100g of grape skin extract powder in 1000mL of 60% ethanol solution and stir at 20-30℃ (extract to solvent mass-to-volume ratio is 1:10 g / mL); adjust the pH of the solution to 8 with 5% sodium bicarbonate aqueous solution. Load the pH-adjusted solution onto a 110 cation exchange resin column (column volume 200mL), wash the column with 200mL of 60% ethanol, and collect the eluent.

[0036] S2: Add 1% sodium bicarbonate aqueous solution to the effluent collected in S1 to adjust the pH to 5; concentrate the adjusted eluent at -0.09 MPa and 45°C, and spray dry to remove the product as a powder.

[0037] Example 4 S1 Take 100g of ginseng extract, add 2000mL of water and stir at 20~30℃ to dissolve it completely; load the solution onto a DM131 macroporous adsorption resin chromatography column (column volume 2.5L). After loading, rinse with 2BV of water, then wash with 2BV of 2% hydrochloric acid aqueous solution, and then wash with water until the pH of the effluent is 5. Next, the solution was desorbed with 2 BV 70% ethanol aqueous solution, and the desorbed solution (i.e., the solution) was recovered. The pH of the solution was adjusted to 9 with 1% sodium hydroxide aqueous solution, and the solution was loaded onto a D113 cation exchange resin chromatography column (column volume 400 mL). The column was rinsed with 400 mL of water and the eluent was collected.

[0038] S2: Add 1% sodium carbonate aqueous solution to the effluent collected in S1 to adjust the pH to 6; concentrate the adjusted eluent at -0.09 MPa and 45°C, and spray dry to remove the product as a powder.

[0039] Example 5 S1. Add 100g of Ginkgo biloba extract to 1000mL of 60% methanol aqueous solution and stir to dissolve at 20-30℃. Adjust the pH of the solution to 9 with 5% sodium carbonate aqueous solution. Load the adjusted solution onto an LX-50 cation exchange resin chromatography column (column volume 200mL), wash the column with 200mL of 60% methanol, and collect the eluent.

[0040] S2. Add 5% sodium carbonate aqueous solution to the eluent collected in S1 to adjust the pH to 4; concentrate the adjusted eluent at -0.09 MPa and 45°C, and spray dry to obtain a powdered removal product.

[0041] Comparative Example 1 S1. Take 1 kg of monk fruit raw material and extract it with water to obtain 2 kg of water extract; load the extract onto a D101 macroporous adsorption resin chromatography column (column volume 1 L), and rinse with 2 BV of water after loading. The solution was desorbed using 2 BV of 60% ethanol aqueous solution, and the eluent (i.e., the solution) was recovered. The solution was not adjusted for alkaline pH, and it was directly loaded onto a 001×7 cation exchange resin chromatography column (column volume 200 mL), rinsed with 200 mL of water, and the eluent was collected.

[0042] S2: The pH of the eluent collected in S1 was adjusted to 6 with 1% sodium hydroxide aqueous solution, concentrated at -0.09 MPa and 45°C, and then spray-dried to obtain a powdered product.

[0043] Test case Table 1 compares the results of the component analysis of the extracts from the above examples and comparative examples after the removal of cymoxanil.

[0044]

[0045] Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in this invention can be purchased commercially or prepared using existing methods. The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this invention. It should be understood that the above descriptions are merely specific embodiments of this invention and are not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for removing propamocarb from plant extracts, characterized in that, Includes the following steps: S1. Adjust the pH of the solution after dissolving the extract to 8-12, then pass it through cation exchange resin chromatography and collect the eluent; S2. Adjust the pH of the eluent to 4-6, concentrate it to obtain the removed product.

2. The method for removing propamocarb from plant extracts as described in claim 1, characterized in that, The extract contains ≥0.1 ppm of cymoxanil.

3. The method for removing propamocarb from plant extracts as described in claim 1, characterized in that, The solvent used for dissolution is at least one of water, ethanol, or methanol; And / or, the mass-to-volume ratio of the extract to the solvent in the solution is 1:1~10 g / mL.

4. The method for removing propamocarb from plant extracts as described in claim 1, characterized in that, The cation exchange resin is selected from at least one of 001×7 cation exchange resin, 732 cation exchange resin, 110 cation exchange resin, D113 cation exchange resin, and LX-50 cation exchange resin.

5. The method for removing propamocarb from plant extracts as described in claim 1, characterized in that, The active ingredients in the extract are one or more of glycosides, polyphenols, and flavonoids.

6. The method for removing propamocarb from plant extracts as described in claim 1, characterized in that, The solution can also undergo a pretreatment process for macroporous resin adsorption. And / or, the macroporous adsorption resin is of type D101, LX-T28 or DM131.

7. The method for removing cymoxanil from plant extracts as described in claim 1, characterized in that, The pH is adjusted using an alkaline solution or anion exchange resin.

8. The method for removing cymoxanil from plant extracts as described in claim 7, characterized in that, The alkaline solution is at least one of sodium hydroxide aqueous solution, calcium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and sodium carbonate aqueous solution; And / or, the mass concentration of the alkaline solution is 0.5% to 5%; And / or, the anion exchange resin is of type LX-T2, LX-762, LX-94, D941, D285 or 330.

9. The method for removing cymoxanil from plant extracts as described in claim 1, characterized in that, The concentration temperature is 40~68℃, and the concentration pressure is -0.06~-0.09MPa; And / or, the concentration may further include a drying process, wherein the drying process is vacuum freeze drying or spray drying.

10. The method for removing cymoxanil from plant extracts as described in claim 1, characterized in that, The content of cymoxanil in the removed product is <0.01ppm.

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