Method for removing pesticide residues in traditional Chinese medicine and application of method in preparation of eighteen-ingredient rhododendron pills

Abstract

The invention discloses a method for removing pesticide residues in traditional Chinese medicine and application of the method in preparation of eighteen-ingredient rhododendron pills, the method comprises the following steps: S1, mixing modified montmorillonite with a traditional Chinese medicine extract solution, and separating to obtain filtrate and insoluble substances; and S2, washing the insoluble substance with water, mixing the water washing liquid with the filtrate obtained in the step S1, and drying, the preparation method of the modified montmorillonite comprises the following steps: (1) adding water into montmorillonite and mixing to obtain a suspension; and (2) adding quaternary ammonium salt and disodium ethylene diamine tetraacetate into the suspension, stirring, and centrifuging and drying after the reaction is finished to obtain the modified montmorillonite. According to the method, the modified montmorillonite is used as an adsorbent, so that pesticide residues, such as organochlorine pesticides, organophosphorus pesticides and pyrethroid pesticides, in the traditional Chinese medicine extract can be effectively removed, the loss of active ingredients of traditional Chinese medicines is avoided to the greatest extent, and the reliability of the traditional Chinese medicines is ensured.

Description

Technical Field

[0001] The invention relates to the technical field of traditional Chinese medicines, and more particularly to a method for removing pesticide residues in traditional Chinese medicines and an application of the method in preparing Eighteen-flavor Dujuan pills. Background Art

[0002] In order to meet the growing demand for traditional Chinese medicine, the varieties and planting areas of traditional Chinese medicine are constantly expanding, and the problem of exogenous harmful residue pollution caused by artificial planting has become the focus of social attention.

[0003] At present, the residual pesticides in Chinese medicinal materials are mainly organochlorine, organophosphorus and pyrethroid. It is difficult to solve the problem of excessive pesticide residues in agricultural products from the source in a short period of time. In order to protect the physical and mental health and life safety of consumers, taking effective technical means to remove residual pesticides in agricultural products is an emergency measure that can be adopted.

[0004] CN101838356A discloses an application of a chelating polymer resin in removing pesticide residues, wherein the resin is a polystyrene polymer resin in which cross-linked benzylamino dithiocarboxylate and trivalent iron ions are loaded on benzylamino methylene phosphate groups. The chelating polymer resin of the invention is relatively convenient to prepare; because the dithiocarboxylate groups are introduced, the chelating capacity of the resin for heavy metals is greatly increased; and the resin can efficiently, quickly and conveniently remove various pesticide residues in agricultural and sideline products or foods, so that the agricultural and sideline products or foods can meet the national standards for pesticide residues.

[0005] CN102091438A discloses a method for removing residual pesticides from ginkgo leaf extract, comprising the following steps: step 1. sending the extracted ginkgo leaf extract into a high-speed centrifuge, centrifuging at a speed of 14,000 rpm, and collecting the supernatant after centrifugation; step 2. directly entering the ginkgo leaf extract after centrifugation in step 1 into a macroporous adsorption resin for adsorption, and collecting the target product after analysis. Step 3. concentrating the target product analyzed in step 2 to a specified concentration, then adding 2-3 times the volume of the concentrated solution in batches, heating to 60-70°C under a vacuum condition of -0.04 to -0.095MPa, decompressing and distilling the remaining pesticide residues, and then transferring to a spray drying procedure for treatment when the concentration reaches a specified value. The invention does not need to be limited by the molecular size of the residual pesticides and the active ingredients, so that the content of various residual pesticides can be removed to a large extent.

[0006] CN109078610A discloses a preparation method of silane-modified attapulgite and its application in the removal of pesticide residues from Chinese herbal medicines. The preparation method of silane-modified attapulgite includes purification of attapulgite, acidification of attapulgite and silane modification of attapulgite; the application steps of silane-modified attapulgite in the removal of pesticide residues from Chinese herbal medicines include: weighing Chinese herbal medicine extracts and silane-modified attapulgite in a mixed pesticide aqueous solution, adsorbing at a constant temperature of 15℃-25℃ for 1-2h, and centrifuging at a speed of 11000r·min-1 for 5-10min. The invention has a simple process, convenient operation, and no safety hazards. After the pesticide residues in the Chinese herbal medicine extracts are removed, they meet the standards of the maximum pesticide residue limit in countries and regions such as China, the European Union and the United States.

[0007] At present, there are many methods for removing pesticide residues by adsorption, most of which are concentrated in the field of food such as tea, and there are few studies on Chinese herbal medicines. Therefore, developing a method with good selectivity, safety and effectiveness to remove pesticide residues from Chinese herbal medicines is still a very challenging task. Summary of the invention

[0008] The purpose of the present invention is to provide a method for removing pesticide residues in traditional Chinese medicine and application of the method in preparing Eighteen-flavor Dujuan Pills.

[0009] In order to achieve the above object, the present invention provides the following technical solutions:

[0010] A method for removing pesticide residues in traditional Chinese medicine comprises the following steps:

[0011] S1, mixing the modified montmorillonite with the Chinese medicine extract solution, separating and obtaining a filtrate and an insoluble matter;

[0012] S2, washing the insoluble matter with water, combining the washing liquid with the filtrate obtained in step S1, mixing and concentrating, and drying.

[0013] The preparation method of the modified montmorillonite of the present invention comprises the following steps:

[0014] (1) adding water to montmorillonite to obtain a suspension;

[0015] (2) adding quaternary ammonium salt and disodium ethylenediaminetetraacetate to the suspension and stirring; after the reaction is completed, filtering and drying are performed to obtain the modified montmorillonite.

[0016] Preferably, the amount of water added in step (1) is 5-10 times the mass of montmorillonite; more preferably, it is 7-8 times.

[0017] Preferably, the amount of the quaternary ammonium salt added in step (2) is 30-50% of the mass of the montmorillonite; more preferably 40-45%.

[0018] Preferably, the amount of disodium ethylenediaminetetraacetate added in step (2) is 5-10% of the mass of montmorillonite; more preferably 6-7%.

[0019] Preferably, the stirring in step (2) is: stirring at 70-90° C. and 200-500 rpm for 60-120 h.

[0020] Preferably, the drying in step (2) is: drying at 80-100° C. for 8-12 h.

[0021] In some embodiments, the pesticides include organochlorine pesticides, organophosphorus pesticides and pyrethroid pesticides, preferably organochlorine pesticides.

[0022] In some embodiments, the mass percentage of the Chinese medicine extract solution in step S1 is 10-20%, and the ratio of the modified montmorillonite to the Chinese medicine extract solution is: 1g:40-80mL. If the ratio of the modified montmorillonite is too large, the loss of active ingredients in the Chinese medicine extract is too large, and if the ratio of the modified montmorillonite is too low, the removal effect of pesticides in the Chinese medicine extract is not ideal. Preferably, the mass percentage of the Chinese medicine extract solution is 15%, and the ratio of the modified montmorillonite to the Chinese medicine extract solution is: 1g:60mL.

[0023] In some embodiments, the Chinese medicine extract is prepared by decocting the Chinese medicine in water. Further preferably, the Chinese medicine extract is liquorice paste.

[0024] In some embodiments, the preparation method of the traditional Chinese medicine extract solution is: dissolving licorice paste in water.

[0025] In some embodiments, the mixing in step S1 is at least one of stirring, shaking and ultrasound. Preferably, ultrasound. Further preferably, the ultrasound condition is: 100-300W ultrasound for 5-10 min.

[0026] In some embodiments, the separation in step S1 is at least one of filtration, centrifugation and filter pressing.

[0027] In some embodiments, the number of water washing in step S2 is 1-3 times, preferably 2-3 times.

[0028] In some embodiments, before drying in step S2, a concentration step is also included, wherein the concentration step is to concentrate to 1 / 3-1 / 2 of the original volume.

[0029] In some embodiments, the drying in step S2 is at least one of vacuum drying, freeze drying and spray drying.

[0030] In a second aspect, the present invention provides application of the above method in preparing a traditional Chinese medicine preparation.

[0031] The aforementioned method of the present invention can effectively remove pesticide residues in traditional Chinese medicines and avoid the loss of active ingredients in traditional Chinese medicines to the greatest extent. The prepared traditional Chinese medicine preparations have high reliability and good safety.

[0032] In some embodiments, the traditional Chinese medicine preparation is a traditional Chinese medicine preparation containing liquorice paste.

[0033] In some embodiments, the traditional Chinese medicine preparation is Shibawei Dujuan Pills.

[0034] Preferably, the 18-flavor azalea pill includes licorice paste, azalea, tsaoko, terminalia chebula, sandalwood, terminalia chebula, aloeswood, emblica, alum leaves, madder, safflower, lithospermum officinale, nutmeg, macrophylla, cloves, licorice, cardamom, agarwood and travertine.

[0035] The beneficial effects of the present invention are:

[0036] (1) The method for removing pesticide residues in traditional Chinese medicine of the present invention uses modified montmorillonite as an adsorbent and can effectively remove pesticide residues in traditional Chinese medicine extracts, such as organochlorine pesticides, organophosphorus pesticides and pyrethroid pesticides.

[0037] (2) The present invention has experimentally found that adding disodium ethylenediaminetetraacetate during modification of montmorillonite can promote the adsorption of pesticides and stably combine with solid phase materials, making the adsorbed pesticides not easily desorbed.

[0038] (3) The present invention can remove organic pesticides while avoiding the loss of active ingredients of traditional Chinese medicine to the greatest extent, thus ensuring the reliability of traditional Chinese medicine.

[0039] (4) The preparation method of the present invention is simple, low-cost, and suitable for large-scale production and application. DETAILED DESCRIPTION

[0040] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0041] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for describing specific embodiments rather than for limiting the scope of protection of the present invention.

[0042] When the embodiment gives a numerical range, it should be understood that, unless otherwise specified in the present invention, the two endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those of ordinary skill in the art to which the present invention belongs.

[0043] Unless otherwise specified, the raw materials used in the present invention are all common commercial products. The preparation of the licorice paste in this embodiment is as follows: the licorice is soaked with a solution containing 4.0 mg / L hexachloronitrobenzene, 4.0 mg / L bifenthrin and 4.0 mg / L parathion, sliced, decocted three times with water, each time for 2 hours, the decoction is combined, placed overnight to precipitate, and the supernatant is concentrated to a thick paste with a relative density of 1.13-1.15 at 60°C. The preparation method of the licorice paste solution is as follows: the licorice paste is dissolved in water. The quaternary ammonium salt is chitosan quaternary ammonium salt, purchased from Shandong Fengtai Biotechnology Co., Ltd., with a substitution degree of 90-95%. The montmorillonite 44μm sieving rate is %>99%, the apparent viscosity is 2000-2200MPa·s, the colloid value is 120-150ml / 15g, and the montmorillonite content is>95%.

[0044] Example 1 A method for removing pesticide residues in traditional Chinese medicine

[0045] The method comprises the following steps:

[0046] S1. Add 1 g of modified montmorillonite to 60 ml of 15% by mass liquorice paste solution, mix with 200W ultrasonic for 7 min, centrifuge, and obtain the filtrate and insoluble matter;

[0047] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0048] Wherein, the preparation method of the modified montmorillonite is:

[0049] (1) Add 8 times the amount of water to 100 g of montmorillonite and mix to obtain a suspension;

[0050] (2) Add 40 g of quaternary ammonium salt and 7 g of disodium ethylenediaminetetraacetate to the suspension, stir at 80° C. and 300 rpm for 90 h, filter after the reaction is completed, and dry at 90° C. for 10 h to obtain the modified montmorillonite.

[0051] Embodiment 2 A method for removing pesticide residues in traditional Chinese medicine

[0052] The method comprises the following steps:

[0053] S1. Add 1 g of modified montmorillonite to 40 ml of 20% by mass liquorice paste solution, mix with 100W ultrasonic for 10 min, centrifuge, and obtain the filtrate and insoluble matter;

[0054] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0055] Wherein, the preparation method of the modified montmorillonite is:

[0056] (1) Add 5 times the amount of water to 100 g of montmorillonite and mix to obtain a suspension;

[0057] (2) Add 30 g of quaternary ammonium salt and 5 g of disodium ethylenediaminetetraacetate to the suspension, stir at 70° C. and 200 rpm for 120 h, filter after the reaction is completed, and dry at 80° C. for 8 h to obtain the modified montmorillonite.

[0058] Example 3 A method for removing pesticide residues from traditional Chinese medicine

[0059] The method comprises the following steps:

[0060] S1. Add 1 g of modified montmorillonite to 80 ml of 10% by mass liquorice paste solution, mix with 300W ultrasonic for 5 min, centrifuge, and obtain the filtrate and insoluble matter;

[0061] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0062] Wherein, the preparation method of the modified montmorillonite is:

[0063] (1) Add 10 times the amount of water to 100 g of montmorillonite and mix to obtain a suspension;

[0064] (2) Add 50 g of quaternary ammonium salt and 10 g of disodium ethylenediaminetetraacetate to the suspension, stir at 90° C. and 500 rpm for 60 h, filter after the reaction is completed, and dry at 100° C. for 8 h to obtain the modified montmorillonite.

[0065] Comparative Example 1 A method for removing pesticide residues in traditional Chinese medicine

[0066] The difference between this comparative example and Example 1 is only that the ratio of modified montmorillonite to liquorice extract solution is different and the ultrasonic conditions are different.

[0067] Specifically, the method comprises the following steps:

[0068] S1. Add 2 g of modified montmorillonite to 60 ml of 15% by mass liquorice paste solution, mix with 200W ultrasonic for 10 min, centrifuge, and obtain the filtrate and insoluble matter;

[0069] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0070] The preparation method of the modified montmorillonite is the same as that of Example 1.

[0071] Comparative Example 2 A method for removing pesticide residues in traditional Chinese medicine

[0072] The difference between this comparative example and Example 1 is only that the ratio of modified montmorillonite to liquorice extract solution is different and the ultrasonic conditions are different.

[0073] Specifically, the method comprises the following steps:

[0074] S1. Add 0.5 g of modified montmorillonite to 60 ml of 15% by mass liquorice paste solution, mix with 200W ultrasonic for 10 min, centrifuge, and obtain the filtrate and insoluble matter;

[0075] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0076] The preparation method of the modified montmorillonite is the same as that of Example 1.

[0077] Comparative Example 3: A method for removing pesticide residues from traditional Chinese medicine

[0078] The difference between this comparative example and Example 1 is that the preparation method of the modified montmorillonite is different and disodium ethylenediaminetetraacetate is not added.

[0079] The method comprises the following steps:

[0080] S1. Add 1 g of modified montmorillonite to 60 ml of 15% by mass liquorice paste solution, mix with 200W ultrasonic for 7 min, centrifuge, and obtain the filtrate and insoluble matter;

[0081] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0082] Specifically, the preparation method of the modified montmorillonite is:

[0083] (1) Add 8 times the amount of water to 100 g of montmorillonite and mix to obtain a suspension;

[0084] (2) adding 47 g of quaternary ammonium salt to the suspension, stirring at 80° C. and 300 rpm for 90 h, filtering after the reaction is completed, and drying at 90° C. for 10 h to obtain the modified montmorillonite.

[0085] Comparative Example 4: A method for removing pesticide residues from traditional Chinese medicine

[0086] The difference between this comparative example and Example 1 is that the preparation method of the modified montmorillonite is different, and the added amounts of the quaternary ammonium salt and disodium ethylenediaminetetraacetate are different.

[0087] The method comprises the following steps:

[0088] S1. Add 1 g of modified montmorillonite to 60 ml of 15% by mass liquorice paste solution, mix with 200W ultrasonic for 7 min, centrifuge, and obtain the filtrate and insoluble matter;

[0089] S2, washing the insoluble matter twice with water twice the amount of modified montmorillonite, combining the washing liquid, mixing with the filtrate, concentrating to 1 / 3 of the original volume (washing liquid + filtrate), spray drying, and obtaining licorice paste (water content <10%) with pesticide residues removed;

[0090] Specifically, the preparation method of the modified montmorillonite is:

[0091] (1) Add 8 times the amount of water to 100 g of montmorillonite and mix to obtain a suspension;

[0092] (2) Add 25 g of quaternary ammonium salt and 22 g of disodium ethylenediaminetetraacetate to the suspension, stir at 80° C. and 300 rpm for 90 h, filter after the reaction is completed, and dry at 90° C. for 10 h to obtain the modified montmorillonite.

[0093] Effect test

[0094] 1. Pesticide removal effect

[0095] According to the method for determining pesticide residues in General Chapter 2341 of Part 4 of the 2020 edition of the Pharmacopoeia, the contents of hexachloronitrobenzene, cypermethrin and parathion in the licorice paste after removing the pesticide residues in the examples and comparative examples were tested.

[0096] The results are shown in Table 1, wherein the reference substance is licorice paste from which the pesticide residues have not been removed.

[0097] Table 1

[0098] sample Hexachloronitrobenzene mg / kg Bifenthrin mg / kg Parathion mg / kg Reference 0.373 0.226 0.39 Example 1 Not detected Not detected Not detected Example 2 Not detected Not detected Not detected Example 3 Not detected Not detected Not detected Comparative Example 1 Not detected Not detected Not detected Comparative Example 2 0.118 0.095 0.14 Comparative Example 3 0.185 0.127 0.18 Comparative Example 4 0.142 0.110 0.15

[0099] 2. Loss rate of active ingredients

[0100] According to high performance liquid chromatography (General Rule 0512), the content of active ingredients in the licorice paste after removing pesticide residues in the embodiments and comparative examples was detected, and the loss rate of the active ingredients was calculated. The calculation method of the loss rate was: (M-M0)*100 / M0, wherein M is the content of active ingredients in the licorice paste after removing pesticide residues, and M0 is the content of active ingredients in the licorice paste without removing pesticide residues.

[0101] The results are shown in Table 2.

[0102] Table 2

[0103] sample Licorice glycoside content Licorice glycoside loss rate % Glycyrrhizic acid content Glycyrrhizic acid loss rate % Reference 0.72 / 7.96 / Example 1 0.65 9.7 6.97 12.4 Example 2 0.63 12.5 6.78 14.8 Example 3 0.62 13.9 6.91 13.2 Comparative Example 1 0.34 52.8 4.19 47.4 Comparative Example 2 0.58 19.4 6.15 22.7 Comparative Example 3 0.44 38.9 4.00 49.7 Comparative Example 4 0.49 31.9 3.74 53.0

[0104] It can be seen from Table 1 and Table 2 that the licorice paste for removing pesticide residues obtained in Examples 1-3 of the present invention has a good pesticide removal effect, and the loss rate of active ingredients is less than 15%.

[0105] According to Comparative Examples 1 and 2, when the ratio of modified montmorillonite is too large, the loss of active ingredients in the licorice paste is too large, and when the ratio of modified montmorillonite is too low, the removal effect of pesticides in the licorice paste is not ideal. When the ratio of modified montmorillonite to licorice paste solution is 1g:60mL, the comprehensive effect is the best.

[0106] According to Comparative Example 3, when disodium ethylenediaminetetraacetic acid is not added during the modification of montmorillonite, the licorice paste for removing pesticide residues obtained in Comparative Example 3 has unsatisfactory pesticide removal effect and active ingredient loss rate. Combined with Example 1, it can be seen that adding disodium ethylenediaminetetraacetic acid during the modification of montmorillonite can promote the adsorption of pesticides and can stably combine with solid phase substances, making the adsorbed pesticides not easily desorbed.

[0107] The modified montmorillonite of the present invention can also be used to remove pesticide residues in traditional Chinese medicine powder. During use, the modified montmorillonite is placed in a filter bag and ultrasonically mixed with the traditional Chinese medicine powder. After removing the pesticide residues, the filter bag containing the modified montmorillonite is eluted to avoid the loss of raw materials and active ingredients, thereby ensuring the reliability of the traditional Chinese medicine preparation.

[0108] The above detailed description is a specific description of one feasible embodiment of the present invention. The embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not deviate from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A method for removing pesticide residues in traditional Chinese medicine, characterized in that: The steps include: S1, mixing the modified montmorillonite with the Chinese medicine extract solution, separating and obtaining a filtrate and an insoluble matter; S2, washing the insoluble matter with water, mixing the washing liquid with the filtrate obtained in step S1, and drying; The preparation method of the modified montmorillonite comprises the following steps: (1) adding water to montmorillonite to obtain a suspension; (2) adding quaternary ammonium salt and disodium ethylenediaminetetraacetate to the suspension and stirring. After the reaction is completed, centrifuging and drying are performed to obtain the modified montmorillonite.

2. The method according to claim 1, characterized in that The amount of the quaternary ammonium salt added in step (2) is 30-50% of the mass of the montmorillonite; the amount of the disodium ethylenediaminetetraacetate added in step (2) is 5-10% of the mass of the montmorillonite.

3. The method according to claim 1, characterized in that The amount of the quaternary ammonium salt added in step (2) is 40% of the mass of the montmorillonite; the amount of disodium ethylenediaminetetraacetate added in step (2) is 7% of the mass of the montmorillonite.

4. The method according to claim 1, characterized in that: The stirring in step (2) is: stirring at 70-90° C. and 200-500 rpm for 60-120 hours.

5. The method according to claim 1, characterized in that The mass percentage of the Chinese herbal medicine extract solution in step S1 is 10-20%, and the ratio of the modified montmorillonite to the Chinese herbal medicine extract solution is: 1g:40-80mL.

6. The method according to claim 1, characterized in that The mass percentage of the Chinese herbal medicine extract solution in step S1 is 15%, and the ratio of the modified montmorillonite to the Chinese herbal medicine extract solution is: 1 g: 60 mL.

7. The method according to any one of claims 1 to 6, characterized in that The pesticides include organochlorine pesticides, organophosphorus pesticides and pyrethroid pesticides.

8. Use of the method according to any one of claims 1 to 6 in the preparation of traditional Chinese medicine preparations.

9. The use according to claim 8, characterized in that: The traditional Chinese medicine preparation contains liquorice paste.

10. The use according to claim 9, characterized in that: The Chinese medicine preparation is Eighteen-flavor Azalea Pill, which includes liquorice paste, azalea, tsaoko, terminalia chebula, sandalwood, terminalia chebula, aloeswood, emblica, alum leaves, madder, safflower, lithospermum officinale, nutmeg, macrophylla, clove, liquorice, cardamom, agarwood and travertine.