Method for degrading pesticide residues in Xuanmaigan granules

Abstract

The invention relates to a method for degrading pesticide residues in Xuanmaigan granules, which comprises the following steps: acidizing Xuanmaigan granules, then alkalizing, and finally carrying out enzymolysis treatment to remove pesticide residues in the medicinal materials. The method effectively degrades various residual pesticides in key traditional Chinese medicinal materials such as radix scrophulariae, radix ophiopogonis, liquorice and platycodon grandiflorum, the process steps are simple, and the pesticide degradation rate is 90% or above.

Description

Technical Field

[0001] This invention belongs to the field of traditional Chinese medicine technology, and in particular relates to a method for degrading pesticide residues in Xuanmai Ganju granules. Background Technology

[0002] With the rapid development of the traditional Chinese medicine (TCM) industry, the demand for TCM resources is gradually expanding. Artificial cultivation of medicinal plants is an effective way to achieve the regeneration and sustainable utilization of TCM resources. Currently, the planting area of ​​TCM herbs in my country exceeds 50 million mu (approximately 3.3 million hectares), and there are more than 270 artificially cultivated varieties of medicinal plants. Due to the increasing market demand for medicinal plants, and in order to increase the yield of wild and artificially cultivated TCM herbs, agricultural artificial cultivation areas are constantly expanding. However, the monoculture ecological environment has led to increasingly serious pests, diseases, and weeds affecting medicinal plants.

[0003] Currently, the control of pests, diseases, and weeds in the cultivation of Chinese medicinal herbs in my country still mainly relies on chemical pesticides. However, most medicinal herbs lack registered pesticide varieties specifically for them, resulting in a lack of guidelines for pesticide use or even a lack of available pesticides. Farmers can only refer to the pesticide application standards of other crops. This leads to farmers blindly increasing pesticide application rates in pursuit of higher profits, resulting in phenomena such as "pesticide abuse and misuse" in some planting areas. Consequently, pesticide residues in medicinal herbs are frequently reported. Pesticide residues not only directly endanger human health, but also, due to the complex chemical composition of medicinal herbs, directly affect their efficacy, thus hindering the healthy and sustainable development of my country's traditional Chinese medicine industry.

[0004] The current problem in the production of Maiganju granules is as follows: Based on the provisions of the National Food Safety Standard "Maximum Residue Limits for Pesticides in Food" (GB2763-2021), the company has formulated pesticide residue standards (internal control standards) for Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus in Maiganju granules. To ensure product quality, it is necessary to test for pesticide residues in Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus. In recent years, the company has found that pesticide residues in Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus exceed the standards during the production process. The specific results are shown in Table 1 below.

[0005] Table 1 Summary of pesticide residues

[0006]

[0007]

[0008]

[0009] Analysis of the test data revealed that, based on the companies' internal quality control standards for pesticide residues, Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus generally had excessive pesticide residues. Not only were the pesticide residue levels more than twice the standard, but the same medicinal herbs also contained pesticides from different fields (including fungicides, insecticides, and herbicides). This rendered the Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus unusable, leading to returns and exchanges, reducing production efficiency, and impacting the companies' economic benefits.

[0010] The pesticides used on traditional Chinese medicinal herbs are diverse, and can be categorized based on their target pests into insecticides (including neonicotinoids, organophosphates, pyrethroids, etc.), fungicides (triazoles and organosulfurs, etc.), and herbicides (sulfonylureas, etc.). Different types of pesticides differ significantly in chemical structure, physicochemical properties, application methods, and application time, resulting in varying degradation mechanisms. Currently, pesticide degradation technologies mainly include biodegradation, physical degradation, and chemical degradation. Biotechnology encompasses various methods such as microbial degradation, enzymatic degradation, genetically engineered bacteria degradation, and degradation assisted by plant growth regulators. Physical technologies include ultrasonic degradation, adsorption removal, ionizing radiation, and cold plasma degradation. Chemical technologies include photochemical, oxidative decomposition, and electrochemical techniques. While these methods can effectively degrade pesticides in a specific field, they cannot degrade multiple pesticides across multiple fields.

[0011] Currently, there is no domestic literature reporting effective methods for degrading multiple pesticide residues in Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus. For these reasons, enterprises urgently need to establish a method for degrading multiple pesticide residues in the key Chinese medicinal herbs Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus granules. This would solve the problem of excessive pesticide residues, meet internal quality control standards, eliminate the need for returns or exchanges, and ultimately improve work efficiency and economic benefits. Summary of the Invention

[0012] The purpose of this invention is to overcome the defects in the prior art and provide a method for degrading the residues of various pesticides in the key Chinese medicinal herbs Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis and Platycodon grandiflorus in Xuanmai Ganju granules, with simple process steps and a pesticide degradation rate of over 90%.

[0013] The technical solution adopted to achieve the above objectives is as follows:

[0014] A method for degrading pesticide residues in *Xuanmai Ganju* granules includes the following steps:

[0015] (1)Acidification

[0016] First, the Scrophularia, Ophiopogon, Licorice, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities.

[0017] Next, place Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus into a far-infrared heated reactor, add tap water, and start the equipment to heat to 75-80℃; add organic acid to adjust the pH to 3-4; stir for 10-20 minutes.

[0018] Finally, add sodium chloride and acidic oxidizing potential water, adjust the pH to 2-3, stir for 10-20 minutes, and then filter to obtain the acidified mixture;

[0019] (2) Washing

[0020] Add purified water to the acidified mixture obtained in step (1) and wash it once at room temperature to obtain the acidified and washed mixture.

[0021] (3) Alkalization

[0022] Add the acidified and washed mixture obtained in step (2) to tap water and heat it to 40-45℃. Add alkali solution, adjust the pH to 9-10, stir for 10-20 minutes, and then filter to obtain the alkalized mixture.

[0023] (4) Washing

[0024] Add the alkalized mixture obtained in step (3) to purified water and wash it once at room temperature to obtain the alkalized and washed mixture.

[0025] (5) Enzymatic hydrolysis

[0026] Add tap water to the alkalized and washed mixture obtained in step (4), adjust the pH to 6.2-6.4 with organic acid, add ester hydrolase (PLE) and laccase respectively, heat to 40-42℃, stir for 20-40 min, and then filter to obtain the enzymatically hydrolyzed mixture;

[0027] (6) Wash with water

[0028] Add purified water to the enzymatically hydrolyzed mixture obtained in step (5) and wash it once at room temperature to obtain the enzymatically hydrolyzed and washed mixture.

[0029] (7) Drying and pulverizing

[0030] The enzymatically hydrolyzed and washed mixture obtained in step (6) is dried and pulverized.

[0031] In the above method for degrading pesticide residues in Xuanmai Ganju granules, the organic acid is citric acid or citric acid.

[0032] In step (1) above, the...

[0033] Mixing ratio: W Scrophularia: W Ophiopogon japonicus: W Glycyrrhiza uralensis: W Platycodon grandiflorus = 1kg: 1kg: 1kg: 1kg

[0034] Tap water usage: W = 1 kg of mixed herbs (Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus) / L of tap water = 10-12 L;

[0035] Sodium chloride dosage: L tap water : W sodium chloride = 1L : 20-30g;

[0036] In step (1) above, the acidic oxidizing potential water refers to acidic oxidizing potential water produced using an acidic oxidizing potential water generator.

[0037] In step (3) above, the alkaline solution refers to a sodium hydroxide or sodium carbonate solution with a concentration of 10-20%.

[0038] In step (5) above, the amount of ester hydrolase (PLE) used is: W alkalized water washing mixture: W ester hydrolase (PLE) = 1kg: 5-6g.

[0039] In step (5) above, the amount of laccase used is: W alkalized water washing mixture: W laccase = 1 kg: 9-10 g.

[0040] In step (5) above, the production process of the laccase includes:

[0041] Fermentation process:

[0042] 1) Seed culture: First, sterilize the seed culture medium and cool it to room temperature. Then, pressurize it with sterile air. Under flame protection, inoculate the pre-cultured *Variegata var. verrucae* mother bottle solution into the seed culture medium for further cultivation. The pressure in the container is 0.03–0.06 MPa; the temperature is 25–28°C; and the air flow rate is 4–8 m³ / min. 3 / h; Stirring speed: 5 hours before seed culture, air stir, and after air stirring, control the stirrer speed at 40-60 r / min; until the cell concentration is 10-14%, then transfer the seed.

[0043] 2) Fermentation culture: First, sterilize the fermentation medium, cool it to room temperature, and pressurize it with sterile air. Then, transfer the cultured seed culture into the fermentation medium for fermentation culture.

[0044] a. Initial pH of the culture medium: The pH of the fermentation medium is controlled at 6-7 after sterilization;

[0045] b. Temperature: Culture temperature 25-28℃;

[0046] c. Stirring speed: The speed should be controlled at 60-80 r / min;

[0047] d. Pressure control: Tank pressure 0.05~0.06MPa;

[0048] e. pH control: The pH should be controlled at 6-7 during fermentation;

[0049] f. Viscosity and dissolved oxygen control:

[0050] During the fermentation process, a digital viscometer was used to measure the viscosity of the fermentation broth. If the viscosity was >20 mPa·s, sterilized drinking water was added to control the viscosity to 10-14 mPa·s.

[0051] During fermentation, the dissolved oxygen content is controlled at above 25% by adjusting the air flow.

[0052] Fermentation was terminated when laccase activity exceeded 220 ug / ml.

[0053] 3) Feeding: The fermentation cycle is 26 hours. Glycerol is added in a continuous flow at a rate of 1-2 kg / m³. 3 Add an inducer (IPTG),

[0054] The addition amount is 0.2-0.3 kg / m³. 3 ;

[0055] Extraction and purification process:

[0056] (1) Preprocessing

[0057] Add perlite to the fermentation broth and stir until homogeneous. Then, separate the solid and liquid components using a metal mesh and collect the filtrate.

[0058] (2) Macroporous adsorption resin

[0059] The filtrate was treated with macroporous adsorption resin to obtain a high-purity eluent.

[0060] (3) Concentration:

[0061] The eluent is concentrated to a high concentration solution using a multi-functional extraction and concentration machine, and the concentrated solution is collected at a concentration temperature of 40-60℃.

[0062] (4) Low-temperature storage

[0063] Cool the concentrate to 0-4℃ and store at low temperature.

[0064] In step (5) above, the fermentation strain in the laccase production process is Aspergillus fumigatus;

[0065] Seed culture medium formula:

[0066] Glucose 4-5 kg / m 3 Glycerin 1-2 kg / m 3 Yeast extract powder 6-8 kg / m 3 Dipotassium hydrogen phosphate 0.18-0.22 kg / m³ 3 Ammonia water (28%) 0.02-0.04 kg / m³ 3 ;

[0067] Fermentation medium formulation:

[0068] Glucose 6-8 kg / m 3 Glycerin 2-3 kg / m 3 Yeast extract powder 6-8 kg / m 3 Peptone 6-8 kg / m 3 Dipotassium hydrogen phosphate 0.18-0.22 kg / m³ 3 Ammonia water (28%) 0.02-0.04 kg / m³ 3 Magnesium sulfate heptahydrate 0.015-0.018 kg / m³ 3 Manganese chloride 0.003-0.005 kg / m³ 3 .

[0069] Technical effects of this invention: Using the process described in this patent, the pesticide degradation rate of residual herbs such as Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus exceeds 90%. Specific data are shown in Table 2 below.

[0070] Table 2 Summary of pesticide residues

[0071]

[0072]

[0073] Detailed Implementation

[0074] The invention is illustrated below with examples. It should be understood that these examples are for illustrative purposes only and not for limiting the invention. The scope and core content of the invention are defined by the claims.

[0075] The acidic oxidizing electrolyzed water comes from an acidic oxidizing electrolyzed water generator, model number: HHEOW-2000.

[0076] The laccase-producing strain, *Aspergillus fumigatus*, was obtained from the China Center for Type Culture Collection, accession number CCTCAF2014029.

[0077] Detection method: derived from "2341 Determination of pesticide residues" in the General Chapter of Part IV of the 2020 edition of the Chinese Pharmacopoeia.

[0078] The far-infrared heated reactor was provided by Jinfeng Chemical Equipment Co., Ltd., with a specification of 2000L, an inner pot diameter of 1400φmm, a heater power of 55KW, and a stirring speed of 60-100r / min.

[0079] Example 1

[0080] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0081] (1)Acidification

[0082] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1000L of tap water is added, and the equipment is started to heat up to 75℃. Citric acid is added to adjust the pH to 3. Stir for 10 minutes. Finally, 20kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2. Stir for 10 minutes and then filter to obtain a mixture.

[0083] (2) Washing

[0084] Add 1500L of purified water to the acidified mixture and wash once with water at room temperature.

[0085] (3) Alkalization

[0086] Add 1000L of tap water to the washed mixture, heat to 40℃, add 10% sodium hydroxide alkaline solution, adjust the pH to 9, stir for 10 minutes, and then filter.

[0087] (4) Washing

[0088] Add 1500L of purified water to the alkalized mixture and wash once with water at room temperature.

[0089] (5) Enzymatic hydrolysis

[0090] Add 1000L of tap water to the washed mixture, adjust the pH to 6.2 with citric acid, add 0.5kg of ester hydrolase (PLE) and 0.9kg of laccase, heat to 40℃, stir for 20min, and then filter.

[0091] (6) Wash with water

[0092] The enzymatically hydrolyzed mixture was added to 1500L of purified water and washed once at room temperature.

[0093] (7) Drying and pulverizing

[0094] The mixture after washing is dried and pulverized.

[0095] Following the process described in Example 1, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected, as detailed in Table 3 below.

[0096] Table 3 Summary of pesticide residues

[0097]

[0098]

[0099]

[0100] Data analysis results show that, using the pesticide degradation method described in Example 1, the average degradation rate of pesticide residues is 90.5%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0101] Example 2

[0102] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0103] (1)Acidification

[0104] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1050L of tap water is added, and the equipment is started to heat up to 76℃. Citric acid is added to adjust the pH to 3.3. The mixture is stirred for 12 minutes. Finally, 23.1kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.3. The mixture is stirred for 12 minutes and then filtered to obtain a mixture.

[0105] (2) Washing

[0106] The acidified mixture was added to 1600L of purified water and washed once at room temperature.

[0107] (3) Alkalization

[0108] After washing, add 1050L of tap water to the mixture, heat to 42℃, add 13% sodium carbonate alkali solution, adjust the pH to 9.2, stir for 12 minutes, and then filter.

[0109] (4) Washing

[0110] After alkalization, add 1600L of purified water and wash once at room temperature.

[0111] (5) Enzymatic hydrolysis

[0112] Add 1050L of tap water to the washed mixture, adjust the pH to 6.3 with citric acid, add 0.52kg of ester hydrolase (PLE) and 0.93kg of laccase, heat to 40.5℃, stir for 25min, and then filter.

[0113] (6) Wash with water

[0114] The enzymatically hydrolyzed mixture was added to 1600L of purified water and washed once at room temperature.

[0115] (7) Drying and pulverizing

[0116] The mixture after washing is dried and pulverized.

[0117] Following the process described in Example 2, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected. The details are shown in Table 4 below.

[0118] Table 4 Summary of pesticide residues

[0119]

[0120]

[0121]

[0122] Data analysis results show that, using the pesticide degradation method described in this patent, the average degradation rate of pesticide residues is 91.2%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0123] Example 3

[0124] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0125] (1)Acidification

[0126] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1100L of tap water is added, and the equipment is started to heat up to 76℃. Citric acid is added to adjust the pH to 3.5. The mixture is stirred for 15 minutes. Finally, 27.5kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.5. The mixture is stirred for 15 minutes and then filtered to obtain a mixture.

[0127] (2) Washing

[0128] The acidified mixture was added to 1700L of purified water and washed once at room temperature.

[0129] (3) Alkalization

[0130] After washing, add 1100L of tap water to the mixture, heat to 45℃, add 15% sodium hydroxide solution, adjust the pH to 9.5, stir for 15 minutes, and then filter.

[0131] (4) Washing

[0132] After alkalization, the mixture was added to 1700L of purified water and washed once at room temperature.

[0133] (5) Enzymatic hydrolysis

[0134] Add 1100L of tap water to the washed mixture, adjust the pH to 6.3 with citric acid, add 0.55kg of ester hydrolase (PLE) and 0.95kg of laccase, heat to 41℃, stir for 30min, and then filter.

[0135] (6) Wash with water

[0136] The enzymatically hydrolyzed mixture was added to 1700L of purified water and washed once at room temperature.

[0137] (7) Drying and pulverizing

[0138] The mixture after washing is dried and pulverized.

[0139] The specific test results are shown in the table below:

[0140] Following the process described in Example 3, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected, as detailed in Table 5 below.

[0141] Table 5 Summary of pesticide residues

[0142]

[0143]

[0144]

[0145] Data analysis results show that, using the pesticide degradation method described in this patent, the average degradation rate of pesticide residues is 91.8%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0146] Example 4

[0147] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0148] (1)Acidification

[0149] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1150L of tap water is added, and the equipment is started to heat up to 78℃. Citric acid is added to adjust the pH to 3.8. Stir for 18 minutes. Finally, 31kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.7. Stir for 18 minutes and then filter to obtain a mixture.

[0150] (2) Washing

[0151] The acidified mixture was added to 1900L of purified water and washed once at room temperature.

[0152] (3) Alkalization

[0153] After washing, add 1150L of tap water to the mixture, heat to 44℃, add 18% sodium carbonate solution, adjust the pH to 9.8, stir for 13 minutes, and then filter.

[0154] (4) Washing

[0155] After alkalization, the mixture was added to 1900L of purified water and washed once at room temperature.

[0156] (5) Enzymatic hydrolysis

[0157] Add 1150L of tap water to the washed mixture, adjust the pH to 6.4 with citric acid, add 0.58kg of ester hydrolase (PLE) and 0.97kg of laccase, heat to 42℃, stir for 35min, and then filter.

[0158] (6) Wash with water

[0159] The enzymatically hydrolyzed mixture was added to 1900L of purified water and washed once at room temperature.

[0160] (7) Drying and pulverizing

[0161] The mixture after washing is dried and pulverized.

[0162] The specific test results are shown in the table below:

[0163] Following the process described in Example 4, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected. The details are shown in Table 6 below.

[0164] Table 6 Summary of Pesticide Residues

[0165]

[0166]

[0167] Data analysis results show that, using the pesticide degradation method described in this patent, the average degradation rate of pesticide residues is 91.4%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0168] Example 5

[0169] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0170] (1)Acidification

[0171] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1200L of tap water is added, and the equipment is started to heat up to 80℃. Citric acid is added to adjust the pH to 4.0. The mixture is stirred for 20 minutes. Finally, 36kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 3.0. The mixture is stirred for 20 minutes and then filtered to obtain a mixture.

[0172] (2) Washing

[0173] Add 2000L of purified water to the acidified mixture and wash once with water at room temperature.

[0174] (3) Alkalization

[0175] After washing, add 1200L of tap water to the mixture, heat to 45℃, add 20% sodium hydroxide solution, adjust the pH to 10, stir for 15 minutes, and then filter.

[0176] (4) Washing

[0177] Add 2000L of purified water to the alkalized mixture and wash once with water at room temperature.

[0178] (5) Enzymatic hydrolysis

[0179] Add 1150L of tap water to the washed mixture, adjust the pH to 6.4 with citric acid, add 0.6kg of ester hydrolase (PLE) and 1kg of laccase, heat to 42℃, stir for 40min, and then filter.

[0180] (6) Wash with water

[0181] Add 2000L of purified water to the enzymatically hydrolyzed mixture and wash once with water at room temperature.

[0182] (7) Drying and pulverizing

[0183] The mixture after washing is dried and pulverized.

[0184] The specific test results are shown in the table below:

[0185] Following the process described in Example 5, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected. The details are shown in Table 7 below.

[0186] Table 7 Summary of pesticide residues

[0187]

[0188]

[0189]

[0190] Data analysis results show that, using the pesticide degradation method described in this patent, the average degradation rate of pesticide residues is 91.0%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0191] Example 6

[0192] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0193] (1)Acidification

[0194] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1200L of tap water is added, and the equipment is started to heat up to 77℃. Citric acid is added to adjust the pH to 2.7. The mixture is stirred for 14 minutes. Finally, 16.7kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.2. The mixture is stirred for 20 minutes and then filtered to obtain a mixture.

[0195] (2) Washing

[0196] The acidified mixture was added to 1560L of purified water and washed once at room temperature.

[0197] (3) Alkalization

[0198] After washing, add 1050L of tap water to the mixture, heat to 43℃, add 14% sodium hydroxide solution, adjust the pH to 9.2, stir for 15 minutes, and then filter.

[0199] (4) Washing

[0200] After alkalization, the mixture was added to 1580L of purified water and washed once at room temperature.

[0201] (5) Enzymatic hydrolysis

[0202] Add 1080L of tap water to the washed mixture, adjust the pH to 6.2 with citric acid, add 0.51kg of ester hydrolase (PLE) and 0.94kg of laccase, heat to 41℃, stir for 30min, and then filter.

[0203] (6) Wash with water

[0204] The enzymatically hydrolyzed mixture was added to 1500L of purified water and washed once at room temperature.

[0205] (7) Drying and pulverizing

[0206] The mixture after washing is dried and pulverized.

[0207] The specific test results are shown in the table below:

[0208] Following the process described in Example 6, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were statistically analyzed, as detailed in Table 8 below.

[0209] Table 8 Summary of Pesticide Residues

[0210]

[0211]

[0212] Data analysis results show that, using the pesticide degradation method described in this patent, the average degradation rate of pesticide residues is 91.4%, and the pesticide residue content in Chinese medicinal materials meets the company's internal quality control standards.

[0213] Comparative Example 1

[0214] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0215] (1)Acidification

[0216] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1100L of tap water is added, and the equipment is started to heat up to 76℃. Citric acid is added to adjust the pH to 3.5. The mixture is stirred for 15 minutes. Finally, 27.5kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.5. The mixture is stirred for 15 minutes and then filtered to obtain a mixture.

[0217] (2) Washing

[0218] The acidified mixture was added to 1700L of purified water and washed once at room temperature.

[0219] (3) Enzymatic hydrolysis

[0220] Add 1100L of tap water to the washed mixture, adjust the pH to 6.3 with citric acid, add 0.55kg of ester hydrolase (PLE) and 0.95kg of laccase, heat to 41℃, stir for 30min, and then filter.

[0221] (4) Washing

[0222] The enzymatically hydrolyzed mixture was added to 1700L of purified water and washed once at room temperature.

[0223] (5) Drying and pulverizing

[0224] The mixture after washing is dried and pulverized.

[0225] The specific test results are shown in the table below:

[0226] Following the process described in Example 3, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were collected. The details are shown in Table 9 below.

[0227] Table 9 Summary of Pesticide Residues

[0228]

[0229]

[0230]

[0231] Data analysis results show that by using the pesticide residue degradation method described in Comparative Example 2, the alkalization process was eliminated, which reduced the degradation rate of some weakly acidic pesticides and ester pesticide residues. The average pesticide residue degradation rate was 88.7%, which is lower than the technical level described in this patent.

[0232] Comparison Implementation 2

[0233] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0234] (1) Preprocessing

[0235] First, the Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus in the Xuanmai Ganju granules are pretreated to remove visible solid impurities, and then mixed.

[0236] (2) Alkalization

[0237] Add 1100L of tap water to the mixture, heat to 45℃, add 15% sodium hydroxide alkaline solution, adjust the pH to 9.5, stir for 15 minutes, and then filter.

[0238] (3) Washing

[0239] After alkalization, the mixture was added to 1700L of purified water and washed once at room temperature.

[0240] (4) Enzymatic hydrolysis

[0241] Add 1100L of tap water to the washed mixture, adjust the pH to 6.3 with citric acid, add 0.55kg of ester hydrolase (PLE) and 0.95kg of laccase, heat to 41℃, stir for 30min, and then filter.

[0242] (5) Wash with water

[0243] The enzymatically hydrolyzed mixture was added to 1700L of purified water and washed once at room temperature.

[0244] 6) Drying and pulverizing

[0245] The mixture after washing is dried and pulverized.

[0246] The specific test results are shown in the table below:

[0247] Following the process described in Example 3, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were statistically analyzed, as detailed in Table 10 below.

[0248] Table 10 Summary of Pesticide Residues

[0249]

[0250]

[0251] Data analysis results show that by using the pesticide residue degradation method described in Comparative Example 2 and eliminating the acidification process, the degradation rate of some weakly alkaline pesticides and ester pesticide residues was reduced. The average degradation rate of pesticide residues was 87.3%, which is lower than the technical level described in this patent.

[0252] Comparative Example 3

[0253] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0254] (1)Acidification

[0255] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1100L of tap water is added, and the equipment is started to heat up to 75℃. Citric acid is added to adjust the pH to 4.0. Stir for 20 minutes. Finally, 31.3kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.5. Stir for 16 minutes and then filter to obtain a mixture.

[0256] (2) Washing

[0257] The acidified mixture was added to 1800L of purified water and washed once at room temperature.

[0258] (3) Alkalization

[0259] After washing, add 1100L of tap water to the mixture, heat to 44℃, add 16% sodium hydroxide solution, adjust the pH to 9.7, stir for 15 minutes, and then filter.

[0260] (4) Washing

[0261] After alkalization, the mixture was added to 1800L of purified water and washed once at room temperature.

[0262] (5) Enzymatic hydrolysis

[0263] Add 1100L of tap water to the washed mixture, adjust the pH to 6.2 with citric acid, add 0.90kg of laccase, heat to 40℃, stir for 34min, and then filter.

[0264] (6) Wash with water

[0265] The enzymatically hydrolyzed mixture was added to 1800L of purified water and washed once at room temperature.

[0266] (7) Drying and pulverizing

[0267] The mixture after washing is dried and pulverized.

[0268] The specific test results are shown in the table below:

[0269] Following the process described in Comparative Example 3, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were statistically analyzed, as detailed in Table 11 below.

[0270] Table 11 Summary of pesticide residues

[0271]

[0272]

[0273]

[0274] Data analysis results show that: by using the pesticide residue degradation method described in Comparative Example 3, without adding ester hydrolase (PLE) process, the degradation rate of pesticide residues is reduced, with an average degradation rate of 68.8%, which is lower than the technical level described in this patent.

[0275] Comparative Example 4

[0276] Weigh out 25kg of Scrophularia ningpoensis, 25kg of Ophiopogon japonicus, 25kg of Glycyrrhiza uralensis, and 25kg of Platycodon grandiflorus, totaling 100kg.

[0277] (1)Acidification

[0278] First, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Second, the Scrophularia, Ophiopogon, Glycyrrhiza, and Platycodon are placed in a far-infrared heating reactor, 1100L of tap water is added, and the equipment is started to heat up to 75℃. Citric acid is added to adjust the pH to 3.2. The mixture is stirred for 20 minutes. Finally, 31.4kg of sodium chloride and acidic oxidizing potential water are added to adjust the pH to 2.4. The mixture is stirred for 12 minutes and then filtered to obtain a mixture.

[0279] (2) Washing

[0280] The acidified mixture was added to 1850L of purified water and washed once at room temperature.

[0281] (3) Alkalization

[0282] After washing, add 1130L of tap water to the mixture, heat to 42℃, add 17% sodium carbonate solution, adjust the pH to 9.4, stir for 15 minutes, and then filter.

[0283] (4) Washing

[0284] After alkalization, the mixture was added to 1850L of purified water and washed once at room temperature.

[0285] (5) Enzymatic hydrolysis

[0286] Add 1130L of tap water to the washed mixture, adjust the pH to 6.2 with citric acid, add 0.52kg of ester hydrolase (PLE), heat to 40℃, stir for 34min, and then filter.

[0287] (6) Wash with water

[0288] The enzymatically hydrolyzed mixture was added to 1800L of purified water and washed once at room temperature.

[0289] (7) Drying and pulverizing

[0290] The mixture after washing is dried and pulverized.

[0291] The specific test results are shown in the table below:

[0292] Following the process described in Comparative Example 4, pesticide residue data (maximum pesticide residue after degradation) for 20 batches were statistically analyzed, as detailed in Table 12 below.

[0293] Table 12 Summary of Pesticide Residues

[0294]

[0295]

[0296] Data analysis results show that: by using the pesticide residue degradation method described in Comparative Example 4, without adding laccase, the degradation rate of pesticide residues is reduced, with an average degradation rate of 42.1%, which is lower than the technical level described in this patent.

Claims

1. A method for degrading pesticide residues in Xuanmai Ganju granules, comprising the following steps: (1)Acidification First, the Scrophularia, Ophiopogon, Licorice, and Platycodon in the Xuanmai Ganju granules are pretreated to remove visible solid impurities. Next, place Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus into a far-infrared heated reactor, add tap water, and start the equipment to heat to 75-80℃; add organic acid to adjust the pH to 3-4; stir for 10-20 minutes. Finally, add sodium chloride and acidic oxidizing potential water, adjust the pH to 2-3, stir for 10-20 minutes, and then filter to obtain the acidified mixture; (2) Washing Add purified water to the acidified mixture obtained in step (1) and wash it once at room temperature to obtain the acidified and washed mixture. (3) Alkalization Add the acidified and washed mixture obtained in step (2) to tap water and heat to 40-45℃. Add alkali solution, adjust the pH to 9-10, stir for 10-20 minutes, and then filter to obtain the alkalized mixture. (4) Washing Add the alkalized mixture obtained in step (3) to purified water and wash it once at room temperature to obtain the alkalized and washed mixture. (5) Enzymatic hydrolysis Add tap water to the alkalized and washed mixture obtained in step (4), adjust the pH to 6.2-6.4 with organic acid, add ester hydrolase (PLE) and laccase respectively, heat to 40-42℃, stir for 20-40 min, and then filter to obtain the enzymatically hydrolyzed mixture; (6) Wash with water Add purified water to the enzymatically hydrolyzed mixture obtained in step (5), and wash once with water at room temperature to obtain the enzymatically hydrolyzed and washed mixture. (7) Drying and pulverizing The enzymatically hydrolyzed and washed mixture obtained in step (6) is dried and pulverized.

2. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... The organic acid is citric acid or citric acid.

3. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... In step (1), the Mixing ratio: W Scrophularia: W Ophiopogon japonicus: W Glycyrrhiza uralensis: W Platycodon grandiflorus = 1kg: 1kg: 1kg: 1kg Tap water usage: W = 1 kg of mixed herbs (Scrophularia, Ophiopogon japonicus, Glycyrrhiza uralensis, and Platycodon grandiflorus) / L of tap water = 10-12 L; Sodium chloride dosage: L tap water : W sodium chloride = 1L : 20-30g.

4. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... In step (1), the acidic oxidizing potential water refers to acidic oxidizing potential water produced using an acidic oxidizing potential water generator.

5. The method for degrading pesticide residues in Xuanmai Ganju granules according to claim 1, characterized in that... In step (3), the alkaline solution refers to a sodium hydroxide or sodium carbonate solution with a concentration of 10-20%.

6. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... In step (5), the amount of ester hydrolase (PLE) used is: W alkalized water washing mixture: W ester hydrolase (PLE) = 1kg: 5-6g.

7. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... In step (5), the amount of laccase used is: Walkalized water-washed mixture: Wlaccase = 1 kg: 9-10 g.

8. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 1, characterized in that... In step (5), the production process of the laccase includes: Fermentation process: 1) Seed culture: First, sterilize the seed culture medium and cool it to room temperature. Then, pressurize it with sterile air. Under flame protection, inoculate the pre-cultured *Variegata var. verrucae* mother bottle solution into the seed culture medium for further cultivation. The pressure in the container is 0.03–0.06 MPa; the temperature is 25–28°C; and the air flow rate is 4–8 m³ / min. 3 / h; Stirring speed: 5 hours before seed culture, air stir, and after air stirring, control the stirrer speed at 40-60 r / min; until the cell concentration is 10-14%, then transfer the seed. 2) Fermentation culture: First, sterilize the fermentation medium, cool it to room temperature, and pressurize it with sterile air. Then, transfer the cultured seed culture into the fermentation medium for fermentation culture. a. Initial pH of the culture medium: The pH of the fermentation medium is controlled at 6-7 after sterilization; b. Temperature: Culture temperature 25-28℃; c. Stirring speed: The speed should be controlled at 60-80 r / min; d. Pressure control: Tank pressure 0.05~0.06MPa; e. pH control: The pH should be controlled at 6-7 during fermentation; f. Viscosity and dissolved oxygen control: During the fermentation process, a digital viscometer was used to measure the viscosity of the fermentation broth. If the viscosity was >20 mPa·s, sterilized drinking water was added to control the viscosity to 10-14 mPa·s. During fermentation, the dissolved oxygen content is controlled at above 25% by adjusting the air flow. Fermentation was terminated when laccase activity exceeded 220 ug / ml. 3) Feeding: The fermentation cycle is 26 hours. Glycerol is added in a continuous flow at a rate of 1-2 kg / m³. 3 Add an inducing agent (IPTG) at a rate of 0.2-0.3 kg / m³. 3 ; Extraction and purification process: (1) Preprocessing Add perlite to the fermentation broth and stir until homogeneous. Then, separate the solid and liquid components using a metal mesh and collect the filtrate. (2) Macroporous adsorption resin The filtrate was treated with macroporous adsorption resin to obtain a high-purity eluent. (3) Concentration: The eluent is concentrated to a high concentration solution using a multi-functional extraction and concentration machine, and the concentrated solution is collected at a concentration temperature of 40-60℃. (4) Low-temperature storage Cool the concentrate to 0-4℃ and store at low temperature.

9. The method for degrading pesticide residues in *Xuanmai Ganju* granules according to claim 8, characterized in that... The fermentation strain used in the production process of laccase is Aspergillus fumigatus. Seed culture medium formula: Glucose 4-5 kg / m 3 Glycerin 1-2 kg / m 3 Yeast extract powder 6-8 kg / m 3 Dipotassium hydrogen phosphate 0.18-0.22 kg / m³ 3 Ammonia water (28%) 0.02-0.04 kg / m³ 3 ; Fermentation medium formulation: Glucose 6-8 kg / m 3 Glycerin 2-3 kg / m 3 Yeast extract powder 6-8 kg / m 3 Peptone 6-8 kg / m 3 Dipotassium hydrogen phosphate 0.18-0.22 kg / m³ 3 Ammonia water (28%) 0.02-0.04 kg / m³ 3 Magnesium sulfate heptahydrate 0.015-0.018 kg / m³ 3 Manganese chloride 0.003-0.005 kg / m³ 3 .

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