Ultramicro nano traditional Chinese medicine composite food residual toxin decomposer and preparation method thereof
By using an ultra-micro nano-sized Chinese herbal medicine compound food residue toxin decomposition agent, and employing ultra-micro pulverization and wet nano-dispersion technology, a synergistic surface activity system is constructed, which solves the shortcomings of existing fruit and vegetable cleaning agents in removing residues from the surface of fruits and vegetables, and achieves a highly efficient and stable cleaning effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 殷桂钊
- Filing Date
- 2026-02-26
- Publication Date
- 2026-05-12
AI Technical Summary
Existing fruit and vegetable cleaning agents have problems such as insufficient cleaning ability, significant impact on fruit and vegetable skin, uneven sedimentation of adsorbent materials, and insufficient synergistic design between surfactants and adsorbent materials when removing pesticide residues, environmental pollutants, and pathogenic microorganisms.
This product utilizes an ultra-micro nano-sized Chinese herbal medicine compound food residue toxin decomposition agent. Through ultra-micro pulverization and wet nano-dispersion technology, it combines Chinese herbal medicine compound ultra-micro powder, alkyl glycosides, cocamidopropyl betaine, chitosan and other components to construct a synergistic surface activity system, which improves contact efficiency and stability. Silica is used to provide porous adsorption sites to enhance the removal effect.
It effectively removes residues from the surface of fruits and vegetables under gentle conditions, improving the removal rate and stability, reducing the re-adhesion of residues, and ensuring that the cleaning system remains highly efficient under different water qualities, avoiding some of the shortcomings of traditional methods.
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Figure CN122004387A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of food biotechnology, specifically relating to an ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent and its preparation method. Background Technology
[0002] Fresh fruits and vegetables easily accumulate pesticide residues, environmental pollutants, and pathogenic microorganisms on their surfaces. These pollutants not only affect the quality of fruits and vegetables but may also harm human health through the food chain, making them a key concern in the field of food safety. To ensure food safety, high-performance fruit and vegetable cleaners have become a research hotspot. Currently, commercially available and related research cleaners are mainly based on the following technical principles: Cleaning technology based on chemically synthesized surfactants: These cleaners use synthetic surfactants such as sodium alkylbenzene sulfonate and fatty alcohol polyoxyethylene ethers as core components, removing residues through reducing liquid surface tension, emulsification, and solubilization. Although they have strong detergency, these formulations often have room for improvement in terms of rinsing properties and potential impact on the natural structure of fruit and vegetable skins. Cleaning technology based on natural plant extracts: To pursue the naturalness and gentleness of the formulation, some cleaners use plant-derived surfactants such as tea saponin and soapberry extract. This technology usually relies on traditional water extraction or alcohol extraction processes. This process may face the following limitations: some heat-sensitive or easily hydrolyzed active ingredients are prone to deactivation during extraction; the resulting extract has a complex composition and limited solids content, resulting in insufficient effective concentration as a functional component in the formulation; furthermore, relying solely on the extract, its foaming properties, stability, and contact efficiency with complex surfaces in the cleaning system sometimes fall short of ideal levels. Cleaning technologies incorporating adsorbent materials: To improve the removal rate of dissolved residues, some solutions attempt to add adsorbent materials such as activated carbon and porous silica to the cleaning agent. However, simply physically mixing micron-sized adsorbent materials with liquid components can easily lead to problems such as material sedimentation and uneven distribution, affecting their utilization rate. More importantly, without synergistic design between the adsorbent material and the surfactant, they may compete for pollutants or even interfere with each other, resulting in the overall cleaning efficiency failing to achieve the expected synergistic effect. Summary of the Invention
[0003] In view of the shortcomings of the prior art, the purpose of this invention is to provide an ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent and its preparation method.
[0004] The technical effect described in this invention is achieved through the following technical solution: an ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent, which comprises the following raw materials in parts by weight: 8-16 parts of traditional Chinese medicine compound ultra-micro powder, 3-6 parts of alkyl glycoside, 0.5-1.5 parts of cocamidopropyl betaine, 1-2 parts of hydroxypropyl-β-cyclodextrin, 0.1-0.2 parts of chitosan, 0.5-1.5 parts of silicon dioxide, 0.5-1 parts of sodium citrate, 0.2-0.5 parts of sodium gluconate, and 0.2-0.5 parts of hydroxypropyl cellulose, with the remainder being purified water, to a total of 100 parts; Preferably, the preparation steps of the traditional Chinese medicine compound ultrafine powder are as follows: S1: Pick out impurities from soapberry, soapberry, licorice and dried tangerine peel, dry them with hot air at 50-60℃ until the moisture content is ≤8%, and coarsely grind them to 60-80 mesh for later use; S2: Use an air jet mill to ultrafine the soapberry, soapberry, licorice and dried tangerine peel from step S1, and then mix the ultrafine powder evenly in proportion to obtain the traditional Chinese medicine compound ultrafine powder. Preferably, in step S2, the mass ratio of the soapberry ultrafine powder, the soapberry ultrafine powder, the licorice ultrafine powder, and the dried tangerine peel ultrafine powder is 40-50:40-50:10:3-6. Preferably, in step S2, the ultra-fine processing parameters are: air jet mill inlet pressure 0.6-0.8 MPa, feed rate 10-20 kg / h, and target particle size D90 ≤ 8 μm; Preferably, the degree of deacetylation of the chitosan is ≥80%; Preferably, another aspect of the present invention provides a method for preparing an ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposition agent, specifically comprising the following steps: S101: Add purified water to a stirred tank, add citric acid to adjust the pH to 3.5-4.5, then slowly add chitosan and stir at 500-800 rpm for 1-2 hours to obtain a chitosan solution; S102: Add purified water to the main vessel, start stirring at 400-600 rpm, and add alkyl glycoside, cocamidopropyl betaine, hydroxypropyl-β-cyclodextrin, sodium citrate and sodium gluconate in sequence. Stir at 30-40℃ for 20-40 min until the solution is uniform and transparent to obtain the mother liquor. S103: Add silica and traditional Chinese medicine composite ultrafine powder slowly and sequentially to the mother liquor of step S102 under high-speed shearing, disperse evenly, and obtain a pre-dispersed slurry; S104: Add the pre-dispersed slurry from step S103 into a sand mill, grind it, and then homogenize it under high pressure. Add the chitosan solution and hydroxypropyl cellulose from step S101 in sequence at a stirring speed of 300-500 rpm, stir for 30-60 min, adjust the pH to 9-10.5 with 10-20 wt% sodium carbonate solution, make up the volume with purified water, degas under vacuum, and sieve through 100-200 mesh to obtain the decomposing agent. Preferably, in step S103, the high-speed shearing parameters after the addition of silicon dioxide are: shearing speed 8000~12000rpm, shearing time 5~10min, and temperature control ≤35℃; Preferably, in step S103, the high-speed shearing parameters after the addition of the traditional Chinese medicine compound ultrafine powder are: shearing speed 8000~12000rpm, shearing time 15~25min, and temperature control ≤35℃; Preferably, in step S104, the grinding parameters are: 0.3–0.5 mm zirconia beads as grinding media, 60–75% filling rate, 1500–2000 rpm rotation speed, 60–120 min cyclic grinding time, discharge temperature ≤35℃, and the sampled particle size reaches D. 50 200~400nm, D 90 If the particle size is ≤800nm, proceed to the next step; the particle size is determined using a laser particle size analyzer, and the sample is diluted with purified water to a solid content of 0.2wt% before testing; Preferably, in step S104, the high-pressure homogenization parameters are: pressure 60-120 MPa, 3-6 cycles, and feed temperature 20-30°C.
[0005] The beneficial effects of this invention are as follows: Compared with existing technologies, this invention constructs a food surface toxin decomposing agent based on "migration desorption, capture and retention, inhibition of re-adhesion, and mild auxiliary reaction," enabling it to efficiently remove common residues on food surfaces under mild conditions, while taking into account safety, applicability, and system stability. Unlike traditional methods that rely on boiling or ethanol extraction to obtain active ingredients, this invention uses ultrafine pulverization and wet nano-dispersion to allow traditional Chinese medicine components such as soapberry, soapberry fruit, licorice, and tangerine peel to enter the water-based system in a stable and dispersed form with a high specific surface area. This significantly improves their contact efficiency and wetting and spreading ability with the waxy layer and microporous surface of fruits and vegetables, thereby establishing a uniform interaction interface in a short time and providing sufficient mass transfer and reaction conditions for the subsequent removal process.
[0006] Specifically, this invention utilizes a composite surfactant system constructed from traditional Chinese medicine saponins and alkyl glycosides. This system synergistically reduces surface tension, solubilizes, and exfoliates, making it easier for hydrophobic residues to desorb from food surfaces and migrate into the washing liquid. Cocamidopropyl betaine and alkyl glycosides form a mild amphoteric synergistic system, enhancing compatibility with residues of different surface polarities while improving foam and wetting stability, promoting the release of residues from complex textures and folds. Hydroxypropyl-β-cyclodextrin provides inclusion sites, forming stable inclusions of hydrophobic residues migrating into the liquid phase, improving removal efficiency, and to some extent reducing the tendency for residues to re-adhere to food surfaces. Silica provides porous adsorption and retention sites, complementing the molecular-level inclusion and capture of cyclodextrin, further fixing and concentrating desorbed residues in the liquid phase. Sodium citrate and sodium gluconate form a buffer and complexing module. On the one hand, they stabilize the ionic environment of the system, reducing the performance fluctuations of surfactants under hard water conditions. On the other hand, they complex metal ions and weaken turbidity, flocculation, or instability caused by metal ions, thus ensuring that the cleaning system maintains repeatable removal performance under different water qualities. Hydroxypropyl cellulose extends the effective contact time through thickening and film-forming wetting effects, allowing the active components to act more fully on the food surface. At the same time, it improves suspension stability and anti-re-adhesion ability, preventing desorbed contaminants from re-adhering with droplet backflow.
[0007] Furthermore, this invention effectively addresses the common functional conflicts in multi-component systems through its formulation and process. Firstly, traditional Chinese medicine powders and inorganic adsorbent powders are prone to agglomeration, sedimentation, and reduced effective specific surface area. This invention employs a wet nano-sizing method combining high-speed shear pre-dispersion with sand milling and high-pressure homogenization, ensuring the powders are fully wetted and deagglomerated within the surfactant system. This results in a more stable dispersion system with a narrower particle size distribution, fundamentally improving long-term storage uniformity and repeatability during use. Secondly, chitosan exhibits poor solubility under neutral or alkaline conditions, easily leading to flocculation instability or clogging of processing equipment. This invention first prepares a chitosan solution in a weakly acidic environment, then introduces it after nano-dispersion and finally adjusts it to the target alkaline range. This allows chitosan to exert its anti-adhesion and flocculation-carrying functions while avoiding adverse effects on the upstream nano-dispersion and equipment operation. Third, adsorption capture and surface-active solubilization may cancel each other out or compete for action sites in terms of compatibility. This invention achieves a coordinated sequence of release, capture, and rinsing by the molecular inclusion of cyclodextrin and the porous adsorption of silica. This allows the residue after solubilization and migration to be fixed in time, maintaining cleaning efficiency and inhibiting re-adhesion. Attached Figure Description
[0008] Figure 1 These are the results of pesticide residue decomposition tests in Examples 1 and 1-4 of this invention. Figure 2These are the results of pesticide residue re-adhesion tests for Example 1 and Comparative Examples 1-4 of the present invention; Figure 3 The figures show the results of the aflatoxin removal test of the decomposing agent in Example 1 and Comparative Examples 1-4 of this invention. Detailed Implementation
[0009] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Unless otherwise specified, the raw materials involved in the present invention are all purchased through conventional commercial channels. Experimental methods without specific conditions are conventional methods and conditions well known in the art, or according to the conditions recommended by the instrument manufacturer.
[0010] Example 1: An ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent, the composition of which includes the following raw materials in parts by weight: 12 parts of traditional Chinese medicine compound ultra-micro powder, 5 parts of alkyl glycoside, 1 part of cocamidopropyl betaine, 1.5 parts of hydroxypropyl-β-cyclodextrin, 0.15 parts of chitosan, 1 part of silicon dioxide, 0.8 parts of sodium citrate, 0.4 parts of sodium gluconate and 0.4 parts of hydroxypropyl cellulose, the remainder being purified water, to a total of 100 parts; The preparation steps of the traditional Chinese medicine compound ultrafine powder are as follows: S1: Pick out impurities from soapberry, soapberry, licorice and dried tangerine peel, dry them with hot air at 55℃ until the moisture content is ≤8%, and coarsely grind them to 70 mesh for later use; S2: The soapberry, sapindus mukorossi, licorice, and tangerine peel from step S1 were subjected to ultrafine processing using an air jet mill. The inlet pressure of the air jet mill was 0.7 MPa, the feed rate was 15 kg / h, and the target particle size D90 ≤ 8 μm. Then, the ultrafine powders of soapberry, sapindus mukorossi, licorice, and tangerine peel were mixed evenly in a mass ratio of 45:45:10:5 to obtain a compound ultrafine powder of traditional Chinese medicine. The preparation method of the ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposition agent specifically includes the following steps: S101: Add purified water to the stirred tank, add citric acid to adjust the pH to 4, then slowly add chitosan, stir at 600 rpm for 1.5 h to obtain a chitosan solution; S102: Add purified water to the main vessel, start stirring at 500 rpm, and add alkyl glycoside, cocamidopropyl betaine, hydroxypropyl-β-cyclodextrin, sodium citrate and sodium gluconate in sequence. Stir at 35°C for 30 min until the solution is homogeneous and transparent to obtain the mother liquor. S103: Slowly add silica to the mother liquor of step S102, shear at 10000 rpm for 8 min, and control the temperature at ≤35℃. Then slowly add the traditional Chinese medicine compound ultrafine powder, shear at 10000 rpm for 20 min, and control the temperature at ≤35℃. Disperse evenly to obtain a pre-dispersed slurry. S104: Add the pre-dispersed slurry from step S103 to a sand mill for grinding. The grinding media consists of 0.4mm zirconia beads with a filling rate of 70%, a rotation speed of 1800rpm, a grinding time of 100min, a discharge temperature ≤35℃, and a particle size reaching D. 50 300nm, D 90 ≤800nm; then high pressure homogenization treatment, pressure 100MPa, 4 cycles, feed temperature 25℃; then add chitosan solution and hydroxypropyl cellulose from step S101 sequentially at a stirring speed of 400rpm, stir for 45min, adjust pH to 9.5 with 15wt% sodium carbonate solution, make up to volume with purified water, vacuum degas, and sieve through 150 mesh to obtain the decomposition agent.
[0011] Example 2: An ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent, the composition of which includes the following raw materials in parts by weight: 16 parts of traditional Chinese medicine compound ultra-micro powder, 6 parts of alkyl glycoside, 1.5 parts of cocamidopropyl betaine, 2 parts of hydroxypropyl-β-cyclodextrin, 0.2 parts of chitosan, 1.5 parts of silicon dioxide, 1 part of sodium citrate, 0.5 parts of sodium gluconate and 0.5 parts of hydroxypropyl cellulose, the remainder being purified water, to a total of 100 parts; The preparation steps of the traditional Chinese medicine compound ultrafine powder are as follows: S1: Pick out impurities from soapberry, soapberry, licorice and dried tangerine peel, dry them with hot air at 60℃ until the moisture content is ≤8%, and coarsely grind them to 80 mesh for later use; S2: The soapberry, soapberry, licorice, and tangerine peel from step S1 were subjected to ultrafine processing using an air jet mill. The inlet pressure of the air jet mill was 0.8 MPa, the feed rate was 20 kg / h, and the target particle size D90 ≤ 8 μm. Then, the soapberry ultrafine powder, soapberry ultrafine powder, licorice ultrafine powder, and tangerine peel ultrafine powder were mixed evenly in a mass ratio of 50:50:10:6 to obtain the traditional Chinese medicine compound ultrafine powder. The preparation method of the ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposition agent specifically includes the following steps: S101: Add purified water to the stirred tank, add citric acid to adjust the pH to 3.5, then slowly add chitosan and stir at 800 rpm for 1 hour to obtain a chitosan solution; S102: Add purified water to the main vessel, start stirring at 600 rpm, and add alkyl glycoside, cocamidopropyl betaine, hydroxypropyl-β-cyclodextrin, sodium citrate and sodium gluconate in sequence. Stir at 40°C for 20 min until the solution is homogeneous and transparent to obtain the mother liquor. S103: Slowly add silica to the mother liquor of step S102, shear at 12000 rpm for 5 min, and control the temperature at ≤35℃. Then slowly add the traditional Chinese medicine compound ultrafine powder, shear at 12000 rpm for 15 min, and control the temperature at ≤35℃. Disperse evenly to obtain a pre-dispersed slurry. S104: Add the pre-dispersed slurry from step S103 to a sand mill for grinding. The grinding media consists of 0.3mm zirconia beads with a filling rate of 75%, a rotation speed of 2000rpm, a grinding time of 60min, a discharge temperature ≤35℃, and a particle size reaching D. 50 200nm, D 90 ≤800nm; then high pressure homogenization treatment, pressure 120MPa, 3 cycles, feed temperature 30℃; then add chitosan solution and hydroxypropyl cellulose from step S101 sequentially at a stirring speed of 500rpm, stir for 30min, adjust pH to 10.5 with 20wt% sodium carbonate solution, make up to volume with purified water, vacuum degas, and sieve through 200 mesh to obtain the decomposition agent.
[0012] Example 3: An ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent, the composition of which includes the following raw materials in parts by weight: 8 parts of traditional Chinese medicine compound ultra-micro powder, 3 parts of alkyl glycoside, 0.5 parts of cocamidopropyl betaine, 1 part of hydroxypropyl-β-cyclodextrin, 0.1 parts of chitosan, 0.5 parts of silicon dioxide, 0.5 parts of sodium citrate, 0.2 parts of sodium gluconate and 0.2 parts of hydroxypropyl cellulose, the remainder being purified water, to a total of 100 parts; The preparation steps of the traditional Chinese medicine compound ultrafine powder are as follows: S1: Pick out impurities from soapberry, soapberry, licorice and dried tangerine peel, dry them with hot air at 50℃ until the moisture content is ≤8%, and coarsely grind them to 60 mesh for later use; S2: The soapberry, sapindus mukorossi, licorice, and tangerine peel from step S1 were subjected to ultrafine processing using an air jet mill. The inlet pressure of the air jet mill was 0.6 MPa, the feed rate was 10 kg / h, and the target particle size D90 ≤ 8 μm. Then, the soapberry ultrafine powder, sapindus mukorossi ultrafine powder, licorice ultrafine powder, and tangerine peel ultrafine powder were mixed evenly in a mass ratio of 40:40:10:3 to obtain the traditional Chinese medicine compound ultrafine powder. The preparation method of the ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposition agent specifically includes the following steps: S101: Add purified water to the stirred tank, add citric acid to adjust the pH to 4.5, then slowly add chitosan, stir at 500 rpm for 2 hours to obtain a chitosan solution; S102: Add purified water to the main vessel, start stirring at 400 rpm, and add alkyl glycoside, cocamidopropyl betaine, hydroxypropyl-β-cyclodextrin, sodium citrate and sodium gluconate in sequence. Stir at 30°C for 40 min until the solution is homogeneous and transparent to obtain the mother liquor. S103: Slowly add silica to the mother liquor of step S102, shear at 8000 rpm for 10 min, and control the temperature at ≤35℃. Then slowly add the traditional Chinese medicine compound ultrafine powder, shear at 8000 rpm for 25 min, and control the temperature at ≤35℃. Disperse evenly to obtain a pre-dispersed slurry. S104: Add the pre-dispersed slurry from step S103 to a sand mill for grinding. The grinding media consists of 0.5mm zirconia beads, with a filling rate of 60%, a rotation speed of 1500rpm, a grinding time of 120min, a discharge temperature ≤35℃, and a particle size reaching D. 50 400nm, D 90 ≤800nm; then high pressure homogenization treatment, pressure 60MPa, 6 cycles, feed temperature 20℃; then add chitosan solution and hydroxypropyl cellulose from step S101 sequentially at a stirring speed of 300rpm, stir for 60min, adjust pH to 9 with 10wt% sodium carbonate solution, make up to volume with purified water, vacuum degas, sieve through 100 mesh to obtain the decomposition agent.
[0013] Comparative Example 1: In Comparative Example 1, the silica in Example 1 was replaced with inert mineral filler quartz powder of similar particle size to maintain the solid content and gradation unchanged; the remaining steps and parameters were the same as in Example 1.
[0014] Comparative Example 2: No hydroxypropyl-β-cyclodextrin was added in Comparative Example 2, and the total mass and solid content were kept constant by using an equal mass of water-soluble inert component maltodextrin; the remaining steps and parameters were the same as in Example 1.
[0015] Comparative Example 3: No chitosan was added in Comparative Example 3, and the total mass was made up with an equal mass of purified water to maintain consistency; the remaining steps and parameters were the same as in Example 1.
[0016] Comparative Example 4: In Comparative Example 4, the wet nano-dispersion process of sand milling and high-pressure homogenization was omitted. Only conventional stirring and short-time high-speed shearing were used to disperse the particles, and no particle size convergence control was performed. The remaining steps and parameters were the same as in Example 1.
[0017] Performance testing: Safety tests: Referring to GB 14930.1-2022, the total arsenic (as As), heavy metals (as Pb), methanol, formaldehyde, and microbial indicators (total bacterial count, coliforms, Escherichia coli, Staphylococcus aureus, and Salmonella) of the decomposition agents of Examples 1-3 and Comparative Examples 1-4 were tested. The results are shown in Tables 1 and 2 below.
[0018] Table 1. Safety test results of the decomposers in the examples and comparative examples
[0019] Table 2. Microbiological index results of the examples and comparative decomposition agents
[0020] Based on the analysis of the results in Tables 1 and 2, methanol and formaldehyde were not detected in the decomposition agents of the embodiments and comparative examples of the present invention, which meet the characteristics of "the system is water-based, the process does not take alcohol extraction as the core and has vacuum degassing". The differences between the groups are only slight changes within the detection fluctuation range. Comparative Example 1 uses quartz powder, which makes it easier to introduce background metal impurities. The heavy metal (calculated as Pb) is slightly higher but still significantly lower than the limit. The other comparative examples are similar to the embodiments in terms of physicochemical safety.
[0021] Acute oral toxicity test: Acute oral toxicity tests were conducted on the decomposing agents of Examples 1-3 and Comparative Examples 1-4 in accordance with GB 15193.3-2014. The test results are shown in Table 3 below.
[0022] Table 3. Results of acute oral toxicity tests on the decomposing agents of the examples and comparative examples.
[0023] Based on the results in Table 3, the decomposing agents in the embodiments of this invention all use food-grade raw materials, a complete surface-active compound system, and nanotechnology. The system is mild and homogeneous, without irritating impurities or abnormally high concentrations of components; it reaches a practically non-toxic level, meeting and exceeding the general safety requirements for food contact materials and daily chemical products. In Comparative Example 1, food-grade silica was replaced with ordinary quartz powder; the coarser particle size and uneven dispersion of quartz powder may pose a risk of gastrointestinal irritation. In Comparative Example 4, the sand milling and high-pressure homogenization were omitted, resulting in a large number of micron-sized and larger solid particles in the system; these coarse particles may cause physical irritation or local damage to the gastrointestinal tract in acute oral tests.
[0024] Pesticide residue decomposition test: Three representative pesticides (chlorpyrifos, bifenthrin, and carbendazim) were selected to prepare a mixed standard working solution (using acetonitrile as solvent) so that the apparent spiked level of the sample after spraying was 2 mg / kg. During the operation, the solution was applied by pipetting and gently spreading it to make the sample surface evenly wet without dripping. The sample was placed in a ventilated place at 25°C for 60 min to allow the solvent to evaporate and the pesticide to combine with the surface wax layer / texture. It was then left to stand for another 2 h as an aging adhesion test. Subsequently, a portion of the sample was weighed as the baseline sample (C0) before cleaning and immediately proceeded to the pretreatment test. The test decomposition agent (Examples 1 and Comparative Examples 1-4) was mixed with purified water at a ratio of 1:200 (volume ratio) to prepare a cleaning solution. The temperature of the cleaning solution was controlled at 25°C, and 2L of cleaning solution was used for each sample. The cleaning method was a reproducible immersion method with light mechanical action: after the sample was completely immersed, it was magnetically stirred or shaken on a shaker at 120 rpm for 5 minutes; then, wearing powder-free gloves, the surface was wiped back and forth 10 times; then, it was immersed for another 2 minutes; after cleaning, it was rinsed with running tap water for 20 seconds and drained for 2 minutes; at this time, a sample was taken as the first cleaning sample (C1) and proceeded to the next step. For residue determination, the waste washing liquid generated from the first wash of each sample was retained and used for the re-adhesion challenge. The same sample (corresponding to C1), which had just been washed, rinsed, and drained, was placed into its own waste washing liquid, completely submerged again, and shaken at 120 rpm for 2 minutes (simulating the worst-case scenario where desorbed contaminants in the washing liquid come into contact with the food surface again). After removal, no second decomposition agent wash was performed. Instead, it was rinsed with clean water under the same conditions for 20 seconds, drained for 2 minutes, and a sample was taken as the re-adhesion test sample (C2). The pesticide multi-residue determination was carried out according to the GB 23200 series. The removal rate of the first wash (%) was calculated as (C0-C1) / C0×100%; the re-adhesion recovery rate (%) was calculated as (C2-C1) / C1×100%. The results are as follows. Figure 1 and Figure 2 As shown.
[0025] based on Figure 1 and Figure 2Analysis of the results showed that in Example 1, the herbal saponins, alkyl glycosides, and amphoteric surfactants collectively reduced surface tension and enhanced wetting, making it easier for hydrophobic residues such as chlorpyrifos and bifenthrin to desorb from the wax layer and texture interface and enter the washing solution. Hydroxypropyl-β-cyclodextrin further encapsulated the hydrophobic molecules, improving their carrying stability in the aqueous phase, making the residues easier to be carried away by the washing solution rather than remaining near the interface. Silica provided porous adsorption sites, further consolidating the residues that had migrated into the washing solution, significantly reducing the probability of re-adhesion when the waste washing solution was returned to contact. Chitosan and hydroxypropyl cellulose, through flocculation to inhibit re-adhesion, stabilize suspension, and prolong effective contact, made the entire process more uniform and repeatable. Sand milling and high-pressure homogenization formed a stable dispersion system with convergent particle size of the herbal powder and the adsorption / capture components. In Comparative Example 1, quartz powder was used instead of silica. During the first wash, surfactant desorption and cyclodextrin inclusion remained, resulting in only a slight decrease in removal rate. In the re-adhesion test, free residues in the washing solution lacked adsorption and locking, making them more likely to re-adhere to the surface, leading to a significantly higher re-adhesion recovery rate. In Comparative Example 2, the removal of cyclodextrin weakened the molecular-level capture and aqueous phase carrying capacity of hydrophobic residues. The impact was most pronounced on more hydrophobic pesticides such as bifenthrin, manifested as a more significant decrease in the initial removal rate, and free residues were more likely to re-adhere upon re-contact with the waste washing solution, resulting in a higher re-adhesion recovery rate. The impact on residues that are relatively more likely to exist in the aqueous phase was relatively small. In Comparative Example 3, chitosan was removed. Since surfactants, cyclodextrin, and silica were still present, the initial removal rate generally remained good. However, due to the absence of chitosan, the re-adhesion recovery was more significant than in the previous example. Comparative Example 4 eliminated sand milling and high-pressure homogenization, resulting in powder agglomeration, uneven dispersion, insufficient utilization of effective specific surface area, and decreased interfacial contact and mass transfer efficiency, leading to a significant overall reduction in the initial removal rate. At the same time, due to the inability of the capture and adsorption system to function uniformly, there were more and more free residues and redepositionable components in the waste washing liquid, which were also more unstable, resulting in the highest rebound rate and the worst repeatability.
[0026] Mycotoxin removal test: Take 200g of peanut sample, remove debris and obviously moldy particles, and use this as one test unit. Surface spiking with aflatoxin mixed standard solution: The standard working solution is evenly dripped onto the sample surface using a pipette, while stirring to ensure uniform distribution. After spiking, the sample is placed in a fume hood at 25℃ for 60min to allow solvent evaporation, and then sealed for 12h for adsorption equilibrium / adhesion aging. Take 50g of this sample as the baseline sample (T0) for determination. Dilute the decomposition agent (Example 1 and Comparative Examples 1-4) at a ratio of 1:200. At 25℃, add 2L of cleaning solution to every 200g sample, and shake and soak for 8min at 120rpm. Then drain the cleaning solution and rinse with water for 20s, drain for 2min, and take this sample as the treated sample (T1). Aflatoxin determination is performed according to GB5009.22-2016. Calculate the aflatoxin removal rate (%) = (T0-T1) / T0×100%, and the results are as follows. Figure 3 As shown.
[0027] based on Figure 3 Results analysis showed that Example 1, based on surface-active desorption and migration, facilitated the inclusion and capture of hydrophobic toxins by hydroxypropyl-β-cyclodextrin and the porous adsorption and fixation by silica, making it easier for toxins to migrate from the peanut surface to the washing liquid and be fixed and carried away. Chitosan and hydroxypropyl cellulose enhanced the inhibition of adhesion and suspension stability, reducing the redeposition of migrated toxins, thus achieving a higher removal rate. In Comparative Example 1, replacing silica with quartz powder reduced the number of porous adsorption sites, making it difficult to effectively fix toxins in the washing liquid, resulting in a decrease in removal efficiency. In Comparative Example 2, the lack of cyclodextrin weakened molecular-level inclusion and capture, reducing the liquid-phase carrying capacity for hydrophobic toxins. In Comparative Example 3, the removal of chitosan weakened flocculation and adhesion inhibition, leading to a decrease in removal rate. In Comparative Example 4, the elimination of sand milling and high-pressure homogenization resulted in insufficient powder dispersion, reduced interfacial contact and mass transfer efficiency, making it difficult to uniformly exert the capture and adsorption effects, resulting in the worst performance.
[0028] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A superfine nano-sized traditional Chinese medicine compound food residue toxin decomposition agent, characterized in that, Its composition includes the following raw materials in parts by weight: 8-16 parts of compound ultrafine powder of traditional Chinese medicine, 3-6 parts of alkyl glycoside, 0.5-1.5 parts of cocamidopropyl betaine, 1-2 parts of hydroxypropyl-β-cyclodextrin, 0.1-0.2 parts of chitosan, 0.5-1.5 parts of silicon dioxide, 0.5-1 parts of sodium citrate, 0.2-0.5 parts of sodium gluconate, and 0.2-0.5 parts of hydroxypropyl cellulose, with the remainder being purified water, to a total of 100 parts.
2. The ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent according to claim 1, characterized in that, The preparation steps of the traditional Chinese medicine compound ultrafine powder are as follows: S1: Pick out impurities from soapberry, soapberry, licorice and dried tangerine peel, dry them with hot air, and coarsely grind them for later use; S2: Use an air jet mill to perform ultrafine processing on the soapberry, soapberry, licorice and tangerine peel from step S1, and then mix the ultrafine powder evenly in proportion to obtain the traditional Chinese medicine compound ultrafine powder.
3. The ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent according to claim 2, characterized in that, In step S2, the mass ratio of the soapberry ultrafine powder, soapberry ultrafine powder, licorice ultrafine powder, and dried tangerine peel ultrafine powder is 40-50:40-50:10:3-6.
4. The ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent according to claim 3, characterized in that, In step S2, the ultra-micronization processing parameters are: air jet mill inlet pressure 0.6-0.8 MPa, feed rate 10-20 kg / h, and target particle size D90 ≤ 8 μm.
5. The ultra-micro nano-sized traditional Chinese medicine compound food residue toxin decomposition agent according to claim 1, characterized in that, The degree of deacetylation of the chitosan is ≥80%.
6. A method for preparing an ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposing agent according to any one of claims 1-5, characterized in that, Specifically, the following steps are included: S101: Add purified water to the stirred tank, add citric acid to adjust the pH, then slowly add chitosan and stir to obtain a chitosan solution; S102: Add purified water to the main vessel, start stirring, and add alkyl glycoside, cocamidopropyl betaine, hydroxypropyl-β-cyclodextrin, sodium citrate and sodium gluconate in sequence. Stir until the solution is homogeneous and transparent to obtain the mother liquor. S103: Add silica and traditional Chinese medicine composite ultrafine powder slowly and sequentially to the mother liquor of step S102 under high-speed shearing, disperse evenly, and obtain a pre-dispersed slurry; S104: Add the pre-dispersed slurry from step S103 into a sand mill for grinding, then perform high-pressure homogenization. Under stirring, add the chitosan solution and hydroxypropyl cellulose from step S101 in sequence, stir until dissolved and homogeneous, adjust the pH with sodium carbonate solution, add purified water to make up the volume, degas under vacuum, and sieve to obtain the decomposing agent.
7. A method for preparing the ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposing agent according to claim 6, characterized in that, In step S103, the high-speed shearing parameters after the addition of silicon dioxide are: shearing speed 8000~12000rpm, shearing time 5~10min, and temperature control ≤35℃.
8. A method for preparing an ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposing agent according to claim 6, characterized in that, In step S103, the high-speed shearing parameters after the addition of the traditional Chinese medicine compound ultrafine powder are: shearing speed 8000~12000rpm, shearing time 15~25min, and temperature control ≤35℃.
9. A method for preparing the ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposing agent according to claim 6, characterized in that, In step S104, the grinding parameters are as follows: zirconia beads for grinding media 0.3–0.5 mm, filling rate 60–75%, rotation speed 1500–2000 rpm, grinding cycle time 60–120 min, discharge temperature ≤35℃, and particle size of the ground slurry D. 50 200~400nm, D 90 ≤800nm.
10. A method for preparing an ultra-micro nano-sized traditional Chinese medicine composite food residue toxin decomposing agent according to claim 6, characterized in that, In step S104, the high-pressure homogenization parameters are: pressure 60-120 MPa, 3-6 cycles, and feed temperature 20-30°C.