Composite mildew removing agent as well as preparation method and application thereof

Abstract

The invention relates to a composite mildew removing agent as well as a preparation method and application thereof, relates to the technical field of mildew removing agents, and aims at solving at least one of the problems that an existing mildew removing agent is low in vomitoxin and zearalenone adsorption rate, low in degradation capacity, high in cost, unstable in performance and the like. The composite mildew removing agent is prepared from the following raw materials in percentage by mass: 30 to 35 percent of calcium-based montmorillonite, 32 to 42.5 percent of sodium-based montmorillonite, 10 to 15 percent of zinc-loaded montmorillonite, 10 to 15 percent of yeast cell wall, 2 to 5 percent of L2-ascorbic acid, 1 to 2 percent of chitosan oligosaccharide, 0.5 to 1 percent of lactobacillus plantarum and 0.0005 to 0.002 percent of mangiferin. According to the composite mildew removing agent, the calcium-based montmorillonite, the sodium-based montmorillonite and the zinc-loaded montmorillonite have a synergistic effect, so that a multi-stage adsorption network is formed, the space barrier effect is enhanced, two toxins DON and ZEN in feed can be effectively removed, the loss that the feed cannot be used or needs to be degraded for use due to toxin pollution is reduced, the utilization rate of the feed is increased, and the feed quality is improved. The production cost of feed enterprises is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of mold removal agents, in particular to a composite mold removal agent and a preparation method and application thereof. Background Art

[0002] Deoxynivalenol (DON) is a type B trichothecenes toxin produced by Fusarium graminearum and Fusarium luteum, which mainly contaminates grains such as wheat, corn, barley and their processing by-products (such as bran and DDGS). The 12,13-epoxy group and 3α,7α,15-trihydroxyl group in its molecular structure are the main toxic sites, which can harm the body through the following mechanisms. 1. Protein synthesis inhibition: DON binds to eukaryotic ribosomes, blocks the activity of peptidyl transferase, and causes cell apoptosis. 2. Intestinal barrier destruction: Activates the p38 MAPK / NF-κB signaling pathway, induces the degradation of tight junction proteins in intestinal epithelial cells, and increases intestinal permeability (transmembrane resistance decreases by 40%). 3. Immunotoxicity: Promotes the secretion of pro-inflammatory factors (IL-6, TNF-α) by monocytes and inhibits lymphocyte proliferation.

[0003] Zearalenone (ZEN), an estrogenic mycotoxin produced by Fusarium spp., is a widespread contaminant of corn, wheat, and other grains. Its stable physical and chemical properties make it difficult to effectively remove via conventional processing. Ingestion by animals can cause reproductive damage, immunosuppression, and carcinogenicity. It is particularly harmful to the reproductive performance of sows, causing false estrus and increased embryonic mortality.

[0004] In feed and feed raw materials, vomitoxin and zearalenone often appear together. The toxins are eaten by animals through feed and are mainly absorbed in the intestines. The vomitoxin first destroys the protective membrane of the animal's intestines, making it less difficult to enter the animal's body, affecting protein synthesis. Due to the destruction of vomitoxin, the defense ability of the animal's intestines decreases, the absorption of zearalenone toxin is accelerated, the estrogen effect is aggravated, the body's immune function is weakened, and the animals are more susceptible to infection by toxins.

[0005] Most commercially available mold removers are composite agents, primarily using montmorillonite as a carrier and compounded with other mold-removing or mold-killing substances. This approach offers the advantage of being relatively inexpensive compared to single enzyme preparations. However, its effectiveness remains relatively low, leaving room for improvement. Furthermore, the product's desorption rate for varying concentrations of vomitoxin and zeaxanthin is not consistently stable within a fixed range, indicating low stability. Ordinary calcium-based montmorillonite has an interlayer spacing of only 1.2-1.4 nm, making it difficult to accommodate ZEN and DON molecules. While activated carbon has a large surface area, it lacks specific binding sites and readily adsorbs nutrients such as vitamins. Summary of the Invention

[0006] In view of the above analysis, the present invention aims to provide a composite mold removal agent and its preparation method and application, so as to solve at least one of the problems of existing mold removal agents, such as low adsorption rate of vomitoxin and zearalenone, low degradation ability, high cost, and unstable performance.

[0007] In a first aspect, the present invention provides a composite mold removal agent, which is made of the following raw materials in terms of mass percentage: calcium montmorillonite: 30-35%, sodium montmorillonite: 32-42.5%, zinc-loaded montmorillonite: 10-15%, yeast cell wall: 10-15%, L2-ascorbic acid: 2-5%, chitosan oligosaccharide: 1-2%, plant lactobacillus: 0.5-1%, and mangiferin: 0.0005-0.002%.

[0008] Furthermore, the composite mildew remover also includes activated carbon: 1 to 3%.

[0009] Furthermore, the calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed and washed with water to obtain the calcium-based montmorillonite.

[0010] Furthermore, the sodium-montmorillonite is prepared by the following method: reacting calcium-montmorillonite with a Na2CO3 solution, extruding, drying, crushing, and sieving to obtain the sodium-montmorillonite.

[0011] Furthermore, the zinc-loaded montmorillonite is prepared by the following method: mixing sodium montmorillonite and ZnCl2 solution, ultrasonically treating, standing, centrifuging, drying, crushing, and sieving to obtain the zinc-loaded montmorillonite.

[0012] In a second aspect, the present invention provides a method for preparing the composite mold removal agent, comprising the following steps:

[0013] (1) Weigh and set aside the raw materials according to their percentages;

[0014] (2) dissolving mangiferin in water, stirring and mixing uniformly, adding calcium montmorillonite, activated carbon, and yeast cell wall in sequence, mixing to obtain a mixture, drying, crushing, and sieving to obtain product A;

[0015] (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water and spraying the mixture on the sodium montmorillonite to obtain product B;

[0016] (4) Mix the product B with the zinc-loaded montmorillonite, add the product A, mix, dry, and crush to obtain the composite mold removal agent.

[0017] Furthermore, in step (2), the solid-liquid ratio of the mixture is 1.5 to 2.

[0018] Furthermore, in step (3), the moisture content of product B is controlled at 10-15%.

[0019] Furthermore, in step (4), the product B and the zinc-loaded montmorillonite are mixed in a double-screw mixer at a rotation speed of 700 to 800 rpm for 10 to 15 minutes.

[0020] Furthermore, in step (4), the drying temperature is 50-60° C., the drying is performed to a moisture content of ≤3%, and the powder is crushed to a particle size of ≤20 μm.

[0021] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0022] (1) The present invention constructs a composite mold removal agent with multi-stage adsorption-catalytic degradation-biological barrier, breaking through the technical bottleneck of traditional adsorbents. It uses the synergistic effect of calcium-based montmorillonite, sodium-based montmorillonite and zinc-loaded montmorillonite to form a multi-stage adsorption network and enhance the spatial barrier effect. The composite mold removal agent of the present invention has a high adsorption rate for vomitoxin (DON) and zearalenone (ZEN), and can effectively remove these two toxins in feed, reducing the loss of feed that cannot be used or needs to be downgraded due to toxin contamination, improving feed utilization, and reducing the production cost of feed companies;

[0023] (2) The outer layer of yeast cell wall is rich in polar groups such as hydroxyl and amino groups, which can bind to vomitoxin through hydrogen bonds, ionic bonds and hydrophobic bonds, thereby adsorbing vomitoxin on the cell wall surface and preventing its further diffusion and absorption. 2+ In a neutral environment, L2-ascorbic acid converts Zn 2+ It is reduced to ZnO, triggering a Fenton-like reaction to generate hydroxyl radicals (-OH), which attack the epoxy groups (C12-C13) of DON, and crack to generate low-toxic DOM-1, thereby reducing toxicity. It inhibits the oxidation of ZEN to generate more toxic α-ZEL, forms an antioxidant microenvironment between the montmorillonite layers, delays the oxidation of functional groups on the surface of activated carbon, chelates with metal ions, and prevents Fe 3+ Mangiferin catalyzes the decomposition of vitamin B1. The multiple phenolic hydroxyl groups within the mangiferin molecule scavenge free radicals and reactive oxygen species (ROS), inhibiting inflammatory signaling pathways (such as NF-κB and MAPK), reducing the release of inflammatory factors, activating the Nrf2 antioxidant signaling pathway, and enhancing cellular antioxidant capacity. While inhibiting pro-inflammatory signaling pathways like NF-κB, this reduces the toxicity of toxins. The amino groups (-NH2) of chitosan oligosaccharides form coordination bonds with the surface hydroxyl groups of calcium montmorillonite, sodium montmorillonite, and zinc-loaded montmorillonite, accelerating redox cycles.

[0024] (3) Dual protection of Lactobacillus plantarum: competitive inhibition, secretion of the antimicrobial peptide Plantaricin A inhibits the proliferation of toxigenic Fusarium; barrier repair, upregulation of the intestinal epithelial cell tight junction protein ZO-1, reducing the efficiency of DON enterohepatic circulation. In addition, the rupture of Lactobacillus plantarum can link L2-ascorbic acid and modified montmorillonite, reducing the mutual adsorption of other components with them. Chitosan oligosaccharide immunomodulation: activation of TLR2 / 4 receptors of DC cells in the intestinal Peyer's patches, promoting IgA secretion, and neutralizing free DON molecules.

[0025] (4) The mold removal agent of the present invention achieves efficient mold removal. Compared with some single high-priced mold removal agents or complex treatment processes, it has a cost advantage and high cost-performance ratio, which helps to improve market competitiveness; extend the shelf life of feed, reduce the company's inventory costs and losses, improve economic benefits; and reduce the cost of drug use.

[0026] In the present invention, the above-mentioned technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of the present invention will be described in the subsequent description, and some advantages will become apparent from the description or be learned through practice of the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the contents particularly pointed out in the description. DETAILED DESCRIPTION

[0027] The preferred embodiments of the present invention are described in detail below. Together with the embodiments of the present invention, they are used to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0028] A specific embodiment of the present invention discloses a composite mold removal agent, which is made of the following raw materials in terms of mass percentage: calcium montmorillonite: 30-35% (for example, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%), sodium montmorillonite: 32-42.5% (32%, 33%, 34%, 35%, 35%), and sodium montmorillonite: 32-42.5%. 36%, 37%, 38%, 39%, 40%, 41%, 42%, 42.5%), zinc-loaded montmorillonite: 10-15% (e.g., 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%), yeast cell wall: 10-15% (e.g., 10%, 10.5%, 11%, 11.5%) %, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%), L2-ascorbic acid: 2-5% (2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%), chitosan oligosaccharide: 1-2% (1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%) , Lactobacillus plantarum: 0.5-1% (for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%), mangiferin: 0.0005-0.002% (for example, 0.0005%, 0.0007%, 0.0009%, 0.0011%, 0.0013%, 0.0015%, 0.0017%, 0.0019%, 0.002%).

[0029] Compared with the existing technology, the present invention constructs a composite mildew removal agent with multi-stage adsorption-catalytic degradation-biological barrier, breaking through the technical bottleneck of traditional adsorbents. It uses the synergistic effect of calcium-based montmorillonite, sodium-based montmorillonite and zinc-loaded montmorillonite to form a multi-stage adsorption network, enhance the spatial barrier effect, and enhance the mildew removal effect.

[0030] The outer layer of yeast cell wall is rich in polar groups such as hydroxyl and amino groups, which can bind to vomitoxin through hydrogen bonds, ionic bonds and hydrophobic bonds, thereby adsorbing vomitoxin on the cell wall surface and preventing its further diffusion and absorption. 2+ In a neutral environment, L2-ascorbic acid converts Zn 2 +It is reduced to ZnO, triggering a Fenton-like reaction to generate hydroxyl radicals (-OH), which attack the epoxy groups (C12-C13) of DON, and crack to generate low-toxic DOM-1, thereby reducing toxicity. It inhibits the oxidation of ZEN to generate more toxic α-ZEL, forms an antioxidant microenvironment between the montmorillonite layers, delays the oxidation of functional groups on the surface of activated carbon, chelates with metal ions, and prevents Fe 3+ Mangiferin catalyzes the decomposition of vitamin B1. The multiple phenolic hydroxyl groups within the mangiferin molecule scavenge free radicals and reactive oxygen species (ROS), inhibiting inflammatory signaling pathways (such as NF-κB and MAPK), reducing the release of inflammatory factors, activating the Nrf2 antioxidant signaling pathway, and enhancing cellular antioxidant capacity. While inhibiting pro-inflammatory signaling pathways like NF-κB, this reduces the toxicity of toxins. The amino groups (-NH2) of chitosan oligosaccharides form coordination bonds with the surface hydroxyl groups of calcium montmorillonite, sodium montmorillonite, and zinc-loaded montmorillonite, accelerating redox cycles.

[0031] Lactobacillus plantarum provides dual protection: competitive inhibition, secreting the antimicrobial peptide Plantaricin A to inhibit the proliferation of toxigenic Fusarium spp.; barrier repair, upregulating the tight junction protein ZO-1 in intestinal epithelial cells and reducing the efficiency of DON enterohepatic circulation. Furthermore, the rupture of Lactobacillus plantarum can bind to L2-ascorbic acid and modified montmorillonite, reducing the adsorption of other components to them. Chitooligosaccharides also provide immune regulation: activating TLR2 / 4 receptors on dendritic cells in Peyer's patches in the intestine, promoting IgA secretion and neutralizing free DON molecules.

[0032] The composite mold removal agent of the present invention has a high adsorption rate for vomitoxin (DON) and zearalenone (ZEN), can effectively remove these two toxins in feed, reduce the loss of feed that cannot be used or needs to be downgraded due to toxin contamination, improve feed utilization, and reduce the production cost of feed companies.

[0033] Specifically, the composite mildew remover further includes activated carbon: 1-3%, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3%.

[0034] It should be noted that activated carbon has a good adsorption effect on gibberellins, but a small amount of activated carbon will cause the de-mold agent or even the de-molded product to turn black, affecting the appearance of the product.

[0035] Specifically, the calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed and washed with water to obtain the calcium-based montmorillonite.

[0036] Preferably, the crushed particle size is ≤5 mm, and the solid-to-liquid ratio during water washing is 0.125 to 0.2, for example, 0.125, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or 0.2. More preferably, a three-stage countercurrent water washing is used to remove impurities such as quartz and feldspar, and the purity of the obtained calcium-montmorillonite is ≥95%.

[0037] Specifically, the sodium montmorillonite is prepared by the following method:

[0038] The sodium montmorillonite is obtained by reacting the calcium montmorillonite with a Na2CO3 solution, extruding, drying, crushing and screening.

[0039] Specifically, the mass ratio of calcium-montmorillonite to Na2CO3 is 23.81-25, for example, 23.81, 23.9, 24.0, 24.1, 24.2, 24.3, 24.4, 24.5, 24.6, 24.7, 24.8, 24.9, 25, and the mass fraction of Na2CO3 solution is 0.5%.

[0040] It should be noted that the stability of the reaction system can be ensured within the above-mentioned ratio. The larger the ratio, the less significant the increase in the sodiumization effect and the higher the cost.

[0041] Specifically, the reaction temperature is 55-60°C, for example, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, and the reaction time is 2-2.5h, for example, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h.

[0042] Specifically, the drying temperature is 90-100°C, for example, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, and the drying time is 3-3.5h, for example, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h.

[0043] It should be noted that if the temperature is too high or the time is too long, some structural water will be lost, which is not conducive to the effectiveness of the modified montmorillonite.

[0044] Specifically, the powder is crushed to a particle size of less than 100 μm and passed through a 200-mesh sieve.

[0045] Specifically, the zinc-loaded montmorillonite is prepared by the following method:

[0046] The sodium montmorillonite and ZnCl2 solution are mixed, ultrasonically treated, allowed to stand, centrifuged, dried, crushed, and sieved to obtain the zinc-loaded montmorillonite.

[0047] Specifically, the mass ratio of sodium montmorillonite to ZnCl2 solution is 0.1 to 0.15, for example, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, and the concentration of ZnCl2 solution is 0.1 mol / L.

[0048] It should be noted that within the above range, the zinc ions of ZnCl2 can fully enter the interlayer. The above range is the inflection point of the zincation mass ratio. The higher the mass ratio, the worse the effect, and the lower the mass ratio, the higher the cost.

[0049] Specifically, the frequency of the ultrasonic treatment is 40-45 kHz, for example, 40 kHz, 41 kHz, 42 kHz, 43 kHz, 44 kHz, 45 kHz, and the time is 25-30 min, for example, 25 min, 26 min, 27 min, 28 min, 29 min, 30 min.

[0050] It should be noted that the frequency within the above range is conducive to the progress of the reaction, and the reaction can be completed within the above time range.

[0051] Specifically, stand for 10 to 12 hours, for example, 10 hours, 10.2 hours, 10.4 hours, 10.6 hours, 10.8 hours, 11.0 hours, 11.2 hours, 11.4 hours, 11.6 hours, 11.8 hours, and 12 hours, at which time the solid is completely settled, and dry at 90 to 100° C. (for example, 90° C., 91° C., 92° C., 93° C., 94° C., 95° C., 96° C., 97° C., 98° C., 99° C., and 100° C.) for 3 hours.

[0052] Specifically, the powder is crushed to a particle size of less than 100 μm and passed through a 200-mesh sieve.

[0053] Specifically, the activated carbon is prepared by the following method:

[0054] The coconut shell activated carbon is acid-washed, water vapor is added, and microwave activation is performed under nitrogen protection to obtain the activated carbon.

[0055] Specifically, the acid is nitric acid with a mass fraction of 9-10% (for example, 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10%).

[0056] Specifically, the pickling temperature is 85-95°C (for example, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C), the time is 1.5h, and the solid-liquid ratio is 0.59-0.6, for example, 0.59, 0.591, 0.592, 0.593, 0.594, 0.595, 0.596, 0.597, 0.598, 0.599, 0.6.

[0057] Specifically, water vapor is introduced into a tubular furnace at a temperature of 800-830°C, for example, 800°C, 805°C, 810°C, 815°C, 820°C, 825°C, and 830°C, and the treatment time is 1-1.2h, for example, 1h, 1.02h, 1.04h, 1.06h, 1.08h, 1.10h, 1.12h, 1.14h, 1.16h, 1.18h, and 1.2h. At this time, the high temperature will activate the activity of the activated carbon.

[0058] Specifically, the power of microwave activation is 800 W, and the time is 10 to 15 min, for example, 10 min, 11 min, 12 min, 13 min, 14 min, and 15 min.

[0059] Another specific embodiment of the present invention discloses a method for preparing the composite mold removal agent, comprising the following steps:

[0060] (1) Weigh and set aside the raw materials according to their percentages;

[0061] (2) dissolving mangiferin in water, stirring and mixing uniformly, adding calcium montmorillonite, activated carbon, and yeast cell wall in sequence, mixing to obtain a mixture, drying, crushing, and sieving to obtain product A;

[0062] (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water and spraying the mixture on the sodium montmorillonite to obtain product B;

[0063] (4) Mix the product B with the zinc-loaded montmorillonite, add the product A, mix, dry, and crush to obtain the composite mold removal agent.

[0064] Specifically, in step (2), the solid-liquid ratio in the mixture is 1.5 to 2, for example, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.

[0065] It should be noted that the above-mentioned solid-liquid ratio is adopted to avoid the increase in subsequent drying costs caused by excessively high moisture content, and to avoid the uneven mixing and increased difficulty caused by excessively low moisture content.

[0066] Specifically, in step (2), the drying temperature is 65-70°C, for example, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, and the product is passed through a 200-mesh sieve.

[0067] It should be noted that the above-mentioned drying temperature is selected to avoid changes in the properties of proteins in the yeast cell walls due to excessively high temperatures.

[0068] Specifically, in step (3), the moisture content in product B is controlled at 10-15%, for example, 10%, 11%, 12%, 13%, 14%, 15%. The above moisture content is conducive to maintaining the activity of Lactobacillus plantarum.

[0069] Specifically, in step (4), the product B and the zinc-loaded montmorillonite are mixed in a double-screw mixer at a speed of 700 to 800 rpm, for example, 700 rpm, 710 rpm, 720 rpm, 730 rpm, 740 rpm, 750 rpm, 760 rpm, 770 rpm, 780 rpm, 790 rpm, 800 rpm, for 10 to 15 min, for example, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min. Within the above range, uniform mixing of the products can be ensured.

[0070] Specifically, in step (4), the product A is added and mixed at a speed of 700 to 800 rpm, for example, 700 rpm, 710 rpm, 720 rpm, 730 rpm, 740 rpm, 750 rpm, 760 rpm, 770 rpm, 780 rpm, 790 rpm, and 800 rpm, and the mixing time is 10 to 20 min, for example, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, and 20 min. Within the above range, uniform mixing of the products can be ensured.

[0071] Specifically, in step (4), the drying temperature is 50-60°C, for example, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, dried to a moisture content ≤3%, and crushed to a particle size ≤20μm. At this temperature, L2-ascorbic acid is not easy to volatilize and decompose, and will not cause the loss of effective ingredients. Moisture ≤3% is conducive to maintaining product stability, and more effective ingredients can be weighed within the unit range to ensure the effect.

[0072] Another specific embodiment of the present invention discloses the use of the above-mentioned composite mold removal agent in feed.

[0073] The following is a further explanation of the technical solution of the present invention in conjunction with specific examples. Among them, all raw materials in the present invention are commercially available products. The following is an explanation of the manufacturers of some raw materials, but it is not limited to this. The manufacturer of yeast cell wall is Qiqihar Longjiang Fufeng Biotechnology Co., Ltd., Fufeng brewer's yeast cell wall; the manufacturer of L2-ascorbic acid is Hebei Shijiao Group, vitamin C powder purity ≥99%; the manufacturer of activated carbon is Changge Tanernuo Catalytic Technology Co., Ltd., Tanernuo activated carbon; the manufacturer of chitosan oligosaccharide is Shandong Jukang Biotechnology Co., Ltd., content 99%, the manufacturer of plant lactobacillus is Guangzhou Haoxiang Fine Chemical Co., Ltd., 20 billion; the manufacturer of mangoside is Guangzhou Xinhuayi Fine Chemical, high-purity product.

[0074] The raw material compositions of the composite mold removal agents of Examples 1-5 are shown in Table 1.

[0075] Table 1

[0076]

[0077]

[0078] Example 1

[0079] A composite mold removal agent, the specific raw material composition is shown in Table 1, wherein the calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed to a particle size of ≤5 mm, washed with water, and the solid-liquid ratio is 0.2 to obtain the calcium-based montmorillonite.

[0080] The sodium montmorillonite is prepared by the following method: calcium montmorillonite and Na2CO3 solution are reacted at 60°C for 2.5 hours, the mass ratio of calcium montmorillonite to Na2CO3 solution is 25, the mass fraction of Na2CO3 solution is 0.5%, extrusion, drying to a particle size of less than 100 μm, and filtration through a 200 mesh sieve to obtain the sodium montmorillonite.

[0081] The zinc-loaded montmorillonite is prepared by the following method: sodium montmorillonite and ZnCl2 solution are mixed, the mass ratio of sodium montmorillonite to ZnCl2 solution is 0.1, the concentration of ZnCl2 solution is 0.1 mol / L, ultrasonic treatment is performed at a frequency of 45 kHz for 25 minutes, standing for 12 hours, centrifuging, drying at 100°C for 3 hours, crushing to a particle size of less than 100 μm, and passing through a 200-mesh sieve to obtain the zinc-loaded montmorillonite.

[0082] The activated carbon is prepared by the following method: coconut shell activated carbon is acid-washed with 10% nitric acid at a temperature of 85° C. for 1.5 hours and a solid-liquid ratio of 0.6, water vapor is introduced into a tubular furnace at a temperature of 800° C. for 1 hour, and microwave activation is performed at a power of 800 W for 15 minutes under nitrogen protection to obtain the activated carbon.

[0083] The preparation method of a composite mold removal agent of this embodiment includes the following steps:

[0084] (1) Weigh and set aside the raw materials according to their percentages;

[0085] (2) dissolving mangiferin in water and stirring to mix uniformly, adding calcium montmorillonite, activated carbon, and yeast cell wall in sequence, and mixing to obtain a mixture, wherein the solid-liquid ratio of the mixture is 1.5, drying at 65° C., crushing, and sieving through a 200-mesh sieve to obtain Product A;

[0086] (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water, and spraying the mixture on the sodium montmorillonite to obtain Product B, wherein the moisture content of Product B is controlled to be 10%;

[0087] (4) The product B and the zinc-loaded montmorillonite were mixed in a double-screw mixer at a speed of 800 rpm for 10 min, and the product A and chitosan oligosaccharide were added and mixed at a speed of 800 rpm for 20 min. The mixture was dried at 50° C. to a moisture content of ≤3%, and crushed to a particle size of ≤20 μm to obtain the composite mold removal agent.

[0088] Example 2

[0089] A composite mold removal agent, the specific raw material composition is shown in Table 1, wherein the calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed to a particle size of ≤5 mm, washed with water, and the solid-liquid ratio is 0.175 to obtain the calcium-based montmorillonite.

[0090] The sodium montmorillonite is prepared by the following method: calcium montmorillonite and Na2CO3 solution are reacted at 55°C for 2h, the mass ratio of calcium montmorillonite to Na2CO3 solution is 23.81, the mass fraction of Na2CO3 solution is 0.5%, extrusion, drying to a particle size of less than 100μm, and passing through a 200-mesh sieve to obtain the sodium montmorillonite.

[0091] The zinc-loaded montmorillonite is prepared by the following method: sodium montmorillonite and ZnCl2 solution are mixed, the mass ratio of sodium montmorillonite to ZnCl2 solution is 0.15, the concentration of ZnCl2 solution is 0.1 mol / L, ultrasonic treatment is performed at a frequency of 40 kHz for 30 minutes, standing for 11 hours, centrifuging, drying at 95°C for 3.5 hours, crushing to a particle size of less than 100 μm, and passing through a 200 mesh sieve to obtain the zinc-loaded montmorillonite.

[0092] The activated carbon is prepared by the following method: coconut shell activated carbon is acid-washed with 9% nitric acid at a temperature of 85° C. for 1.5 hours and a solid-liquid ratio of 0.59, water vapor is introduced into a tubular furnace at a temperature of 830° C. for 1 hour, and microwave activation is performed at a power of 800 W for 10 minutes under nitrogen protection to obtain the activated carbon.

[0093] The preparation method of a composite mold removal agent of this embodiment includes the following steps:

[0094] (1) Weigh and set aside the raw materials according to their percentages;

[0095] (2) dissolving mangiferin in water and stirring to mix uniformly, adding calcium montmorillonite, activated carbon, and yeast cell wall in sequence, and mixing to obtain a mixture, wherein the solid-liquid ratio of the mixture is 3:2, drying at 70° C., crushing, and sieving through a 200-mesh sieve to obtain Product A;

[0096] (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water and spraying the mixture onto the sodium montmorillonite to obtain Product B, wherein the moisture content of Product B is controlled to be 12.5%;

[0097] (4) The product B and the zinc-loaded montmorillonite were mixed in a double-screw mixer at a speed of 700 rpm for 10 min, and the product A was added and mixed at a speed of 700 rpm for 10 min. The mixture was dried at 55° C. to a moisture content of ≤3%, and crushed to a particle size of ≤20 μm to obtain the composite mold removal agent.

[0098] Example 3

[0099] A composite mold removal agent, the specific raw material composition is shown in Table 1, and the preparation method is the same as that in Example 1.

[0100] Example 4

[0101] A composite mold removal agent, the specific raw material composition is shown in Table 1, wherein the calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed to a particle size of ≤5 mm, washed with water, and the solid-liquid ratio is 0.125 to obtain the calcium-based montmorillonite.

[0102] The sodium montmorillonite is prepared by the following method: calcium montmorillonite and Na2CO3 solution are reacted at 55°C for 2.5 hours, the mass ratio of calcium montmorillonite to Na2CO3 solution is 24, the mass fraction of Na2CO3 solution is 0.5%, extrusion, drying at 90°C for 3.25 hours to a particle size of less than 100 μm, and filtration through a 200-mesh sieve to obtain the sodium montmorillonite.

[0103] The zinc-loaded montmorillonite is prepared by the following method: sodium montmorillonite and ZnCl2 solution are mixed, the mass ratio of sodium montmorillonite to ZnCl2 solution is 0.1, the concentration of ZnCl2 solution is 0.1 mol / L, ultrasonic treatment is performed at a frequency of 40 kHz for 25 minutes, standing for 10 hours, centrifuging, drying, crushing to a particle size of less than 100 μm, and passing through a 200 mesh sieve to obtain the zinc-loaded montmorillonite.

[0104] The preparation method of a composite mold removal agent of this embodiment includes the following steps:

[0105] (1) Weigh and set aside the raw materials according to their percentages;

[0106] (2) dissolving mangiferin in water, stirring and mixing uniformly, adding calcium montmorillonite and yeast cell walls in sequence, and mixing to obtain a mixture, wherein the solid-liquid ratio of the mixture is 1.5, drying at 65° C., crushing, and sieving through a 200-mesh sieve to obtain Product A;

[0107] (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water and spraying the mixture on the sodium montmorillonite to obtain Product B, wherein the moisture content of Product B is controlled to be 15%;

[0108] (4) The product B and the zinc-loaded montmorillonite were mixed in a double-screw mixer at a speed of 750 rpm for 15 minutes, and the product A was added and mixed at a speed of 750 rpm for 15 minutes. The mixture was dried at 60° C. to a moisture content of ≤3%, and crushed to a particle size of ≤20 μm to obtain the composite mold removal agent.

[0109] Example 5

[0110] A composite mold removal agent, the specific raw material composition is shown in Table 1, and the preparation method is the same as that in Example 1.

[0111] Comparative Example 1

[0112] The raw materials and preparation method of the composite mildew remover of this comparative example are similar to those of Example 1, except that sodium montmorillonite and zinc-loaded montmorillonite are removed from the raw materials and replaced with calcium montmorillonite of equal mass.

[0113] Comparative Example 2

[0114] The raw materials and preparation method of the composite mildew remover of this comparative example are similar to those of Example 1, except that the calcium-based montmorillonite and zinc-loaded montmorillonite are removed from the raw materials and replaced with sodium-based montmorillonite of equal mass.

[0115] Comparative Example 3

[0116] The raw materials and preparation method of the composite mildew remover of this comparative example are similar to those of Example 1, except that the calcium-based montmorillonite and the sodium-based montmorillonite are removed from the raw materials and replaced with zinc-loaded montmorillonite of the same mass.

[0117] Comparative Example 4

[0118] The raw materials and preparation method of the composite mold removal agent of this comparative example are similar to those of Example 1, except that L2-ascorbic acid is not added to the raw materials and is replaced by sodium montmorillonite of the same mass.

[0119] Comparative Example 5

[0120] The raw materials and preparation method of the composite mold removal agent of this comparative example are similar to those of Example 1, except that Lactobacillus plantarum is not added to the raw materials, but is replaced by sodium montmorillonite of equal mass.

[0121] Comparative Example 6

[0122] The raw materials and preparation method of the composite mold removal agent of this comparative example are similar to those of Example 1, except that mangiferin is not added to the raw materials and is replaced by sodium montmorillonite of the same mass.

[0123] Comparative Example 7

[0124] The raw materials of the composite mold removal agent in this comparative example are the same as those in Example 1. In terms of mass percentage, the composite mold removal agent includes the following raw materials: calcium montmorillonite: 38.4995%, sodium montmorillonite: 30%, zinc-loaded montmorillonite: 9%, yeast cell wall: 20%, L2-ascorbic acid: 1%, chitosan oligosaccharide: 1%, Lactobacillus plantarum: 0.5%, and mangiferin: 0.0005%.

[0125] Comparative Example 8

[0126] The raw materials and preparation method of the composite mildew remover of this comparative example are similar to those of Example 1, except that the calcium montmorillonite, sodium montmorillonite and zinc-loaded montmorillonite in the raw materials are replaced by attapulgite of the same mass.

[0127] Comparative Example 9

[0128] The raw materials and preparation method of the composite mold removal agent of this comparative example are similar to those of Example 1, except that in the preparation method, all the raw materials are added together into a reactor and stirred for 30 minutes to obtain the mold removal agent.

[0129] Test Example 1

[0130] According to GB 13078-2017 "Feed Hygiene Standard", the test method is based on GB / T 30956 and NY / T 2017, and the adsorption rate of the mold removal agents prepared in Examples 1-5 and Comparative Examples 1-9 is tested. The results are shown in Table 2.

[0131] Table 2

[0132]

[0133] As shown in Table 2, the DON adsorption rate of the mold removal agent prepared by the present invention is 89.3-98.7%, the DON resolution rate is 1.5-1.8%, the ZEN adsorption rate is 87-94.7%, the ZEN resolution rate is 0.12-0.24%, the vitamin B1 retention rate is 92.9-97.3%, and the bulk density is 0.50-0.53 g / cm 3 .

[0134] Compared with Example 1, the calcium-montmorillonite combination in Comparative Example 1 cannot achieve the best effect, the adsorption rate of vomitoxin decreases, and the sodium-montmorillonite and zinc-loaded montmorillonite cannot be replaced by the calcium-montmorillonite.

[0135] Comparative Example 2 Compared with Example 1, sodium montmorillonite of the same mass has a better effect in resisting toxins than calcium montmorillonite.

[0136] Comparative Example 3 Compared with Example 1, the zinc-loaded montmorillonite in this experiment could not form a spatial chain structure with the effective ingredient such as L2-ascorbic acid, resulting in the inability of the components to exert a synergistic effect.

[0137] Compared with Example 1, Comparative Example 4 lacks the redox effect of L2-ascorbic acid, and the mold removal effect is weakened.

[0138] Compared with Example 1, Comparative Example 5 lacks plant lactobacillus, and the synergistic effect of the product is weakened, and plant lactobacillus is indispensable.

[0139] Compared with Example 1, in Comparative Example 6, the product mold removal rate decreased after the absence of mangiferin.

[0140] Compared with Example 1, the ratio of each component in Comparative Example 7 is not within the scope of the present application, the synergistic effect of the present application cannot be invented, and the mildew removal effect is worse.

[0141] Compared with Example 1, although the attapulgite clay has similar performance to calcium montmorillonite, sodium montmorillonite and zinc-loaded montmorillonite in Comparative Example 8, it cannot play a synergistic role in the present invention, and the mold removal effect and carrier effect are relatively low.

[0142] Compared with Example 1, in Comparative Example 9, the preparation method of the present invention is not adopted, and the effective component for removing mold reacts with montmorillonite. The preparation method of the present invention can weaken this reaction and retain the removal effect of each component.

[0143] Test Example 2

[0144] The experimental animals, weaned piglets (8-10 kg in weight), were randomly divided into 16 groups, with 7 pigs in each group.

[0145] Experimental groups 1-5 were fed a contaminated diet (a mixture of a basic feed (commercially available product) + 3 ppm DON and + 3 ppm ZEN) + 0.5% of the mold removal agent prepared in Examples 1-5; wherein the basic feed, by mass percentage, included: 17% corn, 25% sorghum, 23.7% soybean cake, 33% bran, and 1.3% bone meal.

[0146] Control groups 1-9: fed with contaminated diet (basic diet + mixture of 3ppm DON and 3ppm ZEN) + 0.5% of the mold removal agent prepared in comparative examples 1-9;

[0147] Control group 10: fed with a basic diet (DON and ZEN were not detected);

[0148] Control group 11: fed with a mixture of basal diet + 3ppm DON and +3ppm ZEN.

[0149] The above experimental and control groups were raised for 28 days, and the growth data of the piglets were observed. The results are shown in Table 3.

[0150] Table 3

[0151]

[0152] As shown in Table 3, after the piglets were fed with the mold removal agent of the present application, the average daily weight gain was 274-300 g, the feed-to-weight ratio was 1.67-1.91, and the diarrhea rate was 0%.

[0153] The composite mold removal agent of the present invention effectively removes mold, reducing the incidence of animal diseases caused by mycotoxin ingestion, alleviating animal mortality, slow growth, and decreased reproductive performance, thereby improving farming efficiency. The average daily weight gain of piglets in test groups 1-5 fed the mold removal agent of the present invention was significantly higher than that in control group 11, and the feed-to-weight ratio was lower, indicating improved animal growth performance and reduced farming costs.

[0154] Compared with experimental group 1, the untreated calcium-montmorillonite combination in control group 1 cannot achieve the best effect. It can alleviate some of the weight loss problems caused by toxins, but cannot make the feed achieve the optimal weight gain. Sodium-montmorillonite and zinc-loaded montmorillonite cannot be replaced by calcium-montmorillonite.

[0155] Compared with Comparative Example 1, the sodium montmorillonite of the same mass is worse than the calcium montmorillonite in resisting toxins, but the experimental results of Control Group 2 are not as good as those of Test Group 1, indicating that when sodium montmorillonite replaces calcium montmorillonite and is mixed with the material, it reacts with the raw materials, damages the effective ingredients for de-mold removal, and causes unsatisfactory weight gain results.

[0156] Compared with the experimental group 1, the zinc-loaded montmorillonite in the control group 3 could not form a spatial chain structure with the effective ingredients such as L-ascorbic acid in this experiment, resulting in the inability of the components to play a synergistic role, and the weight gain value was less than that of the experimental group 1.

[0157] Compared with the experimental group 1, the control group 4 lacked the redox effect of L2-ascorbic acid, the mold removal effect was weakened, and the weight gain value was less than that of the experimental group 1.

[0158] Compared with the experimental group 1, the control group 5 lacked plant lactobacillus, and the probiotics in the animal intestines were not supplemented, so the animals were prone to illness and did not gain weight.

[0159] Compared with the experimental group 1, the weight gain value of the control group 6 was less than that of the experimental group 1 after lacking mangiferin.

[0160] Compared with the test group 1, the weight gain value of the control group 7 is less than that of the test group 1, indicating that the raw materials are not within the scope of the present invention and the effect is poor.

[0161] Compared with the experimental group 1, the mildew removal effect and carrier effect of attapulgite in the control group 8 were not as good as those of montmorillonite.

[0162] Compared with the experimental group 1, the weight gain value of the control group 9 was smaller than that of the experimental group 1.

[0163] The comparison between the control group 10 and the test groups 1-5 shows that the addition of the de-mold agent can achieve the effect of weight gain. This is because the de-mold agent contains nutrients that can accelerate absorption.

[0164] Compared with the experimental groups 1-5, the control group 11 can not only offset the damage of toxins but also achieve the effect of weight gain after adding the de-mold agent.

[0165] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A composite mold removal agent, characterized in that: The composite mold removal agent is made of the following raw materials in percentage by mass: calcium montmorillonite: 30-35%, sodium montmorillonite: 32-42.5%, zinc-loaded montmorillonite: 10-15%, yeast cell wall: 10-15%, L2-ascorbic acid: 2-5%, chitosan oligosaccharide: 1-2%, plant lactobacillus: 0.5-1%, and mangiferin: 0.0005-0.002%.

2. A composite mold removal agent according to claim 1, characterized in that: The composite mildew remover also contains 1-3% activated carbon.

3. The composite mold removal agent according to claim 1 or 2, characterized in that: The calcium-based montmorillonite is prepared by the following method: natural montmorillonite is crushed and washed with water to obtain the calcium-based montmorillonite.

4. The composite mold removal agent according to claim 1 or 2, characterized in that: The sodium montmorillonite is prepared by the following method: reacting calcium montmorillonite with Na2CO3 solution, extruding, drying, crushing and sieving to obtain the sodium montmorillonite.

5. The composite mold removal agent according to claim 1 or 2, characterized in that: The zinc-loaded montmorillonite is prepared by the following method: mixing sodium montmorillonite and ZnCl2 solution, ultrasonically treating, standing, centrifuging, drying, crushing, and sieving to obtain the zinc-loaded montmorillonite.

6. A method for preparing the composite mold removal agent according to any one of claims 1 to 5, characterized in that: The steps include: (1) Weigh and set aside the raw materials according to their percentages; (2) dissolving mangiferin in water, stirring and mixing uniformly, adding calcium montmorillonite, activated carbon, and yeast cell wall in sequence, mixing to obtain a mixture, drying, crushing, and sieving to obtain product A; (3) mixing L2-ascorbic acid and Lactobacillus plantarum in water and spraying the mixture on the sodium montmorillonite to obtain product B; (4) Mix the product B with the zinc-loaded montmorillonite, add the product A, mix, dry, and crush to obtain the composite mold removal agent.

7. The preparation method according to claim 6, characterized in that In step (2), the solid-liquid ratio in the mixture is 1.5-2.

8. The preparation method according to claim 6, characterized in that In step (3), the moisture content of product B is controlled at 10-15%.

9. The preparation method according to claim 6, characterized in that In step (4), the product B and the zinc-loaded montmorillonite are mixed in a double-screw mixer at a rotation speed of 700 to 800 rpm for 10 to 15 minutes.

10. The preparation method according to claim 6, characterized in that In step (4), the drying temperature is 50-60° C., the drying is performed to a moisture content of ≤3%, and the powder is crushed to a particle size of ≤20 μm.

Images