Composite mycotoxin adsorbent, preparation method and application thereof

Abstract

The application provides a composite mycotoxin adsorbent and a preparation method and application thereof, and the method comprises the following steps: crushing, grinding, removing impurities and sieving bentonite raw ore and attapulgite raw ore respectively to prepare montmorillonite ore powder and attapulgite ore powder; respectively performing organic modification treatment on the montmorillonite ore powder and the attapulgite ore powder to prepare organic modified montmorillonite ore powder and organic modified attapulgite ore powder; stirring uniformly after proportioning the montmorillonite ore powder, the attapulgite ore powder, the organic modified montmorillonite ore powder and the organic modified attapulgite ore powder according to mass fraction ratio to prepare the composite mycotoxin adsorbent. The application has excellent broad-spectrum adsorption effect on common mycotoxins such as aflatoxin, zearalenone and ochratoxin; the process is simple, the production cost is low, raw materials are rich, the application is green and environment-friendly, and the application is easy to scale production, and has good economic benefit and social benefit.

Description

Technical Field

[0001] This invention relates to the field of adsorbent materials, and more particularly to the technical field of preparing functional adsorbent materials from non-metallic mineral raw materials for adsorbing toxins of different polarities in feed. Specifically, it relates to composite mycotoxin adsorbents, their preparation methods, and applications. Background Technology

[0002] Mycotoxins are secondary metabolites produced by various fungi. Nearly 400 types have been identified to date, exhibiting a wide variety and high toxicity. Common mycotoxins include aflatoxin, zearalenone, vomitoxin, and ochratoxin. These toxins are frequently found in grain crops and mixed feeds. Mycotoxins have toxic effects such as disrupting the intestinal barrier, modulating the immune system, and causing cell death.

[0003] Clay minerals, such as montmorillonite and attapulgite, are a class of non-metallic minerals with large specific surface areas and strong adsorption properties. They are highly hydrophilic, have large specific surface areas, and good adsorption performance, making them widely used for adsorbing heavy metals in soil and toxic and harmful substances in water. They can also be used as good binders, decolorizing and degreasing agents, and feed additives.

[0004] Currently, in the feed industry, mineral adsorbents show poor removal efficiency for systems containing multiple toxins such as aflatoxin, zearalenone, ochratoxin, and vomitoxin. The main drawback is that single adsorbents are not ideal for adsorbing multiple toxins of different polarities in a complex system; in particular, the adsorption rate for weakly polar mycotoxins, such as zearalenone and ochratoxin, is very poor. Currently, no adsorbents have been reported that can remove weakly polar mycotoxins from feed while simultaneously ensuring high-efficiency adsorption of strongly polar toxins.

[0005] Therefore, it is of great significance to study a composite adsorbent that can remove weakly polar mycotoxins from feed while ensuring high efficiency in adsorbing strongly polar toxins. Summary of the Invention

[0006] The purpose of this invention is to address at least one of the aforementioned shortcomings of the prior art. For example, one objective of this invention is to achieve efficient removal of several common mycotoxins in feed; a second objective is to formulate a composite mycotoxin adsorbent using clay minerals modified by wet and dry methods; a third objective is to reduce the production and time costs of mycotoxin adsorption treatment; and a fourth objective is to reduce the damage to animal bodies caused by mycotoxins through the feed route.

[0007] To achieve the above objectives, the present invention provides a method for preparing a composite mycotoxin adsorbent, the method comprising the following steps:

[0008] After crushing, grinding, impurity removal and sieving, the bentonite ore and attapulgite ore are respectively made into montmorillonite powder and attapulgite powder.

[0009] Montmorillonite powder and attapulgite powder were respectively subjected to organic modification treatment to obtain organically modified montmorillonite powder and organically modified attapulgite powder.

[0010] A composite mycotoxin adsorbent was prepared by mixing montmorillonite powder, attapulgite powder, organically modified montmorillonite powder, and organically modified attapulgite powder in proportion to their mass ratio.

[0011] Optionally, the bentonite ore includes one or both of sodium-based and calcium-based bentonite, wherein the montmorillonite content in the bentonite ore is 50-85%, and the impurity minerals include quartz, illite, calcite, and feldspar.

[0012] Alternatively, the attapulgite ore is sedimentary attapulgite clay, wherein the attapulgite content in the attapulgite ore is 70-80%, and the main impurity mineral is montmorillonite, with a small amount of quartz and dolomite.

[0013] Alternatively, the impurity removal involves separating and removing some of the difficult-to-crush impurity minerals from the raw ore during the crushing and grinding process by screening or gravity classification. The impurity minerals include quartz, feldspar, and dolomite.

[0014] Optionally, the particle size of the montmorillonite powder and the attapulgite powder is -100 to -325 mesh, and the purity is 60 to 95% and 75 to 90%, respectively.

[0015] Alternatively, the organic modification treatment may include both dry and wet organic modification methods.

[0016] Alternatively, the wet organic modification method includes the following steps:

[0017] The organic modifier, glacial acetic acid, and water were mixed in a certain proportion and then stirred to obtain a mixed solution of the organic modifier.

[0018] Weigh the montmorillonite powder or the attapulgite powder and place them in a mixed solution of organic modifier. Stir at 100-200 r / min for 20-120 minutes at 40-70°C to obtain organic modified montmorillonite slurry or organic modified attapulgite slurry.

[0019] The organically modified montmorillonite slurry or organically modified attapulgite slurry is filtered, dried, and pulverized to obtain organically modified montmorillonite powder or organically modified attapulgite powder.

[0020] Alternatively, the organic modifier may include one or more of chitosan, cellulose, and chitin.

[0021] Alternatively, the mass ratio of the organic modifier mixture is: 8-12 parts organic modifier, 2-6 parts glacial acetic acid, and 150-240 parts water.

[0022] Alternatively, the stirring process involves adding weighed organic modifier, glacial acetic acid, and drinking water to a stirring tank and stirring to form a viscous solution.

[0023] Optionally, the organic modification treatment involves weighing 90-110 parts by mass of montmorillonite powder or attapulgite powder, and 162-256 parts by mass of the organic modification mixture.

[0024] Alternatively, the dry organic modification method includes the following steps:

[0025] Weigh the montmorillonite powder or the attapulgite powder and stir at 300-500 r / min for 3-5 minutes at 40-60℃ to bring the material temperature to 100-115℃. Continue stirring for 3-5 minutes to obtain the stirred montmorillonite powder or attapulgite powder.

[0026] Weigh the organic modifier and glacial acetic acid according to the formula and add them to the stirred montmorillonite or attapulgite mineral powder. Stir at 100-300 r / min for 2-3 minutes to obtain dry-modified organic montmorillonite or dry-modified organic attapulgite mineral powder respectively.

[0027] The montmorillonite powder or attapulgite powder is weighed in the amount of 90-110 parts by mass, the organic modifier includes one or more of chitosan, cellulose and chitin, and the organic modifier contains 8-12 parts and glacial acetic acid contains 2-6 parts.

[0028] Optionally, the mass ratio of the montmorillonite powder, the organically modified montmorillonite powder, the attapulgite powder, and the organically modified attapulgite powder is (35-50) parts: (20-10) parts: (25-35) parts: (20-5) parts.

[0029] In another aspect, the present invention provides a composite mycotoxin adsorbent, which is prepared by the above method, wherein the particle size of the adsorbent is -100 to -325 mesh and the cation exchange capacity is 10 to 140 mmol / 100g.

[0030] Optionally, the mycotoxin includes one or more of aflatoxin, zearalenone, vomitoxin, and ochratoxin, and the adsorption rates of the mycotoxin adsorbent for aflatoxin, zearalenone, and ochratoxin are 81.0–88.9%, 72.6–83.3%, and 67.9–87.8%, respectively.

[0031] In another aspect, the present invention provides the application of a composite mycotoxin adsorbent in animal feed, the application method comprising: mixing the composite mycotoxin adsorbent with animal feed at a mass ratio of (2-6):100 and mixing them evenly.

[0032] Alternatively, the composite mycotoxin adsorbent has an adsorption rate of 65.0% to 83.0% for mycotoxins in animal feed.

[0033] Compared with the prior art, the beneficial effects of the present invention include at least one of the following:

[0034] 1) The composite mycotoxin adsorbent prepared in this invention uses montmorillonite, attapulgite, etc. as raw materials, and has a large internal and external specific surface area (the theoretical value of montmorillonite is 800m²). 2 / g, the theoretical value of attapulgite is 915m. 2 The properties of / g) give it a strong adsorption capacity for mycotoxins.

[0035] 2) The composite mycotoxin adsorbent prepared by the present invention using montmorillonite and attapulgite can be used for the effective adsorption and removal of mycotoxins in the feed industry, as well as for the protection and antibacterial effects on the gastrointestinal mucosa of livestock.

[0036] 3) The composite clay mineral mycotoxin adsorbent prepared by this invention has excellent broad-spectrum adsorption efficiency for common mycotoxins such as aflatoxin (adsorption rate 88.9%), zearalenone (adsorption rate 82.6%), and ochratoxin (adsorption rate 78.8%).

[0037] 4) The raw and auxiliary materials used in the production of this invention are green and environmentally friendly, have excellent performance, and contain beneficial substances required by animal bodies, thus having good economic and social benefits.

[0038] 5) The modification process of the present invention is easier to industrialize. The clay minerals modified by wet and dry methods are compounded to have excellent adsorption effects on different mycotoxins, and the adsorption effect on weakly polar zearalenone and ochratoxin is particularly significant.

[0039] 6) The preparation method of this invention is simple, has low production cost, abundant raw materials, is green and environmentally friendly, and is easy to scale up. Detailed Implementation

[0040] The composite mycotoxin adsorbent of the present invention, its preparation method, and its application will be described in detail below with reference to exemplary embodiments.

[0041] Exemplary Example 1

[0042] This exemplary embodiment provides a method for preparing a composite mycotoxin adsorbent, the method comprising the following steps:

[0043] S10: Bentonite ore and attapulgite ore are crushed, ground, impurity removed and sieved respectively to produce montmorillonite powder and attapulgite powder.

[0044] In this embodiment, the bentonite ore includes one or both of sodium-based and calcium-based bentonite. The montmorillonite content in the bentonite ore is 50-85%, and the impurity minerals include quartz, illite, calcite, and feldspar. The attapulgite ore is a sedimentary attapulgite clay. The attapulgite content in the attapulgite ore is 70-80%, and the main impurity mineral is montmorillonite, with a small amount of quartz and dolomite. The impurity removal is performed during the crushing and grinding process by separating and removing some of the difficult-to-crush impurity minerals from the ore through screening or gravity classification. The difficult-to-crush impurity minerals include quartz, feldspar, and dolomite.

[0045] In this embodiment, the particle size of the obtained montmorillonite and attapulgite powders is -100 to -325 mesh, for example, 100 mesh, 150 mesh, 180 mesh, 220 mesh, or 300 mesh. If the particle size is too small, it easily adsorbs water from the air, interfering with accurate weighing and thus affecting the adsorption effect; if the particle size is too large, the specific surface area decreases, reducing the adsorption effect. The purity of the montmorillonite and attapulgite powders is 60-95% and 75-90%, respectively. Within this purity range, the powders contain fewer harmful impurities such as quartz and calcite, achieving food-grade quality and ensuring safe consumption by animals.

[0046] The montmorillonite powder contains ≥80% montmorillonite, such as 80%, 88%, 92%, or 98%; its cation exchange capacity can be 80–150 mmol / 100g, such as 92 mmol / 100g, 98 mmol / 100g, 120 mmol / 100g, or 140 mmol / 100g. The attapulgite powder contains ≥50% attapulgite, such as 50%, 58%, 66%, or 75%; its cation exchange capacity can be 5–20 mmol / 100g, such as 5 mmol / 100g, 10 mmol / 100g, 14 mmol / 100g, or 20 mmol / 100g.

[0047] S20: The montmorillonite powder and attapulgite powder are subjected to organic modification treatment to obtain organically modified montmorillonite powder and organically modified attapulgite powder, respectively.

[0048] In this embodiment, the organic modification treatment includes two organic modification methods: dry method and wet method.

[0049] The wet organic modification method includes the following steps:

[0050] S211: Mix the organic modifier, glacial acetic acid and water according to the specified ratio and then stir to obtain a mixed solution of organic modifier.

[0051] In this embodiment, the organic modifier includes one or more of chitosan, cellulose, and chitin. The mass ratio of the organic modifier mixture is 8-12 parts organic modifier: 2-6 parts glacial acetic acid: 150-240 parts drinking water; for example, the mass ratio of organic modifier, glacial acetic acid, and drinking water can be (10:2:150), (10:4:180), (10:6:200), etc. The advantage of this ratio range is that when the amount of glacial acetic acid added is appropriate, the organic modifier is completely dissolved and uniformly dispersed, allowing for a more complete reaction with the organic matter. Too much glacial acetic acid increases production costs, while too little glacial acetic acid results in incomplete dissolution of the organic matter, affecting the contact area with the mineral powder and thus the reaction effect. If the amount of drinking water added is too little, the organic matter is not completely dispersed, affecting the reaction rate; if it is too much, it reduces the concentration of organic modifier and glacial acetic acid, reducing the organication effect.

[0052] S212: Weigh the montmorillonite powder or the attapulgite powder and place them in a mixed solution of organic modifier. Stir at 100-200 r / min for 20-120 minutes at 40-70°C to obtain organically modified montmorillonite slurry or organically modified attapulgite slurry.

[0053] Montmorillonite powder or attapulgite powder is mixed with an organic modification solution in parts by mass, with a ratio of 90-110 parts powder to 162-256 parts organic modification solution. For example, the mass ratio of montmorillonite powder or attapulgite powder to organic modification solution can be (100:180), (100:200), (100:220), or (100:240), etc. Excessive use of the organic modification solution will increase production costs; using an organic modification solution dosage within this range allows for effective intercalation into the montmorillonite. Using an organic modification solution dosage within this range for attapulgite modification effectively occupies adsorption sites on the attapulgite surface, and the dosage of the organic modification solution is also within the effective acceptable range for animals.

[0054] In this embodiment, the organic modification treatment involves adding a weighed amount of montmorillonite or attapulgite powder and an organic modification mixture to a stirred tank for stirring and reaction. The reaction time can be 20–120 min, such as 80 min, 100 min, or 120 min. If the reaction time is too short, the modification will be incomplete, reducing the adhesion rate of organic matter to the mineral surface; if the reaction time is too long, the adsorption sites of montmorillonite or attapulgite will be occupied by excessive modifier, greatly reducing the adsorption performance for mycotoxins. The reaction temperature can be 40℃–70℃, such as 50℃, 60℃, or 70℃; if the reaction temperature is too low, the modification will be incomplete, affecting the binding rate between the organic modifier and the mineral powder; if the reaction temperature is too high, it will damage the structure of the mineral powder and the modifier, affecting the adhesion rate of organic matter to the mineral powder.

[0055] In this embodiment, the rotation speed of the organic modification treatment can be 100-200 r / min, for example, 101 r / min, 130 r / min, 180 r / min or 199 r / min. If the rotation speed is too slow during the organic modification treatment, the modifier and mineral powder cannot be fully combined, resulting in poor modification effect; if the rotation speed is too fast, it will destroy the structure of the organic modifier itself and the crystal structure of the mineral, leading to a worse modification effect.

[0056] S213: Filter, dry and grind organic modified montmorillonite slurry or organic modified attapulgite slurry to obtain organic modified montmorillonite powder or organic modified attapulgite powder.

[0057] The dry organic modification method includes the following steps:

[0058] S221: Weigh the montmorillonite powder or the attapulgite powder and stir at 300-500 r / min for 3-5 minutes at 40-60℃ to bring the material temperature to 100-115℃. Continue stirring for 3-5 minutes to obtain the stirred montmorillonite powder or attapulgite powder.

[0059] In this embodiment, the organic modification treatment involves adding weighed montmorillonite or attapulgite powder, along with an organic modifier and glacial acetic acid, into a high-speed mixer at a time. The reaction time can be 3–5 minutes, such as 3, 4, or 5 minutes. If the reaction time is too short, the modification and coating will be incomplete, reducing the adhesion rate of organic matter to the mineral surface. If the reaction time is too long, the adsorption sites of montmorillonite or attapulgite will be occupied by excessive modifier, significantly reducing the adsorption performance for mycotoxins. The reaction temperature can be 40℃–60℃, such as 40℃, 50℃, or 60℃. If the reaction temperature is too low, the modification and coating will be incomplete, and the adsorption of moisture from the air will cause the mineral powder to clump, affecting the binding rate between the organic modifier and the mineral powder. If the reaction temperature is too high, it will destroy the clumps between the mineral powder and the modifier, affecting the adhesion rate of organic matter to the mineral powder, while also accelerating equipment wear and increasing costs. The organic modification treatment includes drying, grinding, or dispersing the organically modified montmorillonite and attapulgite slurry in the mixing tank.

[0060] S222: Weigh the organic modifier and glacial acetic acid according to the ratio and add them to the stirred montmorillonite or attapulgite mineral powder. Stir at 100-300 r / min for 2-3 minutes to obtain dry-modified organic montmorillonite or dry-modified organic attapulgite mineral powder respectively.

[0061] In this embodiment, the montmorillonite powder and attapulgite powder are weighed separately with an organic modifier and glacial acetic acid in the following mass ratios: 90-110 parts montmorillonite powder, 8-12 parts organic modifier, and 2-6 parts glacial acetic acid. For example, the mass ratio of montmorillonite powder or attapulgite powder, organic modifier, and glacial acetic acid can be (100:10:2), (100:10:4), or (100:10:6), etc. Excessive organic modifier will result in residual modifier in the reaction system, increasing industrial production costs. Using a modifier within this range to modify montmorillonite can effectively coat the montmorillonite; using a modifier within this range to modify attapulgite can effectively coat the attapulgite surface, and the dosage of this organic modifier is also within the range that animals can effectively tolerate.

[0062] In this embodiment, montmorillonite powder and attapulgite powder are stirred with organic modifier and glacial acetic acid at a speed of 100-300 r / min for 2-3 minutes, where the speed can be 150 r / min, 200 r / min, 250 r / min or 300 r / min, etc. If the stirring speed is too slow or the time is too short, the organic modifier cannot be fully dissolved in the glacial acetic acid, and the modifier is prone to clumping; if the stirring speed is too high or the time is too long, processing costs and time costs are wasted.

[0063] S30: A composite mycotoxin adsorbent is prepared by mixing montmorillonite powder, attapulgite powder, organically modified montmorillonite powder and organically modified attapulgite powder in proportion to mass and stirring evenly.

[0064] In this embodiment, montmorillonite powder, organically modified montmorillonite powder, attapulgite powder, and organically modified attapulgite powder are mixed evenly according to the specified mass ratio to obtain a composite clay mineral mycotoxin adsorbent. The mass ratio of montmorillonite powder, organically modified montmorillonite powder, attapulgite powder, and organically modified attapulgite powder can be (35-50) parts: (20-10) parts: (25-35) parts: (20-5) parts. For example, the mass ratio of montmorillonite powder, organically modified montmorillonite powder, attapulgite powder, and organically modified attapulgite powder can be (35:20:25:20), (40:20:30:10), (45:15:35:5), or (50:20:25:5), etc. Adding different proportions of montmorillonite powder, attapulgite powder, organically modified montmorillonite powder, and organically modified attapulgite powder can effectively improve the adsorption performance of mycotoxins of different polarities in feed, and has a broad-spectrum adsorption effect on different mycotoxins. It can effectively remove a variety of mycotoxins, and the adsorption effect on weakly polar zearalenone and ochratoxin is particularly significant.

[0065] Drying can be achieved through air drying or oven drying. Oven drying can be carried out in an oven not exceeding 200℃, with the drying temperature controlled between 50 and 200℃, such as 60℃, 105℃, or 180℃. Below 50℃, organically modified montmorillonite or organically modified attapulgite powder is difficult to dry, resulting in a low dehydration rate. Above 200℃, organically modified montmorillonite or organically modified attapulgite powder expands and undergoes slight carbonization due to heating, making it more susceptible to combining with moisture in the air, thus affecting the removal efficiency of mycotoxins by the organically modified montmorillonite and organically modified attapulgite adsorbents.

[0066] This invention selects natural montmorillonite and attapulgite, which are crushed, ground, sieved to remove impurities, and then organically modified. The different products are compounded in a certain proportion for adsorbing aflatoxin, zearalenone, ochratoxin, and vomitoxin. It exhibits good broad-spectrum adsorption properties, maintaining the adsorption effect on polar toxins while greatly improving the adsorption effect on weakly polar zearalenone and ochratoxin.

[0067] Exemplary Example 2

[0068] This exemplary embodiment provides a composite mycotoxin adsorbent, which is prepared by the method described in Exemplary Embodiment 1. The particle size of the composite mycotoxin adsorbent can be -100 to -325 mesh, for example, 100 mesh, 120 mesh, 200 mesh, 280 mesh, or 300 mesh; the cation exchange capacity is 40 to 110 mmol / 100g, for example, 40 mmol / 100g, 60 mmol / 100g, 70 mmol / 100g, 90 mmol / 100g, or 110 mmol / 100g; the coating rate is 70 to 85%, for example, 70%, 80%, or 85%. If the adsorbent particle size is too large, the specific surface area is small, the dispersion is insufficient, and the adsorption sites are few, reducing the coating rate of the organic solvent and affecting the adsorption effect of montmorillonite / attapulgite on mycotoxins; if the adsorbent particle size is too small, it wastes grinding processing costs.

[0069] In this embodiment, the mycotoxin adsorbent can adsorb two or more of the following mycotoxins: aflatoxin, zearalenone, vomitoxin, and ochratoxin. Specifically, the adsorbent exhibits an adsorption rate of 81.0–88.9% for aflatoxin, such as 81.6%, 83.1%, and 87.0%; an adsorption rate of 72.6–83.0% for zearalenone, such as 73.1%, 74.8%, and 80.5%; and an adsorption rate of 67.9–78.8% for ochratoxin, such as 67.9%, 70.5%, and 78.6%.

[0070] Exemplary Example 3

[0071] This exemplary embodiment provides the application of a complex mycotoxin adsorbent in animal feed. The complex mycotoxin adsorbent is the same as that described in Exemplary Embodiment 2. The application method includes: mixing the complex mycotoxin adsorbent with animal feed at a mass ratio of (2-6):100 and mixing them evenly; for example, the mass ratio of the complex mycotoxin adsorbent to animal feed can be 2:100, 4:100, 6:100, etc. Adding a small amount of the complex mycotoxin adsorbent is used to remove different mycotoxins from the feed. The effective components in the adsorbent can maximize the adsorption of different types of mycotoxins in the feed. The adsorption rate of the complex mycotoxin adsorbent for mycotoxins in animal feed can be 65.0-83.0%, for example, 66.0%, 71.5%, 75.5%, 82.0%, etc.

[0072] To better understand the exemplary embodiments of the present invention described above, further explanation is provided below with reference to specific examples.

[0073] Example 1

[0074] 1) The bentonite ore and attapulgite ore are crushed, ground, impurity removed and screened respectively to obtain montmorillonite powder and attapulgite powder respectively.

[0075] 2) Chitosan, glacial acetic acid, and drinking water were mixed in a mass ratio of 10:2:180 and added to a mixing tank for stirring and dissolution to obtain a chitosan solution. Montmorillonite powder or attapulgite powder and chitosan solution (CTS) were then added to the mixing tank in a mass ratio of 100:192 for stirring and organic modification reaction for 120 min. The reaction product was dried and pulverized to obtain wet-process chitosan (CTS) type organically modified montmorillonite powder or organically modified attapulgite powder, respectively. Another batch of 100 parts of montmorillonite powder or attapulgite powder was added to a high-speed mixer, and the powder temperature was raised to 100–115℃ and stirred continuously for 3 min. After removing the adsorbed water from the powder, 10 parts of chitosan (CTS) and 2 parts of glacial acetic acid were added at once, and the mixture was stirred for 2 min to obtain dry-process modified organic montmorillonite powder and organically modified attapulgite powder.

[0076] Replace chitosan (CTS) in step 2) with cellulose (MCC), and use the same two organic modification steps and process ratios to obtain cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0077] Then, replace the cellulose (MCC) in step 2) with chitin (CS), and use the same two organic modification steps and process ratios to obtain chitin (CS) type modified organic montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0078] 3) The montmorillonite powder and attapulgite powder obtained in step 1) are mixed with the organic modified montmorillonite powder and organic modified attapulgite powder obtained in step 2) in a mass ratio of 35:20:25:20 and homogenized to obtain a composite mycotoxin adsorbent.

[0079] The composite mycotoxin adsorbent containing chitosan (CTS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CTS-MA1; the composite mycotoxin adsorbent containing cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as MCC-MA1; and the composite mycotoxin adsorbent containing chitin (CS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CS-MA1.

[0080] 4) The compound mycotoxin adsorbent is mixed with pig feed containing mycotoxins such as aflatoxin (AFB1), zearalenone (ZEN) and ochratoxin (OTA) at a mass ratio of 2:100 and homogenized before being fed.

[0081] Example 2

[0082] 1) The bentonite ore and attapulgite ore are crushed, ground, impurity removed and screened respectively to obtain montmorillonite powder and attapulgite powder respectively.

[0083] 2) Chitosan, glacial acetic acid, and drinking water were mixed in a mass ratio of 10:4:200 and added to a mixing tank for stirring and dissolution to obtain a chitosan solution. Montmorillonite powder or attapulgite powder and chitosan solution (CTS) were added to a mixing tank in a mass ratio of 100:214 for stirring and organic modification reaction for 120 min. The reaction product was dried and pulverized to obtain chitosan (CTS) type organic modified montmorillonite powder or organic modified attapulgite powder, respectively. Another batch of 100 parts of montmorillonite powder or attapulgite powder was added to a high-speed mixer, and the powder temperature was raised to 100-115℃ and stirred for 3 min. After removing the adsorbed water from the powder, 10 parts of chitosan (CTS) and 4 parts of glacial acetic acid were added sequentially and stirred for 2 min to obtain dry-modified organic modified montmorillonite powder and organic modified attapulgite powder.

[0084] Replace chitosan (CTS) in step 2) with cellulose (MCC), and use the same two organic modification steps and process ratios to obtain cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0085] Then, replace the cellulose (MCC) in step 2) with chitin (CS), and use the same two organic modification steps and process ratios to obtain chitin (CS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0086] 3) The montmorillonite powder and attapulgite powder obtained in step 1) are mixed with the organic modified montmorillonite powder and organic modified attapulgite powder obtained in step 2) in a mass ratio of 40:20:30:10 and homogenized to obtain a composite mycotoxin adsorbent.

[0087] The composite mycotoxin adsorbent containing chitosan (CTS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CTS-MA2; the composite mycotoxin adsorbent containing cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as MCC-MA2; and the composite mycotoxin adsorbent containing chitin (CS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CS-MA2.

[0088] 4) The compound mycotoxin adsorbent is mixed with pig feed containing mycotoxins such as aflatoxin (AFB1), zearalenone (ZEN) and ochratoxin (OTA) at a mass ratio of 4:100 and homogenized before being fed.

[0089] Example 3

[0090] 1) The bentonite ore and attapulgite ore are crushed, ground, impurity removed and screened respectively to obtain montmorillonite powder and attapulgite powder respectively.

[0091] 2) Chitosan, glacial acetic acid, and drinking water were mixed in a mass ratio of 10:6:220 and added to a mixing tank for stirring and dissolution to obtain a chitosan solution. Montmorillonite powder, attapulgite powder, and chitosan solution (CTS) were mixed in a mass ratio of 100:236 and added to a mixing tank for stirring and organic modification reaction for 120 min. The reaction product was dried and pulverized to obtain chitosan (CTS) type organic modified montmorillonite powder or organic modified attapulgite powder, respectively. Another batch of 100 parts of montmorillonite powder or attapulgite powder was added to a high-speed mixer, and the powder temperature was raised to 100-115℃ and stirred continuously for 3 min. After removing the adsorbed water from the powder, 10 parts of chitosan (CTS) and 6 parts of glacial acetic acid were added at once and stirred for 2 min to obtain dry-modified organic modified montmorillonite powder and organic modified attapulgite powder.

[0092] Replace chitosan (CTS) in step 2) with cellulose (MCC), and use the same two organic modification steps and process ratios to obtain cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0093] Then, replace the cellulose (MCC) in step 2) with chitin (CS), and use the same two organic modification steps and process ratios to obtain chitin (CS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder.

[0094] 3) The montmorillonite powder and attapulgite powder obtained in step 1) are mixed with the organic modified montmorillonite powder and organic modified attapulgite powder obtained in step 2) in a mass ratio of 45:15:35:5 and homogenized to obtain a composite mycotoxin adsorbent.

[0095] The composite mycotoxin adsorbent containing chitosan (CTS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CTS-MA3; the composite mycotoxin adsorbent containing cellulose (MCC) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as MCC-MA3; and the composite mycotoxin adsorbent containing chitin (CS) type organic modified montmorillonite mineral powder and organic modified attapulgite mineral powder is designated as CS-MA3.

[0096] 4) The compound mycotoxin adsorbent is mixed with pig feed containing mycotoxins such as aflatoxin (AFB1), zearalenone (ZEN), vomitoxin (DON) and ochratoxin (OTA) at a mass ratio of 6:100 and homogenized before being fed.

[0097] Test case

[0098] Adsorption tests were conducted on the composite mycotoxin adsorbents in Examples 1-3.

[0099] Take 10 mg of different composite mycotoxin adsorbents from Examples 1-3 and place them into 50 mL centrifuge tubes containing aflatoxin (AFB1), zearalenone (ZEN), and ochratoxin (OTA), respectively. Add a buffer solution with a pH of 3. The initial concentration of each mycotoxin in the buffer solution of the centrifuge tube is 1 mg / L. Shake and adsorb at 37°C for 1 h to ensure that the composite mycotoxin adsorbent is fully mixed with the toxin.

[0100] The supernatant was filtered through a 0.22 μm filter and then detected using a dual ternary-two-dimensional liquid chromatography system (with a fluorescence detector). The adsorption rate was calculated using the following formula: Q = (C0 - C...) t ) / C0×100%; where Q is the adsorption rate, %; C0 and C t The values ​​represent the concentrations of mycotoxins before and after adsorption, in mg / L. Table 1 shows the test results for the adsorption rates of different mycotoxins by various composite mycotoxin adsorbents.

[0101] Table 1. Adsorption rates (%) of a series of adsorbents for mycotoxins

[0102]

[0103] As shown in Table 1, the various composite mycotoxin adsorbents used exhibit significant adsorption effects on aflatoxin (AFB1), zearalenone (ZEN), and ochratoxin (OTA). Furthermore, the adsorption rate of the adsorbent material increases with the increase in the amount of organic modifier added. However, the adsorption effects vary for mycotoxins of different polarities. The adsorption of polar aflatoxin is optimal, while the adsorption of weakly polar or non-polar mycotoxins, such as zearalenone (ZEN) and ochratoxin (OTA), also shows good adsorption effects.

[0104] Therefore, the composite mycotoxin adsorbent obtained by the present invention after dry and wet treatment can effectively remove mycotoxins from feed. It has excellent broad-spectrum adsorption effect on common mycotoxins and significant adsorption effect on weakly polar zearalenone and ochratoxin. It can be used as a highly efficient, green and environmentally friendly mycotoxin remover in feed.

[0105] The composite mycotoxin adsorbent prepared in this invention can be used to adsorb different types of mycotoxins, and can also synergistically adsorb multiple mycotoxins, such as aflatoxin, zearalenone, ochratoxin, vomitoxin, and T-2 toxin. The composite mycotoxin adsorbent prepared in this invention can also be used to protect the gastrointestinal mucosa of animals and provide the necessary nutrients to the animal body.

[0106] Although the present invention has been described above in conjunction with exemplary embodiments, it should be clear to those skilled in the art that various modifications can be made to the above embodiments without departing from the spirit and scope of the claims.

Claims

1. A method for preparing a composite mycotoxin adsorbent, characterized in that, The preparation method includes the following steps: Bentonite ore and attapulgite ore are crushed, ground, impurity removed and sieved respectively to produce montmorillonite powder and attapulgite powder. Montmorillonite powder and attapulgite powder were respectively subjected to organic modification treatment to obtain organically modified montmorillonite powder and organically modified attapulgite powder. A composite mycotoxin adsorbent was prepared by mixing montmorillonite powder, attapulgite powder, organically modified montmorillonite powder and organically modified attapulgite powder in proportion to mass and stirring evenly. The organic modification treatment includes two methods: dry method and wet method. The dry organic modification method includes the following steps: Weigh the montmorillonite powder or the attapulgite powder and stir at 300-500 r / min for 3-5 minutes at 40-60℃ to bring the material temperature to 100℃-115℃. Continue stirring for 3-5 minutes to obtain the stirred montmorillonite powder or attapulgite powder. Weigh the dry organic modifier and glacial acetic acid according to the ratio and add them to the stirred montmorillonite or attapulgite mineral powder. Stir at 100~300r / min for 2~3 minutes to obtain organic modified montmorillonite or organic modified attapulgite mineral powder respectively. The montmorillonite powder or attapulgite powder is weighed in the amount of 90-110 parts, the dry organic modifier includes one or more of chitosan, cellulose, and chitin, and the dry organic modifier contains 8-12 parts and glacial acetic acid contains 2-6 parts. The wet organic modification method includes the following steps: The wet organic modifier, glacial acetic acid, and water were mixed in a certain proportion and then stirred to obtain a mixed solution of organic modifier. Weigh the montmorillonite powder or the attapulgite powder and place them in a mixed solution of organic modifier. Stir at 100-200 r / min for 20-120 minutes at 40-70°C to carry out organic modification treatment, and obtain organic modified montmorillonite slurry or organic modified attapulgite slurry respectively. The organically modified montmorillonite slurry or organically modified attapulgite slurry is filtered, dried and pulverized to obtain organically modified montmorillonite powder or organically modified attapulgite powder. The wet organic modifier includes one or more of chitosan, cellulose, and chitin. The mass ratio of the montmorillonite powder, the organically modified montmorillonite powder, the attapulgite powder, and the organically modified attapulgite powder is (35~50) parts: (20~10) parts: (25~35) parts: (20~5) parts; The mycotoxins include one or more of aflatoxin, zearalenone, and ochratoxin, and the adsorption rates of the mycotoxin adsorbent for aflatoxin, zearalenone, and ochratoxin are 81.0~88.9%, 72.6~83.3%, and 67.9~87.8%, respectively.

2. The preparation method of the composite mycotoxin adsorbent according to claim 1, characterized in that, The bentonite ore includes one or two of sodium-based and calcium-based bentonite, and the montmorillonite content in the bentonite ore is 50-85%, with impurity minerals including quartz, illite, calcite, and feldspar. The attapulgite ore is a sedimentary attapulgite clay, with an attapulgite content of 70-80% and impurity minerals mainly consisting of montmorillonite, containing small amounts of quartz and dolomite.

3. The preparation method of the composite mycotoxin adsorbent according to claim 1, characterized in that, The impurity removal process involves separating and removing some of the difficult-to-crush impurity minerals from the raw ore during the crushing and grinding process by screening or gravity classification. The impurity minerals include quartz, feldspar and dolomite. The montmorillonite powder and the attapulgite powder have purities of 60-95% and 75-90%, respectively.

4. The preparation method of the composite mycotoxin adsorbent according to claim 1, characterized in that, The mass ratio of the organic modifier mixture solution is 8-12 parts organic modifier, 2-6 parts glacial acetic acid, and 150-240 parts drinking water; The stirring process involves adding weighed organic modifier, glacial acetic acid, and drinking water to a stirring tank and stirring to form a viscous solution. The organic modification treatment involves 90-110 parts of montmorillonite or attapulgite powder and 162-256 parts of organic modification mixed solution.

5. A composite mycotoxin adsorbent, characterized in that, The mycotoxin adsorbent is prepared by the method according to any one of claims 1-4, and the cation exchange capacity of the adsorbent is 10-140 mmol / 100g.

6. The application of the composite mycotoxin adsorbent according to claim 5 in animal feed, characterized in that, The application method includes: mixing the compound mycotoxin adsorbent with animal feed at a mass ratio of (2-6):100 and mixing them evenly; The composite mycotoxin adsorbent has an adsorption rate of 65.0-83.0% for mycotoxins in animal feed.

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