Zearalenone adsorbent and preparation method thereof

Abstract

The invention discloses a zearalenone adsorbent and a preparation method thereof. Relates to the technical field of feed additives and feeds. The raw materials comprise natural kaolin and a composite surfactant, the preparation method and the application are provided, the surface charge of the kaolin is changed through modification treatment of the surfactant, and then the adsorption effect on zearalenone is effectively improved. The preparation method is few in flow, simple in technological process, convenient for large-scale production and relatively stable in product quality.

Description

Technical Field

[0001] The present invention relates to the field of feed additives and feed technology, and more particularly to a zearalenone adsorbent and a preparation method thereof. Background Art

[0002] Mycotoxins are secondary metabolites produced by fungi that are harmful to other organisms. Their widespread presence around the world poses serious health problems to humans and animals. Zearalenone is an estrogenic mycotoxin that is widely found in feed and raw materials. Animals that eat feed contaminated with zearalenone may suffer from oxidative damage, endoplasmic reticulum stress, and cell apoptosis, leading to systemic toxic effects, including reproductive toxicity, hepatotoxicity, and immunotoxicity. Since the structure of zearalenone is similar to that of natural estrogen, it can bind to estrogen receptors and cause endocrine disorders, and its reproductive toxicity has received widespread attention.

[0003] According to investigations, zearalenone contamination in corn is most prominent in corn and its by-products. In addition, the contamination rate in grains such as wheat, barley, sorghum, and rice is also high.

[0004] Adsorbents are widely available, stable in nature, low in cost, and easy to operate. The use of adsorbents to adsorb mycotoxins is still a common method in current production. Aluminosilicates are the most abundant rock-forming minerals. The basic structural units of silicate clay minerals are composed of silicon tetrahedrons and aluminum octahedron sheets, and they also carry oxygen and hydroxyl groups. Their strong adsorption properties make them the first choice for adsorbents of toxic and harmful substances such as mycotoxins and heavy metal ions. However, natural aluminosilicates have good adsorption capacity for highly polar toxin molecules such as aflatoxin, but due to the presence of a large number of hydrophilic inorganic cations on the surface, their adsorption capacity for low-polarity and hydrophobic organic pollutants (such as zearalenone) is relatively low.

[0005] Kaolin is a clay and clay rock mainly composed of kaolinite clay minerals. It belongs to 1:1 type layered silicate. The crystals are mainly composed of silicon-oxygen tetrahedrons and hydrogen-oxygen octahedrons. The silicon-oxygen tetrahedrons are connected in two dimensions by sharing the vertex angles to form a hexagonal grid layer. The unshared apex oxygen of each silicon-oxygen tetrahedron faces one side. The apex oxygen of the silicon-oxygen tetrahedron layer shared by the silicon-oxygen tetrahedron layer and the hydrogen-oxygen octahedron layer forms a 1:1 unit layer. Kaolin has a strong adsorption capacity for polar molecules such as aflatoxin, but a poor adsorption capacity for low-polarity and hydrophobic zearalenone.

[0006] Therefore, whether it is possible to provide a zearalenone adsorbent and a preparation method thereof to overcome the above-mentioned technical deficiencies is an urgent problem to be solved by those skilled in the art. Summary of the invention

[0007] In view of this, the present invention provides a zearalenone adsorbent and a preparation method thereof, wherein natural kaolin is first purified by a water medium flotation method, and then the purified kaolin is made into a slurry and a modified mixture of different types of surfactants is added to produce a material with high affinity for hydrophobic molecules with low polarity. The product is screened, washed, dried, and crushed to obtain an adsorbent, which can effectively adsorb zearalenone with low polarity, thereby increasing its application range as a mycotoxin adsorbent.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] A zearalenone adsorbent, the raw materials of which include natural kaolin and a composite surfactant.

[0010] Preferably, the added amount of the composite surfactant is 20% of the mass of kaolin.

[0011] Preferably, the complex surfactant comprises: a long-chain cationic surfactant, and a short-chain cationic surfactant or a nonionic surfactant.

[0012] Preferably, the mass ratio of the long-chain cationic surfactant to the short-chain cationic surfactant or the nonionic surfactant is 1:1.

[0013] Preferred: long-chain cationic surfactants: cetyltrimethylammonium bromide or cetylpyridinium chloride;

[0014] The short-chain cationic surfactant was tetramethylammonium bromide;

[0015] The nonionic surfactant is polyethylene glycol PEG400.

[0016] The present invention also provides a method for preparing any of the above-mentioned zearalenone adsorbents, comprising the following steps:

[0017] (1) Purifying natural kaolin using an aqueous medium flotation method;

[0018] (2) preparing a modified mixture;

[0019] (3) removing impurities from the modified mixture, centrifuging, washing, drying, crushing and screening to obtain a zearalenone adsorbent.

[0020] Preferably, step (1) specifically comprises: weighing kaolin and adding distilled water to prepare a slurry with a mass concentration of 10%.

[0021] Preferably, step (2) is specifically as follows: adding a composite surfactant of 20% of the mass of kaolin, placing in a constant temperature water bath at 50° C., shaking at a speed of 200 rpm, and reacting for 1 hour.

[0022] Preferably, step (3) is specifically as follows: after removing impurities through a 200-mesh sieve, centrifuging, washing with distilled water, drying at 65° C., and crushing through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

[0023] The present invention also provides the use of any of the above-mentioned zearalenone adsorbents or any of the above-mentioned preparation methods in the preparation of feed, feed additives or mycotoxin removal preparations.

[0024] It can be seen from the above technical scheme that, compared with the prior art, the present invention discloses a zearalenone adsorbent and a preparation method thereof, and the technical effects achieved are:

[0025] 1. The surface charge of kaolin is changed by surfactant modification, thereby effectively improving the adsorption effect of zearalenone.

[0026] 2. The preparation method has few processes, simple process, convenient large-scale production, and relatively stable product quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0028] Figure 1 The accompanying drawing is a process flow chart provided by the present invention.

[0029] Figure 2 The accompanying drawing is a comparison diagram of adsorption rates provided by the present invention. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] The embodiment of the present invention discloses a zearalenone adsorbent and a preparation method thereof. Figure 1 .

[0032] The raw materials not mentioned in the examples are all conventional materials, and the processing steps not mentioned are all conventional processing, which will not be repeated here.

[0033] Example 1

[0034] A method for preparing a zearalenone adsorbent comprises the following steps:

[0035] (1) First, natural kaolin was purified by using a water medium flotation method: 100 g of kaolin was weighed and distilled water was added to prepare a slurry with a mass concentration of 10%;

[0036] (2) Preparation of modified mixture: Add 20% of the mass of kaolin to the composite surfactant mixture (10% hexadecyltrimethylammonium bromide, 10% tetramethylammonium bromide), place in a 50°C constant temperature water bath, shake at a speed of 200 rpm, and react for 1 hour;

[0037] (3) After passing through a 200-mesh sieve to remove impurities, the mixture was centrifuged, washed with distilled water, dried at 65° C., and crushed to pass through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

[0038] Example 2

[0039] A method for preparing a zearalenone adsorbent comprises the following steps:

[0040] (1) First, natural kaolin was purified by using a water medium flotation method: 100 g of kaolin was weighed and distilled water was added to prepare a slurry with a mass concentration of 10%;

[0041] (2) Preparation of modified mixture: Add 20% of the mass of kaolin to the composite surfactant mixture (10% hexadecyltrimethylammonium bromide, 10% polyethylene glycol PEG400), place in a 50°C constant temperature water bath, shake at a speed of 200 rpm, and react for 1 hour;

[0042] (3) After passing through a 200-mesh sieve to remove impurities, the mixture was centrifuged, washed with distilled water, dried at 65° C., and crushed to pass through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

[0043] Example 3

[0044] A method for preparing a zearalenone adsorbent comprises the following steps:

[0045] (1) First, natural kaolin was purified by using a water medium flotation method: 100 g of kaolin was weighed and distilled water was added to prepare a slurry with a mass concentration of 10%;

[0046] (2) Preparation of modified mixture: Add 20% of the mass of kaolin to the composite surfactant mixture (10% cetylpyridinium chloride, 10% tetramethylammonium bromide), place in a 50°C constant temperature water bath, shake at a speed of 200 rpm, and react for 1 hour;

[0047] (3) After passing through a 200-mesh sieve to remove impurities, the mixture was centrifuged, washed with distilled water, dried at 65° C., and crushed to pass through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

[0048] Example 4

[0049] A method for preparing a zearalenone adsorbent comprises the following steps:

[0050] (1) First, natural kaolin was purified by using a water medium flotation method: 100 g of kaolin was weighed and distilled water was added to prepare a slurry with a mass concentration of 10%;

[0051] (2) Preparation of modified mixture: Add 20% of the mass of kaolin to the composite surfactant mixture (10% cetylpyridinium chloride, 10% polyethylene glycol PEG400), place in a 50°C constant temperature water bath, shake at a speed of 200 rpm, and react for 1 h;

[0052] (3) After passing through a 200-mesh sieve to remove impurities, the mixture was centrifuged, washed with distilled water, dried at 65° C., and crushed to pass through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

[0053] Comparative experiment

[0054] Accurately weigh 10 mg of natural kaolin or the adsorbent sample prepared in Examples 1 to 4 into a 50 mL sealed conical flask, add 10 mL of phosphate buffer containing 2 mg / L ZEN, and place the mixture on a rotary shaker at 37°C and 200 rpm for 1 hour. After the adsorption is completed, centrifuge at 10000 r / min for 5 minutes, take 1 mL of the supernatant and add it to 5 mL of chloroform for extraction, blow dry with nitrogen, add 1 mL of water mobile phase to dissolve, and pass through a 0.22 μm organic filter. High performance liquid chromatography (HPLC) is used to detect the ZEN concentration. The experiment is repeated 3 times, and the treatment without adsorbent addition is used as the blank control.

[0055] The adsorption rates of natural kaolin and the adsorbent samples prepared in Examples 1 to 4 of the present invention on zearalenone are shown in Figure 2 The results show that the adsorption rate of zearalenone by the adsorbent (modified kaolin) provided by the present invention is about 4 times that of natural kaolin.

[0056] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0057] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A zearalenone adsorbent, characterized in that: Ingredients include: Natural kaolin and complex surfactants.

2. The zearalenone adsorbent according to claim 1, characterized in that: The added amount of the composite surfactant is 20% of the mass of kaolin.

3. The zearalenone adsorbent according to claim 2, characterized in that: The composite surfactant comprises: a long-chain cationic surfactant, and a short-chain cationic surfactant or a nonionic surfactant.

4. The zearalenone adsorbent according to claim 3, characterized in that: The mass ratio of the long-chain cationic surfactant to the short-chain cationic surfactant or the nonionic surfactant is 1:

1.

5. The zearalenone adsorbent according to claim 4, characterized in that: The long-chain cationic surfactant: hexadecyltrimethylammonium bromide or hexadecylpyridinium chloride; The short-chain cationic surfactant is tetramethylammonium bromide; The nonionic surfactant is polyethylene glycol PEG400.

6. The method for preparing the zearalenone adsorbent according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Purifying natural kaolin using an aqueous medium flotation method; (2) preparing a modified mixture; (3) removing impurities from the modified mixture, centrifuging, washing, drying, crushing and screening to obtain a zearalenone adsorbent.

7. The preparation method according to claim 6, characterized in that: Step (1) specifically comprises: weighing kaolin and adding distilled water to prepare a slurry with a mass concentration of 10%.

8. The preparation method according to claim 7, characterized in that: Step (2) specifically includes: adding a composite surfactant in an amount of 20% of the mass of kaolin, placing the mixture in a constant temperature water bath at 50° C., shaking at a speed of 200 rpm, and reacting for 1 hour.

9. The preparation method according to claim 8, characterized in that: Step (3) is specifically as follows: remove impurities through a 200-mesh sieve, centrifuge, wash with distilled water, dry at 65° C., and grind through a 200-mesh sieve to obtain a highly efficient zearalenone adsorbent.

10. Use of the zearalenone adsorbent according to any one of claims 1 to 5 or the preparation method according to any one of claims 6 to 9 in the preparation of feed, feed additives or mycotoxin removal preparations.

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