CN117582946A - High-adsorption rate montmorillonite adsorbent of zearalenone and preparation and application methods thereof - Google Patents

Abstract

The invention provides a zearalenone high adsorption rate montmorillonite adsorbent and a preparation and application method thereof. The method includes: crushing, grinding and removing impurities from bentonite raw ore to obtain montmorillonite powder; After weighing the proportion of powder, amino acid modifier and water, they are placed in the reactor in sequence and stirred to carry out the modification reaction to obtain an amino acid modified montmorillonite suspension; the suspension is dehydrated, dried, ground and sieved ≤ -125 mesh to obtain the zearalenone high adsorption rate montmorillonite adsorbent. The adsorbent of the present invention is a typical organically modified inorganic non-metallic mineral material, has rich raw materials, is green and environmentally friendly and has no toxic and harmful effects; the preparation process is simple, the production cost is low, and it is easy to produce on a large scale.

Description

Zearalenone high adsorption rate montmorillonite adsorbent and its preparation and application method

Technical field

The present invention relates to the technical field of mycotoxin removal, and in particular to the field of amino acid modified montmorillonite mycotoxin adsorption materials. Specifically, it relates to a zearalenone high adsorption rate montmorillonite adsorbent and its preparation and application method.

Background technique

Zearalenone is a highly toxic, teratogenic and highly carcinogenic toxic metabolite produced by fungi or molds under suitable conditions. It is widely present in grain and animal feed. Zearalenone is extremely harmful to both humans and animals. When it enters the body of animals with feed, it will cause immune suppression and change the relative quality of organs, making animals susceptible to diseases and increasing mortality.

The adsorption method is a safe and efficient method for removing zearalenone. Currently, the most studied mycotoxin removal material is montmorillonite, but the adsorption capacity of unmodified natural montmorillonite for zearalenone is relatively low. Low and unstable after adsorption. Selecting a suitable modifier to modify montmorillonite can improve its adsorption effect and adsorption stability for zearalenone. Currently, long-chain alkyl quaternary ammonium salts are commonly used to intercalate and modify montmorillonite to improve the adsorption rate. However, the products modified by the quaternary ammonium salts are slightly toxic and are not suitable for large-scale or long-term use as feed additives. Defects that endanger animal health.

Therefore, the preparation of organically modified montmorillonite adsorbents that have a high adsorption rate for zearalenone, will not produce adverse effects, and can be used for a long time or in large quantities is very critical for industries such as animal husbandry and breeding.

Contents of the invention

The purpose of the present invention is to solve at least one of the above-mentioned deficiencies in the prior art. For example, one object of the present invention is to provide a modified montmorillonite adsorbent with a high adsorption rate of zearalenone with a simple preparation process, and a second object of the present invention is to provide a modified montmorillonite mycotoxin adsorbent. application.

In order to achieve the above object, on the one hand, the present invention provides a method for preparing a montmorillonite adsorbent with a high adsorption rate of zearalenone, which method includes the following steps:

Crush, grind and remove impurities from bentonite raw ore to obtain montmorillonite powder;

After weighing the montmorillonite powder, amino acid modifier and water, they are placed in the reactor in sequence and stirred to perform the modification reaction to obtain an amino acid modified montmorillonite suspension;

The suspension is dehydrated, dried, ground and sieved to ≤-125 mesh to obtain the zearalenone high adsorption rate montmorillonite adsorbent.

Optionally, the bentonite raw ore includes one or more of sodium bentonite, calcium bentonite and transitional bentonite;

The impurity removal is to separate and remove difficult-to-break minerals through sieving during the crushing and grinding process, through selective crushing-sieving method or gravity separation method. The difficult-to-break minerals include quartz, feldspar and mica. one or more;

The main phases in the montmorillonite powder include one or more of sodium montmorillonite, calcium montmorillonite and transitional montmorillonite, with a particle size of -200 to -325 mesh;

The percentage content of montmorillonite in the montmorillonite powder is ≥80%.

Alternatively, the ratio includes a mass ratio of the amino acid modifier to the montmorillonite powder of 1: (4-14), and a mass ratio of the montmorillonite powder to water of 1: (20～200).

Alternatively, the modification reaction is to stir the montmorillonite powder, amino acid modifier and water evenly, and then stir and react under constant temperature conditions for 1 to 2 hours;

After the stirring reaction, the mixture is poured into a aging pool for aging so that the modification can be fully carried out. After the reaction, an amino acid modified montmorillonite suspension is obtained.

Alternatively, the constant temperature reaction temperature is 20-60°C, and the aging time is 10-24 hours.

Alternatively, the amino acid modifier includes one or more hydrophobic amino acids among L-tryptophan, L-leucine, glycine and valine.

Optionally, the suspension does not need to be washed after dehydration, and the dehydrated amino acid-containing solution can be recycled;

The drying method includes natural drying or drying using drying equipment with a temperature not exceeding 80°C. The drying equipment includes a spray dryer, and the moisture content of the dried product is between 10 and 15%;

Another aspect of the present invention provides a zearalenone high adsorption rate montmorillonite adsorbent, which is prepared by the above method;

The adsorption rate of zearalenone by the adsorbent is 75% to 92%.

Another aspect of the present invention provides the application of a zearalenone high adsorption rate montmorillonite adsorbent in feed. The adsorbent is the adsorbent prepared by the above method. The adsorbent is used in the addition of feed. The ratio is 1: (200～500).

Optionally, applying the adsorbent to feed includes the following steps:

Weigh the zearalenone high adsorption rate montmorillonite adsorbent and feed;

Mix the adsorbent and feed weighed according to the proportion evenly.

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

1) The montmorillonite mycotoxin adsorbent prepared by the present invention is a typical organically modified inorganic non-metallic mineral material. It is rich in raw materials, green and environmentally friendly, and has no toxic or harmful effects.

2) The selected modifier of the present invention has no toxic or harmful side effects, and is a beneficial amino acid, which can promote the growth of animals.

3) The preparation method of the adsorbent of the present invention has simple process, low production cost, and is easy to be produced on a large scale.

4) The adsorbent of the present invention has an adsorption rate of zearalenone as high as 92.4%, and also has an adsorption rate of 40.2% and 30.4% for aflatoxin B ₁ and DON.

5) The modified montmorillonite of the present invention has hydrophobic properties and generates hydrophobic interactions with weakly polar zearalenone, thereby having a high adsorption rate.

Detailed ways

In the following, the zearalenone high adsorption rate montmorillonite adsorbent of the present invention and its preparation and application methods will be described in detail with reference to exemplary embodiments.

Exemplary embodiment 1

This exemplary embodiment 1 provides a method for preparing a zearalenone high adsorption rate montmorillonite adsorbent, which method includes the following steps:

S01: Crush, grind and remove impurities from bentonite raw ore to obtain montmorillonite powder.

In this embodiment, the raw bentonite ore includes one or more of sodium bentonite, calcium bentonite and transition bentonite. The impurity removal is to separate and remove difficult-to-break minerals through selective crushing-sieving or gravity separation during the crushing and grinding process, wherein the difficult-to-break minerals include one of quartz, feldspar and mica or Various.

Among them, the selective crushing-screening method takes advantage of the fact that difficult-to-break minerals are difficult to be pulverized during the ore crushing process, making their particle size larger than the target mineral, so that they can be removed through screening. The gravity separation method uses montmorillonite and quartz. , feldspar and mica are sorted and removed according to their different densities.

The main phases in the obtained montmorillonite powder include one or more of sodium montmorillonite, calcium montmorillonite and transitional montmorillonite, and the percentage of montmorillonite in the montmorillonite powder is Content ≥80%, such as 80%, 90% or 95%, etc., particle size is -200~-325 mesh, such as -210 mesh, -255 mesh, -300 mesh or -320 mesh, etc.;

The purpose of selecting the above-mentioned montmorillonite percentage is because montmorillonite is the main phase for adsorption. The montmorillonite content ≥80% can increase the adsorption capacity of mycotoxins; the montmorillonite particle size range is selected from -200 to -325 mesh is a finer particle size montmorillonite mineral powder with a larger specific surface area, providing more adsorption sites for the adsorption of mycotoxins.

S02: After weighing the montmorillonite powder, amino acid modifier and water, they are placed in the reactor in sequence and stirred to perform the modification reaction to obtain an amino acid modified montmorillonite suspension.

In this embodiment, the amino acid modifier and the montmorillonite powder are mixed in a mass ratio of 1: (4-14), such as 1:5, 1:7, 1:10, 1:11 or 1: 13 etc. At the same time, the mass ratio of montmorillonite powder to water is 1: (20~200), such as 1:21, 1:40, 1:80, 1:100, 1:120 or 1:199, etc. The purpose of selecting the mass ratio of the above-mentioned modifier and montmorillonite powder is to allow the modifier to fully modify the montmorillonite without leaving too much modifier to avoid waste. At the same time, the purpose of selecting the mass ratio of the above montmorillonite powder to water is to enable the montmorillonite powder to be fully dispersed in the water, and at the same time, it will not cause an excessive contact area, resulting in a gap between the modifier and the montmorillonite powder. Uneven mixing.

The amino acid modifier includes one or more hydrophobic amino acids among L-tryptophan, L-leucine, glycine and valine. Because amino acids are non-toxic and harmless, and selecting hydrophobic amino acids to modify montmorillonite can make montmorillonite hydrophobic, thereby improving the adsorption rate of the hydrophobic mycotoxin zearalenone.

In this embodiment, the modification reaction is to stir the montmorillonite powder, the amino acid modifier and water evenly, and then stir and react under constant temperature conditions of 20 to 60°C for 1 to 2 hours. For example, the temperature can be 21°C, 30°C, 45°C or 59°C, etc., and the stirring reaction time can be 1.1h, 1.2h or 1.9h, etc.

In the modification reaction, if the temperature is too low, it will be difficult for the modifier to enter the interlayer of montmorillonite. If the reaction temperature is too high, the structure of the modifier will be destroyed. Within the above reaction temperature range, the modifier can enter the interlayer and the structure of the modifier will be destroyed. will not be destroyed; the purpose of selecting the above reaction time range is to fully disperse the montmorillonite and modifier.

After the reaction is stirred, the mixture is poured into an aging pool for aging so that the modification can be fully carried out. After the reaction, an amino acid modified montmorillonite suspension is obtained. Among them, the aging time can be 10 to 24 hours, such as 11 hours, 15 hours or 23 hours, etc., so that the modifier can enter the montmorillonite layer evenly and fully.

S03: Dehydrate, dry, grind and sieve the suspension to ≤-125 mesh to obtain the zearalenone high adsorption rate montmorillonite adsorbent.

In this embodiment, the suspension formed after the reaction of montmorillonite powder and amino acid modifier is completed does not need to be washed after dehydration. At the same time, the solution containing amino acids after dehydration can be recycled; the drying method includes natural drying or the use temperature does not exceed 80 The drying equipment includes a spray dryer, and the moisture content of the dried product can be 10 to 15%, such as 11%, 13%, or 14%.

In this embodiment, the purpose of selecting the above-mentioned drying temperature is to ensure that the sample is dried without destroying the structure of the modifier; the purpose of selecting the above-mentioned moisture content is to dry the surface moisture of the modified product without destroying the montmorillonite. The structural water and adsorbed water in it.

Exemplary embodiment 2

This exemplary embodiment provides a montmorillonite adsorbent with high adsorption rate for zearalenone. The adsorbent is prepared by the method described in Exemplary Embodiment 1. Its adsorption rate for zearalenone is It can be 75% to 92%, such as 76%, 80%, 89%, 90% or 92%, etc. Compared with the adsorption rate of unmodified montmorillonite, the adsorption rate is increased by 26% to 42%.

Exemplary embodiment 3

This exemplary embodiment provides the application of a zearalenone high adsorption rate montmorillonite adsorbent in feed. The adsorbent is the adsorbent described in Exemplary Embodiment 2. The adsorbent application The addition ratio in the feed is 1: (200~500). For example, the ratio of the adsorbent to the feed can be 1:210, 1:300 or 1:490, etc. The adsorption rate can be guaranteed within the above additive dosage range. At the same time, there will be no excess adsorbent and maximum utilization can be achieved.

In this embodiment, the application of the adsorbent in the feed includes: weighing the zearalenone high adsorption rate montmorillonite adsorbent and the feed; weighing the adsorbent and the feed according to the proportion well mixed.

In order to better understand the above-described exemplary embodiments of the present invention, they will be further described below with reference to specific examples.

Example 1

Crush and grind the bentonite raw ores obtained from different mining areas with a grinder to remove impurities such as quartz and grind them respectively until they pass through a 200-mesh sieve to obtain three types of montmorillonite powders, numbered 1-Mt, 2-Mt, 3-Mt.

Example 2

Mix the montmorillonite powder obtained in Example 1 with the modifier L-tryptophan and water in a mass percentage of 4:1:40 respectively. After reacting for 2 hours at a constant temperature of 40°C, dehydrate for 10 hours and then Dry in an oven at 60°C for 10 hours. After drying, grind the sample through a 200-mesh sieve to obtain the montmorillonite mycotoxin adsorbent modified by the montmorillonite from different mining areas and the modifier tryptophan and water, which are numbered 4-Mt. , 5-Mt, 6-Mt.

Example 3

Mix the montmorillonite powder obtained in Example 1 with the modifier L-tryptophan and water at a mass percentage of 4.5:1:80 respectively. After reacting for 1.5 hours under constant temperature conditions of 45°C, dehydrate for 10 hours. Dry in an oven at 60°C for 12 hours. After drying, grind the sample through a 200-mesh sieve to obtain montmorillonite mycotoxin adsorbents modified by montmorillonite from different mining areas and modifiers tryptophan and water. They are numbered 7- The moisture content of Mt, 8-Mt, and 9-Mt is less than 10%.

Example 4

Mix the montmorillonite powder obtained in Example 1 with the modifier L-tryptophan and water at a mass percentage of 5:1:100 respectively. After reacting for 2 hours under constant temperature conditions of 45°C, dehydrate after aging for 12 hours. Dry in an oven at 60°C for 10 hours. After drying, grind the sample through a 200-mesh sieve to obtain the montmorillonite mycotoxin adsorbent modified by the montmorillonite from different mining areas and the modifier tryptophan and water, which are numbered 10-Mt. , 11-Mt, 12-Mt.

Example 5

Mix the montmorillonite powder obtained in Example 1 with the modifier L-tryptophan and water at a mass percentage of 5:1:120 respectively. After reacting for 1.5 hours at a constant temperature of 50°C, dehydrate for 10 hours. Dry in an oven at 60°C for 10 hours. After drying, grind the sample through a 200-mesh sieve to obtain montmorillonite mycotoxin adsorbents modified by montmorillonite from different mining areas and modifiers tryptophan and water. They are numbered 13- Mt, 14-Mt, 15-Mt.

Example 6

Mix the montmorillonite powder obtained in Example 1 with the modifier L-tryptophan and water at a mass percentage of 5.5:1:200 respectively. After reacting for 2 hours at a constant temperature of 50°C, dehydrate after aging for 12 hours. Dry in an oven at 60°C for 10 hours. After drying, grind the sample through a 200-mesh sieve to obtain the montmorillonite mycotoxin adsorbent modified by the montmorillonite from different mining areas and the modifier tryptophan and water, which are numbered 16-Mt. , 17-Mt, 18-Mt.

Test example

An adsorption test was performed on the montmorillonite mycotoxin adsorbent obtained in Examples 1-6 above.

Add 5 mL of zearalenone (ZEN) with a concentration of 2 mg/L in a phosphate buffer with a pH of 3.5 into the centrifuge tubes, and add 5 mg of the montmorillonite mycotoxin adsorbent obtained in the above example into each centrifuge tube. Adsorb with constant temperature shaking for 2 hours at 37°C.

Take the supernatant, pass it through a 0.22 μm filter, and detect it with a high-performance liquid chromatograph (HPLC). The adsorption rate is calculated according to the following formula:

Q＝(C ₀ -C _t )/C ₀ ×100%

Among them, Q is the adsorption rate, %; C ₀ and C _t are the concentrations of mycotoxins before and after adsorption, respectively, mg/L. The adsorption results are shown in Table 1 below.

Table 1 Adsorption rate of zearalenone by adsorbent

It can be seen from the data in Table 1 that the adsorption rate of zearalenone by montmorillonite powder is 47% to 55%. The adsorption rate of tryptophan-modified montmorillonite mycotoxin adsorbent to zearalenone is 75% to 92%, indicating that the adsorption rate of tryptophan-modified montmorillonite mycotoxin agent to zearalenone is obtained. An obvious improvement.

Although the present invention has been described above in conjunction with exemplary embodiments, it will be apparent to those of ordinary skill in the art that various modifications can be made to the above-described embodiments without departing from the spirit and scope of the claims.

Claims (10)

1. A method for preparing a zearalenone high adsorption rate montmorillonite adsorbent, characterized in that the method includes the following steps: Crush, grind and remove impurities from bentonite raw ore to obtain montmorillonite powder; After weighing the montmorillonite powder, amino acid modifier and water, they are placed in the reactor in sequence and stirred to perform the modification reaction to obtain an amino acid modified montmorillonite suspension; The suspension is dehydrated, dried, ground and sieved to ≤-125 mesh to obtain the zearalenone high adsorption rate montmorillonite adsorbent. 2. The preparation method according to claim 1, characterized in that the bentonite raw ore includes one or more of sodium bentonite, calcium bentonite and transitional bentonite; The impurity removal is to separate and remove difficult-to-break minerals through selective crushing and screening or gravity separation during the crushing and grinding process. The difficult-to-break minerals include one of quartz, feldspar and mica or variety; The main phases in the montmorillonite powder include one or more of sodium montmorillonite, calcium montmorillonite and transitional montmorillonite, with a particle size of -200 to -325 mesh; The percentage content of montmorillonite in the montmorillonite powder is ≥80%. 3. The preparation method according to claim 1, characterized in that the proportion includes a mass ratio of the amino acid modifier and the montmorillonite powder of 1: (4-14), and the montmorillonite powder is 1: (4-14). The mass ratio of destoned powder to water is 1: (20~200). 4. The preparation method according to claim 1, characterized in that the modification reaction is to stir the montmorillonite powder, the amino acid modifier and water evenly, and then stir and react under constant temperature conditions for 1 to 2 hours; After the stirring reaction, the mixture is poured into a aging pool for aging so that the modification can be fully carried out. After the reaction, an amino acid modified montmorillonite suspension is obtained. 5. The preparation method according to claim 4, characterized in that the constant temperature reaction temperature is 20-60°C, and the aging time is 10-24 hours. 6. The preparation method according to claim 1, wherein the amino acid modifier includes one or more hydrophobic amino acids among L-tryptophan, L-leucine, glycine and valine. . 7. The preparation method according to claim 1, wherein the suspension does not need to be washed after dehydration, and the dehydrated amino acid-containing solution can be recycled; The drying method includes natural drying or drying using drying equipment with a temperature not exceeding 80°C. The drying equipment includes a spray dryer. The moisture content of the dried product is between 10 and 15%. 8. A zearalenone high adsorption rate montmorillonite adsorbent, characterized in that the adsorbent is obtained by the preparation method described in any one of claims 1-7; The adsorption rate of zearalenone by the adsorbent is 75% to 92%. 9. The application of a zearalenone high adsorption rate montmorillonite adsorbent in feed, characterized in that the adsorbent is the adsorbent of claim 8, and the adsorbent is used in feed. The addition ratio is 1: (200～500). 10. The application according to claim 9, characterized in that applying the adsorbent to feed includes the following steps: Weigh the zearalenone high adsorption rate montmorillonite adsorbent and feed; Mix the adsorbent and feed weighed according to the proportion evenly.