Modified zeolite compound feed additive and preparation method thereof

Abstract

The invention belongs to the technical field of feed additives, and discloses a modified zeolite compound feed additive and a preparation method thereof. The modified zeolite compound feed additive comprises the following raw materials in parts by weight: 66-75 parts of modified zeolite, 11-15 parts of an antibacterial agent, 10-18 parts of vitamins, 4-9 parts of amino acids and 0.05-0.2 part of ethoxyquin. When the modified zeolite compound feed additive is added into feed, the residual quantity of various heavy metals in animal products can be effectively reduced, oxidative damage caused by the heavy metals can be relieved, the stress reaction of the heavy metals in organisms can be balanced, and meanwhile, the quality of the animal products can be improved by utilizing the antibacterial and antioxidant effects of the additive.

Description

Technical Field

[0001] The present invention belongs to the technical field of feed additives, and particularly relates to a modified zeolite composite feed additive and a preparation method thereof. Background Art

[0002] In recent years, the rapid development of China's economy and the improvement of people's living standards have greatly promoted the growth of the livestock and poultry breeding industry. As the cornerstone of animal food safety, the safety of feed not only concerns animal health and breeding efficiency, but also directly affects human health. Among them, heavy metal pollution has become one of the key factors affecting animal food safety, mainly involving lead (Pb), cadmium (Cd), mercury (Hg) and the metalloid arsenic (As).

[0003] Heavy metals mainly enter plants and animals through the biological chain via media such as the atmosphere, water bodies, and soil, resulting in the pollution of plant and animal feed raw materials. After being ingested by animals, these heavy metals enter the body through the digestive system and accumulate in various tissues and organs, and may eventually remain in animal foods such as milk and muscle, posing a long-term hazard to animal and human health. In addition, heavy metals have an accumulation effect in organisms and can cause an in vivo heavy metal stress response, which can lead to loss of appetite, growth retardation, and decreased immunity in animals. After long-term accumulation, they even have reproductive disorders, carcinogenic, teratogenic, and mutagenic effects. In recent years, although the continuous strengthening of feed hygiene standards and relevant laws can reduce the heavy metal content in feed, it is still difficult to avoid the long-term accumulation of low-dose heavy metals in animals. Therefore, effective means must be adopted to reduce the heavy metal residues in animal products to ensure food safety.

[0004] Zeolite has good biocompatibility and has various uses in cosmetics, water purification, and biomedicine. Zeolite itself has adsorption ability and can effectively remove pollutants and harmful substances in water, purifying water quality. However, its pore size is relatively small, which hinders the entry of larger molecules into the zeolite pore channels for adsorption, especially the adsorption effect of high-valent heavy metals is poor; at the same time, it may also over-adsorb beneficial components such as vitamins in feed, resulting in nutrient loss.

[0005] Based on the above background, there is an urgent need for a composite feed additive to reduce the heavy metal residues in animal products. Summary of the Invention

[0006] The first object of the present invention is to provide a modified zeolite composite feed additive, which can reduce the heavy metal content in animal products, slow down the heavy metal stress response in animals, and at the same time improve the antibacterial and antioxidant abilities of animals, promote animal growth, and thus improve the quality of animal products.

[0007] The second object of the present invention is to provide a preparation method of a modified zeolite composite feed additive, which is simple and feasible and can be used for industrial production.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] A modified zeolite composite feed additive, comprising the following raw materials in parts by weight: 66-75 parts of modified zeolite, 11-15 parts of antibacterial agent, 10-18 parts of vitamin, 4-9 parts of amino acid, 0.05-0.2 parts of ethoxyquinoline;

[0010] The preparation method of the modified zeolite comprises the following steps:

[0011] (1) Placing zeolite in a hydrothermal aging furnace for hydrothermal treatment to obtain mesoporous zeolite;

[0012] (2) Adding a metal salt solution to the mesoporous zeolite and stirring evenly to obtain a mixture; the mixture is allowed to stand, dried, calcined, ground and sieved to obtain metal ion-modified mesoporous zeolite;

[0013] (3) Adding glutaraldehyde to the aqueous solution of fucoidan oligosaccharide and stirring for 3-5 h, then adding the metal ion-modified mesoporous zeolite and adjusting the pH of the solution, and then carrying out a crosslinking reaction; after the reaction is completed, the product is collected and washed to neutrality to obtain the modified zeolite.

[0014] Further, in step (1), the heating rate of the hydrothermal aging furnace is 5-8 °C / min; the temperature of the hydrothermal treatment is 350-550 °C, and the time is 2-5 h.

[0015] Further, in step (2), the metal salt is composed of ferric nitrate, zinc nitrate and copper nitrate with a molar ratio of 1:(0.8-1.2):(0.1-0.5); the concentration of cations in the metal salt solution is 0.8-1 mol / L; the liquid-solid ratio of the metal salt solution to the metal ion-modified mesoporous zeolite is (1-2) L / kg.

[0016] Further, in step (2), the standing time is 3-4 h; the drying temperature is 120-130 °C, and the time is 1-2 h; the calcination temperature is 550-600 °C, and the time is 4-5 h.

[0017] Further, in step (3), the concentration of the aqueous solution of fucoidan oligosaccharide is 1-5 w / v%; the mass ratio of the metal ion-modified mesoporous zeolite to fucoidan oligosaccharide and glutaraldehyde is (100-160):(5-10):1; the pH is 7.0-9.0; the crosslinking reaction time is 2-6 h.

[0018] Further, the preparation method of the antibacterial agent comprises the following steps:

[0019] (a) Heat glyceryl myristate to melting, then add acetic acid and an emulsifier and mix. After ultrasonic treatment, an emulsion is obtained.

[0020] (b) At 68 - 75 °C, add water to the emulsion and perform shearing and homogenization, then freeze-dry to obtain an antibacterial agent.

[0021] Furthermore, in step (a), the mass ratio of glyceryl myristate to acetic acid is 10:(1 - 2); the emulsifier is Tween 80; the addition amount of the emulsifier is 1 - 3 wt% of glyceryl myristate.

[0022] Furthermore, in step (b), the mass ratio of the emulsion to water is (3:7)-(7:12); the shearing speed is 10000 - 13000 rmp and the time is 1 - 3 min; the homogenization pressure is 400 - 600 bar and the number of times is 3 - 5 times.

[0023] Furthermore, the vitamin is composed of vitamin A, vitamin B1, vitamin B6, and vitamin E with a mass ratio of (3 - 5):(1 - 2):(1 - 3):(5 - 8), and the amino acid is composed of lysine, methionine, and valine with a mass ratio of (2 - 4):(1 - 3):(1 - 2).

[0024] For the preparation method of the above-mentioned modified zeolite composite feed additive, according to the said weight parts, uniformly mix the modified zeolite with the antibacterial agent, vitamin, amino acid, and ethoxyquinoline to obtain a composite feed additive.

[0025] Compared with the prior art, the beneficial effects of the present invention mainly lie in:

[0026] 1. The present invention provides a modified zeolite composite feed additive, which contains raw materials such as modified zeolite and antibacterial agent. Adding the said modified zeolite composite feed additive to the feed can effectively reduce the residue amounts of various heavy metals in animal products, balance the stress response of heavy metals in organisms, and relieve the oxidative damage caused by heavy metals. At the same time, by utilizing the antibacterial and antioxidant properties of the modified zeolite composite feed additive, the quality of animal products is improved.

[0027] 2. The modified zeolite of the present invention simultaneously loads metal ions (iron, zinc, copper) and fucoidan oligosaccharides. The introduction of metal ions can not only adsorb heavy metals through ion exchange, but also enhance the adsorption effect through mechanisms such as surface functional group complexation and precipitation. Moreover, the iron, zinc, and copper elements released by ion exchange are beneficial to the growth, development, and health of animals. The negative charges on the surfaces of the hydroxyl, carboxyl, and sulfonate groups in fucoidan oligosaccharides can adsorb positively charged heavy metal ions through electrostatic attraction and form stable complexes with heavy metal ions, significantly improving the adsorption capacity of zeolite. The antibacterial agent of the present invention forms a sustained-release effect by coating an antibacterial organic acid in glycerol monomyristate with good biocompatibility and antibacterial activity to protect the animal digestive tract. The combination of the two can replace antibiotics as a bacteriostatic agent with low irritation, high safety, and high efficiency. In addition, glycerol monomyristate also has antioxidant capacity, further balancing the stress response of organisms to heavy metal ions and improving the meat quality of animals.

[0028] 3. The present invention also provides a preparation method of the above-mentioned modified zeolite composite feed additive. The raw materials used in this preparation method are cheap, and the preparation process is simple, which is beneficial to large-scale production. Detailed implementation mode

[0029] The following content is a further detailed description of the present invention in combination with specific preferred implementation modes. It cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or substitutions can be made, which should all be regarded as belonging to the protection scope of the present invention. The specific conditions not specified in the examples are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are all conventional products obtained through commercial channels without special instructions.

[0030] (I) Examples

[0031] Example 1

[0032] Example 1 provides a modified zeolite composite feed additive, which is composed of the following raw materials in parts by weight: 70 parts of modified zeolite, 13 parts of antibacterial agent, 14 parts of vitamins, 5 parts of amino acids, and 0.1 part of ethoxyquinoline; the vitamins are composed of vitamin A, vitamin B1, vitamin B6, and vitamin E in a mass ratio of 4:2:2:6; the amino acids are composed of lysine, methionine, and valine in a mass ratio of 3:2:2.

[0033] The preparation method of the above-mentioned modified zeolite is as follows:

[0034] (1) Place the zeolite in a corundum crucible, and then place the corundum crucible in a hydrothermal aging furnace. Set the water gasification furnace to rise to 400 °C at a rate of 5 °C / min, and at the same time, set the hydrothermal aging furnace to rise to 400 °C at a rate of 7 °C / min. After the water gasification furnace reaches 400 °C and stabilizes, set the water vapor weight hourly space velocity to 2 h -1 , and introduce high-temperature water vapor into the hydrothermal aging furnace for hydrothermal reaction. After reacting for 3 h, mesoporous zeolite is obtained;

[0035] (2) Prepare a metal salt solution with a cation concentration of 0.9 mol / L by mixing iron nitrate, zinc nitrate, and copper nitrate in a molar ratio of 1:1:0.3. Drop the metal salt solution into the mesoporous zeolite and stir well to obtain a mixture, where the liquid-solid ratio of the metal salt solution to the mesoporous zeolite is 1.5 L / kg; let the mixture stand for 4 h, and then dry it at 120 °C for 2 h; calcine the dried mixture at 550 °C for 4 h, grind it through a 200-mesh sieve to obtain metal ion-modified mesoporous zeolite;

[0036] (3) Prepare an aqueous solution of alginate oligosaccharide with a concentration of 3 w / v% for standby; then, according to the mass ratio of metal ion-modified mesoporous zeolite to alginate oligosaccharide and glutaraldehyde of 140:8:1, add the cross-linking agent glutaraldehyde to the aqueous solution of alginate oligosaccharide, stir for 4 h, and then add the metal ion-modified mesoporous zeolite to obtain a mixture; while stirring, add a sodium bicarbonate solution with a concentration of 0.5 mol / L to the mixture to adjust the pH to 8.0, and carry out a cross-linking reaction for 4 h; after the reaction is completed, collect the product and wash it with distilled water until neutral to obtain modified zeolite.

[0037] The preparation method of the above bacteriostatic agent is as follows;

[0038] (a) Heat monoglyceryl myristate to melting, then add acetic acid and Tween 80 and mix, and perform ultrasonic treatment to obtain an emulsion; the mass ratio of monoglyceryl myristate to acetic acid is 10:1.5, and the addition amount of Tween 80 is 2 wt% of monoglyceryl myristate;

[0039] (b) Add water at 70 °C to the above emulsion and stir well. At 70 °C, shear it at 12000 rmp for 2 minutes, where the mass ratio of water to the emulsion is 2:1; then perform high-pressure homogenization at 500 bar for 4 times, and finally carry out freeze-drying to obtain the bacteriostatic agent.

[0040] This example also provides a preparation method of the above modified zeolite composite feed additive, including the following steps:

[0041] According to the above weight parts, uniformly mix the modified zeolite with the antibacterial agent, vitamins, amino acids, and ethoxyquinoline to obtain the modified zeolite composite feed additive.

[0042] Example 2

[0043] Example 2 provides a modified zeolite composite feed additive, which is composed of the following raw materials in parts by weight: 66 parts of modified zeolite, 11 parts of antibacterial agent, 10 parts of vitamins, 4 parts of amino acids, and 0.05 part of ethoxyquinoline; the vitamins are composed of vitamin A, vitamin B1, vitamin B6, and vitamin E with a mass ratio of 3:1:1:5; the amino acids are composed of lysine, methionine, and valine with a mass ratio of 2:1:1.

[0044] The preparation method of the above-mentioned modified zeolite is as follows;

[0045] (1) Put the zeolite into a corundum crucible, and then place the corundum crucible in a hydrothermal aging furnace. Set the water gasification furnace to rise to 350 °C at a rate of 7 °C / min, and at the same time, set the hydrothermal aging furnace to rise to 550 °C at a rate of 5 °C / min. After the water gasification furnace rises to 350 °C and stabilizes, set the water vapor weight hourly space velocity to 2 h -1 , and introduce high-temperature water vapor into the hydrothermal aging furnace for hydrothermal reaction. After reacting for 3 h, mesoporous zeolite is obtained;

[0046] (2) Prepare a metal salt solution with a cation concentration of 0.8 mol / L by mixing ferric nitrate, zinc nitrate, and copper nitrate according to a molar ratio of 1:0.8:0.1. Drop the metal salt solution into the mesoporous zeolite and stir well to obtain a mixture, where the liquid-solid ratio of the metal salt solution to the mesoporous zeolite is 1 L / kg; let the mixture stand for 3 h, and then dry it at 130 °C for 1 h; calcine the dried mixture at 600 °C for 4 h, grind it through a 200-mesh sieve to obtain metal ion-modified mesoporous zeolite;

[0047] (3) Prepare a 1 w / v% aqueous solution of fucoidan for standby; then, according to the mass ratio of metal ion-modified mesoporous zeolite to fucoidan and glutaraldehyde of 100:5:1, add the cross-linking agent glutaraldehyde to the aqueous solution of fucoidan, stir for 3 h, and then add the metal ion-modified mesoporous zeolite to obtain a mixture; add a 0.5 mol / L sodium bicarbonate solution to the mixture under stirring to adjust the pH to 7.0, and carry out a cross-linking reaction at room temperature for 2 h; after the reaction is completed, collect the product and wash it with distilled water until neutral to obtain the modified zeolite.

[0048] The preparation method of the above-mentioned bacteriostatic agent is as follows;

[0049] (a) Heat monoglyceryl myristate to melting, then add acetic acid and Tween 80 and mix, and perform ultrasonic treatment to obtain an emulsion; the mass ratio of monoglyceryl myristate to acetic acid is 10:1, and the addition amount of Tween 80 is 1 wt% of monoglyceryl myristate;

[0050] (b) Add water at 68 °C to the above emulsion and stir well. At 68 °C, shear for 1 minute at 10,000 rmp, where the mass ratio of water to the emulsion is 3:7; then perform high-pressure homogenization at 400 bar three times, and finally conduct freeze-drying to obtain the bacteriostatic agent.

[0051] This example also provides a preparation method of the above-mentioned modified zeolite composite feed additive, including the following steps:

[0052] According to the above weight parts, uniformly mix the modified zeolite with the antibacterial agent, vitamins, amino acids, and ethoxyquinoline to obtain the modified zeolite composite feed additive.

[0053] Example 3

[0054] Example 3 provides a modified zeolite composite feed additive, which is composed of the following raw materials in parts by weight: 75 parts of modified zeolite, 15 parts of antibacterial agent, 18 parts of vitamins, 9 parts of amino acids, and 0.2 parts of ethoxyquinoline; the vitamins are composed of vitamin A, vitamin B1, vitamin B6, and vitamin E with a mass ratio of 5:2:3:8; the amino acids are composed of lysine, methionine, and valine with a mass ratio of 4:3:2.

[0055] The preparation method of the above-mentioned modified zeolite is as follows;

[0056] (1) Put the zeolite into a corundum crucible and then put the corundum crucible into a hydrothermal aging furnace. The heating parameters in the hydrothermal aging furnace are to rise to 550 °C at a rate of 8 °C / min, while the hydrothermal aging furnace rises to 350 °C at a rate of 5 °C / min. After the water gasification furnace rises to 550 °C and stabilizes, set the weight hourly space velocity of water vapor to 3 h -1 , and introduce high-temperature water vapor into the hydrothermal aging furnace for hydrothermal reaction. After reacting for 5 h, mesoporous zeolite is obtained;

[0057] (2) Prepare a metal salt solution with a cation concentration of 1 mol / L by mixing ferric nitrate, zinc nitrate, and copper nitrate according to a molar ratio of 1:1.2:0.5. Drop the metal salt solution into the mesoporous zeolite and stir well to obtain a mixture, where the liquid-solid ratio of the metal salt solution to the mesoporous zeolite is 2 L / kg; let the mixture stand for 4 h, and then dry it at 130 °C for 2 h; calcine the dried mixture at 600 °C for 5 h, grind it through a 200-mesh sieve to obtain the metal ion-modified mesoporous zeolite;

[0058] (3) Prepare an aqueous solution of fucoidan oligosaccharide with a concentration of 5 w / v% for standby; then, according to the mass ratio of metal ion-modified mesoporous zeolite to fucoidan oligosaccharide and glutaraldehyde being 160:10:1, add the cross-linking agent glutaraldehyde to the aqueous solution of fucoidan oligosaccharide, stir for 5 h, and then add the metal ion-modified mesoporous zeolite to obtain a mixture; while stirring, add a sodium bicarbonate solution with a concentration of 0.5 mol / L to the mixture to adjust the pH to 9.0, and carry out a cross-linking reaction at room temperature for 6 h; after the reaction is completed, collect the product and wash it with distilled water until neutral to obtain the modified zeolite.

[0059] The preparation method of the above bacteriostatic agent is as follows;

[0060] (a) Heat monoglyceryl myristate to melting, then add acetic acid and Tween 80 and mix, and perform ultrasonic treatment to obtain an emulsion; the mass ratio of monoglyceryl myristate to acetic acid is 5:1, and the addition amount of Tween 80 is 3 wt% of monoglyceryl myristate

[0061] (b) Add water at 75 °C to the above emulsion and stir well. At 75 °C, shear for 3 minutes at 13000 rmp, where the mass ratio of water to the emulsion is 7:12; then perform high-pressure homogenization at 600 bar for 5 times, and finally carry out freeze-drying to obtain the bacteriostatic agent.

[0062] This example also provides a preparation method of the above modified zeolite composite feed additive, including the following steps:

[0063] According to the said weight parts, uniformly mix the modified zeolite with the antibacterial agent, vitamins, amino acids, and ethoxyquinoline to obtain the composite feed additive.

[0064] (II) Comparative examples

[0065] Comparative example 1

[0066] Comparative example 1 is basically the same as the content of example 1, and the difference is that: the modified zeolite in example 1 is replaced with zeolite.

[0067] Comparative example 2

[0068] Comparative example 2 is basically the same as the content of example 1, and the difference is that: the modified zeolite in example 1 is replaced with a mixture of metal ion-modified mesoporous zeolite and fucoidan oligosaccharide; the usage amounts of metal ion-modified mesoporous zeolite and fucoidan oligosaccharide are the same as those in example 1.

[0069] Comparative example 3

[0070] Comparative example 3 is basically the same as the content of example 1, and the difference is that: steps (1) and (2) in example 1 are omitted, and the metal ion-modified mesoporous zeolite in step (3) is replaced with zeolite.

[0071] Comparative example 4

[0072] Comparative Example 4 is basically the same as Example 1, except that step (3) in Example 1 is omitted.

[0073] Comparative Example 5

[0074] Comparative Example 5 is basically the same as Example 1, except that the bacteriostatic agent in Example 1 is replaced with a mixture of monoglyceryl myristate and acetic acid, and the dosages of monoglyceryl myristate and acetic acid are the same as those in Example 1.

[0075] (III) Test Examples

[0076] Seventy Duroc×Landrace×Yorkshire pigs, healthy and weighing about 70 kg, were selected and divided into 7 groups, namely the control group, the Example 1 group, and the Comparative Example 1-5 groups, with 10 pigs in each group. The test period was 45 days in total. The control group was fed a basal diet for meat pigs, which was a corn-soybean meal type diet. The Example 1 group and the Comparative Example 1-5 groups were fed the basal diet + the corresponding feed additive, and the feed additive was evenly mixed with the pig basal diet at a mass ratio of 1:200.

[0077] During the test period, the following indicators and methods were used to measure the production performance of the test pigs:

[0078] Average daily feed intake (kg / head): Accurately record the amount of feed input each time. Measure the feed intake every 10 days. After the last feeding on the afternoon of the measurement day, use the method of emptying the bag and cleaning the trough to measure the weight of the remaining feed, determine the feed consumption of each group in 10 days, and calculate the average daily feed intake of each group.

[0079] Average daily weight gain (kg / head): Weigh the pigs at the beginning and end of the test respectively. Weigh on an empty stomach at a fixed point in the morning each time, and then calculate the average daily weight gain of each group. Average daily weight gain = (final weight - initial weight) / test days.

[0080] Feed to gain ratio: Calculate the feed to gain ratio of each group from the feed intake and daily weight gain.

[0081] After the test ended, 2 test pigs with good growth and development status were selected from each group, fasted for 24 hours, weighed, and subjected to slaughter determination and meat quality analysis. The following indicators were measured with reference to the "Technical Specification for Determination of Carcass Traits of Lean-Type Pigs" (NY / T 825—2004): dressing percentage, lean meat percentage. At the same time, the content of different heavy metal elements in tissues was detected by inductively coupled plasma mass spectrometry (ICP-MS). The average value of each group was taken, and the results are shown in Table 1.

[0082] Table 1 Comparison table of production performance

[0083]

[0084] Table 2 Comparison Table of Slaughter Performance

[0085]

[0086]

[0087] Table 3 Effects of Different Feed Additives on the Contents of Toxic Heavy Metals in Pig Tissues

[0088]

[0089] Compared with Example 1, in Comparative Example 1, the modified zeolite was replaced with zeolite; in Comparative Example 2, the metal ion-modified mesoporous zeolite and fucoidan were directly physically mixed in step (3); in Comparative Example 3, steps (1) and (2) were omitted, and the metal ion-modified mesoporous zeolite in step (3) was replaced with zeolite; in Comparative Example 4, step (3) was omitted; in Comparative Example 5, the bacteriostatic agent was replaced with a mixture of monoglyceryl myristate and acetic acid.

[0090] It can be seen from Tables 1-3 that compared with the group of Example 1, the growth conditions of pigs in the groups of Comparative Examples 1-5 deteriorated, the slaughter rate decreased significantly, and the content of residual heavy metals in the meat quality was higher.

[0091] Analysis of the reasons shows that: in the present invention, the zeolite with a microporous structure is first hydrothermally treated, and the obtained mesoporous structure can reduce the diffusion resistance of heavy metal ions in the pores, improve the adsorption rate, facilitate the entry of larger heavy metal ions into the pore interior, and increase the adsorption capacity; then the mesoporous zeolite is impregnated with metal salt solutions of iron, zinc, and copper to expose more adsorption sites on its surface, and finally fucoidan is loaded. Utilizing the negative charges on the surfaces of hydroxyl groups (-OH), carboxyl groups (-COOH), and sulfonate groups (-OSO3H) in the structure of fucoidan, positively charged heavy metal ions are adsorbed through electrostatic attraction and form stable complexes with the heavy metal ions, further increasing the adsorption capacity of zeolite for heavy metal ions. Through the adsorption of the modified zeolite, the residues of various heavy metals in animals and animal products are reduced, and the stress response during heavy metal poisoning is regulated. On the other hand, the antibacterial agent forms a sustained-release effect by coating the antibacterial organic acid in monoglyceryl myristate with good biocompatibility and antibacterial activity to protect the animal digestive tract. The combination of the two can replace antibiotics as a bacteriostatic agent with low irritation, high safety, and high efficiency; in addition, monoglyceryl myristate also has antioxidant ability, further balancing the stress response of organisms to heavy metal ions and improving the quality of animal products.

[0092] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. The basic principles and main features of the present invention have been described in the above with specific implementation schemes. On the basis of the present invention, some modifications or replacements can be made, but these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of protection required by the present invention.

Claims

1. A modified zeolite composite feed additive, characterized in that, It comprises the following raw materials in parts by weight: 66 - 75 parts of modified zeolite, 11 - 15 parts of antibacterial agent, 10 - 18 parts of vitamin, 4 - 9 parts of amino acid, and 0.05 - 0.2 part of ethoxyquinoline; The preparation method of the modified zeolite comprises the following steps: (1) Place the zeolite in a hydrothermal aging furnace for hydrothermal treatment to obtain mesoporous zeolite; (2) Add a metal salt solution to the mesoporous zeolite and stir evenly to obtain a mixture; the mixture is allowed to stand, dried, calcined, ground and sieved to obtain metal ion - modified mesoporous zeolite; (3) Add glutaraldehyde to the aqueous solution of fucoidan oligosaccharide and stir for 3 - 5 h, then add the metal ion - modified mesoporous zeolite and adjust the pH of the solution, and then carry out a cross - linking reaction; after the reaction is completed, collect the product and wash it to neutral to obtain the modified zeolite.

2. The modified zeolite composite feed additive according to claim 1, wherein In step (1), the heating rate of the hydrothermal aging furnace is 5 - 8 °C / min; the temperature of the hydrothermal treatment is 350 - 550 °C, and the time is 2 - 5 h.

3. The modified zeolite composite feed additive according to claim 1, wherein In step (2), the metal salt is composed of ferric nitrate, zinc nitrate and copper nitrate with a molar ratio of 1:(0.8 - 1.2):(0.1 - 0.5); the concentration of cations in the metal salt solution is 0.8 - 1 mol / L; the liquid - solid ratio of the metal salt solution to the metal ion - modified mesoporous zeolite is (1 - 2) L / kg.

4. The modified zeolite composite feed additive according to claim 1, characterized in that, In step (2), the standing time is 3 - 4 h; the drying temperature is 120 - 130 °C, and the time is 1 - 2 h; the calcination temperature is 550 - 600 °C, and the time is 4 - 5 h.

5. The modified zeolite composite feed additive according to claim 2, wherein In step (3), the concentration of the aqueous solution of fucoidan oligosaccharide is 1 - 5 w / v%; the mass ratio of the metal ion - modified mesoporous zeolite to fucoidan oligosaccharide and glutaraldehyde is (100 - 160):(5 - 10):1; the pH is 7.0 - 9.0; the cross - linking reaction time is 2 - 6 h.

6. The modified zeolite composite feed additive according to claim 1, wherein The preparation method of the antibacterial agent comprises the following steps: (a) Heat monoglyceryl myristate to melting, then add acetic acid and an emulsifier and mix, and perform ultrasonic treatment to obtain an emulsion; (b) At 68 - 75 °C, add water to the emulsion and carry out shearing and homogenization, and then freeze - dry to obtain the antibacterial agent.

7. The modified zeolite composite feed additive according to claim 6, wherein In step (a), the mass ratio of monoglyceryl myristate to acetic acid is 10:(1 - 2); the emulsifier is Tween 80; the addition amount of the emulsifier is 1 - 3 wt% of monoglyceryl myristate.

8. The modified zeolite composite feed additive according to claim 6, characterized in that, In step (b), the mass ratio of the emulsion to water is (3 - 7):(7 - 12); the shearing speed is 10000 - 13000 rmp, and the time is 1 - 3 min; the homogenization pressure is 400 - 600 bar, and the number of times is 3 - 5 times.

9. The modified zeolite composite feed additive according to claim 1, characterized in that, The vitamin is composed of vitamin A, vitamin B1, vitamin B6, and vitamin E with a mass ratio of (3 - 5):(1 - 2):(1 - 3):(5 - 8), and the amino acid is composed of lysine, methionine, and valine with a mass ratio of (2 - 4):(1 - 3):(1 - 2).

10. The preparation method of the modified zeolite composite feed additive according to any one of claims 1-9, characterized in that, According to the above parts by weight, uniformly mix the modified zeolite with the antibacterial agent, vitamin, amino acid and ethoxyquinoline to obtain a compound feed additive.

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