A feed additive of humic acid chelated non-protein nitrogen and preparation method thereof

Abstract

The invention discloses a humic acid chelated non-protein nitrogen feed additive and a preparation method thereof. The feed additive is prepared from the following components in parts by weight: humic acid, sulfuric acid aqueous solution, nano molecular sieve catalyst, activated carbon, urea, chelating agent, montmorillonite, food-grade white pigment, and coating agent. The preparation steps basically include: 1) catalyzing humic acid raw materials with activated carbon and nano molecular sieve catalyst to obtain modified humic acid solution; 2) adding urea and chelating agent to the modified humic acid solution, and drying at low temperature to obtain humic acid chelated urea powder; 3) mixing the humic acid chelated urea powder and montmorillonite uniformly, wet granulating, and obtaining humic acid chelated urea particles; 4) vacuum coating the humic acid chelated urea particles to obtain the humic acid chelated non-protein nitrogen feed additive. The humic acid chelated non-protein nitrogen feed additive particles are smooth and uniform in size, and urea can be sustained-released.

Description

Technical Field

[0001] The invention relates to the technical field of feed additives, and in particular to a humic acid chelated non-protein nitrogen feed additive and a preparation method thereof. Background Art

[0002] Urea is an organic compound composed of carbon, nitrogen, oxygen and hydrogen. It is a white crystal that can be used as an animal feed additive. If ruminants drink water immediately after eating feed containing urea, the urea in the stomach will be decomposed into ammonia in large quantities. A large amount of ammonia enters the gastrointestinal tract through the tumor mesh, and thus cannot be fully utilized by microorganisms, resulting in waste; if urea is dissolved in water or mixed in liquid feed for direct consumption by ruminants, the dissolved urea will produce a large amount of ammonia, causing poisoning of ruminants.

[0003] Urea generates ammonia and carbon dioxide under the action of bacterial enzymes in the body. Humic acid can slow down the release of ammonia by inhibiting the activity of bacterial enzymes, so that urea will not be rapidly degraded in the rumen. Moreover, humic acid can absorb part of the ammonia generated by urea in the rumen and part of the ammonia generated by microbial decomposition of protein and nitrogen-containing substances, so that it can be reused by rumen microorganisms, alleviating the toxic side effects of urea on ruminants. In addition, humic acid can absorb ammonia in feces when it is absorbed by ruminants and excreted with feces, reducing fecal odor and environmental pollution.

[0004] Montmorillonite is widely used in animal feed additives. It can reduce the incidence of diarrhea, replace zinc oxide and antibiotics, and play a role in increasing animal appetite, regulating body levels, and enhancing immunity. At the same time, the cation exchange capacity and adsorption capacity of montmorillonite can absorb harmful intestinal bacteria and toxic elements in animals, thereby reducing body damage and maintaining body health.

[0005] CN 206565215 U discloses a sodium humate coated feed additive, comprising an irregularly shaped sodium humate core, an intermediate layer and an outer shell layer sequentially coated from the inside to the outside of the sodium humate core surface, the outer shell layer is a particle mixed layer composed of one or more of stone powder, medical stone, gypsum and animal edible substances, and the intermediate layer is a resin coating material. In this production process, one or more of the stone powder, medical stone, and gypsum coated on the outermost surface will cause uneven color of the particle appearance, affecting the sensory perception, and the stone powder, medical stone, and gypsum on the surface will fall off during storage and transportation.

[0006] CN 101429063 A discloses a humic acid urea and a preparation method thereof. The product of the invention has a solid outer shell composed of urea or a mixture mainly composed of urea, and the nutrient humic acid is wrapped in the middle of the product. Not only are the product particles crystal white and smooth and beautiful in appearance, but the product has no powder, the nutrient is built-in and will not fall off, and the product has a beautiful appearance. However, the urea of ​​the invention is wrapped outside, which cannot reduce the urea release rate and cannot achieve the effect of improving the utilization rate of urea.

[0007] Although patent CN 206565215 U can reduce the urea release rate, the granules are uneven in appearance and powdering occurs during storage and transportation; although CN 101429063 A has smooth granules and no powder, it cannot reduce the urea release rate and cannot improve the urea utilization rate. Therefore, there is an urgent need for a technical solution that can reduce the urea release rate and ensure that the granules are smooth, crystal white, uniform in size, and do not fall off during storage and transportation. Summary of the invention

[0008] In order to solve the above problems existing in the prior art, the present invention provides a feed additive for chelating non-protein nitrogen with humic acid and a preparation method thereof, the steps comprising: 1) catalyzing humic acid raw materials with activated carbon and nano molecular sieve catalyst to obtain a modified humic acid reaction solution; 2) centrifuging the humic acid reaction solution to obtain a humic acid supernatant solution; 3) adding urea and a chelating agent to the humic acid supernatant solution, and after the reaction, drying it through a low-temperature mixed spray drying tower to obtain powdered humic acid chelated urea; 4) mixing the powdered humic acid chelated urea with montmorillonite evenly, and performing efficient wet extrusion granulation to obtain humic acid chelated urea particles; 5) performing fluidized bed vacuum coating on the obtained humic acid chelated urea particles, a coating agent, and food-grade white pigment to obtain a feed additive for chelating non-protein nitrogen with humic acid. The feed additive for chelating non-protein nitrogen with humic acid has smooth particles and uniform size, and urea can be sustained-released.

[0009] In order to achieve the above effects, the present invention adopts the following technical solutions:

[0010] On one hand, the present invention provides a feed additive for chelating non-protein nitrogen with humic acid. The feed additive is prepared from the following components in parts by weight: 50-60 parts of humic acid, 300 parts of sulfuric acid aqueous solution, 2-4 parts of nano molecular sieve catalyst, 0.5-1.5 parts of activated carbon, 40-50 parts of urea, 3-5 parts of chelating agent, 20-30 parts of montmorillonite, 2-4 parts of food-grade white pigment and 10-15 parts of coating agent.

[0011] The chelating agent is any one of the following: sodium metaphosphate, calcium acetate, sodium acid pyrophosphate.

[0012] Food grade white pigment is titanium dioxide.

[0013] The coating agent is palm oil.

[0014] The concentration of the aqueous sulfuric acid solution was 10% wt.

[0015] Another aspect of the present invention provides a method for preparing a humic acid chelated non-protein nitrogen feed additive, comprising the following steps:

[0016] 1) Screening humic acid raw materials, and crushing the screened humic acid raw materials;

[0017] 2) subjecting the crushed humic acid to an oxidative degradation reaction with a sulfuric acid aqueous solution in an aqueous medium to obtain an activated humic acid solution;

[0018] 3) adding activated carbon and nano molecular sieve catalyst to the activated humic acid solution, heating for reaction, and obtaining a modified humic acid reaction solution after heavy metals are removed;

[0019] 4) centrifuging the modified humic acid reaction solution to obtain a humic acid supernatant solution;

[0020] 5) After the humic acid supernatant solution is fully reacted with urea and a chelating agent, low-temperature spray drying is performed to obtain humic acid chelated urea powder;

[0021] 6) stirring and mixing the humic acid chelated urea powder and montmorillonite evenly;

[0022] 7) subjecting the mixture of the humic acid chelated urea powder and montmorillonite obtained in step 6) to high-efficiency wet extrusion granulation to obtain humic acid chelated urea granules;

[0023] 8) Using food-grade white pigment titanium dioxide and a coating agent to perform fluidized bed vacuum coating on humic acid chelated urea particles to obtain a humic acid chelated non-protein nitrogen feed additive.

[0024] Furthermore, the water medium in step 2) is magnetized water.

[0025] Furthermore, the magnetized water is obtained by treating normal drinking water with a magnetic water device, the magnetic field treatment intensity is 1000-2500Gs, and the treatment time is 1.8-2.2h.

[0026] Furthermore, in step 3), the heating temperature is 80-85° C. and the heating time is 1.5-2.5 h.

[0027] Furthermore, the low temperature in step 5) is 50-60°C.

[0028] The water used in the reaction process of step 2) of the present invention is magnetized. After being treated under a certain magnetic field, the surface tension, viscosity, permeability and solubility of the water are increased. At the same time, the conductivity and digestibility of the water react. The magnetized water can enhance the enzyme and protein activity in the animal body and improve the growth rate of the animal. The activated humic acid in step 2) can increase the transformation of the humic acid macromolecular structure into small molecules, increase the content of humic acid active functional groups, and reduce the content of humic acid insoluble matter. Step 3) The activated carbon has the function of adsorbing heavy metals in the humic acid itself to reduce heavy metals. The modified humic acid can introduce new active groups such as carboxyl, quinone and cresol hydroxyl groups on the basis of humic acid, increase the content of acidic groups, and reduce the pH value of humic acid. The mild pH value is more conducive to animal feeding. Step 4) After the humic acid reaction liquid is centrifuged, the content of humic acid insoluble matter is reduced.

[0029] Beneficial effects:

[0030] 1) The present invention uses humic acid coated urea technology to slow down the decomposition rate of urea, reduce the damage of ammonia to ruminants, and achieve full utilization of urea.

[0031] 2) The modified humic acid used in the present invention will not increase the pH value of rumen fluid, thus reducing damage to the stomach of ruminants.

[0032] 3) The present invention is carried out under low temperature conditions, thereby avoiding the loss of nitrogen and the formation of biuret, and ensuring that urea is fully utilized; the food-grade white titanium dioxide enables the obtained humic acid to chelate non-protein nitrogen feed additive, and the prepared finished product particles are smooth, crystal clear and pure white, solving the problem of animal refusal to eat due to blackening of humic acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a physical picture of the appearance of the feed additive prepared in Example 1, A is a plurality of feed particles, and B is a single feed particle. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to these embodiments. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope limited by the claims attached to the application.

[0035] The equipment and reagents used in the present invention are: humic acid, sulfuric acid aqueous solution, activated carbon, urea, montmorillonite, sodium metaphosphate, calcium acetate, sodium acid pyrophosphate, titanium dioxide, and palm oil, all of which are commercially available without special requirements; the nano molecular sieve catalyst is prepared by the method described in Example 1 of patent CN201010297898.5, a multi-level pore structure nano molecular sieve catalyst and its preparation method.

[0036] Example 1

[0037] A method for preparing a humic acid chelated non-protein nitrogen feed additive, the specific process steps are as follows:

[0038] 1. Classify the initial raw materials of humic acid, remove impurities such as coal dry stone and stone, and obtain humic acid raw materials; use a crusher to crush the humic acid raw materials to 80-100 mesh;

[0039] 2. Take 50 kg of crushed humic acid raw material and place it in a reactor; add 15 kg of magnetized water into the reactor; the magnetized water is obtained by treating normal drinking water with a magnetic water device, and the treatment conditions are that the magnetic field intensity is 1000 Gs and the treatment time is 2 hours; then add 300 kg of 10% sulfuric acid aqueous solution into the reactor, seal it, and carry out oxidative degradation reaction at a reaction temperature of 70°C and a reaction time of 1.5 hours to obtain an activated humic acid solution;

[0040] 3. Add 1 kg of activated carbon and 2 kg of nano molecular sieve catalyst to the activated humic acid solution, react at 80°C for 2 hours, and obtain a modified humic acid reaction solution after heavy metals are removed;

[0041] 4. Centrifuge the modified humic acid reaction solution at 2000 rpm / min for 20 min to obtain a humic acid supernatant solution;

[0042] 5. Add 40 kg urea and 3 kg calcium acetate to the humic acid supernatant solution, react at 60 ° C for 1 hour, and dry it in a low-temperature mixed spray drying tower with a low temperature parameter of 50 ° C to obtain humic acid chelated urea powder;

[0043] 6. Place humic acid chelated urea powder and 20 kg of montmorillonite in a stirrer and mix evenly at a stirring speed of 1000 rpm / min for 5 min;

[0044] 7. The sample mixed in step 6 is subjected to efficient wet extrusion granulation to obtain humic acid chelated urea granules with uniform particle size and a particle size of about 6 mm;

[0045] 8. The humic acid chelated urea particles are subjected to fluidized bed vacuum coating, and 10 kg of palm oil and 3 kg of food-grade white titanium dioxide are used to obtain the final humic acid chelated non-protein nitrogen feed additive. The actual picture of the feed additive is as follows: Figure 1 described.

[0046] Example 2

[0047] A humic acid chelated non-protein nitrogen feed additive, the specific process steps are as follows:

[0048] 1. Classify the initial raw materials of humic acid, remove impurities such as coal dry stone and stone, and obtain humic acid raw materials; use a crusher to crush the humic acid raw materials to 80-100 mesh;

[0049] 2. Take 55 kg of crushed humic acid raw material and place it in a reactor; add 17 kg of magnetized water into the reactor; the magnetized water is normal drinking water treated by a magnetic water device, the magnetic field strength is 2500 Gs, and the treatment time is 2 hours; then add 300 kg of 10% sulfuric acid aqueous solution into the reactor, seal it, and carry out oxidative degradation reaction at a reaction temperature of 80° C. for a reaction time of 1.5 hours to obtain an activated humic acid solution.

[0050] 3. Add 1 kg of activated carbon and 3 kg of nano molecular sieve catalyst to the activated humic acid solution, react at 80°C for 2 hours, and obtain a modified humic acid reaction solution after heavy metals are removed;

[0051] 4. Centrifuge the modified humic acid reaction solution at 2000 rpm / min for 20 min to obtain a humic acid supernatant solution;

[0052] 5. Add 45 kg urea and 4 kg sodium metaphosphate to the humic acid supernatant solution, react at 70 ° C for 1 hour, and dry it in a low-temperature mixed spray drying tower with a low-temperature parameter of 55 ° C to obtain humic acid chelated urea powder;

[0053] 6. Place humic acid chelated urea powder and 25 kg of montmorillonite in a stirrer and mix evenly at a stirring speed of 1000 rpm / min for 5 min;

[0054] 7. The sample mixed in step 6 is subjected to efficient wet extrusion granulation to obtain humic acid chelated urea granules with uniform particle size and a particle size of about 6 mm;

[0055] 8. The humic acid chelated urea granules were vacuum coated in a fluidized bed using 12 kg of palm oil and 3 kg of food-grade white pigment titanium dioxide to obtain the final humic acid chelated non-protein nitrogen feed additive.

[0056] Example 3

[0057] A humic acid chelated non-protein nitrogen feed additive, the specific process steps are as follows:

[0058] 1. Classify the initial raw materials of humic acid, remove impurities such as coal dry stone and stone, and obtain humic acid raw materials; use a crusher to crush the humic acid raw materials to 80-100 mesh;

[0059] 2. Take 60 kg of crushed humic acid raw material and place it in a reactor; add 20 kg of magnetized water into the reactor; the magnetized water is normal drinking water treated by a magnetic water device, the magnetic field strength is 2500 Gs, and the treatment time is 2 hours; then add 300 kg of 10% sulfuric acid aqueous solution into the reactor, seal it, and carry out oxidative degradation reaction at a reaction temperature of 80° C. for a reaction time of 1.5 hours to obtain an activated humic acid solution.

[0060] 3. Add 1 kg of activated carbon and 4 kg of nano molecular sieve catalyst to the activated humic acid solution, react at 80°C for 2 hours, and obtain a modified humic acid reaction solution after heavy metals are removed;

[0061] 4. Centrifuge the modified humic acid reaction solution at 2000 rpm / min for 20 min to obtain a humic acid supernatant solution;

[0062] 5. Add 50 kg urea and 5 kg sodium acid pyrophosphate to the humic acid supernatant solution, react at 70 ° C for 1 hour, and dry it in a low-temperature mixed spray drying tower with a low temperature parameter of 60 ° C to obtain humic acid chelated urea powder;

[0063] 6. Place humic acid chelated urea powder and 30 kg of montmorillonite in a stirrer and mix evenly at a stirring speed of 1000 rpm / min for 5 min;

[0064] 7. The sample mixed in step 6 is subjected to efficient wet extrusion granulation to obtain humic acid chelated urea granules with uniform particle size and a particle size of about 6 mm;

[0065] 8. The humic acid chelated urea granules were subjected to fluidized bed vacuum coating, and 15 kg of palm oil and 3 kg of food grade white pigment titanium dioxide were used to obtain the final humic acid chelated non-protein nitrogen feed additive.

[0066] Experimental results:

[0067] The granular appearance of the humic acid chelated non-protein nitrogen feed additives obtained in Examples 1-3 was observed, and the urea release of the feed additive prepared in Example 1 was measured. The measurement methods included a urea water dissolution test and an in vitro artificial simulated rumen fluid urea dissolution test.

[0068] (1) Urea dissolution test in water

[0069] The humic acid chelated non-protein nitrogen feed additive prepared in Example 1 is placed in a 100ml volumetric flask, fixed to volume with distilled water, sealed in a 25°C constant temperature incubator, sampled every 2h, and the dissolution was slowly poured into a 250ml conical flask for detection. After pouring the dissolution each time, the 100ml volumetric flask was fixed to the scale with distilled water. Repeat this operation for each sampling. The absorbance was measured with an ultraviolet spectrophotometer at 420nm, and the release of urea at each time point of the water-soluble coated urea at normal temperature was analyzed according to the absorbance value. The dissolution rate results (%) of the feed additive prepared in Example 1 and ordinary urea in water are shown in Table 1.

[0070] Table 1 Dissolution rate results of feed additives prepared in Example 1 and ordinary urea in water (%)

[0071] time 2 4 6 8 10 12 14 16 18 20 22 24 Example 1 11.29 12.49 13.72 20.11 25.32 37.89 40.32 65.54 69.31 70.19 75.87 84.32 Ordinary urea 56.13 98.78 / / / / / / / / / /

[0072] (2) In vitro artificial rumen fluid urea dissolution test

[0073] ① Preparation method of artificial simulated rumen fluid: Take 16.4mL of dilute hydrochloric acid, add 800mL of water and 10g of pepsin, stir well, and add water to make up to 1000mL.

[0074] ② The humic acid chelated non-protein nitrogen feed additive prepared in Example 1 was placed in 100 ml of artificial rumen fluid, and stirred in a constant temperature water bath at 37°C at a stirring speed of 100 rpm to simulate the environment in the stomach of ruminants. The control group was tested with ordinary urea. The absorbance was measured at 420 nm using an ultraviolet spectrophotometer every 2 hours, and the release amount of urea at each time point was calculated based on the absorbance value. The release amount (%) of the feed additive prepared in Example 1 and ordinary urea in artificial simulated rumen fluid is shown in Table 2.

[0075] Table 2 Release amount of feed additives prepared in Example 1 and common urea in artificial simulated rumen fluid (%)

[0076] time 2 4 6 8 10 12 14 16 18 20 22 24 Example 1 11.34 16.56 23.19 28.52 24.53 27.01 27.54 19.56 27.11 24.58 27.32 23.48 Ordinary urea 9.68 50.23 41.58 30.46 20.25 28.02 29.63 25.48 18.20 19.68 15.00 14.69

[0077] (3) pH value of artificial simulated rumen fluid after consuming different amounts of the feed additive prepared in Example 1

[0078] ① Preparation method of artificial simulated rumen fluid: Take 16.4mL of dilute hydrochloric acid, add 800mL of water and 10g of pepsin, stir well, and add water to make up to 1000mL.

[0079] ② Take 1L of the humic acid chelated non-protein nitrogen feed additive prepared in Example 1, add it into 100ml of artificial rumen fluid according to the addition amount in Table 3, stir it in a constant temperature water bath at 37°C, and stir it at a speed of 100 rpm. After 2h, measure the pH value of the rumen fluid with a pH meter. The measurement results are shown in Table 3.

[0080] Table 3 pH value of rumen fluid after consuming different amounts of the feed additive prepared in Example 1

[0081] Addition amount 0 0.5‰ 1‰ 3‰ 5‰ 1％ pH 7.17 7.56 7.32 7.10 6.99 6.86

[0082] The appearance of the humic acid chelated non-protein nitrogen feed additive obtained in Examples 1-3 was observed, and it was found that the prepared feed additive particles were smooth, crystal white, uniform in size, and had no powder falling off.

[0083] It can be seen from Table 1 that when the urea release amount is detected in water, the humic acid chelated non-protein nitrogen feed additive prepared in Example 1 has a dissolution rate of 40.32% at 14 h, 65.54% at 16 h, and 84.32% at 24 h compared with ordinary urea; the latter has a dissolution rate of 56.13% at 2 h and 98.78% at 4 h. The humic acid chelated non-protein nitrogen feed additive prepared in Example 1 achieves a good sustained release effect in water.

[0084] As can be seen from Table 2, when the urea release amount is detected in the artificial simulated rumen fluid, the humic acid chelated non-protein nitrogen feed additive prepared in Example 1 is compared with ordinary urea. The former has a release amount of 16.56% at 4 hours; the latter has a release amount of 50.23% at 4 hours. The ordinary urea releases faster and reaches the maximum value in a short time, while the humic acid chelated non-protein nitrogen feed additive prepared in Example 1 is slowly and steadily released. Between 6 hours and 24 hours, the release amount is maintained between 23.19% and 28.52%, showing a better sustained release effect, which can be beneficial to the utilization of microorganisms to synthesize bacterial protein.

[0085] It can be seen from Table 3 that since the normal pH of the rumen is 5.5-7.5, after consuming different amounts of the humic acid chelated non-protein nitrogen feed additive prepared in Example 1, it was measured that the pH value of the rumen fluid was between 7.17 and 6.86. The humic acid chelated non-protein nitrogen feed additive prepared by the present invention does not lead to an increase in the pH value of the rumen fluid, and can reduce the damage to the stomach of ruminants.

[0086] In addition, the specific embodiments of the present invention are merely descriptions of the present invention, and they are not limitations of the present invention. After reading this specification, those skilled in the art can make modifications based on personal needs without departing from the design purpose of the present invention and without affecting the creative value of the present invention.

Claims

1. A feed additive of humic acid chelated non-protein nitrogen, characterized in that: The invention is prepared from the following components in parts by weight: 50-60 parts of humic acid, 300 parts of sulfuric acid aqueous solution, 2-4 parts of nano molecular sieve catalyst, 0.5-1.5 parts of activated carbon, 40-50 parts of urea, 3-5 parts of chelating agent, 20-30 parts of montmorillonite, 2-4 parts of food grade white pigment and 10-15 parts of palm oil; The chelating agent is any one of the following: sodium metaphosphate, calcium acetate, sodium acid pyrophosphate; The preparation method of the feed additive comprises the following steps: 1) Crush the humic acid raw materials; 2) The crushed humic acid and sulfuric acid aqueous solution are subjected to an oxidative degradation reaction in an aqueous medium to obtain an activated humic acid solution; 3) Adding activated carbon and nano molecular sieve catalyst to the activated humic acid solution, heating the solution for reaction, and obtaining a modified humic acid reaction solution after heavy metal removal; 4) Centrifuging the modified humic acid reaction solution to obtain a humic acid supernatant solution; 5) After the humic acid supernatant solution is fully reacted with urea and a chelating agent, low-temperature spray drying is performed to obtain humic acid chelated urea powder; 6) Stir and mix the humic acid chelated urea powder and montmorillonite evenly; 7) subjecting the mixture of the humic acid chelated urea powder and montmorillonite obtained in step 6) to high-efficiency wet extrusion granulation to obtain humic acid chelated urea granules; 8) Food grade white pigment and palm oil were used to perform fluidized bed vacuum coating on humic acid chelated urea granules to obtain humic acid chelated non-protein nitrogen feed additive.

2. The feed additive according to claim 1, characterized in that The food-grade white pigment is titanium dioxide.

3. The feed additive according to claim 1, characterized in that The concentration of the sulfuric acid aqueous solution is 10%wt.

4. The feed additive according to claim 1, characterized in that Step 2) The aqueous medium is magnetized water.

5. The feed additive according to claim 4, characterized in that The magnetized water is obtained by treating normal drinking water with a magnetic water device, the magnetic field treatment intensity is 1000-2500Gs, and the treatment time is 1.8-2.2h.

6. The feed additive according to claim 1, characterized in that Step 3) The heating temperature is 80-85°C and the time is 1.5-2.5h.

7. The feed additive according to claim 1, characterized in that Step 5) The low temperature is 50-60°C.

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