Humic acid adhesive and preparation method thereof

Abstract

The invention discloses a humic acid adhesive and a preparation method thereof.The humic acid adhesive is prepared from, by weight, 70-80 parts of sodium humate, 10-15 parts of calcium chloride and magnesium chloride saturated solution, 10-15 parts of amino acid and 900-1100 parts of water.The humic acid adhesive is wide in raw material source and simple in preparation process, the sodium humate serves as a molecular basis, and the humic acid adhesive is prepared from the sodium humate, the calcium chloride and magnesium chloride saturated solution, the amino acid and the water. Sodium humate molecules are continuously polymerized to form reticular macromolecules through bridging and Maillard reaction, and feed raw materials such as starch and protein are wrapped and bonded in the feed granulation process, so that the hardness of feed particles can be remarkably improved, the pulverization rate can be reduced, and the production cost can be reduced. The humic acid adhesive with the mass ratio of 0.1-0.2% is applied to preparation of the feed, the obtained humic acid adhesive feed can be rapidly decomposed in animal intestines, the burden of the animal intestines and digestion is not increased, and the humic acid adhesive feed is an animal-friendly adhesive.

Description

Technical Field

[0001] The invention belongs to the technical field of feed adhesives, and particularly relates to a humic acid adhesive and a preparation method thereof. Background Art

[0002] Adhesives, also known as excipients, are mainly used to improve feed quality, ensure that feed does not break during transportation and storage, reduce powder content, reduce the proportion of return materials, and improve feed utilization. Feed adhesives can be roughly divided into two categories: natural substances and chemical synthetic substances. The former can be divided into those derived from terrestrial plants, seaweed, and animals. Adhesives derived from terrestrial plants are commonly starches. Common starch adhesives on the market include wheat flour, corn starch, potato starch, potato starch, etc. The more commonly used ones are wheat flour and α-starch. The viscosity of starch adhesives is mainly related to the gelatinization degree of starch. Generally, the higher the starch content in the raw material, the more sufficient the hydrothermal effect, the higher the gelatinization degree of starch, and the better the granulation effect. However, due to the large fluctuations in wheat prices, sometimes the high raw material prices limit its application. In addition, the use of starch is also limited by processing technology. In recent years, due to the improvement of processing technology, sugar-based adhesives in the industry have been able to better ensure the stability of feed. In addition, sodium alginate, kelp glue, agar and gelatin are used as feed granulation adhesives, but their large-scale application is also limited by cost issues.

[0003] At present, there are many kinds of artificially synthesized adhesives, including polyurea formaldehyde, urea-formaldehyde resin, lignin sulfonate, polyvinyl alcohol (PVA), polyacrylic acid, various starch phosphates, etc. CN110003347A discloses a modified starch adhesive processing technology and processing equipment, which can produce modified starch adhesives with different requirements by adjusting the formula and process, and can be applied to industries such as food, medicine, chemical industry, feed, casting, oil drilling, textile and papermaking, but it is not a special adhesive in the field of animal feed, and is also limited by the cost of use. CN117158511A discloses a preparation method and application of a fermented protein peptide attapulgite aquatic granular feed adhesive, and prepares an aquatic feed adhesive, reduces the use of chemical adhesives in aquatic feed, and reduces production cost and breeding cost. Due to the problem that artificially synthesized adhesives are not easy to degrade in the intestinal tract of animals, excessive intake may have an adverse effect on the digestive system of animals, which also limits its application.

[0004] At present, there are still few binders specifically for the feed field, and they are limited by cost. Therefore, developing an adhesive with strong bonding ability and rapid degradation in the intestine is of great significance for the feed production industry to improve feed granulation level and reduce production costs. Summary of the invention

[0005] Based on the above technical background, the present invention provides a humic acid adhesive and a preparation method thereof. The humic acid adhesive consists of 70-80 parts of sodium humate, 10-15 parts of saturated solution of calcium chloride and magnesium chloride, 10-15 parts of amino acids, and 900-1100 parts of water. The humic acid adhesive takes sodium humate as the molecular basis, realizes the continuous polymerization of sodium humate molecules through bridging and Maillard reaction to form a network macromolecule, and wraps and bonds feed raw materials such as starch and protein during feed granulation, which can significantly improve the hardness of feed particles and reduce the pulverization rate; the obtained humic acid adhesive feed can be quickly decomposed in the animal intestine without increasing the animal's intestinal and digestive burden, and is an animal-friendly adhesive.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A humic acid adhesive, comprising the following raw materials in parts by weight:

[0008] Sodium humate: 70-80 parts;

[0009] Calcium chloride and magnesium chloride saturated solution: 10-15 parts;

[0010] Amino acids: 10-15 parts;

[0011] Water: 900-1100 parts.

[0012] Furthermore, the molar ratio of calcium chloride to magnesium chloride is 2:2-5.

[0013] A method for preparing a humic acid adhesive comprises the following steps:

[0014] (1) Preparation of sodium humate: grind and sieve humic acid mineral powder, mix it with sodium hydroxide, add deionized water, stir to react, and dry to obtain sodium humate;

[0015] (2) Preparation of calcium chloride and magnesium chloride solution: Dissolve calcium chloride and magnesium chloride in preheated deionized water to prepare a saturated solution of calcium chloride and magnesium chloride;

[0016] (3) Sodium humate, calcium chloride, saturated magnesium chloride solution and water are mixed and stirred according to the above weight proportions, and then amino acid is added and stirred, and the mixture is heated in a drum, and then naturally cooled and crushed to obtain a humic acid adhesive.

[0017] Furthermore, the sieve aperture of step (1) is 100-120 mesh; the mass ratio of the sodium hydroxide, humic acid mineral powder and deionized water is 1:8-12:100-110; the reaction temperature is 60-80°C, and the reaction time is 1-2h.

[0018] Furthermore, the soluble humic acid content in the sodium humate in step (1) is ≥ 60%.

[0019] Furthermore, the temperature of the deionized water in step (2) is 30-35°C.

[0020] Furthermore, in step (3), the stirring speed is 100-150 r / min, and the time is 20-30 min; the heating temperature is 130-180° C., and the time is 5-10 min.

[0021] Furthermore, the amino acid in step (3) is an amino acid containing two amino groups at the same time, which is one or two of lysine, glutamine, asparagine, arginine and histidine.

[0022] The present invention also provides an application of a humic acid adhesive, and the specific method is: the humic acid adhesive obtained above is first mixed with 10-15% of the total mass of the feed raw materials and stirred for 2-5 minutes, and then mixed with the remaining feed to be uniformly stirred until the humic acid adhesive content in the feed is 0.1-0.2%, and granulated to obtain the humic acid adhesive feed.

[0023] Furthermore, the granulation conditions are: granulator feeding frequency 20-30Hz, steam pressure 0.1-0.3MPa, steam flux 30%-60%, ring die aperture 3-4mm, compression ratio 1:8-10, granulation temperature 70-80°C.

[0024] Humic acid mineral powder reacts with sodium hydroxide to generate sodium humate, and sodium humate, calcium chloride, magnesium chloride and amino acids are used as raw materials. The humic acid molecules are connected by bridging reaction between calcium and magnesium ions and phenolic hydroxyl groups and carboxyl groups in humic acid molecules, and further Maillard reaction is carried out between amino groups in amino acids and carbonyl groups in humic acid molecules, and protein molecules are grafted on the surface of humic acid. At the same time, since the amino acids used are all amino acids containing two amino groups, they can react with carbonyl groups in two humic acid molecules at the same time, and further connect the two humic acid molecules together. Finally, under the joint action of bridging reaction and Maillard reaction, humic acid-humic acid is continuously connected to form a macromolecular network structure, and then starch, protein, trace elements and the like in feed are wrapped and bonded. The humic acid adhesive prepared by the present invention realizes the synergistic effect of various material components through a unique process formula and special process conditions, and the obtained humic acid adhesive can significantly improve the hardness of feed and reduce the powdering rate of feed.

[0025] Beneficial effects:

[0026] 1. Humic acid adhesive uses sodium humate as its molecular basis, and uses the phenolic hydroxyl, carboxyl and carbonyl groups in the sodium humate molecules as bridges and active sites for Maillard reactions, to achieve continuous polymerization of sodium humate molecules to form network macromolecules. During the feed granulation process, it wraps and bonds feed raw materials such as starch and protein, significantly improving the hardness of feed particles and effectively reducing the powdering rate of feed.

[0027] 2. After entering the animal digestive tract, the humic acid adhesive rapidly dissociates into humic acid, calcium and magnesium ions and amino acids under the action of digestive juice, so that nutrients are rapidly released, and the calcium and magnesium ions and amino acids can be absorbed and utilized as nutrients; the humic acid molecules released by the dissociation of the humic acid adhesive further play an anti-inflammatory and astringent role in the intestine, improve intestinal function, and reduce the occurrence of diarrhea. The humic acid adhesive prepared by the present invention does not produce other additional substances after digestion, does not increase the intestinal and digestive burdens of animals, and is an animal-friendly adhesive.

[0028] 3. The humic acid adhesive prepared by the present invention has a wide range of raw materials, a simple preparation process, and significant effects. It can effectively reduce material consumption and save feed costs, and provides a new type of feed binder that can be used as a feed binder specifically for animals. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a feed processed by a rotary pulverizer; among them, a is a feed prepared with a competitor's adhesive attapulgite, and b is a humic acid adhesive feed. DETAILED DESCRIPTION

[0030] The following will combine the contents 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 raw materials used in the present invention are all commercially available.

[0032] Feed raw materials: a typical poultry feed formula is adopted: 55% corn, 22% soybean meal, 15% bran, 8% premix (including vitamin A 12000IU / kg, vitamin D3 3000IU / kg, vitamin E 20IU / kg, iron 80mg / kg, copper 10mg / kg, zinc 60mg / kg, manganese 100mg / kg, iodine 0.5mg / kg, selenium 0.3mg / kg), and the above raw materials are mixed in a mixer to prepare feed raw materials.

[0033] Example 1

[0034] A preparation method of a humic acid adhesive, the specific steps are as follows:

[0035] (1) Preparation of sodium humate: Grind humic acid mineral powder through a 110-mesh sieve, mix with sodium hydroxide and deionized water in a mass ratio of 10:1:100, stir and react at 70°C for 1.5h, and dry to obtain sodium humate with a soluble humic acid content of ≥60%.

[0036] (2) mixing calcium chloride and magnesium chloride in a molar ratio of 2:3, dissolving in an appropriate amount of deionized water preheated to 30-35° C., to prepare a saturated solution of calcium chloride and magnesium chloride;

[0037] (3) 75 parts of the sodium humate obtained in step (1), 12 parts of the calcium chloride obtained in step (2), a saturated magnesium chloride solution and 1000 parts of water were mixed, and stirred at 120 r / min for 25 min to dissolve and fully bridge; then 12 parts of lysine were added, stirred at 120 r / min for 20 min, heated at 150° C. for 5 min, scraped with the drum, cooled under natural ventilation, and put into a high-speed grinder to obtain a humic acid adhesive with uniform particle size.

[0038] Example 2

[0039] A preparation method of a humic acid adhesive, the specific steps are as follows:

[0040] 75 parts of sodium humate prepared in Example 1, 12 parts of calcium chloride prepared in Example 1, saturated magnesium chloride solution and 1000 parts of water were mixed, and stirred at 120 r / min for 25 minutes to dissolve and fully bridge; then 12 parts of glutamine were added, stirred at 120 r / min for 20 minutes, heated at 150° C. for 5 minutes, scraped with a drum, cooled under natural ventilation, and put into a high-speed grinder to obtain a humic acid adhesive with uniform particle size.

[0041] Comparative Example 1

[0042] The difference from Example 1 is that no bridging reaction is performed.

[0043] A method for preparing an adhesive, the specific steps are as follows:

[0044] 75 parts of the sodium humate prepared in Example 1 were mixed with 1000 parts of water, stirred at 120 r / min for 25 min, and then 12 parts of lysine were added. After stirring at 120 r / min for 20 min, the mixture was heated in a drum at 150°C for 5 min. After the drum was scraped, the mixture was cooled under natural ventilation and then put into a high-speed grinder to obtain an adhesive.

[0045] Comparative Example 2

[0046] The difference from Example 1 is that the Maillard reaction is not performed.

[0047] A method for preparing an adhesive, the specific steps are as follows:

[0048] 75 parts of the sodium humate prepared in Example 1, 12 parts of the saturated solution of calcium chloride and magnesium chloride prepared in Example 1 were mixed with 1000 parts of water, stirred at 120 r / min for 25 minutes to dissolve and fully bridge, heated in a drum at 150° C. for 5 minutes, scraped from the drum, cooled under natural ventilation conditions, and then put into a high-speed crusher to obtain an adhesive.

[0049] Comparative Example 3

[0050] The difference from Example 1 is that magnesium chloride is not added.

[0051] A method for preparing an adhesive, the specific steps are as follows:

[0052] (1) dissolving calcium chloride in an appropriate amount of deionized water preheated to 30-35° C. to prepare a saturated calcium chloride solution;

[0053] (2) 75 parts of the sodium humate prepared in Example 1, 12 parts of the saturated calcium chloride solution obtained in step (1) were mixed with 1000 parts of water, stirred at 120 r / min for 25 min to dissolve and fully bridge, and then 12 parts of lysine were added. After stirring at 120 r / min for 20 min, the mixture was heated at 150° C. for 5 min, the drum was scraped, cooled under natural ventilation conditions, and then put into a high-speed grinder to obtain an adhesive.

[0054] Comparative Example 4

[0055] The difference from Example 1 is that no calcium chloride is added.

[0056] A method for preparing an adhesive, the specific steps are as follows:

[0057] (1) dissolving magnesium chloride in an appropriate amount of deionized water preheated to 30-35° C. to prepare a saturated magnesium chloride solution;

[0058] (2) 75 parts of the sodium humate prepared in Example 1, 12 parts of the saturated magnesium chloride solution obtained in step (1) were mixed with 1000 parts of water, stirred at 120 r / min for 25 min to dissolve and fully bridge, and then 12 parts of lysine were added. After stirring at 120 r / min for 20 min, the mixture was heated at 150° C. for 5 min, the drum was scraped, cooled under natural ventilation conditions, and then put into a high-speed grinder to obtain an adhesive.

[0059] Comparative Example 5

[0060] The difference from Example 1 is that the amino acid methionine used has only one amino group.

[0061] A method for preparing an adhesive, the specific steps are as follows:

[0062] 75 parts of the sodium humate prepared in Example 1, 12 parts of the calcium chloride prepared in Example 1, a saturated magnesium chloride solution and 1000 parts of water were mixed, and stirred at 120 r / min for 25 minutes to dissolve and fully bridge; then 12 parts of methionine were added, stirred at 120 r / min for 20 minutes, heated at 150° C. for 5 minutes, scraped with a drum, cooled under natural ventilation conditions, and then put into a high-speed grinder to obtain an adhesive.

[0063] Comparative Example 6

[0064] The difference from Example 1 is that sodium humate, magnesium chloride, calcium chloride solution and amino acid are simply mixed.

[0065] A method for preparing an adhesive, the specific steps are as follows:

[0066] 75 parts of the sodium humate prepared in Example 1, 12 parts of the calcium chloride prepared in Example 1 and a saturated magnesium chloride solution, 12 parts of lysine and 1000 parts of water were mixed, and the mixture was heated in a drum at 150° C. for 5 min. After the drum was scraped, the mixture was cooled under natural ventilation conditions and then put into a high-speed grinder to obtain an adhesive.

[0067] Test example

[0068] (1) Preparation of humic acid binder feed

[0069] The humic acid binder obtained in the above Examples 1-2 was first mixed with 10% of the total mass of the feed raw materials and stirred for 5 minutes, and then mixed with the remaining feed raw materials to make the humic acid binder content in the feed 0.15%, and fed into a pelletizer to obtain a humic acid binder feed.

[0070] The granulation conditions are as follows: granulator feeding frequency 20-30 Hz, steam pressure 0.1-0.3 MPa, steam flux 30%-60%, ring die aperture 3.5 mm, compression ratio 1:9, granulation temperature 75°C.

[0071] (2) Preparation of adhesive feed

[0072] The adhesives obtained in the above comparative examples 1-6 were mixed with 10% of the total mass of the feed raw materials for 5 minutes, and then mixed with the remaining feed raw materials to make the humic acid adhesive content in the feed 0.15%, and fed into the pelletizer for pelleting to obtain different adhesive feeds. The pelletizing conditions of the pelletizer were the same as those of the preparation of the humic acid adhesive feed.

[0073] (3) Preparation of feed without adhesive

[0074] The feed raw materials are placed in a mixer and mixed evenly, and then fed into a pelletizing machine for pelleting to obtain a feed without adhesive. The pelleting conditions of the pelletizing machine are the same as those for the preparation of the humic acid adhesive feed.

[0075] (4) Preparation of competitive adhesive feed

[0076] 0.5% of the total weight of the feed raw material, the competitive adhesive attapulgite, was mixed evenly with the feed raw material in a mixer, and fed into a granulator for granulation to obtain the competitive adhesive feed. The granulation conditions of the granulator were the same as those of the preparation of the humic acid adhesive feed.

[0077] (5) Preparation of wheat flour adhesive feed

[0078] 0.5% of the total weight of the feed raw materials is mixed evenly with the wheat flour and the feed raw materials in a mixer, and then fed into a granulator for granulation to obtain a wheat flour adhesive feed. The granulation conditions of the granulator are the same as those of the preparation of the humic acid adhesive feed.

[0079] The feed hardness and PDI of the different types of feed obtained above were tested. The specific testing methods are as follows:

[0080] Feed hardness (kgf) testing method: Use a single-particle radial pressure method. The maximum force corresponding to the instantaneous deformation of the particle is the hardness of the particle. The instrument used is a grain (feed) hardness tester. Randomly select 30 feed particles, align the hardness tester probe vertically with the center of the particle, and apply pressure to the particle at a constant speed. When the particle breaks, record the peak pressure displayed by the hardness tester. After removing the maximum and minimum values, calculate the average value of the remaining 28 data as the hardness value of this type of feed.

[0081] PDI (Pellet Durability Index) is one of the important indicators for evaluating feed pellet quality. It reflects the ability of feed to resist breakage during loading, unloading, transportation and automatic feed line conveying. The higher the PDI value, the better the durability of the feed, the higher the utilization rate, and the better the growth performance of animals.

[0082] PDI test method: accurately weigh 500g of the above feed pellets and put them into a special rotary pulverizer, set the speed to 50rpm, and the rotation time to 10min. After the rotation is completed, sieve through a 2.5mm standard sieve, collect the sieve material and weigh it accurately. According to the formula PDI = (mass of sieve material / initial mass of sample) × 100%, repeat the measurement 3 times and take the average value as the test result.

[0083] After testing, the feed hardness and PDI of the feed prepared above are shown in Table 1:

[0084] Table 1 Test table of different feed hardness and PDI

[0085] Group Processing conditions Feed hardness (kgf) PDI (%) Example 1 This program 5.93 96.51 Example 2 This program 5.87 96.01 Comparative Example 1 No bridging 4.82 85.80 Comparative Example 2 No Maillard 4.71 85.73 Comparative Example 3 Only calcium chloride 5.31 91.42 Comparative Example 4 Only magnesium chloride 5.35 91.28 Comparative Example 5 Replace with an amino acid 5.29 90.08 Comparative Example 6 Simple mixing of raw materials 4.86 88.06 - No adhesive 4.02 85.32 - Competitive Adhesives 4.11 86.10 - Wheat flour 4.80 91.12

[0086] According to the test results of feed hardness and PDI Figure 1 It can be seen that the granulation effect of the humic acid binder prepared in Examples 1 and 2 is not only better than that of the group without adding binder, but also better than that of the group adding competing binder and wheat flour, indicating that the humic acid binder of the present invention can improve the hardness of feed pellets and reduce the powdering rate.

[0087] The difference between Comparative Examples 1 and 2 and Examples 1 and 2 is the lack of a bridging process or a Maillard reaction process, and it can be seen that the bonding effect is significantly reduced. Comparative Examples 3 and 4 are compared with Example 1, but the calcium chloride and magnesium chloride in the bridging agent are replaced with one of them. Although the adhesive still has a good bonding effect, even higher than the competitive adhesive group and the wheat flour group, it is significantly reduced compared with Examples 1 and 2. Comparative Example 5 is compared with Examples 1 and 2, but the amino acid is replaced with methionine with only one amino group. Although the adhesive still has a good bonding effect, even higher than the competitive adhesive group, the feed hardness and PDI are also significantly reduced compared with Examples 1 and 2, indicating that the two amino groups in the amino acid can achieve the effect of connecting two humic acid molecules. Comparative Example 6 is compared with Examples 1 and 2, but simply mixes the bridging agent and the amino acid of the Maillard reaction, without performing a bridging reaction or a Maillard reaction. The sample is not much different from the control group without an adhesive, which further illustrates that the bonding effect of the adhesive of the present invention is not only related to the raw material composition, but more importantly, the reaction process gives the product good bonding properties.

Claims

1. A humic acid adhesive, characterized in that: The following raw materials are used in proportion by weight:

2. The humic acid adhesive according to claim 1, characterized in that: The molar ratio of calcium chloride to magnesium chloride is 2:2-5.

3. A method for preparing the humic acid adhesive according to claim 1-2, characterized in that: The steps include: (1) Preparation of sodium humate: grind and sieve humic acid mineral powder, mix it with sodium hydroxide, add deionized water, stir to react, and dry to obtain sodium humate; (2) Preparation of calcium chloride and magnesium chloride solution: Dissolve calcium chloride and magnesium chloride in preheated deionized water to prepare a saturated solution of calcium chloride and magnesium chloride; (3) Sodium humate, calcium chloride, saturated solution of magnesium chloride and water are mixed and stirred, and then amino acid is added and stirred, and the mixture is heated in a drum, and then naturally cooled and crushed to obtain a humic acid adhesive.

4. The method for preparing the humic acid adhesive according to claim 3, characterized in that: In step (1), the mass ratio of the sodium hydroxide, humic acid mineral powder and deionized water is 1:8-12:100-110; the soluble humic acid content in the sodium humate is ≥60%.

5. The method for preparing the humic acid adhesive according to claim 3, characterized in that: The sieve aperture of step (1) is 100-120 mesh; the reaction temperature is 60-80° C., and the reaction time is 1-2 h.

6. The method for preparing the humic acid adhesive according to claim 3, characterized in that: The temperature of the deionized water in step (2) is 30-35°C.

7. The method for preparing the humic acid adhesive according to claim 3, characterized in that: In step (3), the stirring speed is 100-150 r / min, and the time is 20-30 min; the heating temperature is 130-180° C., and the time is 5-10 min.

8. The method for preparing the humic acid adhesive according to claim 3, characterized in that: The amino acid in step (3) is one or two of lysine, glutamine, asparagine, arginine and histidine.

9. Use of the humic acid adhesive according to claim 1 in preparing feed.

10. A method for preparing feed using the humic acid adhesive according to claim 1, characterized in that: The humic acid binder is first mixed with 10-15% of the total mass of the feed raw materials and stirred for 2-5 minutes, and then mixed with the remaining feed to be uniformly mixed until the humic acid binder content in the feed is 0.1-0.2%, and granulated to obtain the humic acid binder feed.

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