Livestock breeding manure deodorant and its production process

Abstract

The application discloses a deodorant for livestock and poultry breeding manure and a production process thereof, and relates to the technical field of deodorants. The production process of the deodorant comprises the steps of preparing L-theanine inclusion compound, preparing oxidized sodium alginate, preparing chelating liquid and compounding functional additives. The L-theanine inclusion compound is prepared from hydroxypropyl-beta-cyclodextrin and L-theanine. The oxidized sodium alginate is prepared from sodium periodate and sodium alginate. The chelating liquid is prepared from raw materials including wood vinegar, ferric citrate and L-theanine inclusion compound. The compounding of the functional additives adopts raw materials including carboxymethyl cellulose sodium, oxidized sodium alginate and bamboo leaf flavone. The prepared deodorant has good deodorizing performance and long-term deodorizing effect.

Description

Technical Field

[0001] This invention relates to the field of deodorant technology, specifically to a deodorant for livestock and poultry manure and its production process. Background Technology

[0002] With the rapid development of my country's livestock and poultry farming industry towards large-scale and intensive operations, the amount of livestock manure produced has increased dramatically. The resulting odor pollution has become a key bottleneck restricting the green and sustainable development of the livestock and poultry farming industry. The odorous components of livestock and poultry manure are complex, mainly including hundreds of substances such as ammonia, hydrogen sulfide, methanethiol, skatole, and isovaleric acid. This not only seriously pollutes the atmospheric environment around farms and affects the quality of life of residents, but also reduces livestock and poultry production performance, increases the incidence of respiratory diseases, and poses a direct threat to the health of those working in the livestock and poultry farming industry.

[0003] Currently, mainstream deodorization technologies on the market all have intractable shortcomings: chemical deodorizers use strong oxidants such as chlorine preparations and peroxides, which can only treat surface odors in the short term, easily generate carcinogenic byproducts such as chloroform, and also destroy beneficial microorganisms in feces, hindering the resource utilization of composting and biogas fermentation; single microbial deodorizers are slow to take effect, and their activity decreases significantly under low temperature and high-impact odor environments, making it difficult for exogenous bacteria to colonize stably in the fecal system; ordinary ferric deodorizers quickly convert to non-deodorizing ferrous iron in the strong reducing environment of feces, and their penetration depth is only 1 to 5 centimeters, making it impossible to deal with deep and continuous odor problems; conventional compound deodorizers often add artificial fragrances to mask odors, which can easily cause secondary odor pollution, and some illegally add antibiotics, bringing the risk of drug-resistant bacteria to the environment. At the same time, they generally have defects such as poor component dispersion, short activity retention time, and insufficient storage stability.

[0004] Therefore, developing a deodorant specifically designed for the characteristics of livestock and poultry manure, with good deodorizing performance and excellent long-lasting deodorizing effect, and its production process, has extremely important practical significance and industrial application value. Summary of the Invention

[0005] In order to solve the above-mentioned problems in the prior art, the present invention provides a deodorizing agent for livestock and poultry manure and its production process, and achieves the following objectives: to prepare a deodorizing agent with good deodorizing performance and excellent long-lasting deodorizing effect.

[0006] To achieve the above objectives, the following technical solution is adopted: A production process for a deodorizing agent for livestock and poultry manure includes the following steps: Step 1: Preparation of L-theanine inclusion complex Hydroxypropyl-β-cyclodextrin was prepared into a saturated aqueous solution, and L-theanine was slowly added while controlling the temperature at 50-55℃. The mixture was stirred for 2-3 hours at a speed of 400-600 rpm. Then, it was allowed to stand at 4-5℃ for 12-24 hours, filtered, and freeze-dried to obtain the L-theanine inclusion complex.

[0007] The mass ratio of hydroxypropyl-β-cyclodextrin to L-theanine is (3-5):1.

[0008] The freeze-drying process involves a temperature of -40℃, a vacuum degree of ≤20Pa, and a drying time of 12-24 hours.

[0009] Step 2: Preparation of sodium alginate oxide Sodium alginate was dissolved in distilled water, sodium periodate was added, and the mixture was stirred in the dark for 6-7 hours at a speed of 200-400 rpm. Then, the mixture was dialyzed and freeze-dried to obtain oxidized sodium alginate.

[0010] The mass ratio of sodium alginate, distilled water, and sodium periodate is 1:(80-100):(0.32-0.43).

[0011] The dialysis process involves placing the reaction solution into a dialysis bag with a molecular weight cutoff of 4000-8000 Da, placing it in deionized water, and dialyzing at a temperature of 4-10℃ in the dark for 48-72 hours. The deionized water is replaced every 6-8 hours until the difference between the conductivity of the dialysis fluid at 25℃ and the conductivity of deionized water at the same temperature is less than 5 μS / cm.

[0012] The freeze-drying process involves a temperature of -45℃, a vacuum degree of ≤20Pa, and a drying time of 24-48 hours.

[0013] Step 3: Preparation of chelation solution Wood vinegar and food-grade ferric citric acid were added to a sealed reactor. Nitrogen gas was introduced to replace the air in the reactor. Stirring was started at 60-80 rpm and the temperature was controlled at 40-45℃. L-theanine inclusion complex was added and the mixture was kept warm and stirred to disperse, thus obtaining a chelated solution.

[0014] The mass ratio of the wood vinegar, ferric citric acid, and L-theanine inclusion complex is (90-92):(8-10):(0.2-0.25).

[0015] The wood vinegar is birch-derived wood vinegar with a pH of 2.5-3.8 and an organic acid content of 3-7%.

[0016] Step 4: Compounding of functional additives Add food-grade sodium carboxymethyl cellulose, sodium alginate, and bamboo leaf flavonoids to the chelating solution in sequence, and stir until completely dissolved and homogeneous; then let it stand at 25±2℃ for 2-2.5 hours to mature, and filter through a 200-mesh screen to obtain the finished liquid deodorant.

[0017] The amount of sodium carboxymethyl cellulose added is 0.1-0.3% of the mass of the chelating solution.

[0018] The amount of sodium alginate added is 0.05-0.15% of the mass of the chelating solution.

[0019] The amount of bamboo leaf flavonoids added is 0.05-0.1% of the mass of the chelate.

[0020] The beneficial effects of this invention are as follows: (1) In this invention, hydroxypropyl-β-cyclodextrin is used to include L-theanine. The hydrophobic ethyl side chain of L-theanine is embedded in the hydrophobic cavity of cyclodextrin through hydrophobic interaction, and the hydrophilic amino and carboxyl ends face the outside of the cavity. In the reaction system of this invention, the L-theanine inclusion complex has a stable structure, which can effectively prevent the primary amino group of L-theanine from undergoing Schiff base crosslinking with the aldehyde group of sodium alginate oxidation in advance, ensuring low viscosity and high stability of the system during storage. After spraying into the fecal matter, ammonia neutralizes the acidity of the system, causing the local pH to rise, increasing the proportion of free primary amino groups, and enhancing the reactivity. It can undergo Schiff base reaction with the aldehyde group of sodium alginate oxidation, continuously consuming the free L-theanine in the solution, breaking the dynamic equilibrium of inclusion-dissociation, promoting the continuous dissociation and release of the inclusion complex, and triggering subsequent crosslinking and functional effects.

[0021] This invention introduces highly reactive aldehyde groups by oxidizing sodium alginate with a glycocyclic diol using sodium periodate. Upon contact with fecal matter, the slowly released L-theanine provides a primary amino group, while free amino groups from proteins, peptides, and other organic matter in the fecal matter participate in a Schiff base reaction with the aldehyde groups of oxidized sodium alginate, forming a cross-linked adhesion layer on the surface of the fecal particles. This adhesion layer slows down the diffusion rate of malodorous gases and anchors chelated ferric iron and active components of wood vinegar around the fecal particles, reducing their loss with leachate. Furthermore, the aldehyde groups of oxidized sodium alginate can covalently bind with the organic matter in the fecal matter, further enhancing the adhesion strength and the longevity of the effect.

[0022] The carboxyl groups retained by oxidized sodium alginate can react with the abundant calcium in fecal waste. 2+ Mg 2+ The divalent cations undergo ion coordination, further enhancing the structural stability and sustained-release performance of the adhesion layer.

[0023] (2) The deodorizing agent for livestock and poultry manure of the present invention has significant deodorizing performance. In the deodorizing performance test, after spraying the deodorizing agent for 1.5 hours, the hydrogen sulfide concentration decreased from 15.1-15.6 mg / m³. 3 Reduced to 0.5-0.7 mg / m³ 3 The hydrogen sulfide removal rate was 95.5-96.7%; the ammonia concentration was 91.5-92.2 mg / m³. 3Reduced to 3.6-3.8 mg / m³ 3 The ammonia removal rate is 95.9-96.6%.

[0024] (3) The livestock and poultry manure deodorizer of this invention has excellent long-lasting deodorizing effect. After 10 days of spraying, the hydrogen sulfide concentration of the prepared deodorizer is 1.3-1.7 mg / m³. 3 The ammonia concentration was 15.2-17.6 mg / m³. 3 . Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0026] Example 1: A deodorizing agent for livestock and poultry manure and its production process A production process for a deodorizing agent for livestock and poultry manure includes the following steps: Step 1: Preparation of L-theanine inclusion complex Hydroxypropyl-β-cyclodextrin was prepared into a saturated aqueous solution, and L-theanine was slowly added while maintaining the temperature at 50°C. The mixture was stirred for 3 hours at a speed of 400 rpm. Then, it was allowed to stand at 4°C for 24 hours, filtered, and freeze-dried to obtain the L-theanine inclusion complex.

[0027] The mass ratio of hydroxypropyl-β-cyclodextrin to L-theanine is 3:1.

[0028] The freeze-drying process involves a temperature of -40℃, a vacuum degree of ≤20Pa, and a drying time of 12 hours.

[0029] Step 2: Preparation of sodium alginate oxide Sodium alginate was dissolved in distilled water, sodium periodate was added, and the mixture was stirred in the dark for 6 hours at a speed of 400 rpm. Then, it was dialyzed and freeze-dried to obtain oxidized sodium alginate.

[0030] The mass ratio of sodium alginate, distilled water, and sodium periodate is 1:80:0.32.

[0031] The dialysis process involves placing the reaction solution into a dialysis bag with a molecular weight cutoff of 4000 Da, placing it in deionized water at 4°C, and dialyzing in the dark for 72 hours. The deionized water is replaced every 8 hours until the difference between the conductivity of the dialysis fluid at 25°C and the conductivity of deionized water at the same temperature is less than 5 μS / cm.

[0032] The freeze-drying process involves a temperature of -45℃, a vacuum degree of ≤20Pa, and a drying time of 24 hours.

[0033] Step 3: Preparation of chelation solution Wood vinegar and food-grade ferric citric acid were added to a sealed reactor. Nitrogen gas was introduced to replace the air in the reactor. Stirring was started at 60 rpm and the temperature was controlled at 40°C. L-theanine inclusion complex was added and the mixture was kept warm and stirred to disperse, thus obtaining a chelated solution.

[0034] The mass ratio of the wood vinegar, ferric citric acid, and L-theanine inclusion complex is 90:10:0.2.

[0035] The wood vinegar is birch-derived wood vinegar with a pH of 2.5-3.8 and an organic acid content of 3-7%.

[0036] Step 4: Compounding of functional additives Food-grade sodium carboxymethyl cellulose, sodium alginate, and bamboo leaf flavonoids were added sequentially to the chelating solution and stirred until completely dissolved and homogeneous. Then, the solution was allowed to stand and mature at 25±2℃ for 2 hours and passed through a 200-mesh filter to obtain the finished liquid deodorant.

[0037] The amount of sodium carboxymethyl cellulose added is 0.1% of the mass of the chelating solution.

[0038] The amount of sodium alginate added is 0.05% of the mass of the chelate solution.

[0039] The amount of bamboo leaf flavonoids added is 0.05% of the mass of the chelate.

[0040] Example 2: A deodorizing agent for livestock and poultry manure and its production process A production process for a deodorizing agent for livestock and poultry manure includes the following steps: Step 1: Preparation of L-theanine inclusion complex Hydroxypropyl-β-cyclodextrin was prepared into a saturated aqueous solution, and L-theanine was slowly added while maintaining the temperature at 52°C. The mixture was stirred for 2.5 hours at a speed of 500 rpm. Then, it was allowed to stand at 4°C for 18 hours, filtered, and freeze-dried to obtain the L-theanine inclusion complex.

[0041] The mass ratio of hydroxypropyl-β-cyclodextrin to L-theanine is 4:1.

[0042] The freeze-drying process involves a temperature of -40℃, a vacuum degree of ≤20Pa, and a drying time of 18 hours.

[0043] Step 2: Preparation of sodium alginate oxide Sodium alginate was dissolved in distilled water, sodium periodate was added, and the mixture was stirred in the dark for 7 hours at a speed of 300 rpm. Then, it was dialyzed and freeze-dried to obtain oxidized sodium alginate.

[0044] The mass ratio of sodium alginate, distilled water, and sodium periodate is 1:90:0.36.

[0045] The dialysis process involves placing the reaction solution into a dialysis bag with a molecular weight cutoff of 6000 Da, placing it in deionized water at 7°C, and dialyzing in the dark for 60 hours. The deionized water is replaced every 7 hours until the difference between the conductivity of the dialysis fluid at 25°C and the conductivity of deionized water at the same temperature is less than 5 μS / cm.

[0046] The freeze-drying process involves a temperature of -45℃, a vacuum degree of ≤20Pa, and a drying time of 36 hours.

[0047] Step 3: Preparation of chelation solution Wood vinegar and food-grade ferric citric acid were added to a sealed reactor. Nitrogen gas was introduced to replace the air in the reactor. Stirring was started at 70 rpm and the temperature was controlled at 45°C. L-theanine inclusion complex was added and the mixture was kept warm and stirred to disperse, thus obtaining a chelated solution.

[0048] The mass ratio of the wood vinegar, ferric citric acid, and L-theanine inclusion complex is 91:9:0.25.

[0049] The wood vinegar is birch-derived wood vinegar with a pH of 2.5-3.8 and an organic acid content of 3-7%.

[0050] Step 4: Compounding of functional additives Food-grade sodium carboxymethyl cellulose, sodium alginate, and bamboo leaf flavonoids were added sequentially to the chelating solution and stirred until completely dissolved and homogeneous. Then, the solution was allowed to stand and mature at 25±2℃ for 2.5 hours and passed through a 200-mesh filter to obtain the finished liquid deodorant.

[0051] The amount of sodium carboxymethyl cellulose added is 0.2% of the mass of the chelating solution.

[0052] The amount of sodium alginate added is 0.1% of the mass of the chelate solution.

[0053] The amount of bamboo leaf flavonoids added is 0.08% of the mass of the chelate.

[0054] Example 3: A deodorizing agent for livestock and poultry manure and its production process A production process for a deodorizing agent for livestock and poultry manure includes the following steps: Step 1: Preparation of L-theanine inclusion complex Hydroxypropyl-β-cyclodextrin was prepared into a saturated aqueous solution, and L-theanine was slowly added while maintaining the temperature at 55°C. The mixture was stirred for 2 hours at a speed of 600 rpm. Then, it was allowed to stand at 5°C for 12 hours, filtered, and freeze-dried to obtain the L-theanine inclusion complex.

[0055] The mass ratio of hydroxypropyl-β-cyclodextrin to L-theanine is 5:1.

[0056] The freeze-drying process involves a temperature of -40℃, a vacuum degree of ≤20Pa, and a drying time of 24 hours.

[0057] Step 2: Preparation of sodium alginate oxide Sodium alginate was dissolved in distilled water, sodium periodate was added, and the mixture was stirred in the dark for 7 hours at a speed of 200 rpm. Then, it was dialyzed and freeze-dried to obtain oxidized sodium alginate.

[0058] The mass ratio of sodium alginate, distilled water, and sodium periodate is 1:100:0.43.

[0059] The dialysis process involves placing the reaction solution into a dialysis bag with a molecular weight cutoff of 8000 Da, placing it in deionized water at 10°C, and dialyzing in the dark for 48 hours. The deionized water is replaced every 6 hours until the difference between the conductivity of the dialysis fluid at 25°C and the conductivity of deionized water at the same temperature is less than 5 μS / cm.

[0060] The freeze-drying process involves a temperature of -45℃, a vacuum degree of ≤20Pa, and a drying time of 48 hours.

[0061] Step 3: Preparation of chelation solution Wood vinegar and food-grade ferric citric acid were added to a sealed reactor. Nitrogen gas was introduced to replace the air in the reactor. Stirring was started at 80 rpm and the temperature was controlled at 45°C. L-theanine inclusion complex was added and the mixture was kept warm and stirred to disperse, thus obtaining a chelated solution.

[0062] The mass ratio of the wood vinegar, ferric citric acid, and L-theanine inclusion complex is 92:8:0.25.

[0063] The wood vinegar is birch-derived wood vinegar with a pH of 2.5-3.8 and an organic acid content of 3-7%.

[0064] Step 4: Compounding of functional additives Food-grade sodium carboxymethyl cellulose, sodium alginate, and bamboo leaf flavonoids were added sequentially to the chelating solution and stirred until completely dissolved and homogeneous. Then, the solution was allowed to stand and mature at 25±2℃ for 2.5 hours and passed through a 200-mesh filter to obtain the finished liquid deodorant.

[0065] The amount of sodium carboxymethyl cellulose added is 0.3% of the mass of the chelating solution.

[0066] The amount of sodium alginate added is 0.15% of the mass of the chelating solution.

[0067] The amount of bamboo leaf flavonoids added is 0.1% of the mass of the chelate.

[0068] Comparative Example 1 A production process for a deodorizing agent for livestock and poultry manure includes the following steps: Step 1: Preparation of sodium alginate oxide This step is the same as the step "preparing oxidized sodium alginate" in Example 2.

[0069] Step 2: Preparing a chelating solution In this step, the L-theanine inclusion complex is replaced with common L-theanine, and the other steps are the same as the step "preparing a chelating solution" in Example 2.

[0070] Step 3: Compounding functional auxiliaries This step is the same as the step "compounding functional auxiliaries" in Example 2.

[0071] Comparative Example 2 A production process of a deodorant for livestock and poultry breeding manure, comprising the following steps: Step 1: Preparing an L-theanine inclusion complex This step is the same as the step "preparing an L-theanine inclusion complex" in Example 2.

[0072] Step 2: Preparing a chelating solution This step is the same as the step "preparing a chelating solution" in Example 2.

[0073] Step 3: Compounding functional auxiliaries In this step, oxidized sodium alginate is replaced with common sodium alginate, and the other steps are the same as the step "compounding functional auxiliaries" in Example 2.

[0074] Example 4 Performance Test

[0075] (1) The deodorization performance test is carried out on the finished deodorants prepared in Examples 1 to 3 and Comparative Examples 1 to 2. Referring to the supporting analysis method of the Emission Standard for Odor Pollutants, a 100L sealed glass chamber is used, and 200g of fresh pig manure is added to the bottom; the deodorant is diluted with water at a mass ratio of 1:40, and is used at 0.6L / m 2 The diluted deodorant is sprayed at the dosage, the gas in the chamber 1.5 hours after spraying is collected, the concentrations of hydrogen sulfide and ammonia are detected, and the removal rates are calculated. The test results are shown in Table 1.

[0076] Table 1

[0077] It can be seen from the test results in Table 1 that after the deodorants prepared in Examples 1 to 3 are sprayed for 1.5 hours, the hydrogen sulfide concentration is reduced from 15.1-15.6mg / m 3 to 0.5-0.7mg / m 3 , and the hydrogen sulfide removal rate is 95.5-96.7%; the ammonia concentration is reduced from 91.5-92.2mg / m 3 to 3.6-3.8mg / m 3The ammonia removal rate was 95.9-96.6%, demonstrating the excellent deodorizing performance of the deodorizer prepared in this invention.

[0078] (II) The long-term deodorizing effect of the deodorizing agents prepared in Examples 1-3 and Comparative Examples 1-2 was tested. In performance test (I), the gas inside the cabin was collected 10 days after spraying, and the concentrations of hydrogen sulfide and ammonia were measured. The test results are shown in Table 2.

[0079] Table 2

[0080] As shown in Table 2, the hydrogen sulfide concentration of the deodorants prepared in Examples 1-3 was 1.3-1.7 mg / m³ after 10 days of spraying. 3 The ammonia concentration was 15.2-17.6 mg / m³. 3 This demonstrates that the deodorant prepared according to the present invention has excellent and long-lasting deodorizing properties.

[0081] Unless otherwise specified, all ratios mentioned in this invention are mass ratios.

[0082] Obviously, there are many other possible implementation methods under the concept of this invention. It should be stated here that any changes made under the inventive concept of this invention will fall within the protection scope of this invention.

Claims

1. A production process for a deodorizing agent for livestock and poultry manure, characterized in that, The process includes steps such as preparing L-theanine inclusion complex, preparing oxidized sodium alginate, preparing chelate solution, and compounding functional additives. The preparation of L-theanine inclusion complex: Hydroxypropyl-β-cyclodextrin was prepared into a saturated aqueous solution, L-theanine was slowly added, the temperature was controlled, and the mixture was stirred to include L-theanine; then it was allowed to stand at low temperature, filtered and dried to obtain L-theanine inclusion complex. The preparation of oxidized sodium alginate involves dissolving sodium alginate in distilled water, adding sodium periodate, stirring and reacting in the dark, followed by dialysis and drying to obtain oxidized sodium alginate. The preparation of the chelate solution is as follows: wood vinegar and ferric citric acid are added to a closed reaction vessel, nitrogen is introduced to replace the air in the vessel, stirring is started, the temperature is controlled, L-theanine inclusion complex is added, and the mixture is kept warm and stirred to disperse, thus obtaining the chelate solution. The functional additives are compounded as follows: sodium carboxymethyl cellulose, sodium alginate, and bamboo leaf flavonoids are added sequentially to the chelating solution and stirred until completely dissolved and homogeneous; then the solution is matured, filtered, and the liquid deodorant product is obtained.

2. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the step of preparing L-theanine inclusion complex, the mass ratio of hydroxypropyl-β-cyclodextrin to L-theanine is (3-5):

1.

3. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the step of preparing oxidized sodium alginate, the mass ratio of sodium alginate, distilled water, and sodium periodate is 1:(80-100):(0.32-0.43).

4. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, The dialysis process in the preparation of sodium oxidized alginate involves: placing the reaction solution into a dialysis bag with a molecular weight cutoff of 4000-8000 Da, placing it in deionized water, maintaining a temperature of 4-10℃, and dialyzing in the dark for 48-72 hours, changing the deionized water every 6-8 hours.

5. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the step of preparing the chelate solution, the mass ratio of wood vinegar, ferric citric acid, and L-theanine inclusion complex is (90-92):(8-10):(0.2-0.25).

6. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the step of preparing the chelate solution, the pH value of the wood vinegar solution is 2.5-3.8, and the organic acid content is 3-7%.

7. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the functional additive compounding step, the amount of sodium carboxymethyl cellulose added is 0.1-0.3% of the mass of the chelating solution.

8. The production process of the livestock and poultry manure deodorizer according to claim 1, characterized in that, In the functional additive compounding step, the amount of sodium alginate added is 0.05-0.15% of the mass of the chelate solution.

9. The production process of a deodorizing agent for livestock and poultry manure according to claim 1, characterized in that, In the compounding step of the functional additives, the amount of bamboo leaf flavonoids added is 0.05-0.1% of the mass of the chelate.

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