A biological deodorant for a pasture and a method of preparing the same

Abstract

The present application relates to the technical field of deodorant, and disclose a kind of biological deodorant for pasture and preparation method thereof, the present application is by adding cortex moutan extract, alkyl dimethyl benzyl ammonium chloride, modified chitosan, imidazole modified triazine base compound, lemon essential oil into stirrer, stir, after obtaining biological deodorant for pasture.The imidazole group, quaternary ammonium salt group, sulfonate sodium group triazine group in imidazole modified triazine base compound and modified chitosan all have good bactericidal effect.The triazine group in it can effectively kill bacteria, fungi and other microorganisms in animal manure, feed residue and other organic matters, thereby preventing the spread of odor;The imidazole group in it can inhibit the growth and reproduction of pathogenic bacteria, reduce the occurrence and spread of disease, and play a role in killing bacteria;The quaternary ammonium salt can effectively inhibit the growth and reproduction of microorganisms, can reduce the foul-smelling gas generated by the decomposition of organic matter by microorganism, thereby achieving the effect of deodorization.

Description

Technical Field

[0001] This invention relates to the field of deodorant technology, specifically to a biological deodorant for ranches and its preparation method. Background Technology

[0002] Pasture refers to land suitable for grazing or raising livestock, typically including grassland, arable land, and woodland. During long-term grazing, animal excrement accumulates on the grassland, leading to the proliferation of bacteria, environmental pollution, and unpleasant odors. Therefore, avoiding this phenomenon is crucial to solving the problem. For example, patent CN104667320 discloses a composite microbial deodorizer for treating municipal solid waste and its preparation method. This invention effectively improves the ecological environment of municipal solid waste and significantly reduces the emission of hydrogen sulfide, ammonia, and fatty acid-based odors; however, its bactericidal effect is not improved. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a biological deodorizer for ranches and its preparation method, which has good deodorizing and bactericidal effects.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a biological deodorizer for pastures, comprising the following weight components: 8-14 parts by weight of peony bark extract, 10-12 parts by weight of alkyl dimethyl benzyl ammonium chloride, 2-3 parts by weight of modified chitosan, 2-4 parts by weight of imidazole-modified triazine compound, and 1-4 parts by weight of lemon essential oil.

[0007] Preferably, the method for preparing the imidazole-modified triazine compound is as follows:

[0008] (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 30-45℃ and react for 6-9h, cool to room temperature, add sodium borohydride, react at 40-60℃ for 1-3h, after the reaction is completed, add dilute hydrochloric acid to adjust the pH of the solution to 3-3.5, precipitate out, filter and recrystallize the product with ethanol to obtain triazinylthiazole;

[0009] (2) Add 6-8 parts by weight of triazinylthiazole and 5-10 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 55-70°C, remove the solvent by rotary evaporation after the reaction is completed, recrystallize the ethanol to obtain intermediate 1.

[0010] (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. Then add sodium hydroxide solution with a molar concentration of 5-6 mol / L dropwise and react at 70-80℃ for 11-13 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3-3.5 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2.

[0011] (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, continue to add triethylamine catalyst, react at 75-90℃ for 6-10h, after which distill under reduced pressure and wash to obtain imidazolium-modified triazine compound.

[0012] Preferably, the mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole, and sodium borohydride in (1) is 1:1.3-2.2:0.4-0.6.

[0013] Preferably, the reaction time in (2) is 10-14h.

[0014] Preferably, the mass ratio of intermediate 1,2,2-di(bromomethyl)-1,3-propanediol in (3) is 1.1-1.6:1.

[0015] Preferably, in (4), the ratio of 1-methyl-1H-imidazolium-2-carbonyl chloride, intermediate 2, and triethylamine catalyst is 0.8-1.4:1:0.01-0.03.

[0016] Preferably, the modified chitosan is prepared by:

[0017] S1. Dissolve 6-9 parts by weight of chitosan in dimethyl sulfoxide solvent, heat in a water bath at 65-90°C, add 5-8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 65-80°C for 6-8 hours, wash with anhydrous ethanol after reaction, dry, dialyze, and concentrate to obtain quaternized chitosan.

[0018] S2. Add 5-8 parts by weight of quaternized chitosan and 12-15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 70-90℃ for 6-8 hours, distill under reduced pressure after reaction, filter to obtain modified chitosan.

[0019] Preferably, the preparation method of the biological deodorizer for pasture is as follows: peony bark extract, alkyl dimethyl benzyl ammonium chloride, modified chitosan, imidazole-modified triazine compound, and lemon essential oil are added to a mixer and stirred for 10-15 minutes to obtain the biological deodorizer for pasture.

[0020] (iii) Beneficial technical effects

[0021] This invention involves adding peony bark extract, alkyl dimethyl benzyl ammonium chloride, modified chitosan, imidazole-modified triazine compound, and lemon essential oil to a mixer, stirring, and then obtaining a biological deodorizer for ranches.

[0022] Imidazole-modified triazine compounds and the imidazole, quaternary ammonium salt, sodium sulfonate, and triazine groups in modified chitosan all exhibit good bactericidal effects. The triazine groups effectively kill bacteria, fungi, and other microorganisms in organic matter such as animal feces and feed residues, thus preventing the spread of odors. The imidazole groups inhibit the growth and reproduction of pathogens, reducing the occurrence and spread of diseases and thus protecting the health of crops and pastures. The quaternary ammonium salts effectively inhibit the growth and reproduction of microorganisms, reducing the malodorous gases produced by the decomposition of organic matter by microorganisms, thereby achieving a deodorizing effect. The chitosan molecule itself has good bactericidal effects. In this invention, intermediate 1 reacts with 2,2-di(bromomethyl)-1,3-propanediol to generate intermediate 2, further increasing the degree of substitution of the quaternary ammonium salt and improving its bactericidal effect. Detailed Implementation

[0023] Example 1

[0024] (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 30℃ and react for 6h, cool to room temperature, add sodium borohydride, wherein the mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole and sodium borohydride is 1:1.3:0.4, react at 40℃ for 1h, after which dilute hydrochloric acid is added to adjust the pH of the solution to 3, precipitate, filter and recrystallize the product with ethanol to obtain triazinylthiazole;

[0025] (2) Add 6 parts by weight of triazinethiazole and 5 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 55°C for 10 h, remove the solvent by rotary evaporation after the reaction, recrystallize the ethanol to obtain intermediate 1.

[0026] (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. The mass ratio of intermediate 1 to 2,2-di(bromomethyl)-1,3-propanediol is 1.1:1. Then add sodium hydroxide solution with a molar concentration of 5 mol / L dropwise and react at 70°C for 11 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2.

[0027] (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, and continue to add triethylamine catalyst, wherein 1-methyl-1H-imidazolium-2-carbonyl chloride, intermediate 2 and triethylamine catalyst are in a ratio of 0.8:1:0.01, react at 75°C for 6 h, and after the reaction is completed, distill under reduced pressure and wash to obtain imidazolium-modified triazine compound;

[0028] (5) Add 6 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heat it in a water bath at 65°C, add 5 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 65°C for 6 hours, wash with anhydrous ethanol after reaction, dry, dialyze and concentrate to obtain quaternized chitosan.

[0029] (6) Add 5 parts by weight of quaternized chitosan and 12 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 70°C for 6 hours, and then distill under reduced pressure and filter to obtain modified chitosan.

[0030] (7) Add 8 parts by weight of peony bark extract, 10 parts by weight of alkyl dimethyl benzyl ammonium chloride, 2 parts by weight of modified chitosan, 2 parts by weight of imidazole modified triazine compound, and 1 part by weight of lemon essential oil to a mixer and stir for 10 minutes. After stirring, a biological deodorizer for ranches is obtained.

[0031] Example 2

[0032] (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 45℃ and react for 9 h, cool to room temperature, add sodium borohydride, wherein the mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole and sodium borohydride is 1:2.2:0.6, react at 60℃ for 3 h, after which dilute hydrochloric acid is added to adjust the pH of the solution to 3.5, the precipitate is precipitated, the product is filtered and recrystallized from ethanol to obtain triazinylthiazole;

[0033] (2) Add 8 parts by weight of triazinylthiazole and 10 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 70°C for 14 h, remove the solvent by rotary evaporation after the reaction, recrystallize the ethanol to obtain intermediate 1.

[0034] (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. The mass ratio of intermediate 1 to 2,2-di(bromomethyl)-1,3-propanediol is 1.6:1. Then add sodium hydroxide solution with a molar concentration of 6 mol / L dropwise and react at 80°C for 13 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3.5 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2.

[0035] (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, and continue to add triethylamine catalyst, wherein 1-methyl-1H-imidazolium-2-carbonyl chloride, intermediate 2 and triethylamine catalyst are in a ratio of 1.4:1:0.03, react at 90℃ for 10 h, and after the reaction is completed, distill under reduced pressure and wash to obtain imidazolium-modified triazine compound;

[0036] (5) Add 9 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heat it in a water bath at 90°C, add 8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 80°C for 8 hours, wash with anhydrous ethanol after reaction, dry, dialyze and concentrate to obtain quaternized chitosan.

[0037] (6) Add 8 parts by weight of quaternized chitosan and 15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 90°C for 8 hours, and then distill under reduced pressure and filter to obtain modified chitosan.

[0038] (7) Add 14 parts by weight of peony bark extract, 12 parts by weight of alkyl dimethyl benzyl ammonium chloride, 3 parts by weight of modified chitosan, 4 parts by weight of imidazole modified triazine compound, and 4 parts by weight of lemon essential oil to a mixer and stir for 15 minutes. After stirring, a biological deodorizer for ranches is obtained.

[0039] Example 3

[0040] (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 35℃ and react for 7 h, cool to room temperature, add sodium borohydride, wherein the mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole and sodium borohydride is 1:1.6:0.5, react at 50℃ for 2 h, after which dilute hydrochloric acid is added to adjust the pH of the solution to 3.2, the precipitate is precipitated, the product is filtered and recrystallized from ethanol to obtain triazinylthiazole;

[0041] (2) Add 7 parts by weight of triazinethiazole and 7 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 65°C for 12 h, remove the solvent by rotary evaporation after the reaction, recrystallize the ethanol to obtain intermediate 1.

[0042] (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. The mass ratio of intermediate 1 to 2,2-di(bromomethyl)-1,3-propanediol is 1.4:1. Then add sodium hydroxide solution with a molar concentration of 5 mol / L dropwise and react at 75°C for 12 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3.2 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2.

[0043] (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, and continue to add triethylamine catalyst, wherein 1-methyl-1H-imidazolium-2-carbonyl chloride, intermediate 2 and triethylamine catalyst are in a ratio of 1.2:1:0.023, react at 80℃ for 8h, and after the reaction is completed, distill under reduced pressure and wash to obtain imidazolium-modified triazine compound;

[0044] (5) Add 8 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heat it in a water bath at 75°C, add 6 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 70°C for 7 hours, wash with anhydrous ethanol after reaction, dry, dialyze and concentrate to obtain quaternized chitosan.

[0045] (6) Add 6 parts by weight of quaternized chitosan and 14 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 80°C for 7 h, and then distill under reduced pressure and filter to obtain modified chitosan.

[0046] (7) Add 10 parts by weight of peony bark extract, 11 parts by weight of alkyl dimethyl benzyl ammonium chloride, 2 parts by weight of modified chitosan, 4 parts by weight of imidazole modified triazine compound, and 3 parts by weight of lemon essential oil to a mixer and stir for 12 minutes. After stirring, a biological deodorant for ranches is obtained.

[0047] Example 4

[0048] (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 30℃ and react for 6h, cool to room temperature, add sodium borohydride, wherein the mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole and sodium borohydride is 1:1.3:0.4, react at 40℃ for 1h, after which dilute hydrochloric acid is added to adjust the pH of the solution to 3, precipitate, filter and recrystallize the product with ethanol to obtain triazinylthiazole;

[0049] (2) Add 6 parts by weight of triazinethiazole and 5 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 55°C for 10 h, remove the solvent by rotary evaporation after the reaction, recrystallize the ethanol to obtain intermediate 1.

[0050] (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. The mass ratio of intermediate 1 to 2,2-di(bromomethyl)-1,3-propanediol is 1.6:1. Then add sodium hydroxide solution with a molar concentration of 6 mol / L dropwise and react at 80°C for 13 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3.5 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2.

[0051] (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, and continue to add triethylamine catalyst, wherein 1-methyl-1H-imidazolium-2-carbonyl chloride, intermediate 2 and triethylamine catalyst are in a ratio of 1.4:1:0.03, react at 90℃ for 10 h, and after the reaction is completed, distill under reduced pressure and wash to obtain imidazolium-modified triazine compound;

[0052] (5) Add 8 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heat it in a water bath at 75°C, add 6 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 70°C for 7 hours, wash with anhydrous ethanol after reaction, dry, dialyze and concentrate to obtain quaternized chitosan.

[0053] (6) Add 6 parts by weight of quaternized chitosan and 14 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 80°C for 7 h, and then distill under reduced pressure and filter to obtain modified chitosan.

[0054] (7) Add 10 parts by weight of peony bark extract, 11 parts by weight of alkyl dimethyl benzyl ammonium chloride, 2 parts by weight of modified chitosan, 4 parts by weight of imidazole modified triazine compound, and 3 parts by weight of lemon essential oil to a mixer and stir for 12 minutes. After stirring, a biological deodorant for ranches is obtained.

[0055] Comparative Example 1

[0056] The difference between this comparative example and Example 4 is that no imidazole-modified triazine compound was added.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Example 4 is that no modified chitosan was added.

[0059] The concentration is 2×10 8A CFU / mL Staphylococcus aureus bacterial suspension was added to a sterilized petri dish as the test strain. Solid agar medium was then added to dissolve the bacteria, and the mixture was cooled to 45°C. The solution was then poured into the petri dishes, 20 mL for each 10 cm inner diameter dish. The deodorant (3 cm in diameter and 1 mm thick) from the embodiments and comparative examples of this invention was then placed on the culture medium plates. The plates were incubated at 37°C for 12 hours. The diameter of the inhibition zone was measured after incubation. The test results are shown in Table 1.

[0060] Table 1: Antibacterial test.

[0061]

[0062] As shown in Table 1, the deodorant of the present invention in Examples 1-4 has a better bactericidal effect than that in Comparative Examples 1-2.

[0063] Five 150L plastic containers were selected in the laboratory, each containing a 120L plastic container. A small hole was made at the bottom of the outer container to allow air in, and a small hole at the top to allow air out. Each inner container contained 100L of fresh biogas slurry. The experimental group added deodorizing agent at a volume ratio of 0.4%. The experimental results are shown in Table 2. Ammonia was measured using Nessler's reagent spectrophotometry (HJ533-2009).

[0064] Table 2: Deodorization test.

[0065]

[0066] As shown in Table 2, the deodorizing agents of the present invention in Examples 1-4 have better deodorizing effects than those in Comparative Examples 1-2.

[0067] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A biological deodorizer for ranches, characterized in that, It includes the following components by weight: 8-14 parts by weight of peony bark extract, 10-12 parts by weight of alkyl dimethyl benzyl ammonium chloride, 2-3 parts by weight of modified chitosan, 2-4 parts by weight of imidazole-modified triazine compound, and 1-4 parts by weight of lemon essential oil. The method for preparing the imidazole-modified triazine compound is as follows: (1) Add 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine and 2-aminothiazole to ethanol, heat to 30-45℃ and react for 6-9h, cool to room temperature, add sodium borohydride, react at 40-60℃ for 1-3h, after the reaction is completed, add dilute hydrochloric acid to adjust the pH of the solution to 3-3.5, precipitate out, filter and recrystallize the product with ethanol to obtain triazinylthiazole; (2) Add 6-8 parts by weight of triazinylthiazole and 5-10 parts by weight of 2-bromoethanol to isopropanol solvent, reflux at 55-70°C, remove the solvent by rotary evaporation after the reaction is completed, recrystallize the ethanol to obtain intermediate 1. (3) Add intermediate 1 and 2,2-di(bromomethyl)-1,3-propanediol to acetone solvent and stir until homogeneous. Then add sodium hydroxide solution with a molar concentration of 5-6 mol / L dropwise and react at 70-80℃ for 11-13 h. After the reaction is completed, add dilute hydrochloric acid with a molar concentration of 3-3.5 mol / L dropwise to neutralize. Concentrate, filter, wash and dry to obtain intermediate 2. (4) Add 1-methyl-1H-imidazolium-2-carbonyl chloride and intermediate 2 to N,N-dimethylformamide solvent, stir and mix, continue to add triethylamine catalyst, react at 75-90℃ for 6-10h, after which vacuum distillation and washing are performed to obtain imidazolium-modified triazine compound; The modified chitosan is prepared by: S1. Dissolve 6-9 parts by weight of chitosan in dimethyl sulfoxide solvent, heat in a water bath at 65-90°C, add 5-8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride under constant pressure, react at 65-80°C for 6-8 hours, wash with anhydrous ethanol after reaction, dry, dialyze, and concentrate to obtain quaternized chitosan. S2. Add 5-8 parts by weight of quaternized chitosan and 12-15 parts by weight of sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stir and mix, react at 70-90℃ for 6-8 hours, distill under reduced pressure after reaction, filter to obtain modified chitosan.

2. The biological deodorizer for pastures according to claim 1, characterized in that, The mass ratio of 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2-aminothiazole, and sodium borohydride in (1) is 1:1.3-2.2:0.4-0.

6.

3. The biological deodorizer for pastures according to claim 1, characterized in that, The reaction time in (2) is 10-14h.

4. The biological deodorizer for pastures according to claim 1, characterized in that, The mass ratio of intermediate 1,2,2-di(bromomethyl)-1,3-propanediol in (3) is 1.1-1.6:

1.

5. The biological deodorizer for pastures according to claim 1, characterized in that, In (4), the ratio of 1-methyl-1H-imidazol-2-carbonyl chloride, intermediate 2, and triethylamine catalyst is 0.8-1.4:1:0.01-0.

03.

6. A method for preparing a biological deodorizer for pastures as described in any one of claims 1-5, characterized in that, The preparation method of the biological deodorizer for ranches is as follows: Paeonia suffruticosa extract, alkyl dimethyl benzyl ammonium chloride, modified chitosan, imidazole-modified triazine compound, and lemon essential oil are added to a mixer and stirred for 10-15 minutes. After stirring, the biological deodorizer for ranches is obtained.

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