A formula and preparation process for eliminating ammonia nitrogen in water environment

Abstract

The present application relates to the technical field of water treatment, and discloses a formula for eliminating ammonia nitrogen in water environment, which takes tetraethyl orthosilicate as a precursor molecule, is subjected to acid catalysis hydrolysis, pH adjustment and addition of a silicon solution stimulant, so that active intermediate of silicon dioxide is aggregated to form a wet gel with nanoscale micropores, and effective components are added in the gel forming process to be wrapped in the micropores, the effective components including sodium thiosulfate, glycerol, enzymes and / or active bacteria, and the effective components accounting for 10-80% of the total weight of the preparation; in the gel solidification process, part of the effective components seep out to form a first-aid liquid which can quickly reduce ammonia nitrogen, and the gel slow-release part can continuously and stably release the effective components, so that the formula has the characteristics of quick effect and long-term stability, and does not harm aquatic organisms, and is suitable for ammonia nitrogen treatment of various natural water bodies.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to a formula and preparation process for eliminating ammonia nitrogen in aquatic environments. Background Technology

[0002] The removal of ammonia nitrogen from water bodies is a crucial issue in water environment management. Currently, the methods available for ammonia nitrogen removal in water bodies are very limited, and no new technological approaches have emerged for many years. However, there is an urgent market demand for safe and efficient ammonia nitrogen removal technologies.

[0003] Existing methods for removing ammonia nitrogen from water bodies mainly include physicochemical methods and biological methods.

[0004] Physical methods typically require supporting infrastructure construction, including the use of stripping towers. While this method is fast, efficient, and can recover ammonia nitrogen, it suffers from high energy consumption, decreased efficiency at low temperatures, the need for pH adjustment, and the requirement for tail gas treatment.

[0005] Chemical methods utilize strong oxidizing agents (such as Cl2, NaClO) or flocculants (such as polyferric chloride) to remove NH4+. + It can oxidize to N2 or convert ammonia nitrogen into precipitates. However, these methods are not suitable for natural water bodies containing aquatic organisms, and their application scenarios are very limited. Furthermore, there are certain risks associated with the storage and use of strong oxidants, which can easily cause the death of aquatic organisms and produce toxic byproducts.

[0006] Biological methods are currently the most commonly used method for ammonia nitrogen treatment. This method relies on various functional bacteria (ammonia oxidizing bacteria, nitrite oxidizing bacteria, denitrifying bacteria, etc.) to convert NH4+ into nitrogen. + It is oxidized to N2. Biological treatment is effective, but it still has shortcomings such as high energy consumption, high input costs, large sludge production, slow reaction in low-temperature environments, and inability to adapt to water bodies with high concentrations of ammonia nitrogen.

[0007] In summary, existing ammonia nitrogen removal technologies have the following drawbacks: (1) Physical methods require supporting engineering construction, which requires huge initial investment and is difficult to cope with emergencies; (2) The chemical method uses high concentrations of reagents with strong oxidizing properties, which pose safety risks during storage and use, and can easily cause the death of aquatic organisms and produce toxic byproducts; (3) Biological methods cannot effectively treat water bodies with high concentrations of ammonia nitrogen, and the reaction is slow under low temperature conditions; (4) Frequent drug administration increases labor costs; (5) Overall, existing ammonia nitrogen removal technologies have problems such as high pollution, environmental unfriendliness, high cost, and limited application scenarios. Summary of the Invention

[0008] The purpose of this invention is to provide a formulation and preparation process for ammonia nitrogen removal in aquatic environments, so as to solve the problems mentioned in the background art.

[0009] To achieve the above objectives, the present invention provides the following technical solution: a formulation for ammonia nitrogen removal in aquatic environments, comprising: a silica hydrogel carrier, and an active ingredient encapsulated in the nanoscale micropores of the silica hydrogel carrier; the silica hydrogel carrier is formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate, adjusting the pH to 6.5-7.5, and then adding a silica solution stimulant to promote the aggregation of silica active intermediates; the active ingredient comprises sodium thiosulfate, and at least one of glycerol, enzymes, and active bacteria; the active ingredient accounts for 10%-80% of the total weight of the formulation.

[0010] Preferably, the active ingredients include: a 50%-300% sodium thiosulfate solution, 10%-60% glycerol, 10%-30% enzymes, and 10%-30% active bacteria, wherein the percentages are the mass percentages of each component relative to the total weight of the active ingredients.

[0011] Preferably, the enzyme includes at least one of ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, and urease.

[0012] Preferably, the active bacteria include at least one of the following: active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia oxidizing archaea, aerobic denitrifying bacteria, and COD degrading bacteria.

[0013] Specifically, the preparation method of the formula includes the following steps: (1) Hydrolyze the precursor molecule tetraethyl orthosilicate in an acidic environment for 20-100 minutes, stirring continuously at a speed of 300-500 rpm and cooling in an ice bath during the hydrolysis process; (2) Prepare a silicon solution stimulating solution, and dilute it with water to a concentration of 15%-40% according to the concentration of the silicon solution; (3) Preparation of active ingredient solution: Sodium thiosulfate is prepared into a sodium thiosulfate solution with a concentration of 50%-300% by ultrasonic oscillation and water bath heating; other active ingredients are prepared into solutions according to the proportions, including 10%-60% glycerol, 10%-30% enzymes, and 10%-30% active bacteria; (4) Adjust the pH of the hydrolysate to 6.5-7.5 using sodium bicarbonate solution, quickly add the active ingredient solution, and stir rapidly; (5) Finally, add the prepared silicon solution to stimulate the solution, stir appropriately, and let it stand. (6) After the gel has solidified, seal it for storage.

[0014] Compared with the prior art, the beneficial effects of this invention are as follows: (1) Rapid onset of action: The emergency solution can rapidly reduce ammonia nitrogen. Experimental data shows that by testing the ammonia nitrogen of a 1L water sample, after adding 1-1.5ml of emergency solution, the ammonia nitrogen can be reduced to below 0.6mg / L. (2) Long-term stability: The concentration of ammonia nitrogen in the solution of the gel sustained-release agent gradually decreased after 30 hours of continuous testing, and the concentration of ammonia nitrogen decreased to below 0.5 mg / L after 30 hours; (3) Safe and environmentally friendly: The hydrogel ensures that the dose released each time is small enough to avoid harming aquatic organisms by slow release; (4) Wide range of applications: It is applicable to the treatment of ammonia nitrogen in various natural water bodies, overcoming the shortcomings of traditional methods with limited application scenarios. Attached Figure Description

[0015] Figure 1 This is a flowchart of the method of the present invention; Figures 2-7 This is a schematic diagram of the aggregation process of the precursor molecule tetraethyl orthosilicate and the active intermediate. Figure 8 Ammonia nitrogen slow-release agent treatment efficiency diagram; Figure 9 Graph showing the change in sodium thiosulfate concentration of the slow-release agent at different soaking times. Detailed Implementation

[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 The precursor molecule, tetraethyl orthosilicate, was hydrolyzed for 20 minutes in an acidic environment, with continuous stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process. A silica-stimulated solution was prepared and diluted with water to a concentration of 15%-40% according to the silica concentration. An effective ingredient solution was prepared: sodium thiosulfate was prepared into a 50%-300% sodium thiosulfate solution by ultrasonic oscillation and water bath heating. Other effective ingredients were prepared into solutions according to the specified proportions, including 10%-60% glycerol and 10%-30% enzymes (packaged in a container). Including but not limited to ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, urease), and 10%-30% active bacteria (including but not limited to active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia-oxidizing archaea, aerobic denitrifying bacteria, COD-degrading bacteria, etc.); adjust the pH of the hydrolysate to 7 using sodium bicarbonate solution, quickly add the active ingredient solution, stir rapidly, and finally add the prepared silica stimulation solution, stir appropriately, and let stand; after standing, the gel solidifies and is sealed for storage.

[0018] Example 2 The precursor molecule, tetraethyl orthosilicate, was hydrolyzed for 40 minutes in an acidic environment, with continuous stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process. A silica-stimulated solution was prepared and diluted with water to a concentration of 15%-40% according to the silica concentration. An effective ingredient solution was prepared: sodium thiosulfate was prepared into a 50%-300% sodium thiosulfate solution by ultrasonic oscillation and water bath heating. Other effective ingredients were prepared into solutions according to the specified proportions, including 10%-60% glycerol and 10%-30% enzymes (packaged in a container). Including but not limited to ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, urease), and 10%-30% active bacteria (including but not limited to active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia-oxidizing archaea, aerobic denitrifying bacteria, COD-degrading bacteria, etc.); adjust the pH of the hydrolysate to 7 using sodium bicarbonate solution, quickly add the active ingredient solution, stir rapidly, and finally add the prepared silica stimulation solution, stir appropriately, and let stand; after standing, the gel solidifies and is sealed for storage.

[0019] Example 3 The precursor molecule, tetraethyl orthosilicate, was hydrolyzed for 60 minutes in an acidic environment, with continuous stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process. A silica-stimulated solution was prepared and diluted with water to a concentration of 15%-40% according to the silica concentration. An effective ingredient solution was prepared: sodium thiosulfate was prepared into a 50%-300% sodium thiosulfate solution by ultrasonic oscillation and water bath heating. Other effective ingredients were prepared into solutions according to the specified proportions, including 10%-60% glycerol and 10%-30% enzymes (packaged in a container). Including but not limited to ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, urease), and 10%-30% active bacteria (including but not limited to active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia-oxidizing archaea, aerobic denitrifying bacteria, COD-degrading bacteria, etc.); adjust the pH of the hydrolysate to 7 using sodium bicarbonate solution, quickly add the active ingredient solution, stir rapidly, and finally add the prepared silica stimulation solution, stir appropriately, and let stand; after standing, the gel solidifies and is sealed for storage.

[0020] Example 4 The precursor molecule, tetraethyl orthosilicate, was hydrolyzed for 80 minutes in an acidic environment, with continuous stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process. A silica-stimulated solution was prepared and diluted with water to a concentration of 15%-40% according to the silica concentration. An effective ingredient solution was prepared: sodium thiosulfate was prepared into a 50%-300% sodium thiosulfate solution by ultrasonic oscillation and water bath heating. Other effective ingredients were prepared into solutions according to the specified proportions, including 10%-60% glycerol and 10%-30% enzymes (packaged in a container). Including but not limited to ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, urease), and 10%-30% active bacteria (including but not limited to active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia-oxidizing archaea, aerobic denitrifying bacteria, COD-degrading bacteria, etc.); adjust the pH of the hydrolysate to 7 using sodium bicarbonate solution, quickly add the active ingredient solution, stir rapidly, and finally add the prepared silica stimulation solution, stir appropriately, and let stand; after standing, the gel solidifies and is sealed for storage.

[0021] Example 5 The precursor molecule, tetraethyl orthosilicate, was hydrolyzed for 100 minutes in an acidic environment, with continuous stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process. A silica-stimulated solution was prepared and diluted with water to a concentration of 15%-40% according to the silica concentration. An effective ingredient solution was prepared: sodium thiosulfate was prepared into a 50%-300% sodium thiosulfate solution using ultrasonic oscillation and water bath heating. Other effective ingredients were prepared into solutions according to the specified proportions, including 10%-60% glycerol and 10%-30% enzymes (packaged in a container). Including but not limited to ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, urease), and 10%-30% active bacteria (including but not limited to active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia-oxidizing archaea, aerobic denitrifying bacteria, COD-degrading bacteria, etc.); adjust the pH of the hydrolysate to 7 using sodium bicarbonate solution, quickly add the active ingredient solution, stir rapidly, and finally add the prepared silica stimulation solution, stir appropriately, and let stand; after standing, the gel solidifies and is sealed for storage.

[0022] Example 6 The difference between this embodiment and Embodiment 1 is that the active ingredients do not contain live bacteria, but only sodium thiosulfate, glycerol and enzymes. The other steps are the same as in Embodiment 1.

[0023] Example 7 The difference between this embodiment and Embodiment 2 is that the active ingredients do not contain live bacteria, but only sodium thiosulfate, glycerol and enzymes. The other steps are the same as in Embodiment 2.

[0024] Example 8 The difference between this embodiment and Embodiment 3 is that the active ingredients do not contain live bacteria, but only sodium thiosulfate, glycerol and enzymes. The other steps are the same as in Embodiment 3.

[0025] Example 9 The difference between this embodiment and embodiment four is that the active ingredients do not contain live bacteria, but only sodium thiosulfate, glycerol and enzymes. The other steps are the same as in embodiment four.

[0026] Example 10 The difference between this embodiment and embodiment five is that the active ingredients do not contain live bacteria, but only sodium thiosulfate, glycerol and enzymes. The other steps are the same as in embodiment five.

[0027] Example 11 The difference between this embodiment and Embodiment 1 is that the active ingredients do not contain enzymes, but only sodium thiosulfate, glycerol and active bacteria. The other steps are the same as in Embodiment 1.

[0028] Example 12 The difference between this embodiment and Embodiment 2 is that the active ingredients do not contain enzymes, but only sodium thiosulfate, glycerol and active bacteria. The other steps are the same as in Embodiment 2.

[0029] Example 13 The difference between this embodiment and Embodiment 3 is that the active ingredients do not contain enzymes, but only sodium thiosulfate, glycerol and active bacteria. The other steps are the same as in Embodiment 3.

[0030] Example 14 The difference between this embodiment and embodiment four is that the active ingredients do not contain enzymes, but only sodium thiosulfate, glycerol and active bacteria. The other steps are the same as in embodiment four.

[0031] Example 15 The difference between this embodiment and embodiment five is that the active ingredients do not contain enzymes, but only sodium thiosulfate, glycerol and active bacteria. The other steps are the same as in embodiment five.

[0032] The effectiveness of the technical method proposed in this invention is verified below. The treatment effect of the emergency fluid is as follows: by detecting ammonia nitrogen in a 1L water sample, the changes in ammonia nitrogen concentration after adding different amounts of emergency fluid are shown in Table 1 below.

[0033] Table 1 Results of ammonia nitrogen concentration changes The results showed that after adding 1-1.5 ml of emergency fluid, ammonia nitrogen could be reduced to below 0.6 mg / L.

[0034] Effect of sustained-release agent treatment: After 30 hours of continuous monitoring, the concentration of ammonia nitrogen in the solution of the gel sustained-release agent gradually decreased, and after 30 hours the concentration of ammonia nitrogen decreased to below 0.5 mg / L.

[0035] Release characteristics of the slow-release agent: The concentration change of sodium thiosulfate was detected by measuring the slow-release agent at different soaking times.

[0036] Table 2 Results of sustained-release agent treatment The experimental data above show that the present invention can achieve a combination of rapid onset and long-term release, which can rapidly reduce ammonia nitrogen, and the gradually released dose is small enough not to harm aquatic organisms, while continuously and stably reducing ammonia nitrogen.

[0037] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A formulation for the elimination of ammonia nitrogen in water environment, characterized in that, include: The silica hydrogel carrier, and the active ingredients encapsulated in the nanoscale micropores of the silica hydrogel carrier; the silica hydrogel carrier is formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate, adjusting the pH to 6.5-7.5, and then adding a silica solution stimulant to promote the aggregation of silica active intermediates; the active ingredients include sodium thiosulfate, and at least one of glycerol, enzymes, and active bacteria; the active ingredients account for 10%-80% of the total weight of the formulation.

2. The formulation of claim 1, wherein, The active ingredients include: a 50%-300% sodium thiosulfate solution, 10%-60% glycerol, 10%-30% enzymes, and 10%-30% active bacteria, wherein the percentages are the mass percentages of each component relative to the total weight of the active ingredients.

3. The formulation of claim 1, wherein, The enzymes include at least one of ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, and urease.

4. The formulation of claim 1, wherein, The active bacteria include at least one of the following: active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia oxidizing archaea, aerobic denitrifying bacteria, and COD degrading bacteria.

5. The method for preparing a formula for eliminating ammonia nitrogen in water environment according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Hydrolyze tetraethyl orthosilicate in an acidic environment for 20-100 minutes, stirring at 300-500 rpm and cooling in an ice bath during the hydrolysis process to obtain the hydrolysate; (2) Prepare a silicon solution and dilute it with water to a concentration of 15%-40% as a stimulating solution; (3) Preparation of active ingredient solution: Sodium thiosulfate is prepared into a sodium thiosulfate solution with a concentration of 50%-300% by ultrasonic oscillation and water bath heating, and glycerol, enzymes and / or active bacteria are added; (4) Adjust the pH of the hydrolysate to 6.5-7.5 using sodium bicarbonate solution, quickly add the active ingredient solution and stir rapidly; (5) Add the stimulating solution, stir and let stand until the gel solidifies, then seal and store.

6. The preparation method according to claim 5, characterized in that, The hydrolysis temperature is 18-27℃.

7. The preparation method according to claim 5, characterized in that, In the active ingredient solution, the mass percentage of glycerol is 10%-60%, the mass percentage of enzymes is 10%-30%, and the mass percentage of active bacteria is 10%-30%.

8. The preparation method according to claim 5, characterized in that, The enzymes include at least one of ammonia monooxygenase, hydroxylamine dehydrogenase, nitrite oxidoreductase, and urease.

9. The preparation method according to claim 5, characterized in that, The active bacteria include at least one of the following: active nitrifying bacteria, denitrifying bacteria, nitrite oxidizing bacteria, nitrate oxidizing bacteria, ammonia oxidizing archaea, aerobic denitrifying bacteria, and COD degrading bacteria.

10. The application of the formulation according to any one of claims 1-4 or the formulation prepared by the preparation method according to any one of claims 5-9 in the treatment of ammonia nitrogen in water bodies.

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