Eco-purification and restoration agent and method for eutrophication landscape water body

Abstract

The application discloses an ecological purification and restoration agent for eutrophication landscape water body and a restoration method, and belongs to the technical field of water, waste water, sewage or sludge treatment. The ecological purification and restoration agent for eutrophication landscape water body comprises the following components in parts by weight: 2.4-5.5 parts of a composite microbial agent, 3.5-6.0 parts of a porous functional polymer material, 12-16 parts of bentonite, and 18-30 parts of clinoptilolite. The porous functional polymer material is adopted to reduce the content of nitrogen and phosphorus in a short time through chemical adsorption, and the composite microbial agent prepared according to a specific proportion of bacillus subtilis, bacillus amyloliquefaciens, pseudomonas denitrificans and nitrobacter winogradskyi is used to comprehensively restore the water body, so that the eutrophication of the water body is effectively relieved, and the cost is low and the purification is complete.

Description

Technical Field

[0001] The present invention relates to the technical field of water, wastewater, sewage or sludge treatment, and in particular to an ecological purification and restoration agent for eutrophic landscape water bodies and a restoration method. Background Art

[0002] Nitrogen, phosphorus and organic matter are essential nutrients for organisms in nature. Due to the excessive discharge of urban domestic wastewater, natural water bodies often cause eutrophication, leading to the outbreak of blue-green algae blooms. Due to the decrease in dissolved oxygen in the water, the mortality rate of fish and shrimp in the water increases, and the harmful substances produced by decay cause serious degradation of water quality, destroying the ecological balance of the water body.

[0003] Using water remediation agents is a viable method for remediating eutrophic water bodies. Chinese Patent CN112707515A discloses a water remediation agent for reducing nitrogen and phosphorus in water, its preparation method, and its use. The invention comprises a composite bacterial agent composed of Enterococcus faecalis, Bacillus coagulans, Bacillus licheniformis, yeast, cellulase, and phosphatase, as well as corn starch and attapulgite. The preparation method for the remediation agent is as follows: Step 1: Add attapulgite to corn starch in appropriate proportions, followed by the addition of the various bacteria and enzymes in appropriate proportions; Step 2: Stir at a constant speed for 20 minutes using a V-type blender or a triple-V blender; Step 3: Mix with pond water at a ratio of 1:100 to 1:400 and stir evenly to obtain the water remediation agent for reducing nitrogen and phosphorus in water, its preparation method, and its use. This invention provides a sufficient content of effective bacteria and stabilizes the water pH, resolving the problem of insufficient beneficial bacteria in water. It reduces harmful indicators such as ammonia and nitrogen in water, hydrogen sulfide, and decomposes organic matter and residual bait in the water, providing a high-quality ecological environment for aquaculture.

[0004] Chinese patent CN103351061A provides a bioremediation agent for organically contaminated water bodies and its preparation method. The raw materials include the following components and their weight percentages: 0.6-1.0% Aspergillus oryzae solution, 0.6-1.0% Bacillus cereus solution, 0.6-1.0% Aspergillus terreus solution, 0.6-1.0% Aspergillus nidulans solution, 50-60% rice husks, and the balance is natural river water. The bioremediation agent for organically contaminated water bodies is prepared through mixing, fermentation, and acclimation. Compared with existing technologies, this invention allows the black, smelly, and eutrophic organic pollutants in water bodies to be decomposed and removed from the water, thereby improving water quality. Combined with other technologies, such as aquatic plants and animals, it can restore contaminated water bodies to surface water Class IV-V.

[0005] In the existing technology, it usually takes a long time to use microbial agents to degrade organic matter, nitrogen and phosphorus in eutrophication. In particular, the degradation ability of microorganisms is easily affected by environmental factors such as weather and temperature, which will lead to a decrease in the remediation effect. Summary of the Invention

[0006] In view of the above-mentioned defects of the prior art, the problem to be solved by the present invention is to provide a repair agent and a repair method having excellent ecological purification effect on eutrophic landscape water bodies.

[0007] Microorganisms utilize and decompose various organic matter and nutrients in water through metabolic activity, reducing eutrophication and achieving ecological purification. Microbial purification can significantly reduce energy consumption for water treatment and eliminate odors. This invention uses a composite bacterial agent made from Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans, and Nitrifying Bacterium Vernix in a specific ratio to purify eutrophic landscape water bodies at low cost and with thorough purification.

[0008] The key to reducing eutrophication in landscape waters lies in the rapid fixation of free nitrogen and phosphorus in the form of ammonium salts or phosphates. Therefore, the present invention prepares a porous functional polymeric material with a porous structure and rich adsorption groups. This material reduces nitrogen and phosphorus levels in a short period of time through chemical adsorption. Combined with a composite bacterial agent, it comprehensively remediates the water, effectively alleviating eutrophication.

[0009] An ecological purification and restoration agent for eutrophic landscape water bodies comprises the following components in parts by weight: 2.4 to 5.5 parts of a composite bacterial agent, 3.5 to 6.0 parts of a porous functional polymer material, 12 to 16 parts of bentonite, and 18 to 30 parts of clinoptilolite.

[0010] Preferably, the composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans, and Nitrifying Bacterium Vernix in a mass ratio of (2.1-2.7): (0.8-1.3): (1.1-1.9): 1.

[0011] Preferably, the standard mesh numbers of the bentonite and clinoptilolite are independently 70 to 230 meshes.

[0012] The present invention uses (3,4-dihydroxyphenyl)acetonitrile and β-chlorophenylethane as raw materials, which are combined under catalysis to produce a reactive monomer. This monomer then undergoes an addition reaction with hydroxylamine hydrochloride, and then reacts with dichloromethane under the catalysis of a Lewis acid to produce a porous polymer. The hydroxyl groups in the porous polymer are deprotonated under alkaline conditions, converting them into nucleophilic intermediates that undergo ring-opening addition with sodium oxirane methanesulfonate and 2,3-epoxypropyltrimethylammonium chloride to produce a porous functional polymer material.

[0013] The porous functional polymer material absorbs free nitrogen and phosphorus in eutrophic water bodies through physical adsorption in the pores and chemical adsorption involving chemical groups. In water bodies, phosphorus mainly exists in the form of phosphates, which easily connect with the protonated amino groups in the porous functional polymer material; while ammonium ions are fixed in the porous functional polymer material by combining with the anionic sulfonic acid groups. Because the porous functional polymer material has abundant active adsorption sites, free nitrogen and phosphorus quickly migrate from the water body to its outer surface through boundary diffusion and continuously diffuse into the internal voids of the porous functional polymer material. Compared with traditional porous polymers, the present invention carries out an electrophilic substitution reaction under Lewis acid catalysis, and connects a large number of rigid methylene groups to monomers through Friedel-Crafts reaction, which produces abundant micropores in the internal structure and greatly increases the specific surface area of ​​the porous polymer. During the adsorption process, the rigid structure of the porous polymer can prevent the migration and folding of long molecular chains, which would cause the accommodating pores to shrink and the specific surface area to decrease.

[0014] Preferably, the preparation method of the porous functional polymer material is as follows:

[0015] M1. Evenly mix (3,4-dihydroxyphenyl)acetonitrile, β-chlorophenylethane, potassium carbonate, and N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions; after the reaction is completed, pour the product into excess water, add hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use;

[0016] M2. Separately, the compound product, hydroxylamine hydrochloride, triethylamine and anhydrous ethanol are mixed evenly, and then an addition reaction is carried out under anaerobic conditions; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use;

[0017] M3. Taking another addition product and mixing it with dichloromethane, then adding Lewis acid, and refluxing under anaerobic conditions to carry out Friedel-Crafts reaction; after the reaction is completed, the product is washed with anhydrous ethanol and then extracted with anhydrous ethanol using Soxhlet extraction method, and the extract is dried to obtain a porous polymer for standby use;

[0018] M4. Take another porous polymer, use alkaline solution as the reaction catalytic medium, mix the two evenly, and then continue to add sodium ethylene oxide methane sulfonate and 2,3-epoxypropyltrimethylammonium chloride, and then carry out a ring-opening addition reaction under anaerobic conditions; after the reaction is completed, use hydrochloric acid to adjust the pH of the product to neutral, collect the filter cake by filtration, wash the filter cake with anhydrous ethanol, and dry it to obtain a porous functional polymer material.

[0019] Specifically, the preparation method of the porous functional polymer material is as follows, in parts by weight:

[0020] M1. Evenly mix 1.50-1.95 parts of (3,4-dihydroxyphenyl)acetonitrile, 3.35-4.40 parts of β-chlorophenylethane, 2.10-2.70 parts of potassium carbonate, and 7.5-10.0 parts of N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions. After the reaction is completed, pour the product into an excess of 0-4°C water, add hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use.

[0021] M2, taking another 3.60-4.65 parts of the compound product, 1.05-1.35 parts of hydroxylamine hydrochloride, 1.70-2.25 parts of triethylamine and 15-20 parts of anhydrous ethanol, mixing them uniformly, and then conducting an addition reaction under anaerobic conditions; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use;

[0022] M3. Taking another 2.30-2.95 parts of the addition product and mixing them with 50-75 parts of dichloromethane, then adding 0.45-0.60 parts of ferric chloride, and refluxing under anaerobic conditions to carry out Friedel-Crafts reaction; after the reaction is completed, the product is washed with anhydrous ethanol and then extracted with anhydrous ethanol by Soxhlet extraction method, and the extract is dried to obtain a porous polymer for standby use;

[0023] M4. Take another 3.40 to 4.75 parts of the porous polymer, use 50 to 75 parts of sodium hydroxide aqueous solution as the reaction catalytic medium, mix the two evenly, and then continue to add 2.10 to 3.50 parts of sodium ethylene oxide methane sulfonate and 1.95 to 3.35 parts of 2,3-epoxypropyltrimethylammonium chloride, and then carry out a ring-opening addition reaction under anaerobic conditions; after the reaction is completed, adjust the pH of the product to neutral with hydrochloric acid, collect the filter cake by filtration, wash the filter cake with anhydrous ethanol, and dry it to obtain a porous functional polymer material.

[0024] Preferably, the temperature of the combination reaction in step M1 is 105-120° C., and the reaction time is 1.5-4.0 h.

[0025] Preferably, the temperature of the addition reaction in step M2 is 70-85° C., and the reaction time is 8-30 h.

[0026] Preferably, the temperature of the Friedel-Crafts reaction in step M3 is 75-90° C., and the reaction time is 12-36 h.

[0027] Preferably, the mass percentage of sodium hydroxide in the sodium hydroxide aqueous solution in step M4 is 8-15%.

[0028] Preferably, the temperature of the ring-opening addition reaction in step M4 is 75-95° C., and the reaction time is 3-8 h.

[0029] Preferably, the concentration of the hydrochloric acid is 0.5-1.0 mol / L.

[0030] The present invention provides a method for preparing the above-mentioned eutrophic landscape water ecological purification and restoration agent, comprising the following steps:

[0031] According to the ratio of raw material formula, the composite bacterial agent, porous functional polymer material, bentonite and clinoptilolite are weighed; first, the bentonite and clinoptilolite are evenly mixed, and then the composite bacterial agent and porous functional polymer material are added in sequence to obtain the ecological purification and restoration agent for eutrophic landscape water bodies.

[0032] The present invention also provides a method for using the above-mentioned eutrophic landscape water ecological purification and restoration agent for water purification, comprising the following steps:

[0033] Add 0.01-0.08wt% of eutrophic landscape water ecological purification and restoration agent to the eutrophic water body, and use auxiliary means to fully mix the restoration agent and the water body; according to the degree of eutrophication of the water body, the water body purification cycle is 7-28 days. For extremely concentrated black and smelly water bodies, the duration of this stage can be appropriately extended according to actual conditions.

[0034] On the basis of conforming to the common sense in this field, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0035] The introduction and functions of some raw materials in the formula of the present invention are as follows:

[0036] Bacillus subtilis: A species of Bacillus spore, it lacks a capsule and possesses peritrichous flagella, enabling it to move. It utilizes proteins, various sugars, and starch, breaking down tryptophan to form indoles. It is widely distributed in soil and decaying organic matter, and thrives in the sap of dead grass, hence its name.

[0037] Bacillus amyloliquefaciens: Bacillus genus, is a bacterium that is highly related to Bacillus subtilis. During its growth, it can produce a series of metabolites that can inhibit the activity of fungi and bacteria.

[0038] Pseudomonas denitrificans: A species of Pseudomonas, anucleate bacterium that moves by polar flagella, does not form spores, is chemoorganic, and is strictly aerobic.

[0039] Nitrifying bacteria: a type of nitrifying bacteria that lives in aerobic water or sand layers and plays a very important role in the nitrogen cycle and water purification process.

[0040] Beneficial effects of the present invention:

[0041] Compared with the existing technology, the present invention uses a composite bacterial agent prepared by Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans and Nitrifying Bacterium Vernix in a specific proportion to purify eutrophic landscape water bodies, has the ability to degrade sewage, relies on metabolism to decompose organic matter in wastewater, and reduces the content of organic matter, nitrogen, phosphorus and other components in eutrophic water bodies. It has low cost and thorough purification.

[0042] Compared with the existing technology, the present invention provides a porous functional polymer material with a porous structure and rich in adsorption groups. It reduces the nitrogen and phosphorus content in a short time through chemical adsorption, and cooperates with composite bacterial agents to comprehensively repair the water body, effectively alleviating the eutrophication of the water body. DETAILED DESCRIPTION

[0043] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0044] Some raw material parameters in the comparative examples and embodiments of the present invention are as follows:

[0045] Bacillus subtilis, Bacillus subtilis, ACCC10719, Catalog No. XK-SH-13056, provided by Shanghai Xuanke Biotechnology Co., Ltd.

[0046] Bacillus amyloliquefaciens, Bacillus amyloliquefaciens AS1.892, Catalog No. XK-SH-6096, provided by Shanghai Xuanke Biotechnology Co., Ltd.

[0047] Pseudomonas denitrificans, Pseudomonas sp., ATCC 13867, Catalog No. XY-WSW-1932, provided by Shanghai Xuanya Biotechnology Co., Ltd.

[0048] Nitrobacter winogradskyi, Latin name: Nitrobacter winogradskyi, ATCC25391, serial number: VIP(S)10024, provided by Xinyang Laiyao Biotechnology Co., Ltd.

[0049] (3,4-Dihydroxyphenyl)acetonitrile, CAS number: 1126-62-1, provided by Shanghai Jixiang Biotechnology Co., Ltd.

[0050] β-Chlorophenylethane, CAS number: 622-24-2, provided by Jiangsu Leien Environmental Protection Technology Co., Ltd.

[0051] 2,3-Epoxypropyltrimethylammonium chloride, CAS No. 3033-77-0, provided by Shanghai MacLean Biochemical Technology Co., Ltd.;

[0052] Sodium ethylene oxide methane sulfonate, CAS No.: 1193-15-3, provided by Shanghai Kaiyin Chemical Co., Ltd.

[0053] Example 1

[0054] An ecological purification and restoration agent for eutrophic landscape water bodies is prepared by the following method: 4.0 kg of a composite bacterial agent, 4.8 kg of a porous functional polymer material, 14 kg of bentonite, and 24 kg of clinoptilolite are weighed; first, the bentonite and the clinoptilolite are evenly mixed, and then the composite bacterial agent and the porous functional polymer material are added in sequence to obtain the ecological purification and restoration agent for eutrophic landscape water bodies.

[0055] The composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans and Nitrifying Bacterium Vernix in a mass ratio of 2.4:1.1:1.5:1.

[0056] The standard mesh number of the bentonite and clinoptilolite is 200 mesh.

[0057] The preparation method of the porous functional polymer material is as follows:

[0058] M1. Evenly mix 1.50 kg (3,4-dihydroxyphenyl)acetonitrile, 3.35 kg β-chlorophenylethane, 2.10 kg potassium carbonate and 7.5 kg N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions at a temperature of 110° C. for 2.5 h. After the reaction is completed, pour the product into excess 0° C. water, add 1.0 mol / L hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use.

[0059] M2, take another 3.60kg of the compound product, 1.05kg of hydroxylamine hydrochloride, 1.70kg of triethylamine and 15kg of anhydrous ethanol and mix them evenly, then carry out an addition reaction under anaerobic conditions, the addition reaction temperature is 80°C, and the reaction time is 18h; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use;

[0060] M3. Take another 2.30 kg of the addition product and mix it evenly with 50 kg of dichloromethane, then add 0.45 kg of ferric chloride, and reflux under anaerobic conditions to carry out Friedel-Crafts reaction. The temperature of the Friedel-Crafts reaction is 85° C. and the reaction time is 24 hours. After the reaction is completed, the product is washed with anhydrous ethanol and then extracted with anhydrous ethanol by Soxhlet extraction. The extract is dried to obtain a porous functional polymer material.

[0061] Example 2

[0062] An ecological purification and restoration agent for eutrophic landscape water bodies is prepared by the following method: 4.0 kg of a composite bacterial agent, 4.8 kg of a porous functional polymer material, 14 kg of bentonite, and 24 kg of clinoptilolite are weighed; first, the bentonite and the clinoptilolite are evenly mixed, and then the composite bacterial agent and the porous functional polymer material are added in sequence to obtain the ecological purification and restoration agent for eutrophic landscape water bodies.

[0063] The composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans and Nitrifying Bacterium Vernix in a mass ratio of 2.4:1.1:1.5:1.

[0064] The standard mesh number of the bentonite and clinoptilolite is 200 mesh.

[0065] The preparation method of the porous functional polymer material is as follows:

[0066] M1. Evenly mix 1.50 kg (3,4-dihydroxyphenyl)acetonitrile, 3.35 kg β-chlorophenylethane, 2.10 kg potassium carbonate and 7.5 kg N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions at a temperature of 110° C. for 2.5 h. After the reaction is completed, pour the product into excess 0° C. water, add 1.0 mol / L hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use.

[0067] M2, take another 3.60kg of the compound product, 1.05kg of hydroxylamine hydrochloride, 1.70kg of triethylamine and 15kg of anhydrous ethanol and mix them evenly, then carry out an addition reaction under anaerobic conditions, the addition reaction temperature is 80°C, and the reaction time is 18h; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use;

[0068] M3. Another 2.30 kg of the addition product was mixed evenly with 50 kg of dichloromethane, and then 0.45 kg of ferric chloride was added. The mixture was refluxed under anaerobic conditions to perform a Friedel-Crafts reaction at a temperature of 85° C. for 24 h. After the reaction was completed, the product was washed with anhydrous ethanol and then extracted with anhydrous ethanol using a Soxhlet extraction method. The extract was dried to obtain a porous polymer for later use.

[0069] M4. Take another 3.40 kg of the porous polymer, use 50 kg of 8% by mass sodium hydroxide aqueous solution as the reaction catalytic medium, mix the two evenly, and then add 2.10 kg of sodium ethylene oxide methane sulfonate and 1.95 kg of 2,3-epoxypropyltrimethylammonium chloride, and then carry out a ring-opening addition reaction under anaerobic conditions. The temperature of the ring-opening addition reaction is 90°C and the reaction time is 5 hours. After the reaction is completed, the pH of the product is adjusted to neutral with hydrochloric acid with a concentration of 1.0 mol / L, and the filter cake is collected by filtration. The filter cake is washed with anhydrous ethanol and dried to obtain a porous functional polymer material.

[0070] Example 3

[0071] The preparation methods of this embodiment are basically the same as those of Example 2, with the only difference being that the composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans, and Nitrifying Bacterium Vernix in a mass ratio of 2.1:0.8:1.1:1.

[0072] Example 4

[0073] The preparation methods of this embodiment are basically the same as those of embodiment 2, with the only difference being that the composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans, and Nitrifying Bacterium Vernix at a mass ratio of 2.7:1.3:1.9:1.

[0074] Example 5

[0075] An ecological purification and restoration agent for eutrophic landscape water bodies is prepared by the following method: 4.0 kg of a composite bacterial agent, 4.8 kg of a porous functional polymer material, 14 kg of bentonite, and 24 kg of clinoptilolite are weighed; first, the bentonite and the clinoptilolite are evenly mixed, and then the composite bacterial agent and the porous functional polymer material are added in sequence to obtain the ecological purification and restoration agent for eutrophic landscape water bodies.

[0076] The composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans and Nitrifying Bacterium Vernix in a mass ratio of 2.4:1.1:1.5:1.

[0077] The standard mesh number of the bentonite and clinoptilolite is 200 mesh.

[0078] The preparation method of the porous functional polymer material is as follows:

[0079] M1. Evenly mix 1.95 kg (3,4-dihydroxyphenyl)acetonitrile, 4.40 kg β-chlorophenylethane, 2.70 kg potassium carbonate, and 10.0 kg N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions at a temperature of 110° C. for 2.5 h. After the reaction is completed, pour the product into excess 0° C. water, add 1.0 mol / L hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use.

[0080] M2, take another 4.65kg of the compound product, 1.35kg of hydroxylamine hydrochloride, 2.25kg of triethylamine and 20kg of anhydrous ethanol and mix them evenly, then carry out an addition reaction under anaerobic conditions, the addition reaction temperature is 80°C, and the reaction time is 18h; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use;

[0081] M3. Taking another 2.95 kg of the addition product and mixing it evenly with 75 kg of dichloromethane, then adding 0.60 kg of ferric chloride, and reflux under anaerobic conditions to carry out Friedel-Crafts reaction at a temperature of 85° C. and a reaction time of 24 h. After the reaction is completed, the product is washed with anhydrous ethanol and then extracted with anhydrous ethanol by Soxhlet extraction. The extract is dried to obtain a porous polymer for later use;

[0082] M4. Take another 4.75 kg of the porous polymer, use 75 kg of 8% by mass sodium hydroxide aqueous solution as the reaction catalytic medium, mix the two evenly, and then add 2.10 kg of sodium ethylene oxide methane sulfonate and 3.35 kg of 2,3-epoxypropyltrimethylammonium chloride, and then carry out a ring-opening addition reaction under anaerobic conditions. The temperature of the ring-opening addition reaction is 90°C and the reaction time is 5 hours. After the reaction is completed, the pH of the product is adjusted to neutral with hydrochloric acid with a concentration of 1.0 mol / L, and the filter cake is collected by filtration. The filter cake is washed with anhydrous ethanol and dried to obtain a porous functional polymer material.

[0083] Example 6

[0084] This embodiment is basically the same as Example 2, with the only difference being that the composition of the eutrophic landscape water ecological purification and restoration agent is: 2.4 kg of composite bacterial agent, 3.5 kg of porous functional polymer material, 12 kg of bentonite, and 18 kg of clinoptilolite.

[0085] Example 7

[0086] This embodiment is basically the same as Example 2, with the only difference being that the composition of the eutrophic landscape water ecological purification and restoration agent is: 5.5 kg of composite bacterial agent, 6.0 kg of porous functional polymer material, 16 kg of bentonite, and 30 kg of clinoptilolite.

[0087] Comparative Example 1

[0088] An ecological purification and restoration agent for eutrophic landscape water bodies is prepared by the following method: 4.0 kg of a composite bacterial agent, 14 kg of bentonite, and 24 kg of clinoptilolite are weighed; first, the bentonite and the clinoptilolite are evenly mixed, and then the composite bacterial agent is added in sequence, and the mixture is mixed to obtain the ecological purification and restoration agent for eutrophic landscape water bodies.

[0089] The composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans and Nitrifying Bacterium Vernix in a mass ratio of 2.4:1.1:1.5:1.

[0090] The standard mesh number of the bentonite and clinoptilolite is 200 mesh.

[0091] Test Example 1

[0092] An artificially simulated eutrophic water body was added to an aquarium with a volume of 50L, and the eutrophic landscape water ecological purification and restoration agent of the present invention was used to restore the eutrophic water body. The restoration effect of the present invention was tested by the changes in total nitrogen and total phosphorus in the eutrophic water body. The initial content of total nitrogen in the eutrophic water body was 4mg / L, and the content of total phosphorus was 0.4mg / L. The test temperature was 23°C, and the test period was 28d. The experimental groups were Example 1, Example 2, and Control Example 1, which adopted the optimal bacterial strain ratio. The experimental group added 0.04wt% of the eutrophic landscape water ecological purification and restoration agent to the eutrophic water body, and used auxiliary means to fully mix the restoration agent and the water body; the blank control group did not add the restoration agent. The total nitrogen and total phosphorus contents of the eutrophic water samples were measured every 4d, and the removal rates of total nitrogen and total phosphorus were calculated. Total nitrogen was determined according to the methods and procedures specified in the standard HJ / T 199-2005, "Water Quality—Determination of Total Nitrogen—Gas Phase Molecular Absorption Spectrometry." Total phosphorus was determined according to the methods and procedures specified in the standard GB 11893-1989, "Water Quality—Determination of Total Phosphorus—Ammonium Molybdate Spectrophotometry." Removal rate = [(initial content - measured content) / initial content] × 100%. See Table 1 for the total nitrogen removal rate test results, and Table 2 for the total phosphorus removal rate test results.

[0093] Table 1:

[0094]

[0095] Table 2:

[0096]

[0097]

[0098] The results in Tables 1 and 2 show that Example 2 has the best nitrogen and phosphorus removal efficiency in water. Compared to Example 1 and Control Example 1, Example 2 achieved a removal rate of >85% within 12 days. This result may be due to the fact that the key to reducing eutrophication in landscape waters lies in the rapid fixation of free nitrogen and phosphorus in the form of ammonium salts or phosphates. Example 2 reduces nitrogen and phosphorus levels in a short period of time through chemical adsorption, and combines this with a composite bacterial agent for comprehensive water remediation, effectively alleviating eutrophication. The porous functional polymer material in Example 2 absorbs free nitrogen and phosphorus in eutrophic water through physical adsorption within its pores and chemical adsorption involving chemical groups. In water, phosphorus primarily exists in the form of phosphates, which readily bind to protonated amino groups in the porous functional polymer material. Ammonium ions, on the other hand, are fixed within the porous functional polymer material by binding to anionic sulfonic acid groups. Because the porous functional polymer material has abundant active adsorption sites, free nitrogen and phosphorus quickly migrate from the water body to its outer surface through boundary diffusion, and continue to diffuse into the internal voids of the porous functional polymer material, achieving the effect of rapidly reducing total nitrogen and total phosphorus.

[0099] Test Example 2

[0100] The specific surface area of ​​the porous functional polymeric material in the preferred embodiment of the present invention was measured using the gas adsorption BET method. The test was conducted in accordance with the specific methods and procedures specified in the standard GB / T 19587-2017, "Determination of the Specific Surface Area of ​​Solid Substances by the Gas Adsorption BET Method." The static volumetric method was used, and the adsorbent was nitrogen gas with a purity of no less than 99.99%. The specific surface area test results of the porous functional polymeric material in Example 2 are shown in Table 3.

[0101] Table 3:

[0102] name <![CDATA[Specific surface area (m 2 / g)]]> Example 1 549 Example 2 964

[0103] In the preferred embodiment of the present invention, the porous functional polymer material has a large specific surface area, which facilitates its absorption of free nitrogen and phosphorus in water. Compared to conventional porous polymers, the porous functional polymer material of Example 2 undergoes an electrophilic substitution reaction catalyzed by a Lewis acid, connecting a large number of rigid methylene groups to the monomer via a Friedel-Crafts reaction. This creates abundant micropores within the porous polymer structure, significantly increasing its specific surface area. During the adsorption process, the porous polymer's rigid structure also prevents the migration and folding of long molecular chains, which could cause the pores to shrink and the specific surface area to decrease.

[0104] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A method for preparing an ecological purification and restoration agent for eutrophic landscape water bodies, characterized in that: The steps include: According to the raw material formula ratio, 2.4-5.5 parts of composite bacterial agent, 3.5-6.0 parts of porous functional polymer material, 12-16 parts of bentonite, and 18-30 parts of clinoptilolite are weighed; first, the bentonite and clinoptilolite are evenly mixed, and then the composite bacterial agent and the porous functional polymer material are added in sequence to obtain an ecological purification and restoration agent for eutrophic landscape water bodies; The composite bacterial agent is a mixture of Bacillus subtilis, Bacillus amyloliquefaciens, Pseudomonas denitrificans, and Nitrifying Bacterium Vernix in a mass ratio of (2.1-2.7): (0.8-1.3): (1.1-1.9): 1; The preparation method of the porous functional polymer material is as follows, in parts by weight: M1. Evenly mix 1.50-1.95 parts of (3,4-dihydroxyphenyl)acetonitrile, 3.35-4.40 parts of β-chlorophenylethane, 2.10-2.70 parts of potassium carbonate, and 7.5-10.0 parts of N,N-dimethylformamide, and then carry out a chemical reaction under anaerobic conditions; after the reaction is completed, pour the product into an excess of 0-4°C water, add hydrochloric acid to adjust the pH of the mixture formed by the product and water to neutral, filter and collect the filter cake, wash the filter cake with water, and dry it to obtain a compound product for later use; the temperature of the chemical reaction in step M1 is 105-120°C, and the reaction time is 1.5-4.0h; M2. Further, 3.60-4.65 parts of the compound product, 1.05-1.35 parts of hydroxylamine hydrochloride, 1.70-2.25 parts of triethylamine and 15-20 parts of anhydrous ethanol are mixed uniformly, and then an addition reaction is carried out under anaerobic conditions; after the reaction is completed, the anhydrous ethanol is removed by rotary evaporation, and the remaining product is washed with water and dried to obtain an addition product for standby use; the temperature of the addition reaction in step M2 is 70-85° C., and the reaction time is 8-30 hours; M3, taking another 2.30-2.95 parts of the addition product and mixing it with 50-75 parts of dichloromethane, then adding 0.45-0.60 parts of ferric chloride, and refluxing under anaerobic conditions to carry out Friedel-Crafts reaction; After the reaction is completed, the product is washed with anhydrous ethanol and then extracted with anhydrous ethanol using the Soxhlet extraction method. The extract is dried to obtain a porous polymer for later use. The temperature of the Friedel-Crafts reaction in step M3 is 75-90° C., and the reaction time is 12-36 hours. M4. Take another 3.40-4.75 parts of the porous polymer, use 50-75 parts of sodium hydroxide aqueous solution as the reaction catalytic medium, mix the two evenly, and then continue to add 2.10-3.50 parts of sodium ethylene oxide methane sulfonate and 1.95-3.35 parts of 2,3-epoxypropyltrimethylammonium chloride, and then carry out a ring-opening addition reaction under anaerobic conditions; after the reaction is completed, adjust the pH of the product to neutral with hydrochloric acid, collect the filter cake by filtration, wash the filter cake with anhydrous ethanol, and dry it to obtain a porous functional polymer material; the temperature of the ring-opening addition reaction in step M4 is 75-95°C, and the reaction time is 3-8h.

2. The method for preparing the ecological purification and restoration agent for eutrophic landscape water bodies according to claim 1, characterized in that: In the sodium hydroxide aqueous solution in step M4, the mass percentage of sodium hydroxide is 8-15%.

3. An ecological purification and restoration agent for eutrophic landscape water bodies, characterized by: The method is prepared by the method according to any one of claims 1 to 2.

4. The method for applying the eutrophic landscape water ecological purification and restoration agent according to claim 3 in the ecological purification of eutrophic landscape water bodies is characterized in that: The steps include: Add 0.01~0.08wt% of eutrophic landscape water ecological purification and restoration agent to the eutrophic water body, and use auxiliary means to fully mix the restoration agent and the water body; according to the degree of eutrophication of the water body, the water body purification cycle is 7~28 days. For extremely concentrated black and smelly water bodies, the stage duration can be appropriately extended according to actual conditions.

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