Micro-ecological system for purifying river water quality

Abstract

The invention discloses a micro-ecological system for purifying river water quality. The micro-ecological system comprises timber piles, functional ecological bags, geogrids and submerged plants, the micro-ecological system is round or square, the periphery of the micro-ecological system is fixed by timber piles, and a solar microporous aeration disc is arranged in the center of the micro-ecological system; at least one functional ecological bag is arranged in the micro-ecological system, modified functional filler is filled in the functional ecological bag, a geogrid is arranged above the functional ecological bag, the geogrid is fixedly connected with the timber piles on the periphery, and submerged plants are arranged on the geogrid. The system organically integrates the stability of civil engineering, the activity enhancement of environmental engineering and the natural restoration capability of ecological engineering, and realizes long-term, stable and low-energy-consumption purification of nitrogen, phosphorus, organic matters and other pollutants in river water.

Description

Technical Field

[0001] This invention belongs to the field of river water purification technology, specifically relating to a micro-ecosystem for purifying river water quality. Background Technology

[0002] Rivers are an important part of the natural ecosystem and a vital water resource for human survival and development. However, with the rapid advancement of industrialization and urbanization, large amounts of wastewater and waste containing pollutants such as nitrogen, phosphorus, organic matter, and heavy metals are being discharged into rivers. This has led to increasingly serious problems such as eutrophication, blackening and odor of river water, and reduction in biodiversity, which not only damage the ecological functions of rivers but also threaten regional water security and the health of the human living environment.

[0003] To restore and improve the quality of polluted river water, various treatment methods have been developed in existing technologies. Physical methods, such as dredging and flushing, can quickly remove pollutants from sediment or dilute the concentration of pollutants in the water, but they are usually large-scale and costly projects, and fail to fundamentally block the negative impacts of pollution input, easily leading to secondary pollution or pollutant transfer. Chemical methods, such as adding flocculants and phosphorus removal agents, have the advantage of rapid effectiveness, but the dosage is difficult to control precisely, can easily cause toxic side effects on aquatic organisms, and have high operating costs, making it difficult to achieve long-term and stable water purification.

[0004] In recent years, ecological restoration technologies, such as artificial wetlands, ecological floating beds, and ecological revetments, have been widely used due to their environmental friendliness and low operating costs. These technologies mainly utilize the absorption of aquatic plants and the degradation of attached microorganisms to remove pollutants. However, existing ecological restoration technologies still have some shortcomings in practical applications: (1) For rivers with fast flow, the ecological restoration effect is limited. The scouring effect of water flow makes it difficult for submerged plants to establish and survive, and facilities such as ecological floating beds are easily destroyed. In addition, the short hydraulic residence time also limits the degradation efficiency of microorganisms on pollutants. Therefore, how to construct a stable microenvironment with sufficient purification reaction time in a dynamic water environment is a major challenge faced by existing technologies. (2) The system is susceptible to high concentrations of pollution, and the treatment efficiency is a bottleneck. Traditional ecological restoration technologies mainly rely on the biological action of plants and microorganisms. When faced with high loads of organic pollution or high concentrations of phosphorus and heavy metal pollution, the biological purification capacity is limited, the system is prone to collapse, and even plant death, anaerobic black and smelly bottom sediment, etc. occur, greatly reducing the purification effect. Strengthening the system's own resistance to impact and its ability to target and remove specific pollutants is the key to improving the restoration effect. (3) The restoration materials have limited functions and the engineering stability needs to be improved. Existing ecological restoration projects mostly use ordinary sand, gravel or ceramsite as microbial carriers and plant root substrates. These materials only provide physical attachment surfaces and have weak chemical adsorption capacity for pollutants such as phosphorus and heavy metals. At the same time, the conventional methods for fixing ecological bags and plants are relatively simple. Under complex water quality conditions, there is a risk that plants will be washed away and substrate will be lost, affecting the long-term stable operation of the entire ecosystem.

[0005] Therefore, developing a novel in-situ ecological restoration system that can adapt to dynamic river environments, possess high purification efficiency and long-term stability, and effectively remove multiple complex pollutants such as nitrogen, phosphorus, and heavy metals is of significant practical importance and application value in the current field of river water environment management. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a micro-ecosystem for purifying river water quality.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0008] Preferably, the diameter of the wooden pile is 15-30cm, the installation spacing between the wooden piles is 3-5cm, the exposed portion of the wooden pile above the riverbed is greater than 50cm, and the portion of the wooden pile extending into the riverbed is greater than 120cm.

[0009] Preferably, the submerged plant is one or more of Elodea nuttallii, Vallisneria natans, Myriophyllum spicatum, Potamogeton crispus, Ceratophyllum demersum, and Potamogeton crispus.

[0010] Preferably, the preparation method of the modified functional filler includes the following steps: S1. Add zeolite powder to a mixed metal salt solution, then add ammonia dropwise to adjust the pH, heat and stir, and after stirring, filter, wash, dry and calcine to obtain composite zeolite powder. S2. Add the composite zeolite powder to an ethanol aqueous solution, add γ-glycidyl etheroxypropyltrimethoxysilane, stir and react. After the reaction is complete, filter, wash and dry to obtain epoxy composite zeolite powder. S3. Add 5-amino-2-mercaptobenzimidazole and 4-vinylphenylboronic acid to toluene, then add benzophenone and carry out ultraviolet irradiation reaction. After the reaction is completed, remove toluene by vacuum distillation to obtain the intermediate product. S4. Add epoxy-based composite zeolite powder and intermediate product to toluene, then add triethylamine and carry out a constant temperature reaction. After the reaction is completed, filter, wash and dry to obtain modified zeolite filler. S5. Mix the modified zeolite filler, fly ash, biochar, and maifanite evenly to obtain a dry powder. Then add sodium alginate solution and stir to obtain a paste-like slurry. Then drop the paste-like slurry into calcium chloride solution, soak and age it, and then filter, wash, and dry to obtain the final product.

[0011] Preferably, the mixed metal salt solution in step S1 is composed of lanthanum salt and zirconium salt, with the concentration of lanthanum salt being 0.1-0.3 mol / L and the concentration of zirconium salt being 0.1-0.3 mol / L; the mass concentration of the ammonia water is 20-25%, and the pH is 10-11; the mass ratio of the zeolite powder to the mixed metal salt solution is 100:1000-1500; the heating and stirring temperature is 60-80℃, the stirring speed is 300-500 r / min, and the time is 4-6 h; the calcination temperature is 450-550℃, and the time is 1-2 h.

[0012] In this invention, zeolite powder is used as raw material. Zeolite itself has a regular pore structure and a large number of exchangeable cations. Through ion exchange, ammonia nitrogen ions in water are captured. Lanthanum zirconium metal oxide is generated in situ on the zeolite using an in-situ co-precipitation method. Lanthanum and zirconium metal ions are strong Lewis acids and have a very high natural affinity for phosphate, which is a Lewis base. Compared with simply physically mixing two powders (such as zeolite powder and lanthanum oxide powder), the in-situ generation method can make the metal oxide firmly loaded on the inner and outer surfaces of the zeolite in the form of highly dispersed nanoparticles, which greatly increases the effective contact area and bonding stability.

[0013] Preferably, in step S2, the ethanol concentration in the aqueous ethanol solution is 90-95%, the mass ratio of the composite zeolite powder to γ-glycidyl etheroxypropyltrimethoxysilane is 100:5-8, and the heating reaction temperature is 50-60℃ for 6-8 hours.

[0014] In this invention, active epoxy groups are introduced onto the zeolite powder by reacting composite zeolite powder with γ-glycidyl etheroxypropyltrimethoxysilane, which is beneficial to the subsequent reaction.

[0015] Preferably, in step S3, the mass ratio of 5-amino-2-mercaptobenzimidazole, 4-vinylphenylboronic acid, and benzophenone is 10-15:15-20:0.5-0.8, the ultraviolet irradiation reaction temperature is 25-40℃, and the light intensity is 40-50 mW / cm². 2 The time is 2-3 hours.

[0016] In this invention, a photo-initiated free radical polymerization reaction is used to react the thiol group in 5-amino-2-mercaptobenzimidazole with the vinyl group in 4-vinylphenylboronic acid, linking two small molecules with different functions into a larger intermediate with "dual functions". The benzimidazole ring, amino group, and thiol group in the 5-amino-2-mercaptobenzimidazole molecule can form stable multidentate chelate rings with various heavy metal ions, thereby significantly reducing water toxicity. At the same time, benzimidazole, as an aromatic heterocycle, can undergo π-π stacking with certain organic pollutants containing benzene rings or other aromatic structures in water, further enhancing the adsorption stability and improving the water purification efficiency of the modified functional filler. Boric acid in the 4-vinylphenylboronic acid structure is a unique Lewis acid that can undergo similar coordination complexation reactions with multiple oxygen atoms in phosphate, exhibiting high selectivity and affinity for phosphate in river water.

[0017] Preferably, in step S4, the mass ratio of the epoxy-based composite zeolite powder, the intermediate product, and triethylamine is 100:10-15:3-5, and the isothermal reaction is carried out at a temperature of 70-80°C for 5-7 hours.

[0018] In this invention, the epoxy groups in the epoxy-based composite zeolite powder react with the amino groups in the intermediate product to introduce multiple functional groups from the intermediate product onto the composite zeolite powder, enabling the modified functional filler to simultaneously and efficiently chemically adsorb and capture multiple key pollutants in water.

[0019] Preferably, in step S5, the mass ratio of the modified zeolite filler, fly ash, biochar, and maifanite is 15-25:30-40:20-30:15-25, the mass ratio of the dry powder to the sodium alginate solution is 100:150-200, the mass concentration of the sodium alginate solution is 2-4%, the mass concentration of the calcium chloride is 2-5%, the aging temperature is 20-30℃, and the time is 4-7 hours.

[0020] In this invention, modified zeolite filler with core functions is uniformly blended with fly ash, biochar, and maifanite with different auxiliary functions, and then sodium alginate molecular chains are used in Ca... 2+ The ion cross-linking under the action of the zeolite powder forms a three-dimensional network hydrogel, which gently encapsulates and solidifies all powder components. This step is not a simple physical granulation. While fully preserving the activity of the organic functional groups in the modified zeolite powder, it achieves multifunctional synergy and solves the fundamental application problem of the core powder being easy to lose and difficult to recycle in actual water bodies.

[0021] Preferably, the microhabitat structures are arranged in an alternating pattern, with 5-10 rows at each location, depending on the size of the river.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) The system for purifying river water provided by the present invention effectively slows down the water flow and delineates an independent purification functional area through the outer array of wooden piles, providing physical protection for the stable operation of the internal ecosystem; through the central solar microporous aeration disc, it provides continuous dissolved oxygen to the system, enhances the activity of aerobic microorganisms, and effectively inhibits the black and odor problem caused by anaerobic processes; through the functional ecological bags at the bottom, the geogrid covering it, and the submerged plants planted on the geogrid, a three-dimensional purification system with three-effect synergy of "chemical adsorption-microbial degradation-plant absorption" is constructed. The system organically integrates the stability of civil engineering, the activity enhancement of environmental engineering, and the natural restoration ability of ecological engineering, and realizes long-term, stable, and low-energy purification of nitrogen, phosphorus, organic matter and other pollutants in river water.

[0023] (2) The micro-ecosystem for purifying river water provided by this invention, and the modified functional filler prepared by in-situ co-precipitation and calcination of lanthanum zirconium metal oxide loaded on the zeolite framework, endow the material with a strong phosphorus adsorption capacity. The inherent ion exchange framework structure of zeolite retains its highly efficient selective adsorption capacity for ammonia nitrogen, while the in-situ generated, highly dispersed lanthanum zirconium metal oxide nanoparticles, as strong Lewis acid sites, can efficiently capture phosphate ions in the water through high-affinity coordination or by forming insoluble phosphate precipitates. This makes the composite zeolite powder contain two adsorption sites for ammonia nitrogen and phosphorus respectively, compared to Through simple physical mixing, this method ensures a tight integration and efficient synergy between the two functional units. Subsequently, γ-glycidoxypropyltrimethoxysilane is used as a bridge to introduce intermediates containing benzimidazole and phenylboronic acid groups onto the composite zeolite. Benzimidazole, as an aromatic heterocycle, can undergo π-π stacking with certain organic pollutants containing benzene rings or other aromatic structures in the water, further enhancing adsorption stability and improving the water purification efficiency of the modified functional packing. The phenylboronic acid groups can undergo reversible covalent interactions with some nitrogen-containing organic matter or biomolecules in the water, broadening the pollutant removal spectrum of the packing. This multifunctional integrated design enables a single packing to simultaneously remove phosphorus, heavy metals, and specific organic pollutants, significantly improving the system's chemical purification efficiency and applicability.

[0024] (3) The micro-ecosystem for purifying river water provided by the present invention combines functionalized modified zeolite filler with inexpensive and readily available materials such as fly ash, biochar, and maifanite, and prepares it into granular finished products through sodium alginate immobilization technology. On the one hand, by introducing materials with large specific surface area such as fly ash and biochar, not only is the overall cost of filler significantly reduced, but also a wider space for microorganisms to attach and grow, thus strengthening the biodegradation function of the system. On the other hand, the addition of maifanite can slowly release a variety of mineral trace elements, providing nutritional supplements for the growth of microorganisms and submerged plants. At the same time, the powdered filler is prepared into granules with a certain mechanical strength, which completely solves the technical problems of active powder being easily lost, easily caking, and easily causing secondary pollution in water bodies, making it more suitable for actual engineering addition. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the micro-ecosystem structure for purifying river water quality according to the present invention. Detailed Implementation

[0026] 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.

[0027] Unless otherwise specified, all chemical reagents and materials in this invention are purchased from the market or synthesized from raw materials purchased from the market.

[0028] Example 1 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0029] The wooden stakes have a diameter of 25cm and an installation spacing of 3-5cm between them. The exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm. The submerged plants are composed of Elodea nuttallii, Vallisneria natans, Myriophyllum spicatum, and Potamogeton pectinatus.

[0030] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1200g of lanthanum chloride and zirconium chloride solution (the concentration of lanthanum chloride is 0.2mol / L and the concentration of zirconium chloride is 0.2mol / L), then add 20% ammonia water dropwise to adjust the pH to 10, heat and stir at 70℃ and 400r / min for 5h. After stirring, filter, wash and dry, and calcine at 500℃ for 1.5h to obtain composite zeolite powder. S2. Add 100g of composite zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 90%), add 7g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 55℃ for 7h, filter, wash and dry after the reaction is completed to obtain epoxy composite zeolite powder. S3. Add 13g of 5-amino-2-mercaptobenzimidazole and 17g of 4-vinylphenylboronic acid to 300mL of toluene, followed by the addition of 0.7g of benzophenone. Perform an ultraviolet irradiation reaction at 35℃ and a light intensity of 45mW / cm². 2The reaction time was 2.5 h. After the reaction was completed, toluene was removed by vacuum distillation to obtain the intermediate product. S4. Add 100g of epoxy-based composite zeolite powder and 13g of intermediate product to 1L of toluene, then add 4g of triethylamine, and react at 75℃ for 6h. After the reaction is complete, filter, wash and dry to obtain modified zeolite filler. S5. By weight, 20 parts of modified zeolite filler, 35 parts of fly ash, 25 parts of biochar, and 20 parts of maifanite are mixed evenly to obtain a dry powder. Then, 180 parts of sodium alginate solution (mass concentration of 3%) are added and stirred to obtain a paste-like slurry. The paste-like slurry is then dripped into a calcium chloride solution with a mass concentration of 4% and soaked and aged at 25°C for 6 hours. After filtration, washing, and drying, the final product is obtained.

[0031] Example 2 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0032] The wooden stakes have a diameter of 25cm and an installation spacing of 3-5cm between them. The exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm. The submerged plants are composed of Elodea nuttallii, Vallisneria natans, and Myriophyllum spicatum.

[0033] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1500g of lanthanum chloride and zirconium chloride solution (the concentration of lanthanum chloride is 0.1mol / L and the concentration of zirconium chloride is 0.1mol / L), then add 25% ammonia water dropwise to adjust the pH to 11, heat and stir at 80℃ and 500r / min for 4h. After stirring, filter, wash and dry, and calcine at 550℃ for 1h to obtain composite zeolite powder. S2. Add 100g of composite zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 95%), add 8g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 50℃ for 8h, filter, wash and dry after the reaction is completed to obtain epoxy composite zeolite powder. S3. Add 15g of 5-amino-2-mercaptobenzimidazole and 20g of 4-vinylphenylboronic acid to 300mL of toluene, followed by the addition of 0.8g of benzophenone. Perform an ultraviolet irradiation reaction at 25℃ and a light intensity of 40mW / cm². 2 The reaction time was 3 hours. After the reaction was completed, toluene was removed by vacuum distillation to obtain the intermediate product. S4. Add 100g of epoxy-based composite zeolite powder and 15g of intermediate product to 1L of toluene, then add 5g of triethylamine, and react at 70℃ for 7h. After the reaction is complete, filter, wash and dry to obtain modified zeolite filler. S5. By weight, mix 15 parts modified zeolite filler, 30 parts fly ash, 20 parts biochar, and 15 parts maifanite evenly to obtain a dry powder. Then add 120 parts sodium alginate solution (mass concentration of 4%) and stir to obtain a paste. Then drop the paste into a 5% calcium chloride solution and soak and age it at 20°C for 7 hours. Then filter, wash, and dry to obtain the final product.

[0034] Example 3 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0035] The wooden stakes have a diameter of 20cm and an installation spacing of 3-5cm between them; the exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm; the submerged plants are composed of Elodea nuttallii, Vallisneria natans, and Myriophyllum spicatum.

[0036] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1000g of lanthanum chloride and zirconium chloride solution (the concentration of lanthanum chloride is 0.3mol / L and the concentration of zirconium chloride is 0.3mol / L), then add 20% ammonia water dropwise to adjust the pH to 10, heat and stir at 60℃ and 300r / min for 6h. After stirring, filter, wash and dry, and calcine at 450℃ for 2h to obtain composite zeolite powder. S2. Add 100g of composite zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 90%), add 5g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 60℃ for 6h, filter, wash and dry after the reaction is completed to obtain epoxy composite zeolite powder. S3. Add 10g of 5-amino-2-mercaptobenzimidazole and 15g of 4-vinylphenylboronic acid to 300mL of toluene, followed by 0.5g of benzophenone, and carry out an ultraviolet irradiation reaction at a temperature of 40℃ and a light intensity of 50mW / cm². 2 The reaction time was 2 hours. After the reaction was completed, toluene was removed by vacuum distillation to obtain the intermediate product. S4. Add 100g of epoxy-based composite zeolite powder and 10g of intermediate product to 1L of toluene, then add 3g of triethylamine, and react at 80℃ for 5h. After the reaction is complete, filter, wash and dry to obtain modified zeolite filler. S5. By weight, 25 parts of modified zeolite filler, 40 parts of fly ash, 30 parts of biochar, and 25 parts of maifanite are mixed evenly to obtain a dry powder. Then, 240 parts of sodium alginate solution (mass concentration of 2%) are added and stirred to obtain a paste-like slurry. The paste-like slurry is then dripped into a calcium chloride solution with a mass concentration of 2% and soaked and aged at 30°C for 4 hours. After filtration, washing, and drying, the final product is obtained.

[0037] Comparative Example 1 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0038] The wooden stakes have a diameter of 25cm and an installation spacing of 3-5cm between them. The exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm. The submerged plants are composed of Elodea nuttallii, Vallisneria natans, Myriophyllum spicatum, and Potamogeton pectinatus.

[0039] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 90%), add 7g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 55℃ for 7h, filter, wash and dry after the reaction is completed to obtain epoxy zeolite powder. S2. Add 13g of 5-amino-2-mercaptobenzimidazole and 17g of 4-vinylphenylboronic acid to 300mL of toluene, followed by the addition of 0.7g of benzophenone. Perform an ultraviolet irradiation reaction at 35℃ and a light intensity of 45mW / cm². 2 The reaction time was 2.5 h. After the reaction was completed, toluene was removed by vacuum distillation to obtain the intermediate product. S3. Add 100g of epoxy zeolite powder and 13g of intermediate product to 1L of toluene, then add 4g of triethylamine, and react at 75℃ for 6h. After the reaction is complete, filter, wash and dry to obtain modified zeolite filler. S4. By weight, mix 20 parts of modified zeolite filler, 35 parts of fly ash, 25 parts of biochar, and 20 parts of maifanite evenly to obtain a dry powder. Then add 180 parts of sodium alginate solution (mass concentration of 3%) and stir to obtain a paste. Then drop the paste into a calcium chloride solution with a mass concentration of 4% and soak and age it at 25°C for 6 hours. Then filter, wash, and dry to obtain the final product.

[0040] Compared to Example 1, the modified zeolite filler in this comparative example did not introduce lanthanum zirconium metal oxide.

[0041] Comparative Example 2 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0042] The wooden stakes have a diameter of 25cm and an installation spacing of 3-5cm between them. The exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm. The submerged plants are composed of Elodea nuttallii, Vallisneria natans, Myriophyllum spicatum, and Potamogeton pectinatus.

[0043] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1200g of lanthanum chloride and zirconium chloride solution (the concentration of lanthanum chloride is 0.2mol / L and the concentration of zirconium chloride is 0.2mol / L), then add 20% ammonia water dropwise to adjust the pH to 10, heat and stir at 70℃ and 400r / min for 5h. After stirring, filter, wash and dry, and calcine at 500℃ for 1.5h to obtain composite zeolite powder. S2. Add 100g of composite zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 90%), add 7g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 55℃ for 7h, filter, wash and dry after the reaction is completed to obtain epoxy composite zeolite powder. S4. Add 100g of epoxy-based composite zeolite powder and 13g of 5-amino-2-mercaptobenzimidazole to 1L of toluene, then add 4g of triethylamine, and react at 75℃ for 6h. After the reaction is complete, filter, wash and dry to obtain the modified zeolite filler. S5. By weight, 20 parts of modified zeolite filler, 35 parts of fly ash, 25 parts of biochar, and 20 parts of maifanite are mixed evenly to obtain a dry powder. Then, 180 parts of sodium alginate solution (mass concentration of 3%) are added and stirred to obtain a paste-like slurry. The paste-like slurry is then dripped into a calcium chloride solution with a mass concentration of 4% and soaked and aged at 25°C for 6 hours. After filtration, washing, and drying, the final product is obtained.

[0044] Compared to Example 1, the modified zeolite filler in this comparative example did not introduce 4-vinylphenylboronic acid.

[0045] Comparative Example 3 A micro-ecosystem for purifying river water quality includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

[0046] The wooden stakes have a diameter of 25cm and an installation spacing of 3-5cm between them. The exposed portion of the wooden stakes above the riverbed is greater than 50cm, and the portion of the wooden stakes extending below the riverbed is greater than 120cm. The submerged plants are composed of Elodea nuttallii, Vallisneria natans, Myriophyllum spicatum, and Potamogeton pectinatus.

[0047] The preparation method of the modified functional filler includes the following steps: S1. Add 100g of zeolite powder to 1200g of lanthanum chloride and zirconium chloride solution (the concentration of lanthanum chloride is 0.2mol / L and the concentration of zirconium chloride is 0.2mol / L), then add 20% ammonia water dropwise to adjust the pH to 10, heat and stir at 70℃ and 400r / min for 5h. After stirring, filter, wash and dry, and calcine at 500℃ for 1.5h to obtain composite zeolite powder. S2. Add 100g of composite zeolite powder to 1L of ethanol aqueous solution (ethanol mass concentration is 90%), add 7g of γ-glycidyl etheroxypropyltrimethoxysilane, stir and react at 55℃ for 7h, filter, wash and dry after the reaction is completed to obtain epoxy composite zeolite powder. S3. Add 100g of epoxy-based composite zeolite powder and 17g of 4-vinylphenylboronic acid to 1L of toluene, followed by the addition of 0.7g of benzophenone, and carry out an ultraviolet irradiation reaction at a temperature of 35℃ and a light intensity of 45mW / cm². 2 The reaction time was 2.5 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain the modified zeolite packing. S4. By weight, mix 20 parts of modified zeolite filler, 35 parts of fly ash, 25 parts of biochar, and 20 parts of maifanite evenly to obtain a dry powder. Then add 180 parts of sodium alginate solution (mass concentration of 3%) and stir to obtain a paste. Then drop the paste into a calcium chloride solution with a mass concentration of 4% and soak and age it at 25°C for 6 hours. Then filter, wash, and dry to obtain the final product.

[0048] Compared with Example 1, the modified zeolite filler in this comparative example did not introduce 5-amino-2-mercaptobenzimidazole, and 4-vinylphenylboronic acid was physically coated onto the epoxy-based composite zeolite powder.

[0049] The micro-ecosystems of Examples 1-3 and Comparative Examples 1-3 were applied to a polluted river in Hubei Province. Water quality indicators were measured before treatment. After three months of ecological restoration, COD, ammonia nitrogen, total phosphorus (TP), and Pb were measured in each group of water samples. 2+ Dissolved oxygen (DO) was measured, and water transparency was observed. Specifically: COD was measured according to the method in HJ 828-2017; ammonia nitrogen was measured according to the method in HJ 536-2009; total phosphorus was measured according to the method in GB11893-1989; and Pb... 2+ The determination was carried out according to the method of GB 7475-1987, and the determination of dissolved oxygen was carried out according to the method of HJ 506-2009. The test results are shown in Table 1 below.

[0050] Table 1 COD (mg / L) Ammonia nitrogen (mg / L) TP (mg / L) Total nitrogen (mg / L) <![CDATA[Pb 2+ (μg / L)]]> DO value (mg / L) Before processing 116 10.2 1.27 16.1 145 1.89 Example 1 23.9 1.13 0.15 2.8 15 5.82 Example 2 26.1 1.25 0.18 3.1 19 5.66 Example 3 24.6 1.08 0.14 3.2 18 5.78 Comparative Example 1 30.7 1.75 0.52 5.9 47 4.65 Comparative Example 2 38.9 1.83 0.36 5.7 53 4.87 Comparative Example 3 29.4 1.46 0.23 3.1 44 5.39 As can be seen from Table 1 above, the micro-ecosystem for purifying river water provided by this invention not only eliminates black and odorous water bodies in the treated river channels, but also significantly reduces COD, ammonia nitrogen, TP, and total nitrogen, while significantly increasing dissolved oxygen (DO), resulting in a fundamental improvement in water quality.

[0051] The above description is a further detailed explanation of the present invention in conjunction with specific implementation examples. It should not be considered that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all such deductions or substitutions should be considered to fall within the protection scope of the present invention.

[0052] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A micro-ecosystem for purifying river water, characterized in that, Includes wooden stakes, functional eco-bags, geogrids, and submerged plants; The micro-ecosystem is circular or square, and its perimeter is fixed with wooden stakes, with a solar microporous aeration disc set in its center. The micro-ecosystem contains at least one functional ecological bag, which is filled with modified functional filler. A geogrid is installed above the functional ecological bag and is fixedly connected to the surrounding wooden piles. Submerged plants are installed on the geogrid.

2. The micro-ecosystem for purifying river water quality according to claim 1, characterized in that, The diameter of the wooden piles is 15-30cm, and the installation spacing between the wooden piles is 3-5cm; the exposed portion of the wooden piles above the riverbed is greater than 50cm, and the portion of the wooden piles extending into the riverbed is greater than 120cm.

3. The micro-ecosystem for purifying river water quality according to claim 1, characterized in that, The submerged plants are one or more of the following: Elodea, Vallisneria, Myriophyllum spicatum, Potamogeton crispus, Ceratophyllum demersum, and Potamogeton crispus.

4. The micro-ecosystem for purifying river water quality according to claim 1, characterized in that, The preparation method of the modified functional filler includes the following steps: S1. Add zeolite powder to a mixed metal salt solution, then add ammonia dropwise to adjust the pH, heat and stir, and after stirring, filter, wash, dry and calcine to obtain composite zeolite powder. S2. Add the composite zeolite powder to an ethanol aqueous solution, add γ-glycidyl etheroxypropyltrimethoxysilane, and stir to react to obtain epoxy-based composite zeolite powder. S3. Add 5-amino-2-mercaptobenzimidazole and 4-vinylphenylboronic acid to toluene, then add benzophenone and carry out ultraviolet irradiation reaction. After the reaction is completed, remove toluene by vacuum distillation to obtain the intermediate product. S4. Add epoxy-based composite zeolite powder and intermediate product to toluene, then add triethylamine and carry out a constant temperature reaction to obtain modified zeolite filler. S5. Mix the modified zeolite filler, fly ash, biochar, and maifanite evenly to obtain a dry powder. Then add sodium alginate solution and stir to obtain a paste-like slurry. Then drop the paste-like slurry into calcium chloride solution, soak and age it, and then filter, wash, and dry to obtain the final product.

5. The micro-ecosystem for purifying river water quality according to claim 4, characterized in that, The mixed metal salt solution in step S1 is composed of lanthanum salt and zirconium salt, with the concentration of lanthanum salt being 0.1-0.3 mol / L and the concentration of zirconium salt being 0.1-0.3 mol / L; the mass concentration of the ammonia water is 20-25%, and the pH is 10-11; the mass ratio of the zeolite powder to the mixed metal salt solution is 100:1000-1500; the heating and stirring temperature is 60-80℃, the stirring speed is 300-500 r / min, and the time is 4-6 h; the calcination temperature is 450-550℃, and the time is 1-2 h.

6. The micro-ecosystem for purifying river water quality according to claim 4, characterized in that, In step S2, the ethanol aqueous solution has a mass concentration of 90-95%, and the mass ratio of the composite zeolite powder to γ-glycidyl etheroxypropyltrimethoxysilane is 100:5-8; the heating reaction is carried out at a temperature of 50-60℃ for 6-8 hours.

7. The micro-ecosystem for purifying river water quality according to claim 4, characterized in that, In step S3, the mass ratio of 5-amino-2-mercaptobenzimidazole, 4-vinylphenylboronic acid, and benzophenone is 10-15:15-20:0.5-0.8, the ultraviolet irradiation reaction temperature is 25-40℃, and the light intensity is 40-50 mW / cm². 2 The time is 2-3 hours.

8. The micro-ecosystem for purifying river water quality according to claim 4, characterized in that, In step S4, the mass ratio of the epoxy-based composite zeolite powder, intermediate product, and triethylamine is 100:10-15:3-5, and the isothermal reaction is carried out at a temperature of 70-80°C for 5-7 hours.

9. The micro-ecosystem for purifying river water quality according to claim 4, characterized in that, In step S5, the mass ratio of modified zeolite filler, fly ash, biochar, and maifanite is 15-25:30-40:20-30:15-25, the mass ratio of dry powder to sodium alginate solution is 100:150-200, the mass concentration of sodium alginate solution is 2-4%, the mass concentration of calcium chloride is 2-5%, the aging temperature is 20-30℃, and the time is 4-7 hours.

10. The micro-ecosystem for purifying river water quality according to claim 1, characterized in that, The microhabitat structures are arranged in an alternating pattern, with 5-10 rows at each location, depending on the size of the river.

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