A rare earth oxide nanoenzyme complex and its application in enhancing the treatment of antibiotic-contaminated water bodies by duckweed.

Abstract

This invention discloses a rare earth oxide nanoenzyme complex and its application in enhancing duckweed treatment of antibiotic-contaminated water bodies, belonging to the field of wastewater treatment technology. The complex comprises the following raw materials in parts by weight: 1-5 parts rare earth oxides, 5-10 parts nanoenzymes, 2-3 parts potassium humate, 15-25 parts bamboo charcoal, and 1-3 parts microbial inoculant. The preparation method of the complex and its application in enhancing duckweed treatment of antibiotic-contaminated water bodies are also disclosed. This invention utilizes rare earth oxides to catalyze the decomposition of antibiotics by nanoenzymes, breaking down antibiotics in wastewater into smaller molecules, which are then readily absorbed by duckweed. This process also promotes the direct absorption of antibiotics by duckweed, achieving effective removal of antibiotics from wastewater and restoring the ecological function of the water body.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, and in particular relates to a rare earth oxide nanoenzyme complex and its application in enhancing the treatment of antibiotic-contaminated water bodies by duckweed. Background Technology

[0002] Currently, antibiotic treatment in water has become a global environmental issue, attracting widespread attention. Traditional wastewater treatment processes are not ideal in removing antibiotics; even after physical, chemical, and biological treatment, antibiotic concentrations in water may still reach levels that threaten human health. Therefore, developing efficient and economical antibiotic removal technologies is particularly important.

[0003] Currently, the treatment of antibiotics in water mainly employs physical, chemical, and biological methods. Physical methods include adsorption and filtration. Commonly used adsorbents include activated carbon, iron oxide, and alumina, which adsorb antibiotic substances in the water onto their surfaces, thereby achieving removal. Filtration involves passing water containing antibiotics through filter media to intercept antibiotic particles or dissolved antibiotic molecules. Chemical methods mainly involve oxidation-reduction reactions, where oxidants or reducing agents are added to induce oxidation-reduction reactions in antibiotics, converting them into non-toxic or low-toxic substances. Biological methods are also a current research hotspot, including biodegradation and plant absorption technologies. Biodegradation technology uses microorganisms to decompose organic matter in water, including antibiotics, and this method is environmentally friendly and highly efficient. Plant absorption technology introduces plants with adsorption and enrichment capabilities into water bodies, utilizing the plants' absorption of antibiotics for water purification. However, plant absorption technology still faces some challenges in practical applications. First, it requires large-scale plant cultivation and management, which may be a problem for areas with limited resources or space. Secondly, the effectiveness of plant absorption technology can be affected by various factors, such as water quality, water temperature, and light intensity, thus requiring strict control and monitoring of these factors. Furthermore, compared to other treatment methods, plant absorption technology may be slower, requiring a longer time to achieve the desired purification effect. Therefore, in practical applications, it may be necessary to combine it with other technologies, such as physical methods and biodegradation technologies, to improve treatment efficiency.

[0004] Therefore, how to provide a highly efficient and simple method for reducing antibiotic content in wastewater using plant absorption technology is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a rare earth oxide nanoenzyme complex and its application in enhancing the treatment of antibiotic-contaminated water bodies by duckweed.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight:

[0008] 1-5 parts rare earth oxides, 5-10 parts nanozymes, 2-3 parts potassium humate, 15-25 parts bamboo charcoal, and 1-3 parts microbial inoculant.

[0009] Preferably, the nanozyme comprises the following raw materials in parts by weight:

[0010] 1-2 parts nano silica, 1-2 parts nano titanium dioxide, 6-11 parts plant protease, 3-7 parts amylase, 3-5 parts pectinase, 5-8 parts cellulase, 5-10 parts β-glucosidase, 1-2 parts chitosanase, 1-2 parts agarase, and 3-5 parts β-lactamase.

[0011] Preferably, the preparation method of the nanozyme includes the following steps:

[0012] The plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase, and β-lactamase were added to a phosphate buffer solution and mixed thoroughly to obtain a biological enzyme buffer solution. Then, the nano-silica and nano-titanium dioxide were added, and the mixture was stirred and mixed at 30-40°C and allowed to stand for 1-2 hours to obtain the nanoenzyme.

[0013] Preferably, the concentration of the biological enzyme buffer is 0.1-0.3 mol / L.

[0014] Beneficial effects: As nanomaterials, nano-silica and nano-titanium dioxide can be loaded with various biological enzymes through the present invention, thereby improving the dispersibility and uniformity of biological enzymes in water. In addition, the titanium element can be used as a beneficial element to supplement the nutrition of crops.

[0015] Preferably, the rare earth oxide includes one rare earth oxide selected from lanthanum, cerium, neodymium, yttrium, and scandium, or a composite rare earth oxide of any combination of these elements.

[0016] Preferably, the microbial agent includes one or more of Bacillus, lactic acid bacteria, yeast, nitrogen-fixing bacteria, rhizobium, and Beauveria bassiana.

[0017] Beneficial Effects: The nanoenzymes and microbial agents in the composite provided by this invention have a certain decomposition effect on antibiotics in water. Furthermore, the addition of rare earth oxides in this invention promotes the decomposition of antibiotics by nanoenzymes and microbial agents, providing a good catalytic effect and thus improving the decomposition efficiency of antibiotics by nanoenzymes and microbial agents. Simultaneously, the bamboo charcoal added in this invention has a highly porous structure, which can adsorb nanoenzymes and microbial agents, improving their dispersibility and uniformity in water, and increasing their contact area with antibiotic-treated wastewater, thereby improving decomposition efficiency. In addition, the bamboo charcoal and potassium humate in this invention have a certain promoting effect on plant growth, promoting the growth of aquatic plants and facilitating the absorption and utilization of antibiotics by some wastewater treatment plants.

[0018] A method for preparing a rare earth oxide nanoenzyme complex includes the following steps:

[0019] The nanoenzyme and microbial agent were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanoenzyme composite.

[0020] Preferably, the mass ratio of the phosphate buffer solution to the nanozyme is (20-50):1.

[0021] Application of a rare earth oxide nanoenzyme complex in enhancing the treatment of antibiotic-contaminated water bodies by duckweed.

[0022] Preferably, the duckweed planted in the antibiotic wastewater treatment pond covers 55-70% of the water surface area of ​​the treatment pond;

[0023] The mass ratio of the rare earth oxide nanoenzyme complex to antibiotic wastewater is (0.5-1):10.

[0024] Preferably, the antibiotics include tetracycline antibiotics and / or sulfonamide antibiotics.

[0025] Preferably, the tetracycline antibiotic is one or more of oxytetracycline, tetracycline, and chlortetracycline;

[0026] The sulfonamide antibiotics are one or any combination of sulfadiazine, sulfaisoxazole, sulfadiazine, sulfamethoxazole, sulfamethoxypyrimidine, and sulfadimethylpyrimidine.

[0027] Beneficial effects: Antibiotic wastewater is not conducive to the survival of microorganisms. This invention uses nanomaterials, enzymes and microorganisms to decompose antibiotics together, ensuring the effectiveness of antibiotic degradation and improving the survival ability of enzymes and microorganisms in antibiotic environments.

[0028] Compared with the prior art, the present invention has the following advantages and technical effects:

[0029] This invention utilizes rare earth oxides to catalyze nanoenzymes to decompose antibiotics in wastewater, breaking them down into smaller molecules that are then readily absorbed by duckweed. This process also promotes direct absorption of antibiotics by the duckweed, effectively removing antibiotics from wastewater and restoring the ecological function of the water body. Furthermore, this invention, by using rare earth oxides to catalyze nanoenzymes and enhance the effects of duckweed in treating antibiotic-contaminated wastewater, offers advantages such as low cost, ease of operation, good treatment effect, and environmental friendliness. During the treatment process, the generation of ROS (reactive oxygen species) within the duckweed may mitigate antibiotic toxicity. Although high concentrations of antibiotics may exert some stress on the duckweed, over a long period, it can reduce intracellular ROS levels, demonstrating adaptability to antibiotics. This method also boasts advantages such as low cost and simple operation, making it suitable for large-scale water pollution treatment. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0031] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to specific embodiments.

[0032] A rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight:

[0033] 1-5 parts rare earth oxides, 5-10 parts nanozymes, 2-3 parts potassium humate, 15-25 parts bamboo charcoal, and 1-3 parts microbial inoculant.

[0034] In a preferred embodiment, the nanozyme comprises the following raw materials in parts by weight:

[0035] 1-2 parts nano silica, 1-2 parts nano titanium dioxide, 6-11 parts plant protease, 3-7 parts amylase, 3-5 parts pectinase, 5-8 parts cellulase, 5-10 parts β-glucosidase, 1-2 parts chitosanase, 1-2 parts agarase, and 3-5 parts β-lactamase.

[0036] In a preferred embodiment, the preparation method of the nanozyme includes the following steps:

[0037] The plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase, and β-lactamase were added to a phosphate buffer solution and mixed thoroughly to obtain a biological enzyme buffer solution. Then, the nano-silica and nano-titanium dioxide were added, and the mixture was stirred and mixed at 30-40°C and allowed to stand for 1-2 hours to obtain the nanoenzyme.

[0038] Preferably, the concentration of the biological enzyme buffer is 0.1-0.3 mol / L.

[0039] In a preferred embodiment, the rare earth oxide includes one rare earth oxide selected from lanthanum, cerium, neodymium, yttrium, and scandium, or a composite rare earth oxide of any combination of these rare earth oxides.

[0040] In a preferred embodiment, the microbial agent includes one or more of Bacillus, lactic acid bacteria, yeast, nitrogen-fixing bacteria, rhizobium, and Beauveria bassiana.

[0041] A method for preparing a rare earth oxide nanoenzyme complex includes the following steps:

[0042] The nanoenzyme and microbial agent were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanoenzyme composite.

[0043] In a preferred embodiment, the mass ratio of the phosphate buffer solution to the nanozyme is (20-50):1.

[0044] This invention also provides an application of rare earth oxide nanoenzyme complex in enhancing the treatment of antibiotic-contaminated water bodies by duckweed.

[0045] In a preferred embodiment, the duckweed planted in the antibiotic wastewater treatment pond covers an area of ​​55-70% of the pond's surface area.

[0046] The mass ratio of the rare earth oxide nanoenzyme complex to antibiotic wastewater is (0.1-0.5):10.

[0047] In a preferred embodiment, the antibiotics include tetracycline antibiotics and / or sulfonamide antibiotics.

[0048] In a preferred embodiment, the tetracycline antibiotic is one or any combination of oxytetracycline, tetracycline, and chlortetracycline;

[0049] The sulfonamide antibiotics are one or any combination of sulfadiazine, sulfaisoxazole, sulfadiazine, sulfamethoxazole, sulfamethoxypyrimidine, and sulfadimethylpyrimidine.

[0050] Unless otherwise specified, "parts" in the embodiments of this invention refers to parts by weight.

[0051] All raw materials used in the embodiments of this invention were purchased through commercial channels.

[0052] In the embodiments of this invention, room temperature refers to 25±2℃.

[0053] Example 1

[0054] A rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight:

[0055] Three parts of rare earth oxides (cerium oxide and lanthanum oxide mixed in a mass ratio of 1:1), seven parts of nanozyme, two parts of potassium humate, 20 parts of bamboo charcoal, and two parts of microbial inoculant (Bacillus, lactic acid bacteria, yeast, nitrogen-fixing bacteria, rhizobium and Beauveria bassiana mixed in a mass ratio of 2:2:2:1:1:1).

[0056] The nanozyme comprises the following raw materials in parts by weight:

[0057] 1.5 parts nano silica, 1.5 parts nano titanium dioxide, 8 parts plant protease, 5 parts amylase, 4 parts pectinase, 7 parts cellulase, 8 parts β-glucosidase, 1.5 parts chitosanase, 1.5 parts agarase, and 4 parts β-lactamase.

[0058] The preparation method of nanozymes includes the following steps:

[0059] Plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase and β-lactamase were added to phosphate buffer solution and mixed evenly to obtain a biological enzyme buffer with a concentration of 0.2 mol / L. Then, nano-silica and nano-titanium dioxide were added, and the mixture was stirred and mixed at 35°C and allowed to stand for 1.5 hours to obtain nanozymes.

[0060] A method for preparing a rare earth oxide nanoenzyme complex includes the following steps:

[0061] Nanozymes and microbial agents were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanozyme composite.

[0062] The mass ratio of phosphate buffer solution to nanozyme is 35:1.

[0063] Example 2

[0064] A rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight:

[0065] 1 part rare earth oxide (neodymium oxide and lanthanum oxide mixed in a mass ratio of 1:1), 10 parts nanozyme, 5 parts potassium humate, 25 parts bamboo charcoal, and 3 parts microbial inoculant (Bacillus, lactic acid bacteria, yeast, and nitrogen-fixing bacteria mixed in a mass ratio of 1:1:1:1).

[0066] The nanozyme comprises the following raw materials in parts by weight:

[0067] 2 parts nano silica, 1 part nano titanium dioxide, 11 parts plant protease, 3 parts amylase, 5 parts pectinase, 8 parts cellulase, 5 parts β-glucosidase, 2 parts chitosanase, 2 parts agarase, and 3 parts β-lactamase.

[0068] The preparation method of nanozymes includes the following steps:

[0069] Plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase and β-lactamase were added to phosphate buffer solution and mixed evenly to obtain a biological enzyme buffer with a concentration of 0.1 mol / L. Then, nano-silica and nano-titanium dioxide were added, and the mixture was stirred and mixed at 40°C and allowed to stand for 1 hour to obtain nanozymes.

[0070] A method for preparing a rare earth oxide nanoenzyme complex includes the following steps:

[0071] Nanozymes and microbial agents were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanozyme composite.

[0072] The mass ratio of phosphate buffer solution to nanozyme is 20:1.

[0073] Example 3

[0074] A rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight:

[0075] Five parts of rare earth oxides (a mixture of cerium oxide and lanthanum oxide in a mass ratio of 1:1), five parts of nanozyme, ten parts of potassium humate, fifteen parts of bamboo charcoal, and one part of microbial inoculant (a mixture of Bacillus, nitrogen-fixing bacteria, rhizobium, and Beauveria bassiana in a mass ratio of 2:1:2:1).

[0076] The nanozyme comprises the following raw materials in parts by weight:

[0077] 1 part nano silica, 2 parts nano titanium dioxide, 6 parts plant protease, 7 parts amylase, 3 parts pectinase, 5 parts cellulase, 10 parts β-glucosidase, 1 part chitosanase, 1 part agarase, and 5 parts β-lactamase.

[0078] The preparation method of nanozymes includes the following steps:

[0079] Plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase and β-lactamase were added to phosphate buffer solution and mixed evenly to obtain a biological enzyme buffer with a concentration of 0.3 mol / L. Then, nano-silica and nano-titanium dioxide were added, and the mixture was stirred and mixed at 30°C and allowed to stand for 2 hours to obtain nanozymes.

[0080] A method for preparing a rare earth oxide nanoenzyme complex includes the following steps:

[0081] Nanozymes and microbial agents were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanozyme composite.

[0082] The mass ratio of phosphate buffer solution to nanozyme is 50:1.

[0083] Comparative Example 1

[0084] A composite that differs from Example 1 only in that it does not contain rare earth oxides.

[0085] Comparative Example 2

[0086] A complex that differs from Example 1 only in that it does not include nanozymes.

[0087] Comparative Example 3

[0088] A compound that differs from Example 1 only in that it does not include bamboo charcoal.

[0089] Comparative Example 4

[0090] A complex, differing from Example 1 only in that it does not include rare earth microbial agents.

[0091] Application examples

[0092] Application of a rare earth oxide nanoenzyme complex in enhancing the treatment of antibiotic-contaminated water bodies by duckweed.

[0093] The rare earth oxide nanoenzyme complexes obtained in Examples 1-3 and Comparative Examples 1-4 were respectively added to the same antibiotic wastewater treatment pond planted with duckweed, wherein the duckweed planting coverage area was 60% of the water surface area of ​​the treatment pond.

[0094] The mass ratio of rare earth oxide nanoenzyme complex to antibiotic wastewater is 0.2:10.

[0095] Technical effects:

[0096] For the blank experiments before and after treatment in the application examples (no compound was added, only duckweed was used for treatment), Examples 1-3 and Comparative Examples 1-4, the treatment time was 30 days. Oxytetracycline, tetracycline, chlortetracycline, sulfadiazine, and sulfamethoxazole were tested respectively, and the test results are shown in Table 1.

[0097] Table 1

[0098]

[0099] As shown in Table 1, the complex obtained in this invention has a significant synergistic effect on antibiotics in duckweed-treated wastewater. Furthermore, the various raw materials exhibit a clear synergistic effect. In contrast, Comparative Example 3, lacking bamboo charcoal, could not guarantee uniform dispersion of the microbial preparation and nanozyme in water. Therefore, although it still showed a good synergistic effect on antibiotic-treated wastewater from duckweed, it could not achieve the degradation effect described in the embodiments of this invention.

[0100] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. Application of a rare earth oxide nanoenzyme complex in enhancing the treatment of antibiotic-contaminated water bodies by duckweed; The rare earth oxide nanoenzyme complex comprises the following raw materials in parts by weight: Rare earth oxides 1-5 parts, nanozymes 5-10 parts, potassium humate 2-3 parts, bamboo charcoal 15-25 parts, and microbial inoculant 1-3 parts; The nanozyme comprises the following raw materials in parts by weight: 1-2 parts of nano silica, 1-2 parts of nano titanium dioxide, 6-11 parts of plant protease, 3-7 parts of amylase, 3-5 parts of pectinase, 5-8 parts of cellulase, 5-10 parts of β-glucosidase, 1-2 parts of chitosanase, 1-2 parts of agarase and 3-5 parts of β-lactamase. The preparation method of the nanozyme includes the following steps: The plant protease, amylase, pectinase, cellulase, β-glucosidase, chitosanase, agarase and β-lactamase are added to a phosphate buffer solution and mixed evenly to obtain a biological enzyme buffer solution. Then, the nano-silica and nano-titanium dioxide are added, and the mixture is stirred and mixed at 30-40°C and allowed to stand for 1-2 hours to obtain the nanoenzyme.

2. The application according to claim 1, characterized in that, The rare earth oxides include one rare earth oxide selected from lanthanum, cerium, neodymium, yttrium, and scandium, or any combination of rare earth oxides of several of these elements.

3. The application according to claim 1, characterized in that, The microbial inoculant includes one or more of Bacillus, lactic acid bacteria, yeast, nitrogen-fixing bacteria, rhizobium, and Beauveria bassiana.

4. The application according to any one of claims 1-3, characterized in that, The preparation method of the rare earth oxide nanoenzyme complex includes the following steps: The nanoenzyme and microbial agent were dispersed in a phosphate buffer solution, and then bamboo charcoal was added and dispersed evenly. After standing for 4-5 hours, the mixture was filtered and dried. The resulting solid composite was then mixed evenly with rare earth oxides and potassium humate to obtain the rare earth oxide nanoenzyme composite.

5. The application according to claim 1, characterized in that, The duckweed planted in the antibiotic wastewater treatment pond covers an area of ​​55-70% of the pond's surface area. The mass ratio of the rare earth oxide nanoenzyme complex to antibiotic wastewater is (0.1-0.5):

10.

6. The application according to claim 1, characterized in that, The antibiotics include tetracycline antibiotics and / or sulfonamide antibiotics.

7. The application according to claim 6, characterized in that, The tetracycline antibiotics are one or more of oxytetracycline, tetracycline, and chlortetracycline. The sulfonamide antibiotics are one or more of sulfadiazine, sulfaisoxazole, sulfadiazine, sulfamethoxazole, and sulfamethoxypyrimidine.

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