Use of antibacterial catalytic metal and magnetic acid lanthanide oxide composite material in elimination of phosphorus and resistance gene pollution in tail water

Abstract

Provided in the present invention is the use of an antibacterial catalytic metal and magnetic acid lanthanide oxide composite material in the elimination of phosphorus and resistance gene pollution in tail water, wherein the preparation process for the composite material is as follows: S01, using a dipping-calcining method, mixing a lanthanide element ion solution, a magnetic element ion solution and a carrier, and uniformly stirring, centrifuging and calcining same to obtain a calcined product, i.e., a magnetic acid lanthanide oxide-carrier; S02, using a heating precipitation method, adding the calcined product in S01 to an antibacterial catalytic metal element precursor solution, adding an ammonia water solution thereto in a dropwise manner, and continuously stirring and heating same in a water bath to obtain a mixed system of the composite material; and S03, using a mixed calcining method, calcining the mixed system obtained in S02 to obtain the composite material, i.e., a magnetic acid lanthanide oxide and antibacterial catalytic oxide heterojunction-carrier. The composite material obtained by using the preparation method can be used in the elimination of phosphorus and resistance genes in an agricultural water environment.

Description

Application of antibacterial catalytic metal & lanthanum magnetic oxide composites in eliminating phosphorus and resistance gene pollution in tailwater Technical Field

[0001] The present invention relates to the application of an antibacterial catalytic metal & lanthanum magnetic acid oxide composite material in reducing phosphorus and resistance gene pollution in agricultural water environments, belonging to the field of environmental pollution control. Background Art

[0002] Phosphorus is a significant pollutant in aquatic environments, particularly in agricultural environments, where it poses a significant threat and requires significant remediation. In recent years, numerous phosphorus removal methods have been developed, most of which are effective at high pollution levels. However, nano-adsorbent materials have demonstrated excellent remediation effects at low phosphorus concentrations.

[0003] Antibiotics are widely used in daily life and in livestock farming, playing a crucial role in preventing and treating livestock diseases. However, excessive antibiotic use can induce antibiotic resistance genes, promoting the development of stronger antibiotic resistance in organisms. These resistance genes pose a potential risk to human health and ecosystems, raising concerns about public health. However, recent research has found that nano-adsorbents can negatively impact drug-resistant bacteria, accelerating the replication and spread of antibiotic resistance genes.

[0004] Advanced oxidation technology is a recognized means of completely cutting off the resistance gene structure. It has the advantages of being fast and efficient. Using advanced oxidation technologies such as photocatalysis to remove resistance genes is more in line with the future development trend of "precise pollution control and scientific pollution control". The key to advanced oxidation is to produce free radicals. The development of advanced oxidation free radical generators with superior performance and low price is of great practical significance for the control of resistance gene pollution.

[0005] Therefore, the present invention couples the phosphorus adsorption capacity with the advanced oxidation treatment capacity to photocatalytically degrade the resistance gene pollution in the agricultural environment, and reduces the phosphorus pollution in the agricultural environment through adsorption, so as to achieve a multi-purpose form to help mitigate agricultural non-point source pollution.

[0006] SUMMARY OF THE INVENTION Technical issues

[0007] To address the aforementioned deficiencies and shortcomings of the prior art, the present invention provides an antimicrobial catalytic metal & lanthanum oxide magnetic acid carrier composite material for use in reducing phosphorus and / or resistance gene contamination in agricultural water environments. A lanthanum oxide magnetic acid carrier with phosphorus adsorption properties and an antimicrobial catalytic metal oxide with degradation properties are co-loaded onto a suitable carrier to form a heterojunction, which is then used to remove phosphorus and resistance gene contamination in water environments. Technical Solutions

[0008] In order to solve the above technical problems,

[0009] The present invention provides an application of an antibacterial catalytic metal & lanthanum magnetic acid oxide composite material in eliminating phosphorus pollution in an agricultural water environment. The composite material is added in an amount of 0.1 to 1 g / L.

[0010] The present invention also provides an application of an antibacterial catalytic metal & magnetic acid lanthanum oxide composite material in eliminating resistance gene pollution in agricultural water environments, characterized in that the composite material is added in an amount of 0.1 to 1 g / L.

[0011] The antimicrobial catalytic metal & lanthanum oxide magnetic acid composite utilizes the La-O chemical coordination of lanthanum oxide to adsorb phosphate ions. Lanthanum oxide magnetic acid is a p-type semiconductor with a narrow bandgap of approximately 2.1 eV. Its activity is low, but it responds to visible light. Titanium dioxide or zinc oxide is an n-type semiconductor with a wide photocatalytic bandgap above 3.0 eV. It is highly active but requires ultraviolet light activation. The composite of an n-type semiconductor and a p-type reporter introduces a heterojunction structure, creating a bandgap between the two. This shifts the interfacial electron transfer pathway, accelerates quantum efficiency, speeds up photogenerated charge separation, expands the photoresponse range and expands application scenarios. This leverages the respective advantages of both materials and their synergistic effects, resulting in a better photocatalytic effect, forming electron holes, and generating reactive oxygen free radical reactions, which further oxidize and degrade resistance genes.

[0012] The method for preparing the above-mentioned antibacterial catalytic metal & magnetic acid lanthanum oxide composite material comprises the following steps:

[0013] S01: mixing a lanthanide ion solution, a magnetic element ion solution, and a carrier so that the lanthanide ions and the magnetic element ions are adsorbed on the carrier surface, stirring evenly, and then centrifuging to obtain a lanthanide ion-carrier-magnetic element ion complex; calcining the lanthanide ion-carrier-magnetic element ion complex to obtain a calcined product, a magnetic acid lanthanide oxide-carrier complex;

[0014] S02: adding the calcined product of S01, the lanthanum oxide magnetic acid series - carrier complex, to the antibacterial catalytic metal element precursor solution, so that the antibacterial catalytic metal element ions are adsorbed on the carrier to form a lanthanum oxide magnetic acid series - carrier - antibacterial catalytic metal element ion complex; adding an ammonia solution dropwise in a water bath, and continuously stirring to obtain a mixed system of lanthanum oxide magnetic acid series - carrier - antibacterial catalytic metal element hydroxide state;

[0015] S03 calcines the mixed system obtained in S02 to obtain an antibacterial metal & lanthanum magnetic acid oxide-carrier composite material.

[0016] Further, the lanthanide element includes but is not limited to lanthanum or cerium, preferably, the lanthanide element is lanthanide;

[0017] or / and

[0018] The magnetic element includes but is not limited to iron, cobalt or nickel; preferably, the magnetic element is iron.

[0019] Furthermore, the lanthanide element ion solution and the magnetic element ion solution are both nitrate ion solutions or chloride ion solutions; wherein the concentration of the nitrate ion or chloride ion is 0.5 to 2 mol / L.

[0020] Furthermore, the carrier is biochar, ceramic sheet, zeolite, volcanic rock, quartz ball or medical stone.

[0021] Furthermore, in step S01 , the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 10-100 mL: 10-100 mL.

[0022] Furthermore, in step S01, the stirring time is 1 to 4 hours, and the stirring speed is 100 to 800 rpm.

[0023] Furthermore, in step S01, the calcination temperature is 400-900° C., and the calcination time is 2 h to 6 h.

[0024] Furthermore, the antibacterial catalytic metal element precursor solution is titanium tetraisopropoxide or basic zinc carbonate.

[0025] Furthermore, the dosage ratio of the calcined product lanthanum magnetic acid oxide-carrier complex, the antibacterial catalytic metal element precursor solution and ammonia water is 1g:10~80mL:5~20mL; wherein, the concentration of the antibacterial catalytic metal element precursor solution is 0.1~1mol / L, and the concentration of ammonia water is 50%~70%.

[0026] Furthermore, in step S02, the stirring speed is 100-500 rpm, the stirring time is 2-6 hours, the water bath heating temperature is 50-100° C., and the heating time is 6-12 hours.

[0027] Furthermore, in step S03, the calcination temperature is 300-500° C., and the calcination time is 1-3 hours. Beneficial effects

[0028] The beneficial technical effects achieved by the present invention include the following: 1. The present invention provides an antimicrobial catalytic metal & lanthanum oxide magnetic acid composite material for use in reducing phosphorus and / or resistance gene pollution in agricultural water environments. Using the composite material to treat actual aquaculture biochemical tailwater, the removal rates for the sulfonamide resistance gene sul1, the class 1 integron gene intl1, the tetracycline resistance gene tetQ, the macrolide resistance gene mefa, and phosphorus were 43.77% to 75.45%, 49.88% to 82.34%, 97.95% to 98.60%, 97.05% to 99.9%, and 72.68% to 95.16%, respectively. 2. The resulting finished product exhibits rapid and effective treatment effects on phosphorus and resistance genes. 3. The composite material has diverse application scenarios, suitable for scenarios with only phosphorus pollution, only resistance gene pollution, or both phosphorus and resistance gene pollution, and can be applied in a targeted manner based on the characteristics of the water pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Type your figure caption description paragraph here. Best Mode for Carrying Out the Invention

[0030] FIG1 is a schematic diagram of a method for preparing a composite material according to the present invention;

[0031] FIG2 is a scanning electron microscope image of the finished composite material 1-3 obtained by the preparation method of the present invention;

[0032] FIG3 is a characterization spectrum of the finished composite material 1-3 obtained by the preparation method of the present invention; wherein A is an X-ray diffraction spectrum of the finished composite material 1-3 obtained by the preparation method of the present invention; B is an ultraviolet-visible diffuse reflectance spectrum of the finished composite material 1-3 obtained by the preparation method of the present invention;

[0033] FIG4 shows the results of the finished product 1 treating simulated tail water as shown in an exemplary embodiment of the present invention; wherein A is the Fourier transform infrared spectrum of the finished product 1 before and after treating the phosphorus simulated tail water and the resistance gene simulated tail water; B is the response of the finished product 1 to different light source types in the resistance gene simulated tail water;

[0034] FIG5 shows the results of the simulated tail water treatment of the finished product 2 shown in an exemplary embodiment of the present invention; wherein A is the Fourier transform infrared spectrum of the finished product 2 before and after treating the phosphorus simulated tail water and the resistance gene simulated tail water; B is the response of the finished product 2 to different light sources in the resistance gene simulated tail water;

[0035] FIG6 shows the results of the simulated tail water treatment of the finished product 3 shown in an exemplary embodiment of the present invention; wherein A is the Fourier transform infrared spectrum of the finished product 3 before and after treating the phosphorus simulated tail water and the resistance gene simulated tail water; B is the response of the finished product 3 to different light sources in the resistance gene simulated tail water;

[0036] FIG7 shows the results of treating aquaculture biochemical tail water with the finished product 1 shown in an exemplary embodiment of the present invention; wherein A is a diagram showing the treatment effect of treating aquaculture biochemical tail water with the finished product 1 having a concentration of 1 g / L in the present invention, and B is a diagram showing the treatment effect of treating aquaculture biochemical tail water with the finished product 1 having a concentration of 0.1 g / L in the present invention;

[0037] FIG8 shows the results of treating aquaculture biochemical tail water with finished product 4 according to an exemplary embodiment of the present invention; wherein A is a diagram showing the treatment effect of treating aquaculture biochemical tail water with finished product 2 at a concentration of 1 g / L according to the present invention, and B is a diagram showing the treatment effect of treating aquaculture biochemical tail water with finished product 1 at a concentration of 0.1 g / L according to the present invention;

[0038] FIG9 shows the results of treating aquaculture biochemical tail water with finished product 3 according to an exemplary embodiment of the present invention; wherein A is a diagram showing the treatment effect of treating aquaculture biochemical tail water with a concentration of 1 g / L with finished product 3 according to the present invention, and B is a diagram showing the treatment effect of treating aquaculture biochemical tail water with a concentration of 0.1 g / L with finished product 1 according to the present invention;

[0039] Figure 10 shows the results of treating aquaculture biochemical tail water with the finished product 4 in an exemplary embodiment of the present invention; wherein, A is a treatment effect diagram of the aquaculture biochemical tail water treated with the finished product 4 at a concentration of 1g / L in the present invention, and B is a treatment effect diagram of the aquaculture biochemical tail water treated with the finished product 5 at a concentration of 1g / L in the present invention. Modes for Carrying Out the Invention

[0040] The present invention will be further described below in conjunction with specific examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0041] The present invention is further described below with reference to the accompanying drawings and embodiments.

[0042] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide composite material, as shown in FIG1 , comprising the following steps:

[0043] S01: mixing a lanthanide ion solution, a magnetic element ion solution, and a carrier so that the lanthanide ions and the magnetic element ions are adsorbed on the carrier surface, stirring evenly and then centrifuging to obtain a lanthanide ion-carrier-magnetic element ion complex; calcining the lanthanide ion-carrier-magnetic element ion complex to obtain a calcined product, a magnetic acid lanthanide oxide-carrier complex; wherein the stirring speed can be 100-800 rpm and the stirring time is 1-4 hours. In the actual preparation process, the stirring speed and stirring time both affect the reaction results. If the stirring speed is too fast, it will affect the adsorption between the carrier and the adsorbate, making it difficult for the adsorbate to be stably adsorbed on the carrier. If the stirring speed is too slow, the adsorbate may agglomerate, resulting in uneven distribution on the carrier surface. Similarly, the stirring time will also affect the reaction effect. Therefore, the stirring speed of this application is preferably 100-800 rpm, and the stirring time is preferably 1-4 hours; preferably, the stirring speed is 300-600 rpm, and the stirring time is 1-3 hours; more preferably, the stirring speed is 500 rpm, and the stirring time is 2 hours. The calcination temperature is preferably 400-900°C, and the calcination time is preferably 2-6 hours. Preferably, the calcination temperature is 500-800°C, and the calcination time is 3-5 hours. More preferably, the calcination temperature is 600°C, and the calcination time is 4 hours.

[0044] S02 adds the calcined product of S01, the lanthanum magnetic acid oxide-carrier complex, to the antibacterial catalytic metal element precursor solution, and the antibacterial catalytic metal element ions are adsorbed on the carrier to form a lanthanum magnetic acid oxide-carrier-antibacterial catalytic metal element ion complex, and adds an ammonia solution dropwise in a water bath, and continuously stirs to obtain a mixed system of lanthanum magnetic acid oxide-carrier-antibacterial catalytic metal element hydroxide state; wherein, the stirring speed is 100-500rpm, and the stirring time is 2-6h, preferably, the stirring speed is 200-400rpm, and the stirring time is 3-5h, more preferably, the stirring speed is 300rpm, and the stirring time is 4h; the water bath heating temperature is 50-100℃, and the heating time is 6-12h, preferably, the heating temperature is 60-80℃, and the heating time is 7-10h, more preferably, the heating temperature is 70℃, and the heating time is 8h.

[0045] S03 calcining the mixed system obtained in S02 to obtain an antibacterial metal & lanthanum magnetic oxide-support composite material, wherein the calcination temperature is 300-500° C. and the calcination time is 1-3 hours, preferably, the calcination temperature is 400° C. and the calcination time is 2 hours.

[0046] As a specific embodiment, the carrier can be a high temperature resistant product, including but not limited to biochar, honeycomb ceramic sheets, zeolite, volcanic rock, quartz balls, medical stone, etc. In order to better illustrate the preparation method of the composite material of the present application, biochar is selected as a specific embodiment of the carrier.

[0047] As a specific embodiment, the lanthanide element can be lanthanum or cerium, and the magnetic element can be iron, cobalt, or nickel. To better illustrate the preparation method of the composite material of the present application, lanthanum is selected as the lanthanide element and iron is selected as the magnetic element as a specific embodiment. Preferably, both the lanthanide element ion solution and the magnetic element ion solution can be a nitrate ion solution or a chloride ion solution; wherein the concentration of the nitrate ion solution or the chloride ion solution is 0.5 to 2 mol / L; preferably, the nitrate or chloride ion concentration is 1 mol / L.

[0048] As a specific embodiment, the antibacterial catalytic metal element precursor solution can be titanium tetraisopropoxide or basic zinc carbonate. In order to better illustrate the preparation method of the composite material of the present application, the antibacterial catalytic metal element precursor solution is titanium tetraisopropoxide.

[0049] The following specific examples further illustrate the preparation method of the antibacterial catalytic metal & magnetic acid lanthanum oxide-carrier composite material provided by the present application, wherein lanthanum is selected as the lanthanide element, iron is selected as the magnetic element, and the antibacterial catalytic metal element precursor solution is titanium tetraisopropoxide; in step S01, the stirring speed is 500rpm and the stirring time is 2h; the calcination temperature is 600℃ and the calcination time is 4h; the centrifugal speed is 2000rpm and the centrifugal time is 10min. In step S02, the stirring speed is 300rpm and the stirring time is 4h; the water bath heating temperature is 70℃ and the heating time is 8h; in step S03, the calcination temperature is 400℃ and the calcination time is 2h. Focus on studying the effect of the amount of each component on the reaction results.

[0050] Example

[0051] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0052] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 20 mL: 30 mL;

[0053] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0054] Example

[0055] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0056] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 60 mL: 30 mL;

[0057] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0058] Example

[0059] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0060] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 80 mL: 50 mL;

[0061] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0062] Example

[0063] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0064] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 90 mL;

[0065] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0066] Example

[0067] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0068] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0069] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:20 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0070] Example

[0071] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0072] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0073] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:15 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0074] Example

[0075] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0076] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0077] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:70 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.5 mol / L and the concentration of the ammonia water is 60%.

[0078] Example

[0079] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0080] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0081] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:50 mL:10 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.1 mol / L and the concentration of the ammonia water is 60%.

[0082] Example

[0083] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0084] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0085] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1g:50mL:10mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 1mol / L and the concentration of the ammonia water is 50%.

[0086] Example

[0087] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0088] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 10 mL: 10 mL;

[0089] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:10 mL:5 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.1 mg / L and the concentration of the ammonia water is 50%.

[0090] Example

[0091] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0092] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 50 mL: 50 mL;

[0093] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1 g:10 mL:5 mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.1 mol / L and the concentration of the ammonia water is 60%.

[0094] Example

[0095] The present invention provides a method for preparing an antibacterial catalytic metal & magnetic acid lanthanum oxide-support composite material:

[0096] In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 100 mL: 100 mL;

[0097] In step S02, the usage ratio of the calcined product of S01, the lanthanum magnetic oxide-carrier complex, the antibacterial catalytic metal element precursor solution and the ammonia water is 1g:80mL:20mL, wherein the concentration of the antibacterial catalytic metal element precursor solution is 1mol / L and the concentration of the ammonia water is 70%.

[0098] The antibacterial catalytic metal & lanthanum magnetic oxide-support composite materials prepared by the methods of Examples 10-12 were characterized, and the results are shown in Figures 2-3.

[0099] Among them, the composite material obtained in Example 10 is named finished product 1, and its scanning electron microscope image is shown in Figure 2. The finished product is in a spherical particle state. Its X-ray diffraction spectrum is shown in Figure 3 A. It can be seen from the figure that 32.01°(121), 39.50°(220), 46.17°(202) and 57.23°(240) belong to the characteristic peaks of lanthanum ferrite, and 25.26°(101), 37.89°(004) and 47.99°(200) belong to the characteristic peaks of titanium dioxide. Finished product 1 is obtained by the above preparation method, and its ultraviolet visible diffuse reflectance spectrum is shown in Figure 3 B. The strong absorption edge of finished product 1 is located near 410nm, indicating that it has the ability to absorb visible light. The band gap is calculated according to the Kubelka-Muck function equation, and the band gap energy level is 2.50eV, which is between lanthanum ferrite (2.1eV) and titanium dioxide (3.1eV).

[0100] The composite material obtained in Example 11 is named Finished Product 2, and its scanning electron microscope image is shown in FIG2 , and the finished product is in a spherical particle state. Its X-ray diffraction spectrum is shown in FIG3 A, from which it can be seen that 32.01°(121), 39.50°(220) and 57.23°(240) belong to the characteristic peaks of lanthanum ferrite, and 37.89(004) and 47.99°(200) belong to the characteristic peaks of titanium dioxide. Finished Product 1 is obtained by the above preparation method, and its UV-visible diffuse reflectance spectrum is shown in FIG3 B. The strong absorption edge of Finished Product 2 is located near 410nm, indicating that it has the ability to absorb visible light. The band gap is calculated according to the Kubelka-Muck function equation, and the band gap energy level is 2.56eV, which is between lanthanum ferrite (2.1eV) and titanium dioxide (3.1eV).

[0101] The composite material obtained in Example 11 is named finished product 3, and its scanning electron microscope image is shown in Figure 2. The finished product is in a spherical particle state. Its X-ray diffraction spectrum is shown in Figure 3A. It can be seen from the figure that 32.01°(121), 39.50°(220), 46.17°(202) and 57.23°(240) belong to the characteristic peaks of lanthanum ferrite, and 25.26(101), 37.89(004) and 47.99°(200) belong to the characteristic peaks of titanium dioxide. Finished product 1 is obtained by the above preparation method, and its ultraviolet visible diffuse reflectance spectrum is shown in Figure 3B. The strong absorption edge of finished product 3 is located near 410nm, indicating that it has the ability to absorb visible light. The band gap is calculated according to the Kubelka-Muck function equation, and the band gap energy level is 2.68eV, which is between lanthanum ferrite (2.1eV) and titanium dioxide (3.1eV).

[0102] Finished products 1, 2 and 3 were used to treat simulated tail water with a phosphorus concentration of 5 mg / L and simulated tail water with a resistance gene concentration of 6 mg / L (visible light), respectively. The addition amount of the composite material was 1 g / L.

[0103] The Fourier transform infrared spectra of Finished Product 1 before and after treatment with simulated tail water are shown in Figure 4A. As can be seen, there is no significant change in Finished Product 1 before and after treatment with the simulated tail water containing the resistance gene, indicating that the properties of the composite material remain unchanged before and after the reaction. However, after treatment with the simulated phosphorus tail water, the peaks at 1070 cm⁻¹ and 1070 cm⁻¹ significantly increase, indicating increased OP bond vibrations and demonstrating successful phosphorus binding to the material. The adsorption mechanism is the formation of an OP complex bond. Therefore, Finished Product 1 exhibits significant removal effectiveness in treating simulated phosphorus tail water.

[0104] The Fourier transform infrared spectra of Finished Product 2 before and after treatment with simulated tail water are shown in Figure 5A. As can be seen from the figure, under visible light conditions, there was no significant change before and after treatment with the simulated tail water containing the resistance gene, indicating that the properties of the composite material remained unchanged. However, after treatment with the simulated phosphorus tail water, the peaks at 1070 cm⁻¹ and 1070 cm⁻¹ significantly increased, indicating increased OP bond vibrations and demonstrating that phosphorus successfully adhered to the material, with the adsorption mechanism being the formation of an OP complex bond. Therefore, Finished Product 2 demonstrated a significant removal effect in treating simulated phosphorus tail water.

[0105] The Fourier transform infrared spectra of finished product 3 before and after treatment with simulated tail water are shown in Figure 6A. There is no significant change in the figure before and after treatment with the resistance gene simulated tail water, indicating that the properties of the composite material remain unchanged before and after the reaction. However, after treatment with the phosphorus simulated tail water, the peaks at 1070 cm-1 and 1070 cm-1 are significantly enhanced, indicating increased OP bond vibration, indicating that phosphorus is successfully bound to the material, and the adsorption mechanism is the formation of OP complex bonds.

[0106] Finished products 1, 2 and 3 were used to treat simulated tail water containing resistance genes with a DNA concentration of 6 mg / L. The addition amount of finished products 1, 2 and 3 was 1 g / L. The light source environments were dark, visible and ultraviolet, respectively. The concentration of DNA before and after the reaction was determined by fluorescence quantification, and the removal rate was calculated.

[0107] As shown in Figure 4B, Product 1 exhibits varying treatment effects on simulated tailwater under different light sources, achieving the best removal under UV conditions and the worst under dark conditions. These results suggest that the material has a certain adsorption capacity for DNA, but the removal efficiency improves under light, suggesting that photocatalysis also plays a role.

[0108] As shown in Figure 5B, Product 2 exhibits varying treatment effects on simulated tailwater under different light sources, achieving the best removal under UV conditions and the worst under dark conditions. These results suggest that the material has a certain adsorption capacity for DNA, but the removal efficiency improves under light, suggesting that photocatalysis also plays a role.

[0109] As can be seen in Figure 6B, Product 3 exhibits varying treatment effects on simulated tailwater under different light sources, achieving the best removal under UV conditions and the worst under dark conditions. These results suggest that the material has a certain adsorption capacity for DNA, but the removal efficiency improves under light, suggesting that photocatalysis also plays a role.

[0110] It should be noted that simulated DNA can only indicate the removal mechanism, and cannot reflect the removal effect of a certain resistance gene. Therefore, the effect of the specific resistance gene still needs to be obtained through actual sewage treatment experiments.

[0111] 1. Finished product 1 for the treatment of actual aquaculture biochemical tail water:

[0112] Finished product 1 was used to treat actual aquaculture biochemical tailwater at a concentration of 1g / L. After two hours of stirring (at 100 rpm) under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal rates were calculated. The results are shown in Figure 7A. The removal rates of Finished Product 1 in the tailwater were 65.45%, 72.34%, 88.36%, 89.09%, and 84.17%, respectively.

[0113] Finished product 1 was used to treat actual aquaculture biochemical tailwater at a concentration of 0.1 g / L. After standing for two hours under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal efficiency was calculated. The results are shown in Figure 7B. Finished product 1 achieved removal efficiencies of 53.18%, 56.04%, 88.48%, 87.96%, and 72.68% in the tailwater.

[0114] 2. Finished product 2 treats actual aquaculture biochemical tail water:

[0115] Finished product 2 was used to treat actual aquaculture biochemical tailwater at a concentration of 1g / L. After two hours of stirring (at 100 rpm) under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal rates were calculated. The results are shown in Figure 8A. The removal rates of Finished product 2 for tailwater were 75.45%, 82.38%, 98.60%, 99.08%, and 95.03%, respectively.

[0116] Finished product 2 was used to treat actual aquaculture biochemical tailwater at a concentration of 0.1 g / L. After standing for two hours under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal rates were calculated. The results are shown in Figure 8B. The removal rates of Finished product 2 in the tailwater were 63.18%, 66.04%, 98.48%, 97.96%, and 72.68%, respectively.

[0117] 3. Finished product 3 treats actual aquaculture biochemical tail water:

[0118] Finished product 3 was used to treat actual aquaculture biochemical tailwater at a concentration of 1g / L. After two hours of stirring (at 100 rpm) under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal efficiency was calculated. The results are shown in Figure 9, A. Finished product 3 achieved removal efficiencies of 75.45%, 82.38%, 98.60%, 99.08%, and 95.16% in the tailwater, respectively.

[0119] Finished product 3 was used to treat actual aquaculture biochemical tailwater at a concentration of 0.1 g / L. After standing for two hours under natural light, the concentrations of sul1, intl1, tetQ, mefa, and phosphorus were measured before and after the reaction using a fluorescence quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, and the removal rates were calculated. The results are shown in Figure 9B. The removal rates of Finished product 3 in the tailwater were 58.31%, 68.38%, 97.95%, 97.12%, and 76.97%, respectively.

[0120] 4. Finished product 4 treats actual aquaculture biochemical tail water:

[0121] The composite material obtained in Example 8 was named Finished Product 4. Finished Product 4 was used to treat actual aquaculture biochemical tail water at a concentration of 1.5 g / L. After two hours of stirring under natural light (at a speed of 100 rpm), the concentrations of sul1, intl1, tetQ, mefa, and phosphorus before and after the reaction were measured using a fluorescent quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, to calculate the removal rate. The results are shown in Figure 10A. The removal rates of Finished Product 4 for tail water were 74.45%, 84.5%, 98.36%, 99.09%, and 94.23%, respectively.

[0122] 5. Finished product 5 treats actual aquaculture biochemical tail water:

[0123] The composite material obtained in Example 9 was named Finished Product 5. Finished Product 5 was used to treat actual aquaculture biochemical tail water at a concentration of 1.5 g / L. After two hours of stirring under natural light (at a speed of 100 rpm), the concentrations of sul1, intl1, tetQ, mefa, and phosphorus before and after the reaction were measured using a fluorescent quantitative PCR instrument and a plasma inductively coupled spectrometer, respectively, to calculate the removal rate. The results are shown in Figure 10B. The removal rates of Finished Product 4 on tail water were 87.29%, 88.52%, 99.94%, 99.99%, and 93.73%, respectively.

[0124] The present invention has been disclosed above with preferred embodiments, which are not intended to limit the present invention. Any technical solutions obtained by adopting equivalent replacement or equivalent transformation solutions fall within the protection scope of the present invention.

Claims

1. Application of antibacterial catalytic metal & lanthanum magnetic acid oxide composite material in eliminating phosphorus and resistance gene pollution in tail water, characterized by: The use amount of the composite material is 0.1-1 g / L. The preparation process of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material is as follows: S01: mixing a lanthanide ion solution, a magnetic element ion solution and a carrier so that the lanthanide ions and the magnetic element ions are adsorbed on the carrier surface, stirring evenly and then centrifuging to obtain a lanthanide ion-carrier-magnetic element ion complex; calcining the lanthanide ion-carrier-magnetic element ion complex to obtain a calcined product, a magnetic acid lanthanide oxide-carrier complex; S02: adding the calcined product of S01, the lanthanum magnetic acid oxide-carrier complex, to the antibacterial catalytic metal element precursor solution, the antibacterial catalytic metal element ions are adsorbed on the carrier to form a lanthanum magnetic acid oxide-carrier-antibacterial catalytic metal element ion complex, adding an ammonia solution dropwise in a water bath, and continuously stirring to obtain a mixed system of lanthanum magnetic acid oxide-carrier-antibacterial catalytic metal element hydroxide state; wherein the antibacterial catalytic metal element precursor solution is titanium tetraisopropoxide or basic zinc carbonate; S03 calcines the mixed system obtained in S02 to obtain an antibacterial catalytic metal & magnetic acid lanthanum oxide composite material.

2. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: The lanthanide element is lanthanum or cerium; or / and The magnetic element is iron, cobalt or nickel.

3. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: The lanthanide element ion solution and the magnetic element ion solution are both nitrate ion solutions or chloride ion solutions; wherein the concentration of the nitrate ion solution or the chloride ion solution is 0.5-2 mol / L.

4. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: The carrier is biochar, ceramic flakes, zeolite, volcanic rock, quartz ball or medical stone.

5. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: In step S01, the addition ratio of each component is carrier: lanthanide element ion solution: magnetic element ion solution = 1 g: 10-100 mL: 10-100 mL.

6. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: In step S01, the stirring time is 1 to 4 hours, and the stirring speed is 100 to 800 rpm.

7. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: In step S01, the calcination temperature is 400-900° C., and the calcination time is 2 h to 6 h.

8. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: The dosage ratio of the calcined product lanthanum magnetic acid oxide-carrier complex, the antibacterial catalytic metal element precursor solution and ammonia water is 1g:10-80mL:5-20mL; wherein the concentration of the antibacterial catalytic metal element precursor solution is 0.1-1mol / L, and the concentration of ammonia water is 50%-70%.

9. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: In step S02, the stirring speed is 100-500 rpm, the stirring time is 2-6 hours, the water bath heating temperature is 50-100°C, and the heating time is 6-12 hours.

10. The use of the antibacterial catalytic metal & lanthanum magnetic acid oxide composite material according to claim 1 in eliminating phosphorus and resistance gene pollution in tail water, characterized in that: In step S03, the calcination temperature is 300-500°C, and the calcination time is 1-3 hours.

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