Iron-based amorphous alloy, preparation method thereof and application of iron-based amorphous alloy in degrading tetracycline antibiotics

Abstract

The present disclosure relates to a kind of iron-based amorphous alloy and its preparation method and the application of degrading tetracycline antibiotics, the molecular formula of iron-based amorphous alloy is FexSiyBz, wherein x, y, z respectively represent the atomic percentage of Fe, Si, B in alloy, 74≤x≤84, 6≤y≤16, 6≤z≤16, and x+y+z=100;Preparation method includes: S1, raw material is proportioned in smelting furnace under inert atmosphere and is smelted to prepare iron-based amorphous alloy;S2, the iron-based amorphous alloy prepared in step S1 is prepared into iron-based amorphous alloy strip by single-roll casting method;The application of degrading tetracycline antibiotics is that the iron-based amorphous alloy is applied to the treatment of wastewater containing tetracycline antibiotics, for degrading tetracycline antibiotics;The present application is more difficult to occur passivation in degradation reaction, and it is convenient to recycle.

Description

Technical Field

[0001] This disclosure relates to the fields of amorphous alloy materials and antibiotic degradation technology, specifically to an iron-based amorphous alloy, its preparation method, and its application in degrading tetracycline antibiotics. Background Technology

[0002] Antibiotics are among the most important drugs for the prevention and treatment of bacterial infections in humans. They are also widely used in animal husbandry and aquaculture as drugs for the prevention and treatment of infectious diseases in animals and as antibacterial and growth-promoting additives. These antibiotics can enter environmental water bodies and soil through agricultural runoff, veterinary wastewater, and excrement, causing environmental pollution problems.

[0003] In recent years, the most widely studied antibiotic wastewater treatment technologies can be broadly categorized into three types: adsorption, biodegradation, and advanced oxidation technologies.

[0004] Adsorption is a common technique for separating and treating pollutants in water. It is simple to operate, cost-effective, efficient, and has no side effects. The core of adsorption technology lies in the development of the adsorbent, which is typically a low-cost, functionally rich, and porous material with a large specific surface area. Common adsorbents in existing research include activated carbon, biochar, bentonite, chitosan, and graphene. Tetracycline is the most common antibiotic studied in adsorption methods due to its strong adsorption properties from polar functional groups such as carboxyl and acylamino groups, making it very suitable for adsorption removal. However, this technology can only achieve the transfer of antibiotic pollutants between different phases, not their degradation. Furthermore, the corrosion resistance, recycling, and disposal of waste adsorbents limit the practical application of adsorption methods.

[0005] Biodegradation is the primary pathway for antibiotic degradation under natural conditions and a commonly used technology in wastewater treatment plants for treating organic wastewater. Research on biodegradation focuses on removal mechanisms and operating conditions. However, for various reasons, not all antibiotics can be effectively degraded. First, microorganisms prefer organic matter in wastewater rich in carbon and nitrogen sources rather than lower concentrations of antibiotics. Second, the specific degradative enzymes required for degradation cannot be induced at low antibiotic concentrations. Furthermore, the biotoxicity of antibiotics significantly inhibits the treatment performance of biodegradation methods.

[0006] Metal-organic frameworks (MOFs) are considered a viable material for the photocatalytic degradation of antibiotics, but their application is limited due to their demanding manufacturing conditions, high cost, and inability to be used in large-scale wastewater treatment.

[0007] In recent years, zero-valent iron (ZVFe) has attracted increasing attention due to its advantages in treating organic matter, including wide applicability, low cost, simple operation, and non-toxicity. Studies have also reported on the adsorption and degradation of tetracycline using ZVFe nanoparticles. The degradation products are mainly deamination-modified tetracycline analogs. ZVFe in water is converted into iron hydroxyl oxide, which then adsorbs tetracycline and forms degradation products within 15–240 minutes. Tetracycline is a highly efficient chelating agent for high-valent metal ions. Tetracycline can chelate with iron ions in water to form Fe-TC complexes. These complexes do not reduce the antibiotic resistance of tetracycline; therefore, it should be removed from polluted wastewater before entering wastewater treatment plants. However, for crystalline elemental ZVFe powder, problems such as agglomeration and oxidation are prone to occur during storage, transportation, and application, leading to a significant decrease in its degradation efficiency. Summary of the Invention

[0008] In order to solve the problems existing in the prior art, the purpose of this disclosure is to provide an iron-based amorphous alloy, its preparation method and its application in degrading tetracycline antibiotics, so as to solve the problem that the prior art cannot effectively degrade tetracycline antibiotic pollution.

[0009] The present disclosure discloses an iron-based amorphous alloy with the molecular formula FexSiyBz, wherein x, y, and z represent the atomic percentages of Fe, Si, and B in the alloy, respectively, 74≤x≤84, 6≤y≤16, 6≤z≤16, and x+y+z=100.

[0010] This disclosure also provides a method for preparing the iron-based amorphous alloy as described above, comprising the following steps:

[0011] S1. The raw materials are melted in a melting furnace under an inert atmosphere according to the proportion to produce an iron-based amorphous alloy;

[0012] S2. The iron-based amorphous alloy obtained in step S1 is prepared into iron-based amorphous alloy strips by single-roller spinning method.

[0013] Preferably, the thickness of the iron-based amorphous alloy strip is 10 μm to 200 μm.

[0014] Preferably, the preparation method further includes:

[0015] S3. Cut the iron-based amorphous alloy strip into sheet strips with a length of 10mm.

[0016] This disclosure also provides an application of an iron-based amorphous alloy, which is used to treat wastewater containing tetracycline antibiotics for the degradation of tetracycline antibiotics.

[0017] Preferably, in the wastewater containing tetracycline antibiotics, the concentration of the tetracycline antibiotics is 10–200 mg / L.

[0018] Preferably, the pH value of the wastewater containing tetracycline antibiotics is 3.3 to 9.

[0019] Preferably, the pH value of the wastewater containing tetracycline antibiotics is 4 to 9.

[0020] Preferably, the amount of the iron-based amorphous alloy strip added is greater than or equal to 10 g / L.

[0021] Preferably, the temperature of the wastewater containing tetracycline antibiotics is 30–40°C.

[0022] The advantages of the iron-based amorphous alloy, its preparation method, and its application in degrading tetracycline antibiotics disclosed in this disclosure are as follows:

[0023] The iron-based amorphous alloy strip of this invention has good amorphous forming ability, and its preparation process is more tolerant of the reaction environment requirements compared to the preparation process of metal-organic framework materials, thus enabling large-scale application.

[0024] Furthermore, as a metastable material, iron-based amorphous alloys have higher thermodynamic energy than their corresponding crystalline alloys and zero-valent iron powder. Therefore, the activation energy required for chemical reactions is lower than that of the corresponding crystalline alloys and zero-valent iron powders, making it easier to adsorb and react to degrade tetracycline antibiotics, thus improving the removal rate of tetracycline antibiotics from water.

[0025] Meanwhile, the iron-based amorphous alloy described in this invention is less prone to surface passivation during degradation reactions, can maintain its activity for a longer period of time compared to iron powder, and is easier to recycle after degradation reactions. Attached Figure Description

[0026] Figure 1 This is a comparison chart of the removal rates of tetracycline hydrochloride between Example 1 and Comparative Example 1.

[0027] Figure 2 The kinetic fitting diagrams for the removal of tetracycline hydrochloride in Example 1 and Comparative Example 1 are shown.

[0028] Figure 3 This is a comparison chart of the total organic carbon removal rates of Example 1 and Comparative Example 1 after reacting in tetracycline hydrochloride wastewater for 30 minutes.

[0029] Figure 4 This is a comparison chart of the removal rates of tetracycline hydrochloride using iron-based amorphous alloys at different initial pH values ​​in Examples 1-7.

[0030] Figure 5This is a comparison of the reaction rates of tetracycline hydrochloride removal using iron-based amorphous alloys at different initial pH values ​​in Examples 1-7.

[0031] Figure 6 This is a graph showing the removal rate of oxytetracycline hydrochloride using an iron-based amorphous alloy in Example 8.

[0032] Figure 7 This is a kinetic fitting diagram of the removal of oxytetracycline hydrochloride using an iron-based amorphous alloy in Example 8;

[0033] Figure 8 This is a graph showing the removal rate of chlortetracycline hydrochloride using an iron-based amorphous alloy in Example 9.

[0034] Figure 9 This is a kinetic fitting diagram of the removal of chlortetracycline hydrochloride using an iron-based amorphous alloy in Example 9. Detailed Implementation

[0035] The iron-based amorphous alloy described in this disclosure has the molecular formula FexSiyBz, where x, y, and z represent the atomic percentages of Fe, Si, and B in the alloy, respectively, with 74≤x≤84, 6≤y≤16, 6≤z≤16, and x+y+z=100.

[0036] Furthermore, this disclosure also provides a method for preparing the above-mentioned iron-based amorphous alloy, comprising the following steps:

[0037] S1. The raw materials are melted in a melting furnace under an inert atmosphere according to the proportion to produce an iron-based amorphous alloy;

[0038] S2. The iron-based amorphous alloy obtained in step S1 is prepared into iron-based amorphous alloy strips by single-roller spinning method.

[0039] S3. Cut the iron-based amorphous alloy strip into sheet strips with a length of 10mm.

[0040] The thickness of the iron-based amorphous alloy strip is 10μm to 200μm.

[0041] Specifically, to prepare Fe 78 Si8B 14 Let's take an example to illustrate:

[0042] S1. Weigh Fe, Si and B according to their composition, put them into a melting furnace, and melt them in an inert gas atmosphere to produce an iron-based amorphous alloy; optionally, the inert atmosphere can be a helium atmosphere or an argon atmosphere.

[0043] S2. The iron-based amorphous alloy obtained in step S1 is prepared into iron-based amorphous alloy strips by a single-roller spinning method. The specific steps include:

[0044] S201. Place the alloy obtained in step S1 into a melting furnace and induction heat it to a molten state in an inert gas atmosphere;

[0045] S202. The molten alloy is poured into the nozzle package and sprayed onto the surface of the cooling roller through the nozzle to cool and form an iron-based amorphous alloy strip.

[0046] It should be noted that before performing single-roller belt spinning, the distance between the nozzle and the cooling roller needs to be adjusted to 1-2 mm, preferably 1.5 mm; and the rotation speed of the cooling roller should be set to 55 m / s before performing the single-roller belt spinning operation.

[0047] After completing the single-roller belt spinning operation, the iron-based amorphous alloy strip obtained in step S2 is cut into sheet-like strips with a length of 10mm.

[0048] During alloy preparation, melting is carried out in an inert gas atmosphere to prevent the metal material from being oxidized. Melting in an inert gas atmosphere can effectively isolate oxygen and protect the metal material from oxidation and contamination.

[0049] In the single-roller belt spinning process, smelting is also required. In order to ensure that the alloy material is not oxidized and contaminated, smelting must be carried out in an inert gas atmosphere.

[0050] Furthermore, this disclosure also provides an application of an iron-based amorphous alloy, which is used to treat wastewater containing tetracycline antibiotics for the degradation of tetracycline antibiotics, including tetracycline hydrochloride, chlortetracycline hydrochloride, and oxytetracycline hydrochloride. The following uses Fe... 78 Si8B 14 As an example, zero-valent iron powder is used as a comparative example, and the experimental content and conclusions are described.

[0051] Example 1

[0052] 250 ml of wastewater containing tetracycline hydrochloride was poured into the reaction tank. The concentration of tetracycline hydrochloride in the wastewater was 40 mg / L. 2.5 g of the iron-based amorphous alloy strip prepared by the above method was placed into the reaction tank, and the pH value was adjusted to 5.0. The reaction tank was placed in a 35°C water bath, and a stirrer was added to the reaction tank. The stirrer speed was adjusted to 350 r / min to carry out the reaction.

[0053] Example 2

[0054] Similar to Example 1, except that the pH value was adjusted to 3.0.

[0055] Example 3

[0056] Similar to Example 1, except that the pH value was adjusted to 4.0.

[0057] Example 4

[0058] Similar to Example 1, except that the pH value was adjusted to 6.0.

[0059] Example 5

[0060] Similar to Example 1, except that the pH value was adjusted to 7.0.

[0061] Example 6

[0062] Similar to Example 1, except that the pH value was adjusted to 9.0.

[0063] Example 7

[0064] Similar to Example 1, except that the pH value was adjusted to 11.0.

[0065] Example 8

[0066] Similar to Example 1, the difference is that 250 ml of wastewater containing oxytetracycline hydrochloride was poured into the reaction tank, and the concentration of tetracycline hydrochloride in the wastewater was 40 mg / L.

[0067] Example 9

[0068] Similar to Example 1, the difference is that 250 ml of wastewater containing chlortetracycline hydrochloride was poured into the reaction tank, and the concentration of tetracycline hydrochloride in the wastewater was 40 mg / L.

[0069] Comparative Example 1

[0070] Similar to Example 1, the difference is that 2.5g of zero-valent iron powder with a particle size of 100 mesh is placed into the reaction tank.

[0071] In the above examples and comparative examples, 5 mL of solution was extracted at regular intervals during the reaction. The samples were filtered through a 0.22 μm filter membrane and then subjected to spectral measurements using a UV-Vis spectrophotometer. The solution was extracted at minutes 0, 2, 5, 10, 20, and 30.

[0072] Figures 1-3 This is a comparison chart between Example 1 and Comparative Example 1, including a comparison of removal rates, kinetic fitting, and total organic carbon removal rates. Figure 1 It can be seen that after 5 minutes of reaction, the removal efficiencies of zero-valent iron powder and iron-based amorphous alloy for tetracycline hydrochloride were 30.3% and 64.2%, respectively. Furthermore, after 30 minutes, the removal efficiency of the iron-based amorphous alloy was still higher than that of zero-valent iron powder, indicating that the metastable amorphous alloy does indeed have a higher removal efficiency than the crystalline zero-valent iron powder.

[0073] also, Figure 2 The figures shown are kinetic fitting plots of tetracycline hydrochloride removal in Example 1 and Comparative Example 1. The reaction rate k was obtained by fitting the first-order reaction kinetics. obs The comparison revealed that the removal rate of tetracycline hydrochloride by iron-based amorphous alloys was 2.75 times that of zero-valent iron powder.

[0074] and, Figure 3 This is a comparison chart of the total organic carbon removal rates of Example 1 and Comparative Example 1 after reacting in tetracycline hydrochloride wastewater for 30 minutes. The organic carbon content in the solution better reflects the final mineralization result of tetracycline hydrochloride. The chart shows that the total organic carbon removal rate in the solution after the iron-based amorphous alloy reacted for 30 minutes was 84.9%, which is much higher than the 76% of zero-valent iron powder. This indicates that the iron-based amorphous alloy can effectively remove tetracycline hydrochloride antibiotics and reduce the organic matter content in the solution.

[0075] Examples 1 to 7 compare the ability of iron-based amorphous alloys to degrade tetracycline hydrochloride in tetracycline hydrochloride wastewater under different pH conditions. Specifically, as follows... Figures 4-5 As shown, where Figure 4 This chart compares the removal rates of tetracycline hydrochloride using iron-based amorphous alloys at different initial pH values. Figure 5 A comparison of reaction rates for removing tetracycline hydrochloride using iron-based amorphous alloys at different initial pH values.

[0076] Depend on Figure 4 It can be seen that when 4.0 ≤ pH ≤ 9.0, 99% of tetracycline hydrochloride can be removed from wastewater within 30 minutes; among which, the... Figure 5 It can be seen that the reaction rate k is within the pH range of 4.0 to 7.0. obs Similarly, when the pH reaches 9.0, the reaction rate decreases significantly. The inventors believe the reason is as follows:

[0077] Tetracycline hydrochloride has three pKa values ​​(3.3, 7.7, and 9.7). When pH < 3.3, tetracycline hydrochloride mainly exists in solution as TCH3. + It exists in the form of TCH2 when 3.3 < pH < 7.7; tetracycline hydrochloride mainly exists in solution as TCH2. 0 It exists in the form of TCH; when 7.7 < pH < 9.7, tetracycline hydrochloride mainly exists in solution as TCH. - It exists in the form of TC2 when pH > 9.7; when pH > 9.7, tetracycline hydrochloride mainly exists in solution as TC2. -The corrosion products (FeO, Fe2O3, Fe3O4, FeOOH) generated during the corrosion process of iron-based amorphous alloys are effective adsorbents. When the pH of the solution is <8.0, the iron oxides are positively charged and can adsorb anions and zwitterions onto the surface of the iron-based amorphous alloy through electrostatic interaction. Iron-based amorphous alloys can generate hydrogen free radicals (H·) with reducing activity, which react with organic ions adsorbed on the surface of the iron-based amorphous alloy through dehydrogenation reactions, double bond addition reactions, and single electron transfer reactions. Therefore, the removal rate of tetracycline hydrochloride is high when the solution pH is between 4.0 and 9.0, while the removal rate is low when the pH is 3.0 or 11.0.

[0078] In summary, the optimal pH range for the degradation of tetracycline hydrochloride is determined to be between 4.0 and 9.0. Since one of the pKa values ​​of tetracycline hydrochloride is 3.3, the inventors believe that the optimal pH range for the degradation of tetracycline hydrochloride is between 3.3 and 9.0.

[0079] Figure 6 This is a graph showing the removal rate of oxytetracycline hydrochloride using an iron-based amorphous alloy in Example 8. Figure 7 Example 8: Kinetic fitting diagram of the removal of oxytetracycline hydrochloride using an iron-based amorphous alloy; by Figure 6 and Figure 7 It can be seen that, after 20 minutes of reaction, the removal rate of oxytetracycline hydrochloride using the iron-based amorphous alloy is as high as 97%. Furthermore, the reaction rate k was obtained through first-order reaction kinetic fitting. obs Under these conditions, the iron-based amorphous alloy achieved a removal rate of up to 0.257 min for oxytetracycline hydrochloride. -1 It is far superior to the currently commonly used biodegradation methods.

[0080] Figure 8 This is a graph showing the removal rate of chlortetracycline hydrochloride using an iron-based amorphous alloy in Example 9. Figure 9 This is a kinetic fitting diagram of the removal of chlortetracycline hydrochloride using an iron-based amorphous alloy in Example 9; (from...) Figure 8 and Figure 9 It can be seen that after 20 minutes of reaction, the removal rate of chlortetracycline hydrochloride using the iron-based amorphous alloy is close to 97%. Furthermore, the reaction rate k was obtained by fitting first-order reaction kinetics. obs Under these conditions, the iron-based amorphous alloy achieved a removal rate of up to 0.323 min for chlortetracycline hydrochloride. -1 It is far superior to the currently commonly used biodegradation methods.

[0081] In the description of this disclosure, it should be understood that the orientation or positional relationship indicated by directional terms such as "front, back, up, down, left, right", "horizontal, vertical, horizontal" and "top, bottom" is usually based on the orientation or positional relationship shown in the accompanying drawings and is only for the convenience of describing this disclosure and simplifying the description. Unless otherwise stated, these directional terms do not indicate or imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the scope of protection of this disclosure.

[0082] For those skilled in the art, various other corresponding changes and modifications can be made based on the technical solutions and concepts described above, and all such changes and modifications should fall within the protection scope of the claims disclosed herein.

Claims

1. An application of an iron-based amorphous alloy, characterized in that, The iron-based amorphous alloy is applied to the treatment of wastewater containing tetracycline antibiotics to degrade tetracycline antibiotics; the pH value of the wastewater containing tetracycline antibiotics is 3.3-9. The molecular formula of the iron-based amorphous alloy is Fe. x Si y B z , where x, y, and z represent the atomic percentages of Fe, Si, and B in the alloy, respectively, 74≤x≤84, 6≤y≤16, 6≤z≤16, and x+y+z=100; The iron-based amorphous alloy Fe 78 Si8B 14 The preparation method includes the following steps: S1. The raw materials are melted in a melting furnace under an inert atmosphere according to the proportion to produce an iron-based amorphous alloy; S2. The iron-based amorphous alloy obtained in step S1 is prepared into iron-based amorphous alloy strips by single-roller spinning method. S3. Cut the iron-based amorphous alloy strip into sheet strips with a length of 10mm; Step S2 specifically includes: S201. Place the alloy obtained in step S1 into a melting furnace and induction heat it to a molten state in an inert gas atmosphere; S202. Before single-roller strip spinning, the distance between the nozzle and the cooling roller needs to be adjusted to 1-2 mm, and the rotation speed of the cooling roller is set to 55 m / s. The molten alloy is poured into the nozzle package, and the molten alloy is sprayed onto the surface of the cooling roller through the nozzle to cool and form an iron-based amorphous alloy strip.

2. The application of the iron-based amorphous alloy according to claim 1, characterized in that, The thickness of the iron-based amorphous alloy strip is 10 μm to 200 μm.

3. The application of the iron-based amorphous alloy according to claim 2, characterized in that, The concentration of the tetracycline antibiotic in the wastewater is 10–200 mg / L.

4. The application of the iron-based amorphous alloy according to claim 1, characterized in that, The wastewater containing tetracycline antibiotics has a pH value of 4 to 9.

5. The application of the iron-based amorphous alloy according to claim 3, characterized in that, The amount of iron-based amorphous alloy strip added is greater than or equal to 10 g / L.

6. The application of the iron-based amorphous alloy according to claim 3, characterized in that, The temperature of the wastewater containing tetracycline antibiotics is 30–40°C.

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