A novel method for activating high ferrate by piezoelectric catalysis and application

Abstract

The application provides a novel piezoelectric catalytic activation method and application of ferrate, and belongs to the technical field of ferrate activation, which comprises the following steps: dissolving potassium ferrate in deionized water; then adding zinc stannate into the potassium ferrate solution; and finally, under the condition of ultrasonic, the piezoelectric property of zinc stannate is used to catalytically activate ferrate. The activation method of ferrate provided by the application can be used for the degradation of sulfonamide antibiotics in water, and the degradation efficiency is significantly better than that of ferrate alone, and the adaptability is strong, and stable activation effect can be shown in various anion environments, and more importantly, the novel activation method solves the problem that the stability and oxidizability of ferrate are incompatible, can react under neutral conditions, ensures the stability, and has the oxidizability at the same time, and is suitable for popularization and application in sewage treatment.

Description

Technical Field

[0001] This invention belongs to the field of ferrate activation technology, specifically relating to a novel piezoelectric catalytic activation method for ferrates and its application. Background Technology

[0002] Since their advent, antibiotics have been widely used due to their significant anti-infective effects. Sulfamethazine, with its relatively low cost and good antibacterial activity, has become the most widely used antibiotic in livestock farming and clinical medicine, and is constantly being discharged into water bodies, causing environmental pollution. Sulfamethazine exhibits ecotoxicity to animals, plants, and microorganisms in the environment. It can also accumulate in the food chain through absorption by plants and animals, affecting human health and even inducing the production and spread of resistance genes, ultimately posing a serious threat to public health. Traditional biological treatment processes in wastewater treatment plants are insufficient to remove these antibiotic pollutants; therefore, new technologies need to be developed to address these problems.

[0003] Numerous studies have shown that activated ferrate, as a green and efficient advanced oxidation technology, has excellent application prospects in many aspects such as the decomposition of organic pollutants. Therefore, it is necessary to develop a new method of activated ferrate to remove sulfadimethylpyrimidine pollution from water bodies.

[0004] Activation of ferrates is an advanced oxidation process that effectively removes contaminants from water and exhibits strong bactericidal properties as a green oxidant. Furthermore, the Fe(OH)3 product of ferrate reduction is a highly efficient coagulant, further enhancing the removal of fine suspended solids from water. However, the stability and oxidizing power of ferrates are affected by various factors. At lower pH conditions, their oxidizing power is stronger, but their stability is weaker. Conversely, at higher pH conditions, their stability improves, but their oxidizing power decreases. Therefore, there is an urgent need to develop new activation methods that can improve the oxidizing power and stability of ferrates while avoiding the shortcomings of existing technologies, thus providing greater potential for large-scale applications.

[0005] Therefore, there is a need to provide an improved technical solution that addresses the shortcomings of the existing technology. Summary of the Invention

[0006] The primary objective of this invention is to provide a novel method for piezoelectric catalytic activation of ferrates, thereby addressing the incompatibility between the oxidizing properties and stability of existing ferrates when degrading pollutants.

[0007] Another object of the present invention is to provide the use of the above-mentioned activated ferrate.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A novel method for piezoelectric catalytic activation of ferrates includes the following steps:

[0010] S1. Dissolve ferrate in deionized water to obtain solution A;

[0011] S2. Add zinc stannate powder to solution A to obtain mixture B;

[0012] S3. The mixture B prepared in step S2 is subjected to ultrasonic treatment for a first preset time to obtain activated ferrate.

[0013] Preferably, in step S1, the ferrate is potassium ferrate and / or sodium ferrate.

[0014] Preferably, in step S1, the concentration of ferrate in solution A is 75~200 µmol / L.

[0015] Preferably, in step S2, based on mixture B, the amount of zinc stannate powder added is 0.02~0.12 g / L.

[0016] Preferably, in step S3, the ultrasonic conditions are: ultrasonic power of 20~200W and ultrasonic frequency of not less than 40kHz.

[0017] Preferably, in step S3, the processing temperature is 10~30℃ and the first preset time is 1~20min.

[0018] The present invention also provides the use of the above-described method in the degradation of sulfadimethylpyrimidine.

[0019] Preferably, in the above-mentioned uses, the method for degrading sulfadimethylpyrimidine is as follows:

[0020] Step 1: Add zinc stannate powder to a solution or wastewater containing sulfadiazine;

[0021] Step 2: Continue to add potassium ferrate solution and react under ultrasonic conditions for a first preset time to degrade sulfadimethylpyrimidine using the activated ferrate produced by the reaction.

[0022] Beneficial effects:

[0023] (1) This invention provides a novel piezoelectric catalytic activation method for ferrates, which mainly generate more reactive Fe(V) or Fe(IV) through single-electron or double-electron transfer. This activation process requires the participation of electrons. The principle of piezoelectric catalysis relies on the non-centrosymmetric structure of piezoelectric materials. When subjected to external pressure, these materials undergo surface deformation and internal charge separation, generating a built-in electric field, thereby forming highly reactive electron-hole pairs at both ends of the material. Based on this characteristic, piezoelectric materials may directly or indirectly provide electrons to high-valence iron, causing it to generate more Fe(V) or Fe(IV), thereby degrading pollutants in water. It has broad application prospects in environmental pollution control, energy, and other fields;

[0024] (2) This invention provides a novel piezoelectric catalytic activation method for ferrates. Compared with traditional activation methods, this method ensures the stability of ferrates while also possessing their oxidizing properties, enabling efficient degradation of pollutants. Furthermore, this activation method is simple to implement and does not require light energy, so it can be carried out in the dark, making it easy to produce and promote. Attached Figure Description

[0025] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. Wherein:

[0026] Figure 1 The figure shows the effect of piezoelectric catalytic activation of ferrate in the degradation of sulfadimethylpyrimidine. US in the figure represents ultrasonic conditions.

[0027] Figure 2 To investigate the degradation effect of piezoelectric catalytic activated ferrate on sulfadimethylpyrimidine under different ionic and humic acid conditions.

[0028] Figure 3 The method provided by this invention demonstrates its degradation effect on different sulfonamide compounds. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention are within the scope of protection of the present invention.

[0030] The present invention will now be described in detail with reference to embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in the embodiments of the present invention can be combined with each other.

[0031] This invention addresses the incompatibility between the oxidizing and stability properties of ferrates in degrading pollutants by providing a novel piezoelectric catalytic activation method for ferrates. This method utilizes zinc stannate to activate ferrates under ultrasonic conditions. Compared to traditional activation methods, this method ensures the stability of ferrates while retaining their oxidizing properties, enabling efficient degradation of pollutants. Furthermore, this activation method is simple, does not require light energy, and can be carried out in the dark, making it easy to produce and promote.

[0032] A novel method for piezoelectric catalytic activation of ferrates includes the following steps:

[0033] S1. Dissolve ferrate in deionized water to obtain solution A;

[0034] S2. Add zinc stannate powder to solution A to obtain mixture B;

[0035] S3. The mixture B prepared in step S2 is subjected to ultrasonic treatment for a first preset time to obtain activated ferrate.

[0036] In a preferred embodiment of the present invention, in step S1, the ferrate is potassium ferrate and / or sodium ferrate.

[0037] In a preferred embodiment of the present invention, in step S1, the concentration of ferrate in solution A is 75~200 (e.g., 75, 100, 120, 140, 150, 160, 180, 200) µmol / L.

[0038] In a preferred embodiment of the present invention, in step S2, based on the mixture B, the amount of zinc stannate powder added is 0.02~0.12 (e.g., 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) g / L.

[0039] In a preferred embodiment of the present invention, in step S3, the ultrasonic conditions are: ultrasonic power of 20~200 (e.g. 20, 40, 60, 80, 100, 120, 140, 160, 180, 200) W, and ultrasonic frequency of not less than 40 kHz.

[0040] In a preferred embodiment of the present invention, in step S3, the processing temperature is 10~30 (e.g., 10, 15, 20, 25, 30) °C, and the first preset time is 1~20 (e.g., 1, 2, 4, 6, 10, 12, 14, 16, 18, 20) min.

[0041] The present invention also provides the use of the above-described method in the degradation of sulfadimethylpyrimidine.

[0042] In a preferred embodiment of the present invention, the method for degrading sulfadimethylpyrimidine in the above-described uses is as follows:

[0043] Step 1: Add zinc stannate powder to a solution or wastewater containing sulfadiazine;

[0044] Step 2: Continue to add potassium ferrate solution and react under ultrasonic conditions for a first preset time to degrade sulfadimethylpyrimidine using the activated ferrate produced by the reaction.

[0045] The following detailed description of a novel piezoelectric catalytic activation method for ferrates and its application is illustrated by specific embodiments.

[0046] The raw materials and equipment used in the following embodiments are as follows:

[0047] Potassium ferrate: analytical grade, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0048] Sodium ferrate: analytical grade, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0049] Zinc stannate: analytical grade, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0050] Ultrasonic machine: purchased from Kunshan Ultrasonic Instruments Co., Ltd.

[0051] Example 1

[0052] This embodiment provides a novel piezoelectric catalytic activation method for ferrates, which includes the following steps:

[0053] S1. Preparation of potassium ferrate solution:

[0054] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0055] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution, which is solution A.

[0056] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker.

[0057] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 3 mg zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0058] Example 2

[0059] S1. Preparation of potassium ferrate solution:

[0060] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0061] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution.

[0062] S2. Weigh 1 mg of zinc stannate powder into a 50 mL beaker system.

[0063] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 1 mg of zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0064] Example 3

[0065] S1. Preparation of potassium ferrate solution:

[0066] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0067] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution.

[0068] S2. Weigh 2 mg of zinc stannate powder into a 50 mL beaker system.

[0069] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 2 mg zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0070] Example 4

[0071] S1. Preparation of potassium ferrate solution:

[0072] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0073] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution.

[0074] S2. Weigh 4 mg of zinc stannate powder into a 50 mL beaker system.

[0075] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 4 mg of zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0076] Example 5

[0077] S1. Preparation of potassium ferrate solution:

[0078] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0079] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution.

[0080] S2. Weigh 5 mg of zinc stannate powder into a 50 mL beaker system.

[0081] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 5 mg of zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0082] Example 6

[0083] S1. Preparation of potassium ferrate solution:

[0084] S11. Add 0.0188g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0085] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 150 μM potassium ferrate solution.

[0086] S2. Weigh 6 mg of zinc stannate powder into a 50 mL beaker system.

[0087] S3. Pour 150 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 6 mg of zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0088] Example 7

[0089] S1. Preparation of potassium ferrate solution:

[0090] S11. Add 0.0095g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0091] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 75 μM potassium ferrate solution.

[0092] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0093] S3. Pour 75 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 3 mg zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0094] Example 8

[0095] S1. Preparation of potassium ferrate solution:

[0096] S11. Add 0.0125g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0097] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 100 μM potassium ferrate solution.

[0098] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0099] S3. Pour 100 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 3 mg zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0100] Example 9

[0101] S1. Preparation of potassium ferrate solution:

[0102] S11. Add 0.0158g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0103] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 125 μM potassium ferrate solution.

[0104] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0105] S3. Pour 125 μM potassium ferrate solution into a beaker to the 50 mL mark, mix with 3 mg zinc stannate powder, and treat under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0106] Example 10

[0107] S1. Preparation of potassium ferrate solution:

[0108] S11. Add 0.0220g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0109] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 175 μM potassium ferrate solution.

[0110] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0111] S3. Pour 175 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 3 mg of zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0112] Example 11

[0113] S1. Preparation of potassium ferrate solution:

[0114] S11. Add 0.0250g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to 25mL in a volumetric flask to obtain a mixture.

[0115] S12. Take 2 mL of the above mixture and add it to a 50 mL beaker system to obtain a 200 μM potassium ferrate solution.

[0116] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0117] S3. Pour 200 μM potassium ferrate solution into a beaker to the 50 mL mark, mix it evenly with 3 mg zinc stannate powder, and treat it under ultrasonic conditions of 200 W and 40 kHz for 15 minutes to complete the activation of potassium ferrate.

[0118] Evaluation of the piezoelectric catalytic degradation effect of sulfadimethylpyrimidine:

[0119] Experimental plan:

[0120] 1. Weigh 3 mg of zinc stannate powder and add it to 50 mL of sulfadimethylpyrimidine solution (concentration 1 μM);

[0121] 2. Add 150 μM potassium ferrate solution and react under ultrasonic conditions of 200 W and 40 kHz for 15 min. After sampling, use high performance liquid chromatography to determine the remaining concentration C of sulfadiazine in the solution.

[0122] 3. Calculate the removal rate of sulfadimethylpyrimidine using the following formula: Where C0 is the initial concentration of sulfadimethylpyrimidine and C is the remaining concentration.

[0123] Investigate the effects of various factors in this experimental design on the residual concentration of the sulfadimethylpyrimidine solution, such as... Figure 1 As shown, zinc stannate and potassium ferrate have a certain degradation effect on sulfadiazine without ultrasonic treatment. However, after adding ultrasonic conditions, the residual concentration C of sulfadiazine decreased significantly from around 45% to below 10%, indicating that ultrasonic treatment can significantly improve the degradation effect.

[0124] Secondly, such as Figure 1 As shown, under the same ultrasonic treatment conditions, the addition of zinc stannate can significantly improve the degradation effect of ferrate on sulfadiazine, indicating that the combined effect of zinc stannate, ferrate and ultrasonic treatment is the best for the degradation of sulfadiazine.

[0125] The degradation effects of ZnSnO3 / Fe(VI) / US on sulfadimethylpyrimidine under different anionic and humic acid conditions were tested as follows:

[0126] The effect of ZnSnO3 / Fe(VI) / US on the degradation of sulfadimethylpyrimidine was tested under different anionic environments, such as Figure 2 As shown, HCO3 2- Cl - SO4 2- These anions have no significant effect on the degradation of sulfadimethylpyrimidine by ZnSnO3 / Fe(VI) / US.

[0127] The effect of ZnSnO3 / Fe(VI) / US on the degradation of sulfadimethylpyrimidine was tested under different anionic environments, such as Figure 2 As shown, humic acid (HA) has no significant effect on the degradation of sulfadimethylpyrimidine by ZnSnO3 / Fe(VI) / US.

[0128] It is evident that the ZnSnO3 / Fe(VI) / US system can adapt to a variety of complex operating environments and is not easily affected by common ions in water.

[0129] The above experimental scheme was used to conduct degradation tests on different sulfonamides, and the results were as follows: Figure 3 In the picture:

[0130] SIZ: sulfisoxazol;

[0131] SMIZ: sulfamethizole;

[0132] SMX: sulfamethoxazole;

[0133] SDZ: sulfadiazine;

[0134] SMR: sulfamerazine;

[0135] SPD: sulfapyridine.

[0136] like Figure 3 As shown, this method has a significant degradation effect on a variety of sulfonamide compounds.

[0137] In summary, the novel ferrate activation method proposed in this invention has a significant effect on the degradation of sulfadiazine and is well adaptable to various ions and humic acids. Its catalytic effect is not easily affected by other factors in the environment, making it very suitable for the degradation treatment of sulfadiazine pollutants in water.

[0138] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A novel method for piezoelectric catalytic activation of ferrates, characterized in that, Includes the following steps: S1. Dissolve ferrate in deionized water to obtain solution A; S2. Add zinc stannate powder to solution A to obtain mixture B; S3. The mixture B prepared in step S2 is subjected to ultrasonic treatment for a first preset time to obtain activated ferrate.

2. The novel piezoelectric catalytic activation method for ferrates as described in claim 1, characterized in that, In step S1, the ferrate is potassium ferrate and / or sodium ferrate.

3. The novel piezoelectric catalytic activation method for ferrates as described in claim 1, characterized in that, In step S1, the concentration of ferrate in solution A is 75~200 µmol / L.

4. The novel piezoelectric catalytic activation method for ferrates as described in claim 1, characterized in that, In step S2, based on mixture B, the amount of zinc stannate powder added is 0.02~0.12 g / L.

5. The novel piezoelectric catalytic activation method for ferrates as described in claim 1, characterized in that, In step S3, the ultrasonic conditions are: ultrasonic power of 20~200W and ultrasonic frequency of not less than 40kHz.

6. A novel piezoelectric catalytic activation method for ferrates as described in any one of claims 1 to 5, characterized in that, In step S3, the processing temperature is 10~30℃, and the first preset time is 1~20min.

7. Use of the method according to any one of claims 1 to 6 in the degradation of sulfadimethylpyrimidine.

8. The use as described in claim 7, characterized in that, The method for degrading sulfadimethylpyrimidine is as follows: Step 1: Add zinc stannate powder to a solution or wastewater containing sulfadiazine; Step 2: Continue to add potassium ferrate solution and react under ultrasonic conditions for a first preset time to degrade sulfadimethylpyrimidine using the activated ferrate produced by the reaction.

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