Novel method for activating ferrate through piezoelectric catalysis and application

Abstract

The invention provides a novel method for activating ferrate through piezoelectric catalysis and application, and belongs to the technical field of ferrate activation. The method comprises the steps that potassium ferrate is dissolved in deionized water; then adding zinc stannate into the potassium ferrate solution; and finally, under an ultrasonic condition, catalyzing and activating the ferrate by utilizing the piezoelectric property of zinc stannate. The ferrate activation method provided by the invention can be used for degrading sulfonamide antibiotics in a water body, the degradation efficiency of the ferrate activation method is remarkably superior to that of single ferrate, the ferrate activation method is high in adaptability, and a stable activation effect can be shown in various anion environments, and more importantly, the novel ferrate activation method can be used for degrading sulfonamide antibiotics in a water body. The problem that the stability and oxidability of ferrate are incompatible is solved, reaction can be carried out under the neutral condition, the stability of the ferrate is guaranteed, meanwhile, the oxidability of the ferrate is achieved, and the ferrate is suitable for being applied and popularized in sewage treatment.

Description

Technical Field

[0001] The invention belongs to the technical field of ferrate activation, and in particular relates to a novel piezoelectric catalytic activation method for ferrate and its application. Background Art

[0002] Since the advent of antibiotics, they have been widely used due to their significant anti-infection effects. Among them, sulfamethazine has become the most used antibiotic in livestock and poultry farming, medical clinics, etc. due to its low cost and good antibacterial activity, and is continuously discharged into water bodies, causing environmental pollution. Sulfamethazine will have ecotoxic effects on animals, plants, and microorganisms in the environment. At the same time, it will enter the food chain through animal and plant absorption and enrichment, affecting human health, and may even induce the production of resistance genes and enhance their spread, ultimately posing a serious threat to public health. The biological treatment process in traditional sewage treatment plants is difficult to remove these antibiotic pollutants, so new technologies need to be developed to solve these problems.

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

[0004] Activated ferrate is an advanced oxidation process that can effectively remove pollutants from water as a green oxidant and exhibits strong bactericidal properties. In addition, the product of ferrate reduction, Fe(OH)3, is a highly effective coagulant that can further enhance the removal of fine suspended solids in water. However, the stability and oxidizability of ferrate are affected by many factors. At lower pH conditions, its oxidizing ability is stronger but its stability is weaker. On the contrary, at higher pH conditions, its stability is improved but its oxidizing ability is reduced. Therefore, there is an urgent need to develop new activation methods that can not only improve the oxidizability and stability of ferrate, but also avoid the defects of existing technologies, thereby providing greater potential for large-scale applications.

[0005] Therefore, it is necessary to provide an improved technical solution to address the above-mentioned deficiencies in the prior art. Summary of the invention

[0006] The first object of the present invention is to provide a novel piezoelectric catalytic activation method for ferrate to solve the problem of incompatibility between the oxidizability and stability of existing ferrate when degrading pollutants.

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

[0008] In order to achieve the above object, the present invention provides the following technical solutions: A novel piezoelectric catalytic activation method for ferrate comprises the following steps: S1. dissolving ferrate in deionized water to obtain solution A; S2, adding zinc stannate powder to solution A to obtain a mixed solution B; S3, treating the mixed solution B prepared in step S2 under ultrasonic conditions for a first preset time to obtain activated ferrate.

[0009] Preferably, in step S1, the ferrate is potassium ferrate and / or sodium ferrate.

[0010] Preferably, in step S1, the concentration of ferrate in the solution A is 75-200 µmol / L.

[0011] Preferably, in step S2, based on the mixed solution B, the amount of zinc stannate powder added is 0.02-0.12 g / L.

[0012] Preferably, in step S3, the ultrasonic conditions are: ultrasonic power is 20-200 W, and ultrasonic frequency is not less than 40 kHz.

[0013] Preferably, in step S3, the processing temperature is 10-30° C., and the first preset time is 1-20 min.

[0014] The present invention also provides the use of the above method in degrading sulfadimethoxine.

[0015] Preferably, in the above-mentioned use, the method for degrading sulfadimethoxine is as follows: Step 1, adding zinc stannate powder into a solution or sewage containing sulfadimethoxine; Step 2: Continue to add potassium ferrate solution thereto, and react under ultrasonic conditions for a first preset time, and utilize the activated ferrate produced by the reaction to degrade sulfadimethoxine.

[0016] Beneficial effects: (1) The present invention provides a novel piezoelectric catalytic activation method for ferrate, which mainly generates 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-valent iron, causing it to generate more Fe (V) or Fe (IV), thereby degrading pollutants in water. It has broad application prospects in the fields of environmental pollution control, energy, etc. (2) The present invention provides a novel piezoelectric catalytic activation method for ferrate. Compared with the traditional activation method, the present invention ensures the stability of ferrate while maintaining its oxidizing property, and can efficiently degrade pollutants. Moreover, the activation method has simple conditions and does not require the aid of light energy, so it can be carried out in dark conditions, which is easy to produce and promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. Among them: Figure 1 This is the effect of piezoelectric catalytic activation of ferrate on the degradation of sulfadimethoxine. In the figure, US stands for ultrasonic conditions.

[0018] Figure 2 The degradation effect of sulfadimethoxine on the piezoelectric catalytic activation of ferrate under different ion and humic acid conditions.

[0019] Figure 3 The invention discloses the degradation effect of the method provided by the invention on different sulfonamide compounds. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0021] The present invention will be described in detail below in conjunction with embodiments. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.

[0022] The present invention aims to solve the problem that the oxidizability and stability of ferrate are incompatible when degrading pollutants. The present invention provides a novel piezoelectric catalytic activation method for ferrate. Zinc stannate is used to activate ferrate under ultrasonic conditions. Compared with the traditional activation method, the stability of ferrate is ensured while its oxidizability is also maintained, and pollutants can be degraded efficiently. Moreover, the activation method has simple conditions and does not require the aid of light energy, so it can be carried out in dark conditions and is easy to produce and promote.

[0023] A novel piezoelectric catalytic activation method for ferrate comprises the following steps: S1. dissolving ferrate in deionized water to obtain solution A; S2, adding zinc stannate powder to solution A to obtain a mixed solution B; S3, treating the mixed solution B prepared in step S2 under ultrasonic conditions for a first preset time to obtain activated ferrate.

[0024] In a preferred embodiment of the present invention, in step S1, the ferrate is potassium ferrate and / or sodium ferrate.

[0025] In a preferred embodiment of the present invention, in step S1, the concentration of ferrate in the solution A is 75-200 (e.g., 75, 100, 120, 140, 150, 160, 180, 200) µmol / L.

[0026] In a preferred embodiment of the present invention, in step S2, based on the mixed solution 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.

[0027] In a preferred embodiment of the present invention, in step S3, the ultrasonic conditions are: the ultrasonic power is 20-200 (e.g., 20, 40, 60, 80, 100, 120, 140, 160, 180, 200) W, and the ultrasonic frequency is not less than 40 kHz.

[0028] 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.

[0029] The present invention also provides the use of the above method in degrading sulfadimethoxine.

[0030] In a preferred embodiment of the present invention, in the above-mentioned use, the method for degrading sulfadimethoxine is as follows: Step 1, adding zinc stannate powder into a solution or sewage containing sulfadimethoxine; Step 2: Continue to add potassium ferrate solution thereto, and react under ultrasonic conditions for a first preset time, and utilize the activated ferrate produced by the reaction to degrade sulfadimethoxine.

[0031] The following is a detailed description of a novel piezoelectric catalytic activation method and application of ferrate according to the present invention through specific examples.

[0032] The raw materials and equipment used in the following examples are as follows: Potassium ferrate: analytical grade, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0033] Sodium ferrate: analytical grade, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0034] Zinc stannate: analytical grade, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0035] Ultrasound machine: purchased from Kunshan Ultrasound Instrument Co., Ltd.

[0036] Example 1 This embodiment provides a novel piezoelectric catalytic activation method for ferrate, which comprises the following steps: S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution, which is solution A.

[0037] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker.

[0038] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 3mg of zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0039] Example 2 S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution.

[0040] S2. Weigh 1 mg of zinc stannate powder into a 50 mL beaker system.

[0041] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 1mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0042] Example 3 S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution.

[0043] S2. Weigh 2 mg of zinc stannate powder into a 50 mL beaker system.

[0044] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 2mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0045] Example 4 S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution.

[0046] S2. Weigh 4 mg of zinc stannate powder into a 50 mL beaker system.

[0047] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 4mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0048] Example 5 S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution.

[0049] S2. Weigh 5 mg of zinc stannate powder into a 50 mL beaker system.

[0050] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 5mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0051] Example 6 S1. Preparation of potassium ferrate solution: S11. Add 0.0188 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 150 uM potassium ferrate solution.

[0052] S2. Weigh 6 mg of zinc stannate powder into a 50 mL beaker system.

[0053] S3. Pour 150uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 6mg of zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to activate potassium ferrate.

[0054] Example 7 S1. Preparation of potassium ferrate solution: S11. Add 0.0095 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 75 uM potassium ferrate solution.

[0055] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0056] S3. Pour 75uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 3mg of zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0057] Example 8 S1. Preparation of potassium ferrate solution: S11. Add 0.0125 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 100 uM potassium ferrate solution.

[0058] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0059] S3. Pour 100uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 3mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0060] Example 9 S1. Preparation of potassium ferrate solution: S11. Add 0.0158 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 125 uM potassium ferrate solution.

[0061] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0062] S3. Pour 125uM potassium ferrate solution into a beaker to the 50mL mark, mix with 3mg zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to activate potassium ferrate.

[0063] Example 10 S1. Preparation of potassium ferrate solution: S11. Add 0.0220 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 175 uM potassium ferrate solution.

[0064] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0065] S3. Pour 175uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 3mg of zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0066] Embodiment 11 S1. Preparation of potassium ferrate solution: S11. Add 0.0250 g of potassium ferrate to a beaker, add a small amount of deionized water, and after it is completely dissolved, dilute to a 25 mL volumetric flask to obtain a mixed solution; S12. Take 2 mL of the above mixed solution and add it to a 50 mL beaker system to obtain a 200 uM potassium ferrate solution.

[0067] S2. Weigh 3 mg of zinc stannate powder into a 50 mL beaker system.

[0068] S3. Pour 200uM potassium ferrate solution into a beaker to the 50mL mark, mix evenly with 3mg of zinc stannate powder, and treat under ultrasonic conditions of 200w and 40kHz for 15min to complete the activation of potassium ferrate.

[0069] Evaluation of the effect of piezoelectric catalytic degradation of sulfadimethoxine: Experimental protocol: 1. Weigh 3 mg of zinc stannate powder and add it into 50 mL of sulfadimethoxine solution (concentration is 1 uM); 2. Add 150uM potassium ferrate solution, react under ultrasonic conditions of 200W and 40kHz for 15 minutes, and use high performance liquid chromatography to measure the residual concentration C of sulfadimethoxine in the solution after sampling; 3. Calculate the removal rate of sulfadimethoxine using the following formula: , where C0 is the initial concentration of sulfadimethoxine and C is the residual concentration.

[0070] The influence of various factors in the experimental scheme on the residual concentration of sulfadimethoxine solution was investigated, such as Figure 1 As shown in the figure, without ultrasonic treatment, zinc stannate and potassium ferrate have a certain degradation effect on sulfamethazine, but after adding ultrasonic conditions, the residual concentration C of sulfamethazine is significantly reduced from about 45% to below 10%. It can be seen that ultrasonic treatment can significantly improve the degradation effect.

[0071] Secondly, if Figure 1 As shown, under the same ultrasonic treatment conditions, the addition of zinc stannate can significantly improve the degradation effect of ferrate on sulfamethazine, indicating that the degradation effect of sulfamethazine is best under the combined action of zinc stannate, ferrate and ultrasonic treatment.

[0072] The degradation effect of ZnSnO3 / Fe (VI) / US on sulfadimethoxine in the presence of different anions and humic acid was tested as follows: The degradation effect of ZnSnO3 / Fe (VI) / US on sulfadimethoxine was tested under different anion environments. Figure 2 As shown, HCO3 2- , Cl - 、SO4 2- These anions had no significant effect on the degradation of sulfamethazine by ZnSnO3 / Fe (VI) / US.

[0073] The degradation effect of ZnSnO3 / Fe (VI) / US on sulfadimethoxine was tested under different anion environments. Figure 2 As shown in the figure, humic acid (HA) had no significant effect on the degradation of sulfamethazine by ZnSnO3 / Fe (VI) / US.

[0074] It can be seen that the ZnSnO3 / Fe (VI) / US system can adapt to a variety of complex usage environments and is not easily affected by common ions in water.

[0075] The above experimental scheme was used to carry out degradation tests on different sulfonamide substances. Figure 3 , in the figure: SIZ: sulfisoxazol, sulfisoxazole; SMIZ: sulfamethizole; SMX: sulfamethoxazole; SDZ: sulfadiazine; SMR: sulfamerazine; SPD: sulfapyridine.

[0076] like Figure 3 As shown, this method has a significant degradation effect on a variety of sulfonamide compounds.

[0077] In summary, the novel ferrate activation method proposed in the present invention can have a significant effect on the degradation of sulfamethazine, and has good adaptability to a variety of ions and humic acid. Its catalytic effect is not easily interfered by other factors in the environment, and is very suitable for the degradation of sulfamethazine pollutants in water bodies.

[0078] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A novel method for activating ferrate by piezoelectric catalysis, characterized in that: The steps include: S1. dissolving ferrate in deionized water to obtain solution A; S2, adding zinc stannate powder to solution A to obtain a mixed solution B; S3, treating the mixed solution B prepared in step S2 under ultrasonic conditions for a first preset time to obtain activated ferrate.

2. A novel piezoelectric catalytic activation method for ferrate according to claim 1, characterized in that: In step S1, the ferrate is potassium ferrate and / or sodium ferrate.

3. A novel piezoelectric catalytic activation method for ferrate according to claim 1, characterized in that: In step S1, the concentration of ferrate in the solution A is 75-200 µmol / L.

4. A novel piezoelectric catalytic activation method for ferrate according to claim 1, characterized in that: In step S2, based on the mixed solution B, the amount of zinc stannate powder added is 0.02-0.12 g / L.

5. A novel piezoelectric catalytic activation method for ferrate according to claim 1, characterized in that: In step S3, the ultrasonic conditions are: ultrasonic power is 20-200W, and ultrasonic frequency is not less than 40kHz.

6. A novel piezoelectric catalytic activation method for ferrate according to any one of claims 1 to 5, characterized in that: In step S3, the processing temperature is 10-30° C., and the first preset time is 1-20 minutes.

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

8. The use according to claim 7, characterized in that The method for degrading sulfadimethoxine is as follows: Step 1, adding zinc stannate powder into a solution or sewage containing sulfadimethoxine; Step 2: Continue to add potassium ferrate solution thereto, and react under ultrasonic conditions for a first preset time, and utilize the activated ferrate produced by the reaction to degrade sulfadimethoxine.

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