Use of a piezoelectric material in the treatment of antibiotic wastewater with catalytic peroxyacetic acid and method

Abstract

The application relates to the field of piezoelectric catalysis, in particular to application and a method of piezoelectric material in treatment of antibiotic wastewater by catalysis of peracetic acid. A divalent metal salt and a trivalent metal salt are dissolved in water to obtain a metal salt solution; then the metal salt aqueous solution is mixed with a urea aqueous solution to generate a hydrothermal reaction, and a piezoelectric material is obtained; then the piezoelectric material is mixed with peracetic acid in antibiotic wastewater, and antibiotics in the wastewater are removed after pH adjustment. The piezoelectric material used in the application can efficiently activate peracetic acid to generate surface hydroxyl, hydrogen peroxide, CH3C(O)O and CH3C(O)OO and hydroxyl radicals, and effectively improve the degradation efficiency of pollutants in water.

Description

Technical Field

[0001] This invention relates to the field of piezoelectric catalysis technology, and in particular to the application and method of piezoelectric materials in the catalytic treatment of antibiotic wastewater with peracetic acid. Background Technology

[0002] Antibiotics have antibacterial and bactericidal effects; however, when they appear in large quantities in the aquatic environment, they cause antibiotic pollution, posing a significant threat to the ecological environment and human health. Currently, advanced oxidation processes (AOPs) have become one of the effective treatment strategies for antibiotic wastewater. This process can generate highly reactive free radicals in situ, such as hydroxyl radicals (·OH) and sulfate radicals (SO4). ·- It directly degrades and mineralizes antibiotic molecules in water.

[0003] Traditional oxidants include ozone, hydrogen peroxide, and persulfate. Among these, peracetic acid (PAA) has advantages over traditional oxidants, such as high oxidation efficiency, a lower tendency to form harmful disinfection byproducts (DBPs), and easier activation. It is used as an effective and cost-effective alternative oxidant to AOPs for wastewater treatment.

[0004] There are generally two ways to activate PAA: one is through energy input, such as heat and ultraviolet light, to directly homolytically cleave the peroxide bonds; the other is through electron transfer, such as through transition metals and carbon materials, where the generated electrons are transferred to the O-O bonds, causing PAA decomposition. However, both methods have limitations: thermal activation efficiency is low; ultraviolet light penetration into water is limited; metal ions dissolve; and carbon materials have low activity, consuming large amounts of chemicals and causing secondary pollution. Therefore, it is necessary to develop a new PAA activation method to form a highly efficient, stable, green, and safe advanced oxidation process for the degradation of antibiotic wastewater. Summary of the Invention

[0005] The purpose of this invention is to provide an application and method of piezoelectric materials in the catalytic treatment of antibiotic wastewater with peracetic acid, thereby improving the degradation efficiency of antibiotic pollutants in water.

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

[0007] An application of a piezoelectric material in the catalytic treatment of antibiotic wastewater with peracetic acid, wherein the piezoelectric material is M-NO2CO3; and wherein M comprises Cu. 2+ Mn 2+ and Ni 2+ At least one of the following; the N includes Bi 3+ and La 3+ At least one of them.

[0008] This invention also provides a method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material, comprising the following steps:

[0009] A metal salt solution is obtained by mixing divalent metal salts, trivalent metal salts, and water.

[0010] The aqueous solution of the metal salt was mixed with an aqueous solution of urea to undergo a hydrothermal reaction, yielding the piezoelectric material M-NO2CO3.

[0011] The piezoelectric material, peracetic acid, and antibiotic wastewater were mixed, and the pH was adjusted to 3-9 for catalytic oxidation.

[0012] The divalent metal salt contains Cu ions. 2+ Mn 2+ and Ni 2+ At least one of the following; the metal ions in the trivalent metal salt contain Bi. 3+ and La 3+ At least one of them.

[0013] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalyzed by the piezoelectric material, the molar ratio of the divalent metal salt to the trivalent metal salt is 1:10-50; and the volume ratio of the divalent metal salt to water is 0.01-1 mmol:50-200 mL.

[0014] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials, the concentration of the urea aqueous solution is 10–50 mmol / L; and the volume ratio of the metal salt aqueous solution to the urea aqueous solution is 3–5:1.

[0015] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalyzed by piezoelectric materials, the hydrothermal reaction temperature is 120–180°C and the time is 20–24 h.

[0016] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalyzed by the piezoelectric material, the divalent metal salt comprises at least one of nickel chloride, copper chloride, and cobalt chloride; and the trivalent metal salt comprises at least one of bismuth nitrate and lanthanum nitrate.

[0017] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalyzed by the piezoelectric material, the ratio of the piezoelectric material to the antibiotic wastewater is 0.02–0.5 g:1 L; and the ratio of the peracetic acid to the antibiotic wastewater is 0.5–2 mmol:1 L.

[0018] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials, the antibiotics in the antibiotic wastewater include at least one of bisphenol A, phenol, tetracycline, sulfonamides, and quinolones; and the concentration of the antibiotics in the antibiotic wastewater is 10–50 mg / L.

[0019] Optionally, in the method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials, the stirring speed of the catalytic oxidation is 380–550 r / min; the time is 10–60 min; and the temperature is 20–25 °C.

[0020] The beneficial effects of this invention are:

[0021] This invention utilizes the piezoelectric material to catalyze the degradation of antibiotics in water by peracetic acid. Under the influence of the surrounding environment, the piezoelectric material undergoes mechanical deformation, generating positive and negative charges that accumulate on its surface. These positive and negative charges can be directly used to induce piezoelectrically catalyzed electrochemical redox reactions. Furthermore, the electron transfer process can break the O2O bonds of peracetic acid (PAA), efficiently activating it to generate surface hydroxyl groups, hydrogen peroxide, CH3C(O)O· and CH3C(O)OO·, and hydroxyl radicals. These active oxygen species are used to degrade pollutants in water, effectively improving the degradation efficiency.

[0022] This invention relates to the preparation of piezoelectric materials for the catalytic oxidation of antibiotics in wastewater via a hydrothermal method. PAA is significantly cheaper than PMS, and piezoelectric catalysis is more practical and cost-effective than photocatalysis. Attached Figure Description

[0023] Figure 1 The degradation curves of sulfamethoxazole in Examples 1-3 are shown.

[0024] Figure 2 The degradation curves of sulfamethoxazole in Examples 1 and 4-5 are shown.

[0025] Figure 3 The degradation curves of sulfamethoxazole in Examples 1 and 6-7 are shown.

[0026] Figure 4 The degradation curves of sulfamethoxazole in Example 1 and Comparative Examples 1-2 are shown. Detailed Implementation

[0027] This invention provides an application of a piezoelectric material in the catalytic treatment of antibiotic wastewater with peracetic acid, wherein the piezoelectric material is M-NO2CO3; and wherein M comprises Cu. 2+ Mn 2+ and Ni 2+ At least one of the following; the N includes Bi 3+and La 3+ At least one of them.

[0028] In this invention, the piezoelectric material is preferably Cu-BiO2CO3.

[0029] This invention also provides a method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material, comprising the following steps:

[0030] A metal salt solution is obtained by mixing divalent metal salts, trivalent metal salts, and water.

[0031] The aqueous solution of the metal salt was mixed with an aqueous solution of urea to undergo a hydrothermal reaction, yielding the piezoelectric material M-NO2CO3.

[0032] The piezoelectric material, peracetic acid, and antibiotic wastewater were mixed, and the pH was adjusted to 3-9 for catalytic oxidation.

[0033] The divalent metal salt contains Cu ions. 2+ Mn 2+ and Ni 2+ At least one of the following; the metal ions in the trivalent metal salt contain Bi. 3+ and La 3+ At least one of them.

[0034] In this invention, the divalent metal salt preferably comprises at least one of nickel chloride, copper chloride, and cobalt chloride; the trivalent metal salt preferably comprises at least one of bismuth nitrate and lanthanum nitrate; the copper chloride is more preferably copper chloride dihydrate; and the bismuth nitrate is more preferably bismuth nitrate pentahydrate.

[0035] In this invention, the molar ratio of the divalent metal salt to the trivalent metal salt is preferably 1:10-50, more preferably 1:15-40, and even more preferably 1:20-30; the ratio of the divalent metal salt to water is preferably 0.01-1 mmol: 50-200 mL, more preferably 0.08-0.5 mmol: 60-150 mL, and even more preferably 0.2-0.4 mmol: 75-100 mL.

[0036] In this invention, the concentration of the urea aqueous solution is preferably 10-50 mmol / L, more preferably 20-40 mmol / L; the volume ratio of the metal salt aqueous solution to the urea aqueous solution is preferably 3-5:1, more preferably 3-4:1.

[0037] In this invention, the mixing of the metal salt aqueous solution and the urea aqueous solution is preferably carried out under stirring conditions, by adding the urea aqueous solution dropwise to the metal salt solution.

[0038] In this invention, the hydrothermal reaction is preferably carried out in a reaction vessel; the temperature of the hydrothermal reaction is preferably 120-180°C, more preferably 140-150°C, and the time is preferably 20-24 hours, more preferably 22-24 hours.

[0039] In this invention, after the hydrothermal reaction is completed, it is preferable to further include washing, drying and grinding the precipitate obtained from the hydrothermal reaction in sequence to obtain the piezoelectric material M-NO2CO3;

[0040] The cleaning is preferably carried out using water, and the number of cleaning cycles is not specifically limited, but depends on actual needs.

[0041] The drying temperature and time are not specifically limited and can be determined according to actual needs, as long as drying can be completed.

[0042] The grinding process is not specifically limited and should be based on actual needs.

[0043] In this invention, the preferred ratio of the piezoelectric material to antibiotic wastewater is 0.02-0.5 g:1 L, more preferably 0.05-0.25 g:1 L, and even more preferably 0.1-0.2 g:1 L; the preferred ratio of the peracetic acid to antibiotic wastewater is 0.5-2 mmol:1 L, more preferably 1-1.5 mmol:1 L.

[0044] In this invention, the antibiotics in the antibiotic wastewater preferably include at least one of bisphenol A, phenol, tetracycline, sulfonamides and quinolones; the concentration of the antibiotics in the antibiotic wastewater is preferably 10-50 mg / L, more preferably 20-45 mg / L, and even more preferably 25-30 mg / L.

[0045] In this invention, the stirring speed for the catalytic oxidation is preferably 380-550 r / min, more preferably 400-500 r / min; the time is preferably 10-60 min, more preferably 30-50 min; and the temperature is preferably 20-25°C, more preferably 22-24.9°C, and even more preferably 24-24.8°C.

[0046] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0047] Example 1

[0048] Dissolve 1.881 g of bismuth nitrate pentahydrate and 0.035 g of copper chloride dihydrate in 75 mL of water to obtain an aqueous solution of the metal salt.

[0049] Prepare a urea aqueous solution with a concentration of 20 mmol / L;

[0050] Under stirring conditions of 400 r / min, 25 ml of the above urea aqueous solution was added dropwise to 75 ml of metal salt solution to obtain a mixed solution; the mixed solution was placed in a reaction vessel and kept at 150 °C for 24 h; then filtered, the obtained precipitate was washed three times with deionized water, the obtained solid powder was dried at 60 °C for 12 h, and ground with a pestle and mortar to obtain the piezoelectric material 5% Cu-BiO2CO3.

[0051] A sulfamethoxazole solution with a concentration of 50 mg / L was prepared using water as a solvent to simulate wastewater.

[0052] The prepared 5% Cu-BiO2CO3 and peracetic acid were added to the above simulated wastewater, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 24.9℃ with a stirring rate of 400 r / min for 60 min.

[0053] The mass ratio of the 5% Cu-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0054] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0055] Example 2

[0056] The 5% Cu-BiO2CO3 and peracetic acid prepared in Example 1 were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 25.0℃ with a stirring rate of 400 r / min for 60 min.

[0057] The mass ratio of the 5% Cu-BiO2CO3 to the wastewater is 0.2g:1L;

[0058] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0059] Example 3

[0060] The 5% Cu-BiO2CO3 and peracetic acid prepared in Example 1 were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 24.8℃ with a stirring rate of 400 r / min for 60 min.

[0061] The mass ratio of the 5% Cu-BiO2CO3 to the wastewater is 0.05 g: 1 L;

[0062] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0063] Example 4

[0064] The 5% Cu-BiO2CO3 and peracetic acid prepared in Example 1 were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 3, and sulfamethoxazole was degraded at 24.9℃ with a stirring rate of 400 r / min for 60 min.

[0065] The mass ratio of the 5% Cu-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0066] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0067] Example 5

[0068] The 5% Cu-BiO2CO3 and peracetic acid prepared in Example 1 were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 9, and sulfamethoxazole was degraded at 24.8℃ with a stirring rate of 400 r / min for 60 min.

[0069] The mass ratio of the 5% Cu-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0070] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0071] Example 6

[0072] Dissolve 1.94 g of bismuth nitrate pentahydrate and 0.0139 g of copper chloride dihydrate in 75 mL of water to obtain an aqueous solution of the metal salt;

[0073] Prepare a urea aqueous solution with a concentration of 20 mmol / L;

[0074] Under stirring conditions, 25 ml of the above urea aqueous solution was added dropwise to 75 ml of metal salt solution to obtain a mixed solution; the mixed solution was placed in a reaction vessel and kept at 150°C for 24 h; then filtered, the obtained precipitate was washed three times with deionized water, the obtained solid powder was dried at 60°C for 12 h, and ground with a pestle and mortar to obtain the piezoelectric material 2% Cu-BiO2CO3.

[0075] The prepared 2% Cu-BiO2CO3 and peracetic acid were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 24.9℃ with a stirring rate of 400 r / min for 60 min.

[0076] The mass ratio of the 2% Cu-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0077] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0078] Example 7

[0079] Dissolve 1.781 g of bismuth nitrate pentahydrate and 0.07 g of copper chloride dihydrate in 75 mL of water to obtain an aqueous solution of the metal salt;

[0080] Prepare a urea aqueous solution with a concentration of 20 mmol / L;

[0081] Under stirring conditions of 400 rpm / min, 25 ml of the above urea aqueous solution was added dropwise to 75 ml of metal salt solution to obtain a mixed solution; the mixed solution was placed in a reaction vessel and kept at 150 °C for 24 h; then filtered, the obtained precipitate was washed three times with deionized water, the obtained solid powder was dried at 60 °C for 12 h, and ground with a pestle and mortar to obtain the piezoelectric material 10% Cu-BiO2CO3.

[0082] The prepared 10% Cu-BiO2CO3 and peracetic acid were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 24.9℃ with a stirring rate of 400 r / min for 60 min.

[0083] The mass ratio of the 10% Cu-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0084] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0085] Example 8

[0086] Dissolve 1.881 g of bismuth nitrate pentahydrate and 0.0486 g of nickel chloride hexahydrate in 75 mL of water to obtain an aqueous solution of the metal salt;

[0087] Prepare a urea aqueous solution with a concentration of 20 mmol / L;

[0088] Under stirring conditions of 400 rpm / min, 25 ml of the above-mentioned urea aqueous solution was added dropwise to 75 ml of metal salt solution to obtain a mixed solution; the mixed solution was placed in a reaction vessel and kept at 150 °C for 24 h; then filtered, the obtained precipitate was washed three times with deionized water, the obtained solid powder was dried at 60 °C for 12 h, and ground with a pestle and mortar to obtain the piezoelectric material 5% Ni-BiO2CO3.

[0089] The prepared 5% Ni-BiO2CO3 and peracetic acid were added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at 24.8℃ with a stirring rate of 400 r / min. After 60 min of degradation, the concentration of sulfamethoxazole in the simulated wastewater was 0.8 mg / L.

[0090] The mass ratio of the 5% Ni-BiO2CO3 to the wastewater is 0.1 g: 1 L;

[0091] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0092] Example 9

[0093] A bisphenol A solution with a concentration of 50 mg / L was prepared using water as a solvent to simulate wastewater;

[0094] The 5% Cu-BiO2CO3 and peracetic acid prepared in Example 1 were added to the above simulated wastewater, the pH of the wastewater was adjusted to 7, and bisphenol A was degraded at 25.0℃ with a stirring rate of 400 r / min. After 60 min of degradation, the concentration of bisphenol A in the simulated wastewater was 0.4 mg / L.

[0095] The mass ratio of Cu-BiO2CO3 to wastewater is 0.1g:1L;

[0096] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0097] Comparative Example 1

[0098] Peracetic acid was added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at a stirring rate of 400 r / min for 60 min.

[0099] The ratio of the amount of peracetic acid to the amount of wastewater used is 2 mmol: 1 L.

[0100] Comparative Example 2

[0101] The 5% Cu-BiO2CO3 prepared in Example 1 was added to the simulated wastewater prepared in Example 1, the pH of the wastewater was adjusted to 7, and sulfamethoxazole was degraded at a stirring rate of 400 r / min for 60 min.

[0102] The mass ratio of Cu-BiO2CO3 to wastewater is 0.1g:1L.

[0103] Performance testing

[0104] Samples were taken at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, and 60 min respectively during the degradation process described in Examples 1-3. The content of sulfamethoxazole was detected by liquid chromatography, and the results are as follows: Figure 1 As shown;

[0105] pass Figure 1 It can be seen that the more Cu-BiO2CO3 (catalyst) added, the better the catalytic degradation effect. When the amount of the piezoelectric material Cu-BiO2CO3 increases, peracetic acid has more opportunities to adsorb and bind to the active sites on the catalyst, resulting in a higher degradation efficiency of sulfamethoxazole. When the amount of the piezoelectric material Cu-BiO2CO3 decreases, the probability of peracetic acid binding to the active sites during the degradation process is lower, resulting in fewer free radicals and inhibiting the degradation rate. A lower concentration of Cu-BiO2CO3 (catalyst) also results in a lower probability of peracetic acid binding to the active sites during the reaction, leading to fewer free radicals and inhibiting the degradation rate.

[0106] Samples were taken at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, and 60 min respectively during the degradation described in Examples 1 and 4-5. The content of sulfamethoxazole was detected by liquid chromatography, and the results are as follows. Figure 2 As shown;

[0107] pass Figure 2 It can be observed that at pH=3, the catalytic degradation rate of sulfamethoxazole by peracetic acid is low, due to the presence of H+ in the solution. + When it interacts with free radicals, it inhibits the oxidation of free radicals. The presence of a large number of hydrogen ions causes the catalyst surface to become protonated and negatively charged, which prevents the active material from binding to the catalyst. This reduces the catalytic degradation rate of sulfamethoxazole compared to neutral conditions. At pH 9, peracetic acid exhibits a low catalytic degradation rate of sulfamethoxazole because the interaction of OH- in the solution with free radicals inhibits their oxidation. The catalytic degradation effect is best at pH 7.

[0108] Samples were taken at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, and 60 min respectively during the degradation described in Examples 1 and 6-7. The content of sulfamethoxazole was detected by liquid chromatography, and the results are as follows. Figure 3 As shown;

[0109] pass Figure 3 It can be observed that when the molar ratio of copper precursor to bismuth precursor is 1:50, excessive bismuth may cover the surface, resulting in fewer catalytic active sites compared to a molar ratio of 1:20. Consequently, peracetic acid has fewer active sites to bind with the catalyst, generating fewer free radicals and leading to lower catalytic degradation efficiency.

[0110] Samples were taken at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, and 60 min after the degradation described in Examples 1 and Comparative Examples 1-2. The content of sulfamethoxazole was determined by liquid chromatography (HPLC), using a Symmetry-C-18 column (5 μm, 4.6 mm × 150 mm). The mobile phase was methanol (40%) and 0.1% acetic acid (60%), and the flow rate was 1.0 mL / min. -1 The detection wavelength was 270nm. The results are as follows: Figure 4 As shown;

[0111] pass Figure 4 It can be observed that peracetic acid without Cu-BiO2CO3 activation produces very few free radicals, and the interaction efficiency between peracetic acid and pollutants is very low. Therefore, under conditions without Cu-BiO2CO3, the degradation efficiency of sulfamethoxazole is very low. Under conditions without peracetic acid, Cu-BiO2CO3 only acts as an adsorbent and cannot activate the oxidant to produce free radicals. Adsorption alone cannot achieve a good removal effect, and the removal efficiency of sulfamethoxazole is very low. Under conditions of piezoelectricity alone and peracetic acid alone, the degradation efficiency is very low. However, the coupling of piezoelectricity and peracetic acid can greatly improve the degradation effect and removal rate of pollutants, achieving the goal of efficient removal of antibiotic pollutants.

[0112] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material, characterized in that, Includes the following steps: A metal salt solution is obtained by mixing divalent metal salts, trivalent metal salts, and water. The metal salt solution was mixed with an aqueous urea solution to undergo a hydrothermal reaction, yielding the piezoelectric material M-NO2CO3; wherein M is Cu. 2+ ;The N is Bi 3+ ; The piezoelectric material, peracetic acid, and antibiotic wastewater were mixed, and the pH was adjusted to 3-9 for catalytic oxidation. The metal ion in the divalent metal salt is Cu. 2+ The metal ion in the trivalent metal salt is Bi. 3+ ; The antibiotics in the antibiotic wastewater include at least one of tetracycline, sulfonamides, and quinolones.

2. The method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material according to claim 1, characterized in that, The molar ratio of the divalent metal salt to the trivalent metal salt is 1:10~50; the volume ratio of the divalent metal salt to water is 0.01~1mmol:50~200mL.

3. The method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material according to claim 1, characterized in that, The concentration of the urea aqueous solution is 10~50 mmol / L; the volume ratio of the metal salt solution to the urea aqueous solution is 3~5:

1.

4. The method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials according to claim 1, characterized in that, The hydrothermal reaction is carried out at a temperature of 120~180℃ for 20~24h.

5. The method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials according to claim 1 or 2, characterized in that, The divalent metal salt is copper chloride; the trivalent metal salt is bismuth nitrate.

6. The method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials according to claim 1, characterized in that, The ratio of the piezoelectric material to antibiotic wastewater is 0.02~0.5g:1L; the ratio of peracetic acid to antibiotic wastewater is 0.5~2mmol:1L.

7. The method for treating antibiotic wastewater by catalyzing peracetic acid with a piezoelectric material according to claim 1 or 6, characterized in that, The concentration of antibiotics in the antibiotic wastewater is 10~50 mg / L.

8. The method for treating antibiotic wastewater by peracetic acid catalysis using piezoelectric materials according to claim 1, characterized in that, The stirring speed for the catalytic oxidation is 380~550 r / min; the time is 10~60 min; and the temperature is 20~25℃.

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