Method for removing antibiotics in water body by using nitrogen-doped biochar supported cuprous oxide to activate peroxyacetic acid

Abstract

The application belongs to the technical field of antibiotic-containing water treatment, and specifically discloses a method for removing antibiotics in water by using nitrogen-doped biochar loaded cuprous oxide to activate peroxyacetic acid, which comprises the following steps: adding nitrogen-doped biochar loaded cuprous oxide material and peroxyacetic acid into antibiotic-containing water to obtain a first mixed solution; the initial concentration of antibiotics in the antibiotic-containing water is 1 μmol / L-10 μmol / L, the addition amount of the nitrogen-doped biochar loaded cuprous oxide material is 0.025 g / L-0.200 g / L, and the addition amount of the peroxyacetic acid is 0.05 mmol / L-0.40 mmol / L; and the first mixed solution is stirred or oscillated to make the first mixed solution undergo a degradation reaction and complete the removal of antibiotics in the water. The method has the advantages of simple process, short reaction time, good removal effect, adaptability to actual water pH, environmental friendliness and the like.

Description

Technical Field

[0001] This invention belongs to the field of antibiotic-containing water treatment technology, and specifically discloses a method for removing antibiotics from water by using nitrogen-doped biochar loaded with cuprous oxide to activate peracetic acid. Background Technology

[0002] Sulfamethazine (SMT), a typical sulfonamide antibiotic, is widely used in livestock and aquaculture for disease prevention and growth promotion due to its broad-spectrum antibacterial activity, low cost, and significant efficacy. However, SMT is incompletely metabolized in animals, and large quantities enter the environment in its original or active metabolites through excrement, frequently detected in water, soil, and sediment. This substance has a stable molecular structure and is difficult to biodegrade; conventional wastewater treatment processes have limited removal efficiency, leading to its continuous accumulation in the aquatic environment. Long-term SMT residues not only threaten the balance of aquatic ecosystems but may also induce and spread antibiotic resistance genes in bacteria, posing a potential risk to public health. Therefore, developing efficient removal technologies for recalcitrant pollutants such as SMT has become crucial for ensuring water environmental safety and public health.

[0003] Peracetic acid (PAA), an organic peroxyacid, has attracted widespread attention in the field of advanced oxidation in recent years due to its combined functions of disinfection, cleaning, and oxidation, as well as its low generation of disinfection byproducts and good economic feasibility during treatment. Compared with hydrogen peroxide (H2O2) and persulfate (PS), the OO bond energy in the PAA molecule is lower, making it easier to be activated to generate highly reactive free radicals. At the same time, its redox potential is comparable to the aforementioned oxidants, showing significant application potential. However, the oxidation capacity of PAA alone is limited; its true application value lies in its ability to catalytically "activate" and generate diverse highly reactive species. Among various activation methods, transition metal catalysis has become a research hotspot due to its high efficiency and lack of external energy input. Copper-based catalysts, in particular, have shown strong competitiveness in both technology and commercial aspects due to their abundant variable valence states, excellent redox performance, wide availability, and low toxicity.

[0004] To date, there are few reports on the efficient degradation of pollutants by peracetic acid activated by copper-based catalysts. In particular, there are no reports on the degradation of antibiotics by peracetic acid activated by nitrogen-doped biochar-supported cuprous oxide (NBC@Cu2O). Therefore, establishing a simple, short-time, highly effective, pH-adaptable, and environmentally friendly method for removing antibiotics from water is of significant scientific and practical value for the effective control of antibiotic pollution in water bodies. Summary of the Invention

[0005] The purpose of this invention is to provide a method for removing antibiotics from water by using nitrogen-doped biochar loaded with cuprous oxide to activate peracetic acid, thereby solving the technical problem that existing methods for removing antibiotics from water have limited removal efficiency.

[0006] This invention provides a method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid, comprising: Step 1: Add nitrogen-doped biochar-supported cuprous oxide and peracetic acid to the antibiotic-treated water to obtain the first mixed solution; The initial concentration of antibiotics in the water is 1 μmol / L to 10 μmol / L, the amount of nitrogen-doped biochar-supported cuprous oxide material added is 0.025 g / L to 0.200 g / L, and the amount of peracetic acid added is 0.05 mmol / L to 0.40 mmol / L. Step 2: Stir or agitate the first mixed solution to induce a degradation reaction and remove antibiotics from the water.

[0007] Preferably, the preparation method of the nitrogen-doped biochar-supported cuprous oxide material is as follows: Preparation of nitrogen-doped biochar; The nitrogen-doped biochar, copper sulfate, sodium hydroxide, glucose, and solvent are mixed and reacted to obtain a nitrogen-doped biochar-supported cuprous oxide material.

[0008] Preferably, nitrogen-doped biochar is prepared as follows: Urea and biochar were added to ultrapure water and stirred, and then subjected to high-temperature pyrolysis after centrifugation, washing and drying. The solid obtained after high-temperature pyrolysis was ground to obtain nitrogen-doped biochar.

[0009] Preferably, the mass ratio of urea to biochar is 1 to 5:1.

[0010] Preferably, the nitrogen-doped biochar, copper sulfate, sodium hydroxide, glucose, and solvent are mixed and reacted to obtain a nitrogen-doped biochar-supported cuprous oxide material, specifically: The nitrogen-doped biochar was added to a flask containing a solvent; Add copper sulfate solution and sodium hydroxide solution to the flask, stir well, and then add glucose solution to obtain a second mixed solution; The second mixed solution was subjected to centrifugation, washing, drying and high-temperature pyrolysis in sequence, and the solid obtained after high-temperature pyrolysis was ground to obtain nitrogen-doped biochar-supported cuprous oxide material.

[0011] Preferably, the mass ratio of biochar to cuprous oxide in the nitrogen-doped biochar-supported cuprous oxide material is 100:0.5~10.

[0012] Preferably, the initial pH value of the antibiotic-treated water is 7.0 to 9.0.

[0013] Preferably, the antibiotic is a sulfonamide antibiotic.

[0014] Preferably, the sulfonamide antibiotic is sulfadimethylpyrimidine.

[0015] Preferably, the temperature of the degradation reaction of the first mixed solution is 15℃~45℃ and the time is 20min~30min.

[0016] The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid, as described in this invention, has the following advantages compared to existing technologies: This invention benefits from the excellent porous structure and chemical stability of biochar, with the doped Cu active sites highly dispersed within the framework, effectively preventing the aggregation and loss of metal particles. During the catalytic process, NBC@Cu2O can efficiently activate PAA, generating the dominant active species, singlet oxygen, via a non-radical pathway. 1 O2) and superoxide anion radicals (O2) -), along with the generation of a small amount of organic free radicals (RO). ) and hydroxyl radicals ( The system exhibits a synergistic effect with OH (sulfamethoxam) and a specific reaction mechanism that enables it to selectively oxidize electron-rich antibiotics (such as sulfamethoxam, SMT), thereby achieving highly efficient degradation of pollutants. Ultimately, these reactive substances are used to oxidize antibiotics in water, achieving effective removal of antibiotics from the water. Taking sulfamethoxam (SMT) as an example, the method of this invention can effectively remove 97.62% of sulfamethoxam from water within 30 minutes.

[0017] In addition, the peracetic acid used in this invention is green and environmentally friendly, and its final decomposition products are mainly acetic acid and water, which will not cause secondary pollution to the environment.

[0018] The method of the present invention has the advantages of simple process, short reaction time, good removal effect, adaptability to actual water pH, and environmental friendliness. Attached Figure Description

[0019] Figure 1 This is a flowchart illustrating a method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid, as described in an embodiment of the present invention.

[0020] Figure 2This is a comparison chart showing the removal effect of sulfadimethylpyrimidine in water under different treatment conditions in Example 1 of the present invention.

[0021] Figure 3 This is a comparison chart of the removal effects of different PAA concentrations on sulfadimethylpyrimidine in Example 2 of the present invention.

[0022] Figure 4 This is a comparison chart showing the removal effect of sulfadimethylpyrimidine on the water pH value after adding peracetic acid in Example 3 of the present invention.

[0023] Figure 5 This is a comparison chart showing the removal effect of the NBC@Cu2O / PAA system on different actual water bodies in Example 4 of the present invention.

[0024] Figure 6 This is a comparison chart of the removal effects of different bicarbonate ion concentrations on sulfadimethylpyrimidine in Example 5 of the present invention. Detailed Implementation

[0025] In the following description, specific details such as particular system architectures and techniques are set forth for illustrative purposes and not for limitation, in order to provide a thorough understanding of the embodiments of the invention. However, those skilled in the art will understand that the invention can be implemented in other embodiments without these specific details. In other instances, detailed descriptions of well-known systems, apparatuses, circuits, and methods are omitted so as not to obscure the description of the invention with unnecessary detail.

[0026] This invention provides a method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid. Figure 1 As shown, it includes: Step 1: Add nitrogen-doped biochar-supported cuprous oxide and peracetic acid to the antibiotic-treated water to obtain the first mixed solution.

[0027] The initial pH value of the antibiotic water in this embodiment of the invention is 7.0 to 9.0, wherein the antibiotic is a sulfonamide antibiotic, specifically sulfadimethylpyrimidine.

[0028] In this embodiment of the invention, the initial concentration of antibiotics in the water is 1 μmol / L to 10 μmol / L. For example, it can be 1 μmol / L, 2 μmol / L, 4 μmol / L, 6 μmol / L, 8 μmol / L, or 10 μmol / L.

[0029] In the embodiments of the present invention, the amount of nitrogen-doped biochar-supported cuprous oxide material added is 0.025 g / L to 0.200 g / L. For example, it can be 0.025 g / L, 0.050 g / L, 0.100 g / L, 0.150 g / L or 0.200 g / L, etc.

[0030] In this embodiment of the invention, the amount of peracetic acid added is 0.05 mmol / L to 0.40 mmol / L. Exemplarily, it can be 0.05 mmol / L, 0.10 mmol / L, 0.15 mmol / L, 0.20 mmol / L, 0.25 mmol / L, 0.30 mmol / L, 0.35 mmol / L, or 0.40 mmol / L, etc.

[0031] Step 2: Stir or shake the first mixed solution to allow it to undergo a degradation reaction, thereby removing the antibiotics from the water.

[0032] In this embodiment of the invention, the stirring or oscillation speed is 200 rpm to 500 rpm, and for example, it can be 200 rpm, 300 rpm, 400 rpm or 500 rpm.

[0033] In this embodiment of the invention, the temperature of the first mixed solution degradation reaction is 15℃~45℃, and the time is 20min~30min. Exemplarily, the reaction temperature is 15℃, 20℃, 25℃, 30℃, 35℃, 40℃ or 45℃, etc.; and the time is 20min, 25min or 30min, etc.

[0034] This invention provides a method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide material (NBC@Cu2O) to activate peracetic acid (PAA). The method utilizes a porous composite material (NBC@Cu2O) with in-situ copper active sites in the biochar as the catalyst. This invention benefits from the excellent porous structure and chemical stability of biochar, with the doped Cu active sites highly dispersed within the framework, effectively preventing metal particle aggregation and loss. During the catalytic process, NBC@Cu2O efficiently activates PAA, generating the dominant active species, singlet oxygen (POO), via a non-radical pathway. 1 O2) and superoxide anion radicals (O2) -), along with the generation of a small amount of organic free radicals (RO). ) and hydroxyl radicals ( The system exhibits a synergistic effect with OH (sulfamethoxam) and a specific reaction mechanism that enables it to selectively oxidize electron-rich antibiotics (such as sulfamethoxam, SMT), thereby achieving highly efficient degradation of pollutants. Ultimately, these reactive substances are used to oxidize antibiotics in water, achieving effective removal of antibiotics from the water. Taking sulfamethoxam (SMT) as an example, the method of this invention can effectively remove 97.62% of sulfamethoxam from water within 30 minutes.

[0035] In addition, the peracetic acid used in this invention is green and environmentally friendly, and its final decomposition products are mainly acetic acid and water, which will not cause secondary pollution to the environment.

[0036] In this embodiment of the invention, the nitrogen-doped biochar-supported cuprous oxide material is a porous composite material in which copper active sites are in situ doped into the biochar framework, and its preparation method is as follows: (1) Preparation of nitrogen-doped biochar, specifically: Urea and biochar were added to ultrapure water and stirred. After centrifugation, washing and drying, the mixture was subjected to high-temperature pyrolysis. The solid obtained after high-temperature pyrolysis was then ground to obtain nitrogen-doped biochar.

[0037] For example, urea (CO(NH2)2) and biochar in a mass ratio of 1 to 5:1 are added to a beaker, along with 250.0 mL of ultrapure water, and the mixture is magnetically stirred at 80°C for 1 h. For example, the mass ratio of urea to biochar in the embodiments of the present invention can be 1:1, 2:1, 3:1, 4:1, or 5:1, etc.

[0038] The above liquid was centrifuged, washed with ultrapure water and anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 h.

[0039] The dried solid was fed into a tube furnace for high-temperature pyrolysis. The specific pyrolysis parameters were as follows: initial pyrolysis temperature 25℃, heating rate 10℃ / min, pyrolysis temperature 800℃, pyrolysis for 2 h, and both heating and pyrolysis processes were carried out in a nitrogen atmosphere.

[0040] Finally, the material was ground using an agate mortar to obtain nitrogen-doped biochar (NBC).

[0041] (2) Nitrogen-doped biochar, copper sulfate, sodium hydroxide, glucose, and solvent are mixed and reacted to obtain nitrogen-doped biochar-supported cuprous oxide material, specifically: Nitrogen-doped biochar was added to a flask containing solvent; then copper sulfate solution and sodium hydroxide solution were added to the flask, stirred until homogeneous, and then glucose solution was added to obtain a second mixed solution; the second mixed solution was then subjected to centrifugation, washing, drying, and high-temperature pyrolysis, and the solid obtained after high-temperature pyrolysis was ground to obtain nitrogen-doped biochar-supported cuprous oxide material. In the nitrogen-doped biochar-supported cuprous oxide material prepared in this embodiment of the invention, the mass ratio of biochar to cuprous oxide is 100:0.5~10. Exemplarily, the mass ratio of biochar to cuprous oxide can be 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, etc.

[0042] In this embodiment of the invention, the solvent is ultrapure water, and the reaction temperature for preparing the second mixed solution is 50℃~80℃, and the reaction time is 1.67 h (1 h + 0.67 h). In this embodiment of the invention, the drying temperature is 60℃~80℃, and the drying time is 10 h~24 h.

[0043] For example, 1.77 g of NBC was added to a beaker, followed by 250.0 mL of ultrapure water, 0.25 mL of 1 mol / L CuSO4 solution, and 0.125 mL of 5 mol / L NaOH solution. The mixture was stirred until homogeneous, and then 2.5 mL of 0.2 mol / L glucose solution was added. The mixture was magnetically stirred at 80 °C for 40 min. The resulting liquid was centrifuged, washed with ultrapure water and anhydrous ethanol, and then dried in a vacuum drying oven at 60 °C for 12 h. The dried solid was then subjected to high-temperature pyrolysis in a tube furnace. The specific pyrolysis parameters were as follows: initial pyrolysis temperature 25 °C, heating rate 5 °C / min, pyrolysis temperature 600 °C, and pyrolysis for 2 h. Both heating and pyrolysis were carried out under a nitrogen atmosphere. Finally, the mixture was ground using an agate mortar to obtain the NBC@Cu2O material.

[0044] The effectiveness of the method of the present invention will be verified below with specific embodiments.

[0045] Example 1 A method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide material to activate peracetic acid, specifically involving the treatment of sulfadiazine-containing water with peracetic acid using nitrogen-doped biochar-supported cuprous oxide material, comprising the following steps: Nitrogen-doped biochar-supported cuprous oxide material (NBC@Cu2O) and peracetic acid (PAA) were added to a sulfadiazine solution with an initial concentration of 10 μmol / L at dosages of 0.1 g / L and 0.2 mmol / L, respectively. The pH was adjusted to 7.0, and the resulting reaction system was placed at room temperature for degradation. During the degradation reaction, the solution was uniformly mixed in a constant-temperature shaking chamber at 25°C, a shaking speed of 300 rpm, and a treatment time of 30 min, thus completing the removal of sulfadiazine from the water.

[0046] Control group 1 (PAA): Only PAA was added to treat sulfadiazine in the water, and all other conditions were the same.

[0047] Control group 2 (nitrogen-doped biochar (NBC)): only NBC was added to treat sulfadiazine in the water, and other conditions were the same.

[0048] Control group 3 (NBC / PAA): NBC-activated PAA was used to treat sulfadiazine in the water, with other conditions remaining the same.

[0049] Control group 4 (Cu2O): Sulfadiazine in water was treated with only Cu2O, and all other conditions were the same.

[0050] Control group 5 (Cu2O / PAA): Sulfadiazine in water was treated with PAA activated by Cu2O, with other conditions being the same.

[0051] Control group 6 (NBC@Cu2O): Only NBC@Cu2O was added to treat sulfadimethylpyrimidine in the water, and other conditions were the same.

[0052] Control group 7 (NBC@Cu2O / H2O2): Sulfadimethylpyrimidine in water was treated with NBC@Cu2O-activated H2O2, with other conditions being the same.

[0053] The preparation method of nitrogen-doped biochar-supported cuprous oxide material in this embodiment of the invention is as follows: Urea (CO(NH2)2) and biochar in a mass ratio of 2:1 were added to a beaker, along with 250.0 mL of ultrapure water. The mixture was then magnetically stirred at 80 °C for 1 h.

[0054] The above liquid was centrifuged, washed with ultrapure water and anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 h.

[0055] The dried solid was fed into a tube furnace for high-temperature pyrolysis. The specific pyrolysis parameters were as follows: initial pyrolysis temperature 25℃, heating rate 10℃ / min, pyrolysis temperature 800℃, and pyrolysis time 2 h. Both heating and pyrolysis processes were carried out in a nitrogen atmosphere. Finally, the solid was ground using an agate mortar to obtain nitrogen-doped biochar (NBC).

[0056] Further, 1.77 g of NBC was added to a beaker, along with 250.0 mL of ultrapure water, 0.25 mL of 1 mol / L CuSO4 solution, and 0.125 mL of 5 mol / L NaOH solution. The mixture was stirred thoroughly, and then 2.5 mL of 0.2 mol / L glucose solution was added. The mixture was magnetically stirred at 80 °C for 40 min. The resulting liquid was centrifuged, washed with ultrapure water and anhydrous ethanol, and then dried in a vacuum drying oven at 60 °C for 12 h. The dried solid was then subjected to high-temperature pyrolysis in a tube furnace. The specific pyrolysis parameters were as follows: initial pyrolysis temperature 25 °C, heating rate 5 °C / min, pyrolysis temperature 600 °C, and pyrolysis time 2 h. Both heating and pyrolysis were carried out under a nitrogen atmosphere. Finally, the mixture was ground using an agate mortar to obtain the NBC@Cu2O material.

[0057] During the constant temperature shaking chamber treatment, samples were taken periodically, and the samples were subjected to 0.22... The solution was filtered through an aqueous membrane, and the concentration of residual sulfadiazine in the water sample was then determined using high-performance liquid chromatography (HPLC). Based on the changes in sulfadiazine concentration before and after treatment, the removal rate of sulfadiazine was calculated, and the results are shown below. Figure 2 As shown.

[0058] Figure 2 This is a comparison chart showing the removal efficiency of sulfadimethylpyrimidine in water under different treatment conditions in Example 1 of the present invention. From... Figure 2 It can be seen that after 30 minutes of reaction, the PAA system alone could only remove 7.56% of sulfadimethylpyrimidine, indicating that PAA itself has a weak oxidizing ability for sulfadimethylpyrimidine. Similarly, the removal efficiency of the NBC@Cu2O system alone was only 2.64%, indicating that the adsorption of sulfadimethylpyrimidine by NBC@Cu2O is negligible. However, NBC@Cu2O can efficiently activate PAA in a neutral reaction medium, meaning that the NBC@Cu2O / PAA system has the best removal effect on sulfadimethylpyrimidine, significantly higher than other individual systems and the NBC@Cu2O / H2O2 system, achieving a pollutant removal rate of 97.62% within 30 minutes.

[0059] like Figure 2As shown, the comparative results of the experimental groups reveal the differences in treatment efficiency among different systems: when PAA was added alone or NBC@Cu2O was used alone, the removal rate of sulfadimethylpyrimidine was negligible (7.56% and 2.64% respectively within 30 min), confirming that neither direct oxidation nor physical adsorption alone is sufficient to achieve effective degradation of pollutants. In contrast, the NBC@Cu2O / PAA system showed a significant synergistic effect, with a removal rate as high as 97.62% within 30 min. This treatment effect not only far exceeded the control groups but was also significantly better than the NBC@Cu2O / H2O2 system under the same conditions. The main reason for this is the better activation matching between NBC@Cu2O and PAA, which can overcome the dependence of traditional hydrogen peroxide systems on acidic pH and efficiently induce the generation of active species with high oxidation potential in neutral water. Furthermore, given that the mineralization end products of PAA (such as acetic acid) have good biocompatibility and the extremely low adsorption ratio confirms that the process is dominated by chemical oxidation, this invention prefers the NBC@Cu2O / PAA system as the best technical route for treating wastewater containing sulfadiazine.

[0060] Example 2 The NBC@Cu2O material prepared in Example 1 was activated at different PAA concentrations to degrade sulfadimethylpyrimidine in water, including the following steps: Different concentrations of PAA were added to sulfadimethylpyrimidine-containing water (the initial concentration of sulfadimethylpyrimidine was 10 μmol / L), the pH was adjusted to 7.0, and then 0.1 g / L NBC@Cu2O was added. During the degradation reaction, the mixture was uniformly mixed in a constant temperature shaking box at 25℃, a shaking speed of 300 rpm, and a treatment time of 30 min to complete the removal of sulfadimethylpyrimidine from the water.

[0061] In this example, the initial concentrations of PAA were 0.05 mmol / L, 0.10 mmol / L, 0.20 mmol / L and 0.40 mmol / L, respectively, and other conditions were the same as in Example 1.

[0062] During the constant temperature shaking chamber treatment, samples were taken periodically, and the samples were subjected to 0.22... The solution was filtered through an aqueous membrane, and the concentration of residual sulfadiazine in the water sample was then determined using high-performance liquid chromatography (HPLC). Based on the changes in sulfadiazine concentration before and after treatment, the removal rate of sulfadiazine was calculated, and the results are shown below. Figure 3 As shown.

[0063] Figure 3 This is a comparison chart of the removal effects of different PAA concentrations on sulfadiazine in Example 2 of the present invention. Figure 3It was found that the degradation rate of SMT significantly increased with the PAA concentration from 0.05 mmol / L to 0.20 mmol / L. This is because the increased PAA concentration provides more precursors of active species, thereby generating more active free radicals to participate in the degradation reaction. When the PAA concentration was 0.20 mmol / L, the removal rate was close to 98% after 30 min of reaction. However, further increasing the PAA concentration to 0.40 mmol / L did not significantly improve the removal effect (the curves basically overlapped). This may be because excess PAA would undergo a self-scavenging reaction with the generated free radicals, thus limiting further improvement in degradation efficiency. Considering both degradation efficiency and economic cost, 0.20 mmol / L was determined to be the optimal PAA dosage in this system.

[0064] Example 3 The NBC@Cu2O prepared in Example 1 was used to activate PAA at different pH values ​​to degrade sulfadimethylpyrimidine in water, including the following steps: PAA was added at a dosage of 0.20 mmol / L to sulfadiazine-containing water bodies (the initial concentration of sulfadiazine in these water bodies was 10 μmol / L), the pH was adjusted to 7.0, and then NBC@Cu2O was added at a dosage of 0.1 g / L. During the degradation reaction, the mixture was uniformly mixed in a constant temperature shaking chamber at a room temperature of 25℃, a shaking speed of 300 rpm, and a treatment time of 30 min, thus completing the removal of sulfadiazine from the water body.

[0065] Control group: Keep the dosage of NBC@Cu2O and PAA unchanged, adjust the pH of the sulfadimethylpyrimidine water after adding PAA to 3.0, 5.0 and 9.0, and then add NBC@Cu2O, with other conditions the same.

[0066] During the constant temperature shaking chamber treatment, samples were taken periodically, and the samples were subjected to 0.22... The solution was filtered through an aqueous membrane, and the concentration of residual sulfadiazine in the water sample was then determined using high-performance liquid chromatography (HPLC). Based on the changes in sulfadiazine concentration before and after treatment, the removal rate of sulfadiazine was calculated, and the results are shown below. Figure 4 As shown.

[0067] Figure 4 This is a graph showing the removal effect of sulfadiazine on the water pH after adding peracetic acid to adjust the water value in Example 3 of the present invention. Figure 4It can be seen that, except for the low SMT removal efficiency at pH 3.0 and 5.0 (only 5.25% and 3.74% respectively), the NBC@Cu2O / PAA system can achieve excellent SMT removal effect (93.36%~97.62%) within the studied pH range (7.0-9.0), indicating that the pH range applicable to the NBC@Cu2O / PAA system is neutral and weakly alkaline.

[0068] Example 4 The NBC@Cu2O material prepared in Example 1 was used to activate PAA in different water bodies to degrade sulfadimethylpyrimidine in water, including the following steps: 0.20 mmol / L PAA was added to ultrapure water containing sulfadiazine (the initial concentration of sulfadiazine in these waters was 10 μmol / L), the pH was adjusted to 7.0, and then 0.1 g / L NBC@Cu2O was added. During the degradation reaction, the mixture was uniformly mixed in a constant temperature shaking chamber at 25°C and 300 rpm for 30 min to complete the removal of sulfadiazine from the water.

[0069] Control group: PAA was first added to different water bodies (lake water, river water, tap water, groundwater) to adjust the pH to 7.0, and then NBC@Cu2O was added, with other conditions remaining the same.

[0070] During the constant temperature shaking chamber treatment, samples were taken periodically, and the samples were subjected to 0.22... The solution was filtered through an aqueous membrane, and the concentration of residual sulfadiazine in the water sample was then determined using high-performance liquid chromatography (HPLC). Based on the changes in sulfadiazine concentration before and after treatment, the removal rate of sulfadiazine was calculated, and the results are shown below. Figure 5 As shown.

[0071] Figure 5 This is a comparison chart of the removal efficiency of the NBC@Cu2O / PAA system for sulfadiazine (SMT) in different actual water bodies in Example 4 of this invention. It can be seen that the NBC@Cu2O / PAA system maintained high catalytic activity in four types of actual water bodies: river water, groundwater, tap water, and lake water, with SMT removal rates of 93.29%, 99.99%, 87.20%, and 93.61%, respectively. The experimental results show that despite the complex environment of actual water bodies, the removal efficiency of this system remained stable at around 90%, confirming that the NBC@Cu2O / PAA system has excellent anti-interference ability and good practical application prospects.

[0072] Example 5 The NBC@Cu2O material prepared in Example 1 was subjected to different bicarbonate ion (HCO3) concentrations. -The degradation of sulfadimethylpyrimidine in water by activated PAA at a concentration of 100% includes the following steps: 0.20 mmol / L PAA was added to sulfamethazine-containing water (initial concentration of sulfamethazine was 10 μmol / L) that did not contain bicarbonate ions. The pH was adjusted to 7.0, and then 0.1 g / L NBC@Cu2O was added. The degradation reaction was carried out by uniform mixing in a constant temperature shaking chamber at 25°C and 250 rpm for 60 min to complete the removal of sulfamethazine from the water.

[0073] Control group and variable settings: The reaction system without added bicarbonate ions was used as the control group. In the experimental group, different amounts of sodium bicarbonate (NaHCO3) were added to the sulfadimethylpyrimidine water before adding PAA and NBC@Cu2O, so that the chloride ion concentrations in the solution were 0.5 mM, 1.0 mM and 2.0 mM, respectively. Other reaction conditions were the same as in Example 1.

[0074] During the constant temperature shaking chamber treatment, samples were taken periodically, and the samples were subjected to 0.22... The solution was filtered through an aqueous membrane, and the concentration of residual sulfadiazine in the water sample was then determined using high-performance liquid chromatography (HPLC). Based on the changes in sulfadiazine concentration before and after treatment, the removal rate of sulfadiazine was calculated, and the results are shown below. Figure 6 As shown.

[0075] Figure 6 This is a comparison chart of the removal effects of different bicarbonate ion concentrations on sulfadimethylpyrimidine in Example 5 of the present invention. Figure 6 It can be seen that when the concentration of bicarbonate ions in the system increases from 0 to 2.0 mM, the degradation kinetic curves of sulfadimethylpyrimidine almost overlap, and no obvious inhibition phenomenon is observed. After 30 min of reaction, the SMT removal rate of each concentration group reached about 97%. Under normal circumstances, inorganic anions (such as HCO3-) - The hydrolysis reaction of peracetic acid may lead to an alkaline environment for its self-decomposition, thus reducing the reaction efficiency. However, the results of this experiment show that the NBC@Cu2O / PAA system has a strong anti-interference ability against low concentrations of bicarbonate ions, which provides strong support for its practical application in the treatment of wastewater containing bicarbonate.

[0076] The significant advantages of this invention are as follows: First, it is suitable for alkaline environments and practical applications, overcoming the shortcomings of traditional copper-based systems that require acidic conditions to operate. It maintains excellent removal rates (93.36%~97.62%) for sulfadiazine within a wide pH range of 7.0–9.0, without requiring pH adjustment. Second, it exhibits excellent economic efficiency and anti-interference capabilities. Experiments have demonstrated that this system achieves efficient degradation with extremely low oxidant dosages, avoiding the free radical self-scavenging effect and cost waste caused by high concentrations of PAA. Furthermore, the system demonstrates strong tolerance to inorganic anions, with degradation efficiency almost unaffected even at bicarbonate ion concentrations as high as 2.0 mM, exhibiting excellent alkali resistance. Third, it has a stable structure and great application potential. After four cycles, the catalyst still achieves a removal rate exceeding 75%, and the removal rate remains around 90% in various complex real-world water bodies such as river water and groundwater. In summary, this invention demonstrates significant advantages such as simple process, low consumption and high efficiency, wide applicability, and strong robustness, making it highly promising for practical application and widespread adoption.

[0077] The above descriptions are merely a few embodiments of the present invention and are not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any modifications or alterations made by those skilled in the art without departing from the scope of the technical solution of the present invention using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid, characterized in that, include: Step 1: Add nitrogen-doped biochar-supported cuprous oxide and peracetic acid to the antibiotic-treated water to obtain the first mixed solution; The initial concentration of antibiotics in the water body is 1 μmol / L to 10 μmol / L, the amount of nitrogen-doped biochar-supported cuprous oxide material added is 0.025 g / L to 0.200 g / L, and the amount of peracetic acid added is 0.05 mmol / L to 0.40 mmol / L. Step 2: Stir or agitate the first mixed solution to induce a degradation reaction and remove antibiotics from the water.

2. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 1, characterized in that, The method for preparing the nitrogen-doped biochar-supported cuprous oxide material is as follows: Preparation of nitrogen-doped biochar; The nitrogen-doped biochar, copper sulfate, sodium hydroxide, glucose, and solvent are mixed and reacted to obtain a nitrogen-doped biochar-supported cuprous oxide material.

3. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 2, characterized in that, The preparation of nitrogen-doped biochar is as follows: Urea and biochar were added to ultrapure water and stirred, and then subjected to high-temperature pyrolysis after centrifugation, washing and drying. The solid obtained after high-temperature pyrolysis was ground to obtain nitrogen-doped biochar.

4. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 3, characterized in that, The mass ratio of urea to biochar is 1 to 5:

1.

5. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 2, characterized in that, The nitrogen-doped biochar, copper sulfate, sodium hydroxide, glucose, and solvent are mixed and reacted to obtain a nitrogen-doped biochar-supported cuprous oxide material, specifically: The nitrogen-doped biochar was added to a flask containing a solvent; Add copper sulfate solution and sodium hydroxide solution to the flask, stir well, and then add glucose solution to obtain a second mixed solution; The second mixed solution was subjected to centrifugation, washing, drying and high-temperature pyrolysis in sequence, and the solid obtained after high-temperature pyrolysis was ground to obtain nitrogen-doped biochar-supported cuprous oxide material.

6. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 5, characterized in that, The mass ratio of biochar to cuprous oxide in the nitrogen-doped biochar-supported cuprous oxide material is 100:0.5~10.

7. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 1, characterized in that, The initial pH value of the antibiotic-treated water is 7.0 to 9.

0.

8. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 1, characterized in that, The antibiotic in question is a sulfonamide antibiotic.

9. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 8, characterized in that, The sulfonamide antibiotic is sulfadimethylpyrimidine.

10. The method for removing antibiotics from water using nitrogen-doped biochar-supported cuprous oxide-activated peracetic acid according to claim 1, characterized in that, The temperature of the first mixed solution degradation reaction is 15℃~45℃, and the time is 20min~30min.

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