Method for treating heavy metals and antibiotics through cooperation of attapulgite / carbon composite material and peracetic acid

Abstract

The invention relates to a method for treating heavy metals and antibiotics by using an attapulgite / carbon composite material and peracetic acid, which comprises the following steps: adding the attapulgite / carbon composite material and peracetic acid into polluted wastewater, and reacting for 6-360 minutes; the polluted wastewater comprises heavy metals and antibiotics. The preparation method of the attapulgite / carbon composite material comprises the following steps: mixing lignin and attapulgite to obtain a mixture; and calcining the mixture in an inert atmosphere to obtain the attapulgite / carbon composite material. According to the invention, the attapulgite / carbon composite material is cooperated with peracetic acid to treat heavy metals and antibiotics, so that the heavy metals can be efficiently absorbed and the antibiotics can be degraded, the problem of water acidification caused by a traditional acidic oxidant can be effectively overcome, and the pH value of the treated wastewater can be regulated and controlled in a neutral range; moreover, the technical problem of heavy metal overflow caused by addition of an acidic oxidant can be successfully overcome while the oxidation efficiency of the peracetic acid is maintained, and 1 + 1gt is realized; and 2, the synergistic effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polluted wastewater treatment, and in particular to a method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid. Background Art

[0002] Currently, most research focuses on the removal of a single heavy metal or antibiotic. However, in real-world environments, synergistic interactions between multiple heavy metals and antibiotics are common. Studies have shown that heavy metals and antibiotics interact with each other, transforming them into more toxic and persistent metal-organic compounds. Extensive data indicate that combined pollution of these two compounds can be observed in rivers, sediments, and agricultural soils. Therefore, developing a method for effectively treating these combined pollutants in water bodies is crucial.

[0003] CN119657083A discloses a method for preparing a plasma-modified attapulgite / carbon composite material. The composite material is simple to prepare and has excellent heavy metal adsorption properties. After adsorption, it can be used as a PDS (peroxydisulfate) system catalyst to treat antibiotics. It can be used to treat wastewater containing heavy metals and antibiotics. However, after the PDS system is degraded, byproducts such as sulfate will be produced, and it takes 6 hours to reach degradation equilibrium. In addition, if this material is to treat wastewater containing both heavy metals and antibiotics, PDS needs to be added. The addition of PDS will cause some of the heavy metals adsorbed on the composite material to be released back into the solution. Therefore, finding a green, safe, and byproduct-free oxidant to replace persulfate has become a key challenge. Summary of the Invention

[0004] Based on this, the object of the present invention is to provide a method for treating heavy metals and antibiotics in pollutant wastewater using attapulgite / carbon composite materials in conjunction with peracetic acid.

[0005] A method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid comprises the following steps:

[0006] The attapulgite / carbon composite material and peracetic acid are added to the polluted wastewater and reacted for 6 to 360 minutes;

[0007] The polluted wastewater includes heavy metals and antibiotics.

[0008] Peracetic acid is a safe, green and strong oxidizing 0=1.06-1.96V) oxidant, the byproducts produced after the activation of peracetic acid are H2O and CO2, without secondary pollution to the environment. After the attapulgite / carbon composite material activates peracetic acid, the peracetic acid can produce active substances such as carbon-centered free radicals and singlet oxygen with high selectivity and longer half-life. These active substances can react with antibiotics through free radical pathways or non-free radical pathways to achieve antibiotic degradation. In addition, peracetic acid, as an acidic oxidant, can also effectively corrode carbonates in the attapulgite / carbon composite material, changing the mechanism of action, thereby increasing the ion exchange rate and adsorption rate of heavy metals and achieving efficient removal of heavy metals.

[0009] The present invention has developed a composite material system with pH self-buffering function, which uses attapulgite / carbon composite materials in conjunction with peracetic acid to treat heavy metal and antibiotic combined pollution. The system has the following outstanding advantages: (1) The treatment efficiency is significantly improved, and degradation equilibrium can be reached in as fast as 1 minute, greatly reducing time costs; (2) The technical system can effectively overcome the problem of water acidification caused by traditional peracetic acid treatment and achieve self-buffering of the system pH. The pH of the treated wastewater is stably regulated in the neutral range (pH~7), greatly reducing the cost of subsequent neutralization treatment; (3) The present invention can successfully overcome the technical problem of heavy metal overflow caused by the addition of acidic oxidants while maintaining the oxidation efficiency of peracetic acid, and at the same time achieve a synergistic effect of 1+1>2 (the addition of peracetic acid not only does not weaken the material's ability to immobilize heavy metals, but also further improves the heavy metal removal efficiency). This breakthrough provides a new, efficient, stable and economical solution for the treatment of heavy metal-antibiotic combined pollution.

[0010] As a preferred embodiment, the method for preparing the attapulgite / carbon composite material comprises the following steps:

[0011] mixing lignin and attapulgite to obtain a mixture;

[0012] The mixed material is placed in an inert atmosphere and calcined to obtain the attapulgite / carbon composite material.

[0013] Lignin and attapulgite are mixed and calcined, and a pyrolysis reaction occurs at a high temperature, wherein some components of the lignin are decomposed into ash substances such as carbonates, and form a composite material with the attapulgite in an inert atmosphere.

[0014] As a preferred solution, the mass ratio of the lignin to the attapulgite is 1:1-5, the calcination temperature is 400-700° C., the calcination time is 1-2 h, and the inert atmosphere includes argon.

[0015] If the proportion of lignin is too low, the carbonate content in the composite material will be reduced, and the subsequent addition of peracetic acid will increase the degree of corrosion of the composite material. At the same time, the H + Will be with the composite material part Na + , K + , Ca 2+ The cations exchange reaction occurs, reducing the active sites of the material for heavy metal adsorption, thereby reducing the removal rate of heavy metals. If the proportion of lignin increases, the carbonate content in the composite material will increase. After the addition of peracetic acid, the material's consumption of peracetic acid will further increase, and the effective amount of peracetic acid used to degrade antibiotics will decrease, which will have an adverse effect on the degradation of antibiotics. If the calcination temperature is too low, some components in the lignin will not be effectively decomposed, ultimately resulting in a reduction in the effective components used to activate peracetic acid, thereby reducing the removal rate of antibiotics. If the calcination temperature is too high, the carbonization degree of the material will be too high, resulting in structural changes in the composite structure, which is not conducive to the treatment of wastewater contaminated with heavy metals and antibiotics.

[0016] As a preferred solution, the addition amount of the attapulgite / carbon composite material is 0.4-1.2 g / L.

[0017] As a preferred embodiment, the amount of peracetic acid added is 0.5-2.5 mmol / L. When the concentration of peracetic acid is too high, it will cause excessive corrosion of the composite material, and the cations in the material (such as Ca 2+ , K + 、Na + ) will dissociate with excess peracetic acid to produce H + A replacement reaction occurs, which is not conducive to the removal of heavy metals; when the peracetic acid concentration is too low, since peracetic acid preferentially reacts with carbonates on the composite material, the effective amount of remaining peracetic acid is reduced, which is not conducive to the degradation of antibiotics.

[0018] As a preferred embodiment, the heavy metal includes at least one of Cd, Ni, Cu, Zn and Pb.

[0019] As a preferred solution, the concentration of the heavy metals is 5-45 ppm. Within this concentration range, the removal rate of heavy metals can reach 85%.

[0020] As a preferred embodiment, the antibiotics include at least one of levofloxacin, ciprofloxacin hydrochloride, norfloxacin, enrofloxacin, and sulfadiazine.

[0021] As a preferred solution, the concentration of the antibiotic is 5-45 ppm. Within this concentration range, the antibiotic removal rate is greater than 78%. Too high a concentration will result in a lower removal rate, but the actual antibiotic concentration in water is generally not greater than 45 ppm.

[0022] As a preferred solution, the initial pH of the polluted wastewater is 2 to 6. When the initial pH is too low, the excessively acidic condition is not conducive to the removal of heavy metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a graph showing the removal efficiency of the composite material for heavy metals and antibiotics in Example 4;

[0024] Figure 2 1 is a graph showing the removal efficiency of the composite material in Example 5 for a solution contaminated with different heavy metals and levofloxacin;

[0025] Figure 3 is a graph showing the removal efficiency of the composite material in Example 6 for a solution contaminated with heavy metals and different antibiotics;

[0026] Figure 4 is a graph showing the removal efficiency of heavy metals by the composite material in Example 8 at different heavy metal concentrations;

[0027] Figure 5 is a graph showing the removal efficiency of levofloxacin by the composite material in Example 8 at different heavy metal concentrations;

[0028] Figure 6 1 is a graph showing the removal efficiency of heavy metals by the composite material in Example 9 at different levofloxacin concentrations;

[0029] Figure 7 1 is a graph showing the removal efficiency of levofloxacin by the composite material in Example 9 at different levofloxacin concentrations;

[0030] Figure 8 is a graph showing the change in the removal efficiency of heavy metals by the composite material in Example 11 over time;

[0031] Figure 9 is a graph showing the change in the removal rate of levofloxacin by the composite material in Example 11 over time;

[0032] Figure 10 1 is a graph showing the removal efficiency of levofloxacin by the composite material at different dosages in Example 12;

[0033] Figure 11 is a graph showing the heavy metal removal efficiency of the composite material pairs at different dosages in Example 12;

[0034] Figure 12 is a graph showing the heavy metal removal efficiency of the composite material in Example 13 at different peracetic acid dosages;

[0035] Figure 13This is a graph showing the levofloxacin removal efficiency of the composite material in Example 13 at different peracetic acid dosages. DETAILED DESCRIPTION

[0036] A method for preparing an attapulgite / carbon composite material comprises the following steps:

[0037] (1) mixing lignin and attapulgite in a mass ratio of 1:1-5 to obtain a mixture;

[0038] (2) placing the mixture in an argon atmosphere, heating it to 400-700° C. at a heating rate of 2-10° C. / min, and calcining it for 1-2 h to obtain a attapulgite / carbon composite material.

[0039] A method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid comprises the following steps:

[0040] Add attapulgite / carbon composite material and peracetic acid to polluted wastewater, place in a shaker at 200 rpm, and react at 20-40°C for 6-360 minutes. The amount of attapulgite / carbon composite material added is 0.4-1.2 g / L, the amount of peracetic acid added is 0.5-2.5 mmol / L, the pH of the polluted wastewater is 2-6, and the polluted wastewater contains 5-45 ppm of heavy metals, 5-45 ppm of antibiotics, and heavy metals including Cd 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ , Pb 2+ At least one of the antibiotics includes at least one of levofloxacin (LEV), ciprofloxacin hydrochloride (HCIP), norfloxacin (NOR), enrofloxacin (ENR), and sulfadiazine (SDZ).

[0041] Example 1

[0042] A method for preparing an attapulgite / carbon composite material comprises the following steps:

[0043] (1) mixing lignin and attapulgite in a mass ratio of 1:1 to obtain a mixture;

[0044] (2) The mixture was placed in an argon atmosphere, heated to 600°C at a heating rate of 2°C / min, and calcined for 1 hour to obtain a convexo-rod / carbon composite material.

[0045] Example 1 is a preferred embodiment of the present invention, and the attapulgite / carbon composite material prepared in Example 1 is used in subsequent treatment of contaminated wastewater.

[0046] Example 2

[0047] A method for preparing an attapulgite / carbon composite material comprises the following steps:

[0048] (1) mixing lignin and attapulgite in a mass ratio of 1:3 to obtain a mixture;

[0049] (2) The mixture was placed in an argon atmosphere, heated to 400°C at a heating rate of 6°C / min, and calcined for 1 hour to obtain a convexo-rod / carbon composite material.

[0050] Example 3

[0051] A method for preparing an attapulgite / carbon composite material comprises the following steps:

[0052] (1) mixing lignin and attapulgite in a mass ratio of 1:5 to obtain a mixture;

[0053] (2) The mixture was placed in an argon atmosphere, heated to 700°C at a heating rate of 10°C / min, and calcined for 1 hour to obtain a convexo-rod / carbon composite material.

[0054] Example 4

[0055] Formulated to contain 15ppm Cu 2+ 100 ml of a composite contaminated solution containing 15 ppm of levofloxacin was prepared, and then 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added. The mixture was then placed in a shaker at 200 r / min and reacted at 25° C. for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0056] like Figure 1 As shown, the removal rates of Cu and levofloxacin by the attapulgite / carbon composite were 98.19% and 87.97%, respectively, demonstrating the composite's excellent ability to treat contaminated wastewater containing both heavy metals and antibiotics. Table 1 shows the EDS spectra of the composite before decontamination, after reaction with peracetic acid, and after decontamination. It can be seen that the heavy metal Cu was adsorbed, and the EDS results indicate that the removal of heavy metals is primarily due to the ion exchange effect of the attapulgite / carbon composite on Cu.

[0057] Table 1 EDS spectrum analysis of attapulgite / carbon composite materials at various stages

[0058]

[0059] Example 5

[0060] Configuration contains 15ppm Pb 2+ and 15ppm levofloxacin composite contaminated solution 100ml, containing 15ppm Ni 2+and 15ppm levofloxacin composite contaminated solution 100ml, prepared containing 15ppm Zn 2+ and 15ppm levofloxacin, 100ml of the composite contaminated solution containing 15ppm Cd 2+ and 100 ml of a composite contaminated solution of 15 ppm levofloxacin.

[0061] Then, 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added to the composite contaminated solution, respectively, and then placed in a shaker at 200 rpm and reacted at 25°C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0062] like Figure 2 As shown in the figure, the attapulgite / carbon composite material shows good performance in treating the composite contaminated solution of any one of the heavy metals Pb, Ni, Zn, and Cd and antibiotics. The removal rate of levofloxacin can reach about 95%, and the removal efficiency of heavy metals Pb, Ni, Zn, and Cd are 96.39%, 86.81%, 96.99%, and 98.46%, respectively.

[0063] Example 6

[0064] Formulated to contain 15ppm Cu 2+ and 15ppm enrofloxacin (ENR) composite contamination solution 100ml, prepared containing 15ppm Cu 2+ and 15ppm ciprofloxacin hydrochloride (HCIP) composite contaminated solution 100ml, prepared containing 15ppm Cu 2+ and 15ppm norfloxacin (NOR) composite contaminated solution 100ml, containing 15ppm Cu 2+ 100ml of a composite contaminated solution of 15ppm sulfadiazine (SDZ).

[0065] Then, 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added to the composite contaminated solution, respectively, and then placed in a shaker at 200 rpm and reacted at 25°C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0066] like Figure 3As shown in the figure, the attapulgite / carbon composite material shows good performance in treating the composite contaminated solution of heavy metals and any one of the antibiotics including enrofloxacin (ENR), ciprofloxacin hydrochloride (HCIP), norfloxacin (NOR), and sulfadiazine (SDZ). The removal rate of heavy metal Cu can reach more than 86%, and the removal efficiencies of enrofloxacin (ENR), ciprofloxacin hydrochloride (HCIP), norfloxacin (NOR), and sulfadiazine (SDZ) are 95.15%, 100%, 100%, and 91.74%, respectively.

[0067] Example 7

[0068] Formulated to contain 15ppm Cu 2+ 、15ppm Pb 2+ 100 ml of a composite contaminated solution containing 15 ppm of levofloxacin was prepared, and then 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added. The mixture was then placed in a shaker at 200 r / min and reacted at 25° C. for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0069] The test results show that the attapulgite / carbon composite material exhibits good performance in treating complex contaminated solutions containing multiple heavy metals and levofloxacin. Among them, the removal rates of heavy metals Cu and Pb are 96.56% and 95.82% respectively, and the removal rate of the antibiotic levofloxacin reaches 89.92%.

[0070] Example 8

[0071] Configuration contains 10ppm Cu 2+ and 15ppm levofloxacin composite contaminated solution 100ml, prepared containing 15ppmCu 2+ and 15ppm levofloxacin, 100ml of the composite contaminated solution containing 25ppm Cu 2+ and 15ppm levofloxacin, 100ml of composite contaminated solution, containing 35ppm Cu 2+ and 15ppm levofloxacin, 100ml of composite contaminated solution containing 45ppm Cu 2+ and 100 ml of a composite contaminated solution of 15 ppm levofloxacin.

[0072] Then, 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added to the composite contaminated solution, respectively, and then placed in a shaker at 200 rpm and reacted at 25°C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0073] like Figure 4-5As shown, the attapulgite / carbon composite material showed good performance in treating the combined pollution of heavy metal Cu and levofloxacin at different concentrations. Among them, the removal rate of Cu at different concentrations of heavy metal Cu was maintained above 95.00%, and the removal rate of levofloxacin at different concentrations of heavy metal Cu was maintained above 81.00%.

[0074] Example 9

[0075] Formulated to contain 15ppm Cu 2+ and 10ppm levofloxacin composite contaminated solution 100ml, containing 15ppmCu 2+ and 15ppm levofloxacin composite contaminated solution 100ml, prepared containing 15ppm Cu 2+ and 25ppm levofloxacin, 100ml of the composite contaminated solution containing 15ppm Cu 2+ and 35ppm levofloxacin, 100ml of the composite contaminated solution containing 15ppm Cu 2+ and 100 ml of a composite contaminated solution of 45 ppm levofloxacin.

[0076] Then, 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added to the composite contaminated solution, respectively, and then placed in a shaker at 200 rpm and reacted at 25°C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0077] like Figure 6-7 As shown in the figures, the attapulgite / carbon composite material showed good performance in treating the combined pollution of heavy metal Cu and different concentrations of levofloxacin. Among them, the removal rate of Cu was maintained above 95.00% at different concentrations of levofloxacin, and the removal rate of levofloxacin was maintained above 78.00% at different concentrations of levofloxacin.

[0078] Example 10

[0079] Prepared with pH = 2 ± 0.05 and containing 15 ppm Cu 2+ 100ml of a composite contaminated solution containing 10ppm levofloxacin and 10ppm levofloxacin, with a pH of 3±0.05 and containing 15ppm Cu 2+ 100ml of a composite contaminated solution containing 10ppm levofloxacin and 10ppm levofloxacin, with a pH of 4±0.05 and containing 15ppm Cu 2+ 100ml of a composite contaminated solution containing 10ppm levofloxacin and 10ppm levofloxacin, with a pH of 5±0.05 and containing 15ppm Cu 2+100ml of a composite contaminated solution containing 10ppm levofloxacin and 10ppm levofloxacin, with a pH of 6±0.05 and containing 15ppm Cu 2+ and 100ml of a composite contaminated solution of 10ppm levofloxacin.

[0080] Then, 100 μL of 2 mol / L peracetic acid solution was added to the above composite contaminated solution, and the pH was immediately measured. After the measurement, 0.1 g of the attapulgite / carbon composite material prepared in Example 1 was added to the above solution, and then placed in a shaker at 200 r / min and reacted at 25°C for 6 h. Finally, the pH in the contaminated solution was detected.

[0081] The results are shown in Table 2. When the initial pH is less than 3, the pH does not change much after the addition of peracetic acid, and the pH increases significantly after the reaction is completed. When the initial pH is greater than 3, the pH of the composite contaminated solution changes significantly after the addition of peracetic acid, dropping to about 3. After the addition of the composite material and the reaction are completed, the pH of the solution can be maintained at about 7, which fully demonstrates the pH adjustment ability of the attapulgite / carbon composite material.

[0082] Table 2 Adjustment ability of attapulgite / carbon composites at different initial pH

[0083]

[0084] Example 11

[0085] Formulated to contain 15ppm Cu 2+ and 100 ml of a composite contaminated solution containing 15 ppm of levofloxacin was added, and then 0.1 g of the attapulgite / carbon composite material prepared in Example 1 and 100 μL of a 2 mol / L peracetic acid solution were added, followed by placing it in a shaker at 200 r / min and reacting at 25° C. After adding peracetic acid, the antibiotic concentration in the contaminated solution was detected at time points of 1 min, 2 min, 3 min, 4 min, 5 min, and 6 min, and the heavy metal concentration in the contaminated solution was detected at time points of 2 min, 4 min, 6 min, 10 min, 15 min, 30 min, 1 h, 2 h, 4 h, and 6 h.

[0086] like Figure 8-9 As shown, the attapulgite / carbon composite, in conjunction with peracetic acid, can rapidly remove heavy metals and antibiotics. For antibiotics, degradation equilibrium is reached within 1 minute, with removal rates exceeding 85%. For heavy metals, 80% removal is achieved after adding peracetic acid for 2 minutes, and over 90% after 2 hours.

[0087] Example 12

[0088] Formulated to contain 15ppm Cu 2+500 ml of the composite contaminated solution containing 15 ppm of levofloxacin and 15 ppm of levofloxacin was divided into 5 equal parts, and then 0.04 g, 0.06 g, 0.08 g, 0.1 g, and 0.12 g of the attapulgite / carbon composite material prepared in Example 1 were added respectively, and 100 μL of a 2 mol / L peracetic acid solution was added to each. The mixture was then placed in a shaker at 200 r / min and reacted at 25 ° C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0089] like Figure 10-11 As shown in the figure, for the removal of heavy metals, when the dosage of the attapulgite / carbon composite material is low (≤0.8g / L), peracetic acid will preferentially react with the carbonates on the surface of the material. When the carbonates are exhausted, the excess peracetic acid will continue to corrode the composite material, for example, by consuming cations on the surface of the composite material through cation exchange. This results in a significant reduction in the active sites of the composite material, so at low dosages, its removal efficiency for heavy metals is low. However, as the dosage of the composite material continues to increase, its own ability to resist peracetic acid corrosion is also correspondingly enhanced. Therefore, within a certain range, its removal efficiency for heavy metals will continue to increase with the increase in dosage.

[0090] The degradation of antibiotics mainly depends on the activation of peracetic acid by the attapulgite / carbon composite material. Even at a low dosage (≤0.8g / L), the composite material can effectively activate peracetic acid, generating highly active substances such as carbon-centered free radicals and singlet oxygen, thereby achieving efficient degradation of levofloxacin. Therefore, at this dosage, although the heavy metal removal efficiency is poor, the degradation effect on levofloxacin is still significant. At the same time, with further increases in the dosage of the composite material, the degradation efficiency of levofloxacin does not improve. This is because when the active substances generated by the composite material activating peracetic acid are excessive, self-quenching occurs between the active substances, resulting in the effective active substances for degradation not increasing synchronously, and therefore the degradation efficiency cannot be further improved.

[0091] Example 13

[0092] Formulated to contain 15ppm Cu 2+ 500 ml of the composite contaminated solution containing 15 ppm of levofloxacin and 15 ppm of levofloxacin was divided into 5 parts, and then 0.1 g of the attapulgite / carbon composite material prepared in Example 1 was added to each part, and 25 μL, 50 μL, 75 μL, 100 μL, and 125 μL of a 2 mol / L peracetic acid solution were added, respectively. The mixture was then placed in a shaker at 200 r / min and reacted at 25 ° C for 6 h. Finally, the concentrations of heavy metals and antibiotics in the contaminated solution were detected.

[0093] like Figure 12-13As shown in the figure, for heavy metal removal, when the peracetic acid dosage is low, it can react with the carbonates on the surface of the attapulgite / carbon composite, exposing more active sites on the composite, thereby effectively removing heavy metals. However, as the peracetic acid dosage continues to increase, the peracetic acid will excessively corrode the material, resulting in a decrease in active sites and a reduction in removal efficiency.

[0094] For antibiotic degradation, increasing the peracetic acid dosage within a certain range can increase free radical generation and reaction rate, thereby enhancing degradation. However, when the dosage is too high, on the one hand, it will trigger the self-quenching of active substances such as free radicals; on the other hand, the excess peracetic acid and its decomposition products (such as acetic acid) will compete with the antibiotics for free radicals. These two factors together lead to a decrease in degradation efficiency.

[0095] In combination with Examples 12-13, when treating actual water bodies, the input amounts of the attapulgite / carbon composite material and peracetic acid can be adjusted according to the different heavy metal and antibiotic contents.

[0096] The above-described embodiments merely illustrate several implementations of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. A person skilled in the art would be able to make numerous modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention.

Claims

1. A method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid, characterized in that: The steps include: The attapulgite / carbon composite material and peracetic acid are added to the polluted wastewater and reacted for 6 to 360 minutes; The polluted wastewater includes heavy metals and antibiotics.

2. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The preparation method of the attapulgite / carbon composite material comprises the following steps: mixing lignin and attapulgite to obtain a mixture; The mixed material is placed in an inert atmosphere and calcined to obtain the attapulgite / carbon composite material.

3. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 2, wherein: The mass ratio of the lignin to the attapulgite is 1:1-5, the calcination temperature is 400-700° C., the calcination time is 1-2 hours, and the inert atmosphere includes argon.

4. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, wherein: The addition amount of the attapulgite / carbon composite material is 0.4-1.2 g / L.

5. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, wherein: The added amount of the peracetic acid is 0.5-2.5 mmol / L.

6. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The heavy metal includes at least one of Cd, Ni, Cu, Zn, and Pb.

7. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The concentration of the heavy metals is 5-45 ppm.

8. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The antibiotics include at least one of levofloxacin, ciprofloxacin hydrochloride, norfloxacin, enrofloxacin, and sulfadiazine.

9. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The concentration of the antibiotic is 5-45 ppm.

10. The method for treating heavy metals and antibiotics using an attapulgite / carbon composite material in collaboration with peracetic acid according to claim 1, characterized in that: The initial pH of the polluted wastewater is 2-6.

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