Method for preparing seaweed biochar composite material using expired milk powder and the resulting product and applications

Abstract

The application discloses a method for preparing seaweed biochar composite material by using expired milk powder and the obtained product and application, and relates to the preparation of seaweed biochar composite material by using expired milk powder and seaweed powder as raw materials and through one-step high-temperature pyrolysis roasting. The method is simple, safe and reliable in operation, and raw materials are easy to obtain, and effective utilization of waste biomass is realized. The obtained composite material has good catalytic effect and high stability, can reduce the secondary pollution of the environment caused by metal ion leaching when a metal-based catalyst is used as a PMS activator, can overcome the problems of poor catalytic activity and instability when a carbon-based catalyst is used as a PMS activator, and has high tetracycline hydrochloride removal efficiency.

Description

Technical Field

[0001] This invention relates to a method for preparing doped seaweed biochar, specifically to a method for preparing seaweed biochar composite material using expired milk powder, and also to a highly catalytically active seaweed biochar composite material obtained by the method, as well as the application of the seaweed biochar composite material, belonging to the field of biochar material technology. Background Technology

[0002] Currently, commonly used methods for water pollution treatment include adsorption, flocculation, and biofilm methods. Adsorption only separates pollutants without effectively degrading them; flocculation requires significant thermal energy, increasing treatment costs and limiting its practical application; and biofilm methods are cumbersome, difficult to operate, and resource-intensive. Therefore, advanced oxidation technologies based on persulfate have attracted researchers' attention. This technology can mineralize target pollutants into smaller molecules, such as carbon dioxide and water, thereby degrading organic pollutants. Compared to the aforementioned methods, advanced oxidation technologies offer advantages such as low cost, high pollutant removal efficiency, fast reaction speed, good recovery performance, simple operation, convenient control and management, and wide applicability. Among these, heterogeneous activation systems using persulfate as the oxidant and metal / non-metal catalysts have received widespread attention. The selection of the activator is crucial for the effective application of persulfate advanced oxidation technologies.

[0003] Among non-metallic PMS activators, carbon-based materials are the most widely studied. Compared to rGO (graphene) and CNTs (carbon nanotubes), biochar (BC) is cheaper and more readily available, possessing a higher specific surface area and abundant PMS catalytic active sites. In recent years, researchers have tended to further enhance the catalytic activity of carbon-based catalysts through heteroatom doping (such as N, P, S, etc.). Meanwhile, among metal-based PMS activators, transition metal elements suitable for PMS activation include cobalt (Co), iron (Fe), and manganese (Mn), which can also improve activation efficiency. However, using either metal or non-metal catalysts alone has certain drawbacks.

[0004] Currently, when doping biochar with iron or nitrogen, the iron source is mostly iron-containing compounds or iron slag, and the nitrogen source is mostly urea (similar patents such as 202211308531.8 and 202211551061.8). There are no reports of using other components as iron or nitrogen sources.

[0005] Currently, there are many methods for preparing iron / nitrogen co-doped carbon-based catalysts, including direct and robust carbonization pyrolysis, continuous doping secondary pyrolysis, hydrothermal carbonization, and ionothermal carbonization. Among these, secondary pyrolysis and hydrothermal carbonization are slow processes, while ionothermal carbonization requires a large amount of energy. Direct pyrolysis is the most conventional method for biochar synthesis, characterized by high porosity and high yield; furthermore, the specific surface area increases with increasing reaction temperature, providing more active sites for PMS activation. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing seaweed biochar composite material using expired milk powder and the resulting product. This method uses expired milk powder as the metal ion source and non-edible seaweed as the carbon source, and prepares the seaweed biochar composite material through a one-step high-temperature pyrolysis process. This method can realize the resource utilization of non-edible seaweed and expired milk powder, reducing the risk of metal sludge formation when metal-based catalysts are used as PMS activators and solving the problem of secondary environmental damage caused by metal ion leaching. It also overcomes the drawbacks of non-metal-based catalysts as PMS activators, such as poor and unstable catalytic activity and easy oxidation and deactivation of catalytic active sites. The resulting seaweed biochar composite material is an iron and nitrogen co-doped metal / non-metal composite catalyst with a high specific surface area, providing more active sites and exhibiting good catalytic effect.

[0007] The specific technical solution of this invention is as follows:

[0008] A method for preparing seaweed biochar composite material using expired milk powder, the method comprising the following steps:

[0009] (1) Dry and pulverize the seaweed to obtain seaweed powder;

[0010] (2) Add expired milk powder to water and dissolve it completely to obtain milk liquid;

[0011] (3) Add seaweed powder to the milk, mix thoroughly, heat to evaporate the water, and then dry to obtain a mixed powder;

[0012] (4) The dried mixed powder was calcined at high temperature under gas protection to obtain seaweed biochar composite material.

[0013] Furthermore, in step (1), the seaweed can be any type of seaweed, preferably non-edible seaweed. The seaweed is ground into powder by crushing, grinding, or other methods, and the particle size of the seaweed powder is 150-250 mesh.

[0014] Furthermore, in step (2), the mass percentage concentration of expired milk powder in the milk is 0.2-0.5%, for example, 0.2%, 0.3%, 0.4%, or 0.5%.

[0015] Furthermore, in step (3), the mass ratio of expired milk powder to seaweed powder is 0.075-0.25:1-2, for example 0.075:1, 0.08:1, 0.085:1, 0.09:1, 0.095:1, 0.10:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.17:1, 0.18:1, 0.19:1, 0.20:1, 0.21:1, 0.22:1, 0.23:1, 0.24:1, 0.25:1, 0.075:2, 0.10:2, 0.15:2, 0.20:2, 0.25:2.

[0016] Furthermore, in step (3), the water is heated to 100°C to evaporate. After the water is evaporated, the remaining material is placed in an oven to dry. The oven temperature is 50-80°C.

[0017] Furthermore, in step (4), the roasting temperature is 700℃-900℃, for example 700℃, 750℃, 800℃, 850℃, 900℃. The roasting time is 60-80 min, for example 60 min, 70 min, 80 min.

[0018] Furthermore, in step (4), the temperature is increased to the calcination temperature at a rate of 8-10℃ / min.

[0019] Furthermore, in step (4), the calcination is carried out under the protection of an inert gas, which can be nitrogen, argon, etc.

[0020] Furthermore, in step (4), the calcined sample is washed to remove ash. The washing is carried out alternately with dilute hydrochloric acid and water. After the ash is washed away, the sample is rinsed repeatedly with water until it is neutral to obtain the final product.

[0021] This invention involves thoroughly mixing expired milk powder and seaweed powder using an impregnation method, followed by evaporation and drying. A one-step high-temperature pyrolysis calcination process yields a seaweed biochar composite material. This composite material is an iron-nitrogen co-doped metal / non-metal composite, representing a high-performance composite catalyst. In this catalyst, the metal is supported on a highly stable biochar carrier. The biochar, formed from seaweed powder at high temperature, contains elements such as carbon, nitrogen, and oxygen, and its surface is rich in functional groups such as carboxyl and hydroxyl groups, which can coordinate and complex with the metal. This biochar effectively prevents the aggregation of adjacent iron-based nanoparticles and acts as a carbon layer, protecting the nanoparticles from iron ion leaching, thus effectively improving the durability of iron in catalytic reactions. Nitrogen doping into the carbon framework can alter the sp... 2 The structure of the carbon skeleton forms a series of nitrogen species with different configurations, while pyridine nitrogen can capture iron to form Fe-N. xThe microstructure fixes the iron. At the same time, the composite catalyst can, to some extent, maintain the high specific surface area of ​​the biochar support, providing more active sites for the activation of persulfate, which is beneficial to the subsequent mass transfer reaction between ROS (reactive oxygen species) and pollutants. Therefore, the seaweed biochar composite material of the present invention can be used as a PMS activator.

[0022] The present invention also provides a method for treating wastewater containing tetracycline hydrochloride, the method being: adding persulfate and the above-mentioned seaweed biochar composite material to the wastewater to remove tetracycline hydrochloride from the wastewater.

[0023] Furthermore, in the above treatment method, the concentration of tetracycline hydrochloride in the wastewater is 10-30 mg / L.

[0024] Furthermore, in the above treatment method, 15-150 mg of persulfate is added per 100 ml of wastewater, and 30-35 mg of seaweed biochar composite material is added per 100 ml of wastewater.

[0025] Furthermore, in the above processing method, the processing time is 10-60 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, and 60 minutes.

[0026] This invention is the first to propose using expired milk powder as both a nitrogen and iron source, co-doped onto biochar materials to prepare a biochar composite catalyst with high catalytic performance. Compared with existing technologies, this invention has the following advantages:

[0027] (1) This invention utilizes the abundant marine resources of Hainan, such as seaweed, as raw materials, which can realize the resource reuse of seaweed. At the same time, the raw materials and reagents required by this invention are in small quantities and are cheap and readily available.

[0028] (2) This invention utilizes expired milk powder as a source of nitrogen and iron, which can achieve the purpose of waste utilization and turning waste into treasure.

[0029] (3) The present invention uses a simple impregnation method and a direct calcination method to prepare materials. There is no complicated preparation process. The operation is simple, the cost is low, and the environmental protection efficiency is significant. The preparation method is simple and safe, and it also realizes the effective utilization of waste biomass.

[0030] (4) The material prepared by the present invention contains C, N, O and Fe, and is coupled through Fe-N, CN and Fe-O bonds, and contains oxygen-containing functional groups, which provide good and stable iron ion and organic carbon group (CO, C=O, OC=O) active sites for activating persulfate.

[0031] (5) Due to the high temperature conditions selected in this invention, the prepared material has a high specific surface area and a large number of pore defects. The porous and carbon-based layer structure disperses the iron-based nanoparticles. At the same time, it provides sufficient active sites, which can efficiently activate persulfate, promote the generation of free radicals and non-free radical active substances, and achieve efficient degradation of persistent organic pollutants in water.

[0032] (6) This invention overcomes some of the drawbacks of using only metal catalysts or non-metal catalysts. The iron in milk powder is dispersed and fixed on biochar, which can reduce the problem of secondary pollution caused by metal ion leaching when metal-based catalysts are used as PMS activators, and also overcome the poor catalytic activity and instability of carbon-based catalysts when used as PMS activators, thereby improving the removal efficiency of organic pollutants.

[0033] (7) The composite material prepared by the present invention has good catalytic effect and high stability. It can be used as a PMS activator and has a good treatment effect on wastewater containing tetracycline hydrochloride. It can be used in the field of wastewater treatment. Attached Figure Description

[0034] Figure 1 Scanning electron microscope images of milk powder charcoal, seaweed charcoal, and milk powder-seaweed charcoal.

[0035] Figure 2 This is an energy dispersive spectroscopy (EDS) analysis diagram of milk powder-seaweed charcoal.

[0036] Figure 3 Nitrogen adsorption-desorption curves of seaweed charcoal and milk powder-seaweed charcoal.

[0037] Figure 4 Infrared spectra of seaweed charcoal, milk powder charcoal, and milk powder-seaweed charcoal.

[0038] Figure 5 XPS image of milk powder-seaweed charcoal.

[0039] Figure 6 The graph shows the removal effect of tetracycline hydrochloride under different amounts of PMS.

[0040] Figure 7 The graph shows the removal effect of tetracycline hydrochloride under different catalyst addition amounts.

[0041] Figure 8 The graph shows the removal effect of tetracycline hydrochloride solutions of different concentrations.

[0042] Figure 9 The images show the removal effects of the milk powder-seaweed charcoal catalyst on tetracycline hydrochloride in Examples 1, 2, and 3.

[0043] Figure 10 The images show the removal effects of the milk powder-seaweed charcoal catalyst on tetracycline hydrochloride in Examples 4, 5, and 6.

[0044] Figure 11 The images show the removal effects of the catalysts in Example 2, Comparative Example 1, and Comparative Example 2 on tetracycline hydrochloride. Detailed Implementation

[0045] The present invention will be further described below through specific embodiments. The following description is merely exemplary and does not limit its content.

[0046] In the following examples, the expired milk powder used was milk powder containing nitrogen and iron.

[0047] Example 1

[0048] (1) Air dry the seaweed naturally, then dry it at 60 ℃ using a crusher and crush it into powder to obtain seaweed powder. The seaweed powder is then passed through a 200-mesh sieve.

[0049] (2) Weigh 0.075 g of expired milk powder and put it into a beaker. Add 30 ml of distilled water and dissolve it by sonication.

[0050] (3) Weigh 2 g of seaweed powder and add it to a beaker. Stir to mix it thoroughly, put it in a water bath at 100℃ to evaporate the moisture, and put it in an oven to dry at 80℃.

[0051] (4) After drying, grind it into powder and put it into a ceramic quartz boat. Place it in a tube furnace and heat it to 900 ℃ at a rate of 10 ℃ / min. Calcine it under nitrogen for 60 min.

[0052] (5) After the reaction is complete, remove the product and wash it with dilute hydrochloric acid / distilled water alternately to remove the ash. Wash it repeatedly with ultrapure water until it is neutral, dry it and pass it through a 200-mesh sieve. Cool it to the ambient temperature and store it for later use. This yields the seaweed biochar composite catalyst, also known as milk powder-seaweed char.

[0053] Example 2

[0054] The seaweed biochar composite catalyst was prepared according to the method in Example 1, except that the amount of expired milk powder was 0.1g.

[0055] Example 3

[0056] The seaweed biochar composite catalyst was prepared according to the method in Example 1, except that the amount of expired milk powder was 0.25g.

[0057] Example 4

[0058] (1) Air dry the seaweed naturally, then dry it at 60 ℃ using a crusher and crush it into powder to obtain seaweed powder. The seaweed powder is then passed through a 200-mesh sieve.

[0059] (2) Weigh 0.1 g of expired milk powder and put it into a beaker. Add 30 ml of distilled water and dissolve it by sonication.

[0060] (3) Weigh 1g of seaweed powder and add it to a beaker. Stir to mix it thoroughly, place it in a 100℃ water bath to evaporate the moisture, and then place it in an oven to dry.

[0061] (4) After drying, grind it into powder and put it into a ceramic quartz boat. Place it in a tube furnace and heat it to 700 ℃ at a rate of 10 ℃ / min. Calcine it under nitrogen for 60 min.

[0062] (5) After the reaction is complete, remove the product and wash it with dilute hydrochloric acid / distilled water alternately to remove the ash. Wash it repeatedly with ultrapure water until it is neutral, dry it and pass it through a 200-mesh sieve. Cool it to the ambient temperature and store it for later use. This yields the seaweed biochar composite catalyst, also known as milk powder-seaweed char.

[0063] Example 5

[0064] The seaweed biochar composite catalyst was prepared according to the method of Example 4, except that in step (4), the temperature was increased to 800°C at a rate of 10°C / min.

[0065] Example 6

[0066] The seaweed biochar composite catalyst was prepared according to the method of Example 4, except that in step (4), the temperature was increased to 900℃ at a rate of 10℃ / min.

[0067] Comparative Example 1

[0068] Seaweed was air-dried naturally, then dried at 60°C using a crusher and crushed into powder to obtain seaweed powder, which was then passed through a 200-mesh sieve. The seaweed powder was heated to 900°C at a rate of 10°C / min and calcined under nitrogen atmosphere for 60 minutes. After the reaction was complete, the powder was removed and washed with dilute hydrochloric acid / distilled water alternately to remove ash. It was then repeatedly washed with ultrapure water until neutral, dried, passed through a 200-mesh sieve, cooled to room temperature, and stored for later use to obtain seaweed char.

[0069] Comparative Example 2

[0070] Expired milk powder was heated to 900 °C at a rate of 10 °C / min and calcined under nitrogen for 60 min. After the reaction was complete, it was removed and washed with dilute hydrochloric acid / distilled water alternately to remove ash. It was then repeatedly washed with ultrapure water until neutral, dried, passed through a 200-mesh sieve, cooled to room temperature, and stored for later use to obtain milk powder charcoal.

[0071] Performance verification

[0072] 1. The seaweed charcoal of Comparative Example 1, the milk powder charcoal of Comparative Example 2, and the milk powder-seaweed charcoal of Example 6 were subjected to scanning electron microscopy. The obtained scanning electron microscopy images are shown below. Figure 1 As shown, by Figure 1 It can be seen that the charcoal from milk powder has fewer pores and a smoother surface; the charcoal from seaweed has obvious structural collapse on its surface, and the charcoal from milk powder and seaweed has severe structural collapse, exhibiting a honeycomb-like porous structure.

[0073] 2. Energy dispersive spectroscopy (EDS) analysis was performed on the milk powder-seaweed charcoal from Example 6. The obtained EDS image is shown below. Figure 2 As shown, by Figure 2 It can be seen that the milk powder-seaweed charcoal contains C, N, O, and Fe, and the elements are evenly distributed without any metal clusters.

[0074] 3. Nitrogen adsorption-desorption and pore size distribution images of the seaweed charcoal in Comparative Example 1 and the milk powder-seaweed charcoal in Example 6 are shown below. Figure 3 As shown, by Figure 3 It can be seen that the milk powder-seaweed charcoal has a large adsorption capacity, and the adsorption is mostly distributed in micropores / mesoporous structures.

[0075] 4. The infrared spectra of the seaweed charcoal of Comparative Example 1, the milk powder charcoal of Comparative Example 2, and the milk powder-seaweed charcoal of Example 6 are as follows: Figure 4 As shown, by Figure 4 It can be seen that at 3421 cm −1 The characteristic peaks near the OH group correspond to the stretching vibration of -OH; the characteristic signal of C=O is at 1560 cm⁻¹. −1 The presence of carboxyl groups in the catalyst is indicated by the presence of these groups, which play a crucial role in PMS activation; 1348 cm −1 The presence of the CN peak indicates that nitrogen is embedded in the carbon structure; 1043 cm⁻¹ −1 The nearby peak represents the bending of CO in esters. At 474 cm⁻¹ −1 The nearby characteristic peaks correspond to the stretching vibrations of Fe-O, confirming the formation of Fe-O.

[0076] 5. The XPS spectrum of the milk powder-seaweed charcoal in Example 6 is shown below. Figure 5 As shown, from Figure 5 The presence of characteristic Fe peaks in the full spectrum confirms the presence of iron. XPS spectra of C, N, and Fe elements in the milk powder-seaweed charcoal indicate the formation of various functional groups. (The text abruptly ends here, likely due to an incomplete sentence or missing information.) 1S The spectrum shows that CN bonds were formed in the milk powder-seaweed charcoal due to the introduction of nitrogen. (The text abruptly ends here, likely due to an incomplete sentence or a formatting error.) 1S The spectrum shows that Fe-N bonds were formed in the milk powder-seaweed charcoal. In addition, graphitic nitrogen, pyridine nitrogen, and pyrrole nitrogen are also present.

[0077] Application example: Tetracycline hydrochloride removal effect

[0078] 1. Take 100 ml of 20 mg / L tetracycline hydrochloride solution, and add 15 mg, 25 mg, 35 mg, 45 mg, and 150 mg of potassium peroxide monosulfonate (PMS) to it, respectively. Then add 30 mg of the milk powder-seaweed charcoal from Example 2, and add it to a 100 ml Erlenmeyer flask. The reaction is carried out on a constant temperature shaker with stirring for 60 min. During the reaction, take a sample of the reaction solution every 5-10 min, i.e., at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, and 60 min, respectively, using a syringe, and quench the reaction with methanol. Measure the absorbance of the sample at each time point using a UV spectrophotometer, and calculate the concentration C of the solution at each time point according to the standard curve. t Calculate C t / C0 (C0 is the initial concentration of the solution), the removal rate is 1-C t / C0. Removal rate of tetracycline hydrochloride under different PMS dosages, as shown in Figure 1. Figure 6 As shown in the figure, the amount of PMS added has little effect on the removal rate of tetracycline hydrochloride; therefore, the preferred amount of PMS added is 15 mg.

[0079] 2. Take 100 ml of 20 mg / L tetracycline hydrochloride solution, add 15 mg of potassium peroxymonosulfonate (PMS) to it, and then add 15 mg, 20 mg, 25 mg, 30 mg, and 35 mg of the milk powder-seaweed charcoal from Example 2, respectively. Stir and react for 60 min. Calculate the removal rate of tetracycline hydrochloride using the same method as above. The removal rates of tetracycline hydrochloride under different catalyst dosages are as follows: Figure 7 As shown. By Figure 7 It can be seen that the removal efficiency can reach 90% or more when the catalyst dosage is 30-35 mg, therefore the preferred catalyst dosage is 30-35 mg.

[0080] 3. Take 100 ml of five different concentrations of tetracycline hydrochloride solutions: 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, and 30 mg / L. Add 15 mg of potassium persulfate (PMS) and 30 mg of the milk powder-seaweed charcoal from Example 2 to each solution, and stir for 60 min. Calculate the removal rate of tetracycline hydrochloride using the same method as above. The results are as follows: Figure 8 As shown in the figure, the removal efficiency of the five different concentrations of tetracycline hydrochloride solutions within the concentration range of 10-30 mg / L is not significantly different.

[0081] 4. Take 100 ml of 20 mg / L tetracycline hydrochloride solution, add 15 mg of potassium persulfonate (PMS) to each solution, then add 30 mg of the milk powder-seaweed charcoal from Examples 1, 2, and 3, and stir for 60 min. Calculate the removal rate of tetracycline hydrochloride using the same method as above. The results are obtained from... Figure 9 As shown in the figure, the removal efficiencies of the catalysts in Examples 1, 2, and 3 for tetracycline hydrochloride are 84.5%, 93.8%, and 88.8%, respectively. This indicates that the catalyst with the amount of expired milk powder added is 0.1 g, which shows the best catalytic effect.

[0082] 5. Take 100 ml of 20 mg / L tetracycline hydrochloride solution, add 15 mg of potassium persulfonate (PMS) to each solution, then add 30 mg of the milk powder-seaweed charcoal from Examples 4, 5, and 6 respectively, and stir for 60 min. Calculate the removal rate of tetracycline hydrochloride using the same method as above. The results are obtained from... Figure 10 As shown in the figure, the removal efficiencies of the catalysts in Examples 4, 5, and 6 for tetracycline hydrochloride are 80%, 92.5%, and 94.3%, respectively. This indicates that the catalyst obtained at a calcination temperature of 900 °C has the best catalytic effect.

[0083] 6. Take 100 ml of 20 mg / L tetracycline hydrochloride solution, add 15 mg of potassium peroxymonosulfonate (PMS) to each solution, then add 30 mg of the catalyst from Example 2, Comparative Example 1, and Comparative Example 2 respectively, and stir the reaction for 60 min. A control group without any catalyst was used. The removal rate of tetracycline hydrochloride was calculated using the same method as above. The results are given by... Figure 11 As shown in the figure, the removal rates of Example 2, Comparative Example 1, and Comparative Example 2 are 93.8%, 84.1%, and 57.9%, respectively. This shows that the biochar composite catalyst obtained by combining milk powder and seaweed has a significantly improved catalytic effect.

Claims

1. A method for preparing seaweed biochar composite material using expired milk powder, characterized in that: Includes the following steps: (1) Dry and pulverize the seaweed to obtain seaweed powder; (2) Add the expired milk powder to water and dissolve it completely to obtain milk liquid; (3) Add seaweed powder to the milk, mix thoroughly, heat to evaporate the water, and then dry to obtain a mixed powder; (4) The dried mixed powder was calcined at high temperature under gas protection to obtain seaweed biochar composite material; In step (3), the mass ratio of expired milk powder to seaweed powder is 0.075-0.25:1-2.

2. The method according to claim 1, characterized in that: In step (1), the particle size of the seaweed powder is 150-250 mesh.

3. The method according to claim 1, characterized in that: In step (2), the mass percentage concentration of expired milk powder in the milk is 0.2-0.5%.

4. The method according to claim 1, characterized in that: In step (3), heat to 100°C to evaporate the moisture. After the moisture is evaporated, put the remaining material into an oven to dry. The oven temperature is 50-80°C.

5. The method according to claim 1, characterized in that: In step (4), the roasting temperature is 700℃-900℃ and the roasting time is 60-80 min.

6. The method according to claim 5, characterized in that: In step (4), the temperature is increased to the calcination temperature at a rate of 8-10℃ / min.

7. The method according to claim 1, characterized in that: In step (4), the calcination is carried out under inert gas protection.

8. The seaweed biochar composite material prepared by the method of preparing seaweed biochar composite material using expired milk powder according to any one of claims 1-7.

9. The application of the seaweed biochar composite material according to claim 8 in the degradation of tetracycline hydrochloride antibiotics.

10. A method for treating wastewater containing tetracycline hydrochloride, characterized in that: Adding persulfate and the seaweed biochar composite material according to claim 9 to the wastewater removes tetracycline hydrochloride from the wastewater.

11. The treatment method according to claim 10, characterized in that: wastewater The concentration of tetracycline hydrochloride is 10-30 mg / L; 15-150 mg of persulfate is added per 100 ml of wastewater, and 30-35 mg of seaweed biochar composite material is added per 100 ml of wastewater; the treatment time is 10-60 min.

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