Phosphorus-sulfur synergistic antibiotic mushroom dreg charcoal as well as preparation method and application thereof

Abstract

The invention discloses phosphorus-sulfur synergistic antibiotic mushroom dreg biochar as well as a preparation method and application thereof, and belongs to the technical field of biochar. According to the invention, penicillin mushroom dregs and wet-process phosphoric acid with high sulfur content are used as raw materials, and biochar is prepared through phosphorus-sulfur synergistic modification and is applied to adsorption of antibiotic wastewater, so that efficient purification of antibiotic wastewater and full recycling of mushroom dregs are realized. According to the method, cheap high-sulfur wet-process phosphoric acid is innovatively used for replacing traditional strong acid (hydrochloric acid, sulfuric acid and the like) for pretreatment, the obtained acidolysis solution can be directly used for preparing the fertilizer, the pyrolysis cost is synchronously reduced, and the nitrogen utilization rate is increased. The phosphorus-sulfur in-situ modification process increases the carbon yield of the biochar by 10%, increases the specific surface area by 45%, and thoroughly eliminates resistance genes in the mushroom dregs. The removal rate of the prepared biochar on antibiotics in antibiotic wastewater such as enramycin and tiamulin exceeds 99%, the removal rates of wastewater COD and ammonia nitrogen reach 96% and 71% respectively, and high-valued utilization of antibiotic residues is achieved while environmental safety is guaranteed.

Description

Technical Field

[0001] The present invention belongs to the technical field of biochar, and particularly relates to a phosphorus-sulfur synergistic antibiotic residue biochar, a preparation method thereof, and an application thereof. Background Art

[0002] Antibiotic mycelium residue is a large amount of solid waste generated during the antibiotic fermentation production process. Producing 1 ton of antibiotics will generate 8 - 10 tons of antibiotic residues. The antibiotic fermentation process generally uses corn steep liquor, glucose, starch, etc. as carbon sources, soybeans, peanut powder, etc. as nitrogen sources, and inorganic salts such as calcium sulfate, ammonium sulfate, potassium phosphate, and magnesium sulfate to provide metal ions necessary for microbial growth. Therefore, the addition of various sulfates and phosphates and the proteins in the bacterial cells (such as sulfur-containing amino acids) make the phosphorus and sulfur contents of the antibiotic residues relatively high (6% - 8%). If the antibiotic residues are not properly treated, it will also lead to serious environmental problems. For example, the secondary fermentation pollution is serious, the solid substances in the residues autolyze to produce a foul smell, causing serious environmental hazards to the atmosphere, water body, and soil; and because the antibiotic residues contain a small amount of antibiotic residues and intermediate metabolites in the antibiotic fermentation process, it is extremely easy to cause the large-scale reproduction of drug-resistant microorganisms, making it inevitable that a large number of resistance genes are contained in the antibiotic residues. Therefore, how to efficiently and safely treat antibiotics in wastewater and the residues generated during the production of antibiotics has become an urgent problem to be solved in the current fields of environmental protection and resource recycling.

[0003] Currently, the main treatment methods for antibiotic residues include pyrolysis, incineration, anaerobic digestion, and aerobic composting. Among them, pyrolysis, as a relatively efficient treatment method, has obvious advantages. Under typical pyrolysis conditions, the antibiotics and resistance genes in the antibiotic residues can be completely eliminated. At the same time, biochar generally has a relatively high specific surface area and good adsorption performance, and can be used as an adsorption material for wastewater treatment to further increase its added value. The removal of antibiotics in antibiotic wastewater mainly focuses on the application and optimization of technologies such as activated sludge, physical adsorption, advanced oxidation, and membrane bioreactor. Among them, the physical adsorption method is considered to be the most promising method for treating antibiotic wastewater because of its high removal efficiency, convenient treatment, low operating cost, etc. Among the many adsorbents currently in use, carbon materials with a high specific surface area, rich pore structure, and excellent chemical stability are widely popular in removing organic pollutants in water. However, for traditional carbon-based materials, due to problems such as high production cost, limited adsorption capacity, poor regenerability after adsorption saturation, and susceptibility to other solutes in a complex water quality environment, it is difficult to achieve large-scale, economical, and effective industrial applications of carbon materials in actual wastewater treatment. Therefore, finding cheap raw materials, comprehensively considering the balance between cost, output, and performance, and ensuring the sustainable application and market acceptance of carbon-based adsorption materials are crucial for the current development of carbon-based adsorption materials.

[0004] Due to reasons such as the raw material composition and process characteristics, the wet-process phosphoric acid prepared by decomposing phosphate rock with sulfuric acid has a relatively high sulfur content. The sulfides (such as FeS2) and sulfates (such as CaSO4) associated with the raw material phosphate rock are converted into sulfate radicals during the sulfuric acid decomposition process. Coupled with the addition of excessive sulfuric acid, the sulfur enrichment in the gypsum filtration residue and the concentration process, a high-sulfur phosphoric acid system is formed. Through the phosphorus-sulfur synergistic modification strategy, the present invention makes full use of the phosphorus and sulfur elements in the wet-process phosphoric acid prepared by the sulfuric acid method to achieve the dual goals of resource utilization of bacterial residues and wastewater purification. Summary of the Invention

[0005] In view of the above-mentioned prior art, the present invention provides a phosphorus-sulfur synergistic antibiotic bacterial residue biochar, its preparation method and application to solve the problems of difficult treatment and high treatment cost of antibiotic bacterial residues and antibiotic wastewater.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is to provide a preparation method of phosphorus-sulfur synergistic antibiotic bacterial residue biochar, which includes the following steps:

[0007] S1: Mix penicillin bacterial residue with wet-process phosphoric acid produced by the sulfuric acid method, and then carry out hydrothermal reaction; after the reaction is completed, filter and collect the filter residue to obtain acidolysis residue; the sulfur content in the wet-process phosphoric acid is 5-15 wt%.

[0008] S2: Disperse the acidolysis residue and alkali in water, heat up to 35-45 °C under closed conditions, and keep warm and stir for 90-150 min to obtain an impregnation system.

[0009] S3: Dry and grind the impregnation system to obtain a precursor.

[0010] S4: Under a protective gas flow, heat the precursor to 500-800 °C, keep warm for 1-4 h, then air-cool to room temperature, and then wash and dry to obtain the product.

[0011] On the basis of the above technical solution, the present invention can also be improved as follows.

[0012] Further, the content of phosphorus pentoxide in the wet-process phosphoric acid is 30-46 wt%, and the mass ratio of penicillin bacterial residue to wet-process phosphoric acid is 1:20.

[0013] Further, the temperature of the hydrothermal reaction in S1 is 120-180 °C, and the hydrothermal reaction time is 1-6 h.

[0014] Further, the mass ratio of the acidolysis residue, alkali and water in S2 is 8-16:15-30:100-300.

[0015] Further, the alkali is potassium hydroxide.

[0016] Further, the drying temperature in S3 is 110 °C.

[0017] Further, the protective gas flow is a nitrogen gas flow, and the flow rate of the nitrogen gas flow is 60 mL·min -1 .

[0018] Further, the heating rate in S4 is 5 - 15 °C·min -1 ; the drying temperature is 80 °C

[0019] The present invention also discloses a phosphorus-sulfur synergistic antibiotic residue biochar prepared by the above preparation method

[0020] The present invention also discloses the application of the above phosphorus-sulfur synergistic antibiotic residue biochar in purifying enramycin wastewater or tylosin wastewater

[0021] The beneficial effects of the present invention are as follows

[0022] 1. The present invention uses antibiotic residue (penicillin residue) and wet-process phosphoric acid produced by the sulfuric acid method as raw materials, without the need to subsequently introduce additional sulfur-containing modifiers. Through hydrothermal reaction, sulfur elements in the residue and wet-process phosphoric acid are enriched, and at the same time, phosphorus elements are in-situ introduced to achieve the organic combination of phosphorus and sulfur through chemical reactions, and finally biochar with a higher specific surface area and adsorption performance is prepared

[0023] 2. The present invention uses cheap wet-process phosphoric acid as a mediated acid to decompose antibiotic residue. Compared with hydrochloric acid and sulfuric acid, the obtained organic wet-process phosphoric acid has more advantages in avoiding secondary pollution and resource integration due to its fertilizer characteristics

[0024] 3. The present invention adopts a phosphorus-sulfur synergistic in-situ modification technology. In an acidic environment with excessive phosphoric acid, phosphorus-containing functional groups such as C-P=O and C-O-P are preferentially formed on the surface of the residue, and then under strong alkaline conditions, the phosphorus-oxygen double bond breaks and combines with the sulfur-rich components in the system to generate P-S and P=S bonds; in the pyrolysis stage, sulfur elements dynamically escape to produce a surface etching effect, constructing a pore structure with a high specific surface area. At the same time, the carbon fixation characteristics of phosphorus elements below 850 °C effectively inhibit carbon loss, and the dual effects significantly improve the carbon yield and adsorption performance

[0025] 4. The phosphorus-sulfur synergistic antibiotic residue biochar obtained by the present invention has good actual application adsorption effect, good resistance to metal ion impurities, and a wide application range. By adsorbing enramycin wastewater and tylosin wastewater with high chemical oxygen demand (COD) from a pharmaceutical enterprise, it can efficiently reduce COD while achieving complete adsorption of residual antibiotics Description of the Drawings

[0026] Figure 1 For the contents of amino acids and polypeptides in the acidolysis solution in Example 1

[0027] Figure 2The infrared spectra of the precursors in Example 1, Comparative Example 1 and Comparative Example 2 are shown;

[0028] Figure 3 The carbon yield of biochar prepared in Example 1, Comparative Example 2 and Comparative Example 3. DETAILED DESCRIPTION

[0029] The specific implementation modes of the present invention are described in detail below with reference to the embodiments.

[0030] Example 1

[0031] A phosphorus-sulfur synergistic antibiotic bacterial residue biochar is prepared by the following steps:

[0032] S1: Add penicillin residue (dry basis) and wet-process phosphoric acid produced by sulfuric acid process into 100ml polytetrafluoroethylene liner at a mass ratio of 1:20, and stir at room temperature for 0.5h;

[0033] S2: Place the liner into a hydrothermal reactor, seal it, and perform a hydrothermal reaction at 150°C for 120 minutes. After the reaction is completed, cool it to room temperature, filter the reaction solution, and collect the residue to obtain the acid hydrolysis residue.

[0034] S3: adding 100 parts by mass of the acid-dissolved residue and 230 parts by mass of potassium hydroxide to 2000 parts by mass of deionized water, heating to 40° C. in a closed condition, and stirring for 2 hours to obtain an impregnation system;

[0035] S4: The impregnation system is transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110° C. and then fully ground to obtain a precursor;

[0036] S5: The precursor was transferred to a tube furnace with nitrogen as the protective gas (gas rate of 60 mL min -1 ), the heating rate of the tube furnace is 5℃·min -1 , heat to 800°C and keep warm for 2h; then air-cool to room temperature, and wash the solid obtained by pyrolysis with water and ethanol until neutral, and then dry in an oven at 80°C to obtain a biochar product.

[0037] Example 2

[0038] A phosphorus-sulfur synergistic antibiotic bacterial residue biochar is prepared by the following steps:

[0039] S1: Add erythromycin residue (dry basis) and wet-process phosphoric acid produced by sulfuric acid method into 100 ml of polytetrafluoroethylene liner at a mass ratio of 1:20, and stir at room temperature for 0.5 h;

[0040] S2: Place the liner into a hydrothermal reactor, seal it, and perform a hydrothermal reaction at 120°C for 6 hours. After the reaction is completed, cool it to room temperature, filter the reaction solution, and collect the filter residue to obtain the acid hydrolysis residue;

[0041] S3: adding 80 parts by mass of the acid-dissolved residue and 150 parts by mass of potassium hydroxide to 1000 parts by mass of deionized water, heating to 35° C. in a closed condition, and stirring for 150 minutes to obtain an impregnation system;

[0042] S4: The impregnation system is transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110° C. and then fully ground to obtain a precursor;

[0043] S5: Transfer the precursor to a tube furnace with nitrogen as the protective gas (gas rate of 60 mL min -1 ), the heating rate of the tube furnace is 5℃·min -1 , heat to 500°C and keep warm for 4 hours; then air-cool to room temperature, and wash the solid obtained by pyrolysis with water and ethanol until neutral, and then dry in an oven at 80°C to obtain a biochar product.

[0044] Example 3

[0045] A phosphorus-sulfur synergistic antibiotic bacterial residue biochar is prepared by the following steps:

[0046] S1: Add tiamulin residue (dry basis) and wet-process phosphoric acid produced by sulfuric acid method into 100 ml of polytetrafluoroethylene liner at a mass ratio of 1:20, and stir at room temperature for 0.5 h;

[0047] S2: Place the liner into a hydrothermal reactor, seal it, and perform hydrothermal reaction at 180°C for 1 hour. After the reaction is completed, cool it to room temperature, filter the reaction solution, and collect the residue to obtain acid hydrolysis residue;

[0048] S3: adding 160 parts by mass of the acid-dissolved residue and 300 parts by mass of potassium hydroxide to 3000 parts by mass of deionized water, heating to 45° C. in a closed condition, and stirring for 90 minutes to obtain an impregnation system;

[0049] S4: The impregnation system is transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110° C. and then fully ground to obtain a precursor;

[0050] S5: Transfer the precursor to a tube furnace with nitrogen as the protective gas (gas rate of 60 mL min -1 ), the heating rate of the tube furnace is 5℃·min -1 , heat to 800°C and keep warm for 1 hour; then air-cool to room temperature, and wash the solid obtained by pyrolysis with water and ethanol until neutral, and then dry in an oven at 80°C to obtain a biochar product.

[0051] Comparative Example 1

[0052] A potassium hydroxide-modified antibiotic waste residue porous biochar is prepared by the following steps:

[0053] S1: Add penicillin residue (dry basis) from the same batch as in Example 1 and deionized water in a mass ratio of 1:20 into a 100 ml polytetrafluoroethylene liner and stir at room temperature for 0.5 h;

[0054] S2: Place the liner into a hydrothermal reactor, seal it, and perform a hydrothermal reaction at 150°C for 120 minutes. After the reaction is completed, cool it to room temperature, filter the reaction solution, and collect the filter residue to obtain a hydrolysis residue.

[0055] S3: adding 100 parts by mass of hydrolysis residue and 230 parts by mass of potassium hydroxide to 2000 parts by mass of deionized water, heating to 40° C. in a closed condition, and stirring for 2 hours to obtain an impregnation system;

[0056] S4: The impregnation system is transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110° C. and then fully ground to obtain a precursor;

[0057] S5: Transfer the precursor to a tube furnace with nitrogen as the protective gas (gas rate of 60 mL min -1 ), the heating rate of the tube furnace is 5℃·min -1 , heat to 800°C and keep warm for 2h; then air-cool to room temperature, and wash the solid obtained by pyrolysis with water and ethanol until neutral, and then dry in an oven at 80°C to obtain a biochar product.

[0058] Comparative Example 2

[0059] A potassium hydroxide and carbon disulfide modified antibiotic waste residue porous biochar is prepared by the following steps:

[0060] S1: Add penicillin residue (dry basis) from the same batch as in Example 1 and wet-process phosphoric acid (concentration of 35.05wt% in terms of P2O5%) into a 100ml polytetrafluoroethylene liner at a mass ratio of 1:20, and stir at room temperature for 0.5h;

[0061] S2: Place the liner into a hydrothermal reactor, seal it, and perform a hydrothermal reaction at 150°C for 120 minutes. After the reaction is completed, cool it to room temperature, filter the reaction solution, and collect the filter residue to obtain the acid hydrolysis residue;

[0062] S3: 100 parts by mass of acid hydrolysis residue, 230 parts by mass of potassium hydroxide and 25 parts by mass of carbon disulfide are added to 2000 parts by mass of deionized water, the temperature is raised to 40° C. under closed conditions, and the mixture is stirred for 2 hours to obtain an impregnation system;

[0063] S4: The impregnation system is transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110° C. and then fully ground to obtain a precursor;

[0064] S5: Transfer the precursor to a tubular furnace with nitrogen as the protective gas (gas velocity: 60 mL·min -1 ), the heating rate of the tubular furnace is 5 °C·min -1 , heat up to 800 °C, and keep the temperature for 2 h; then air-cool to room temperature, wash the pyrolyzed solid with water and ethanol until neutral, and then dry it in an oven at 80 °C to obtain the biochar product.

[0065] Comparative Example 3

[0066] A porous biochar modified by potassium hydroxide and sodium sulfide from antibiotic waste residue is prepared through the following steps:

[0067] S1: Add penicillin residue (dry basis) of the same batch as in Example 1 and deionized water at a mass ratio of 1:20 to a 100 ml polytetrafluoroethylene inner liner, and stir at room temperature for 0.5 h;

[0068] S2: Place the inner liner into a hydrothermal reactor, seal it, and carry out hydrothermal reaction at 150 °C for 120 min. After the reaction, cool it to room temperature, filter the reaction solution, and collect the filter residue to obtain the hydrolyzed residue;

[0069] S3: Add 100 parts by mass of the hydrolyzed residue, 230 parts by mass of potassium hydroxide, and 50 parts by mass of sodium sulfide to 2000 parts by mass of deionized water, heat up to 40 °C under closed conditions, and keep stirring for 2 h to obtain an impregnation system;

[0070] S4: Transfer the impregnation system to an evaporating dish, then evaporate and dry it in an oven at 110 °C and grind it thoroughly to obtain the precursor;

[0071] S5: Transfer the precursor to a tubular furnace with nitrogen as the protective gas (gas velocity: 60 mL·min -1 ), the heating rate of the tubular furnace is 5 °C·min -1 , heat up to 800 °C, and keep the temperature for 2 h; then air-cool to room temperature, wash the pyrolyzed solid with water and ethanol until neutral, and then dry it in an oven at 80 °C to obtain the biochar product.

[0072] Experimental Example 1: Determination of phosphorus and sulfur contents in antibiotic residue and wet-process phosphoric acid in Examples 1 - 3

[0073] The phosphorus and sulfur contents of the antibiotic residue used in Examples 1 to 3 and the wet-process phosphoric acid produced by the sulfuric acid method were measured using an X-ray fluorescence spectrometer, and the results are shown in Table 1. As can be seen from Table 1, the three antibiotic residues selected in Examples 1 to 3 all contain relatively high phosphorus and sulfur contents. Through the hydrothermal acidolysis of wet-process phosphoric acid with a high sulfur content (8% - 13%), using an acidic, high-temperature, and pressurized reaction environment, phosphorus and sulfur elements are in-situ introduced onto the surface of the antibiotic residue, making full use of the phosphorus and sulfur elements in the residue and wet-process phosphoric acid, and there is no need to add sulfur-containing modifiers anymore.

[0074] Table 1 Phosphorus and sulfur contents (expressed in the form of oxides) in the antibiotic residue and wet-process phosphoric acid of Examples 1 to 3

[0075]

[0076] Experimental Example 2: Determination of the nitrogen content of the antibiotic residue before and after hydrothermal reaction and the contents of 18 amino acids and polypeptides in the acidolysis solution in Example 1 and Comparative Example 1

[0077] The nitrogen content and the contents of amino acids and polypeptides were determined using an elemental analyzer and an amino acid analyzer respectively. The results of the nitrogen content determination are shown in Table 2, and the results of the amino acid and polypeptide content determination are as Figure 1 shown. As can be seen from Table 2 and Figure 1 it can be seen that using wet-process phosphoric acid with a high sulfur content as the hydrothermal medium can effectively reduce the nitrogen content in the penicillin residue. This is because the crude protein in the antibiotic residue (accounting for more than 90% of the nitrogen in the residue) decomposes into amino acids and polypeptides ( Figure 1 ) and enters the acidolysis solution. Compared with medium-strength acids such as hydrochloric acid and sulfuric acid, wet-process phosphoric acid can be used for the preparation of subsequent fertilizers, avoiding secondary pollution and cheaply introducing fertilizer synergistic substances.

[0078] Table 2 Nitrogen contents of the antibiotic residue before and after hydrothermal treatment in Example 1 and Comparative Example 1

[0079]

[0080] Experimental Example 3: Infrared spectrum analysis and carbon yield calculation of the precursor

[0081] The precursors obtained in Example 1, Comparative Example 1, and Comparative Example 2 were subjected to infrared spectrum analysis, and the results are as Figure 2 shown. From Figure 2It can be seen from the figure that in Comparative Example 1, due to the absence of the addition of high-sulfur-content wet-process phosphoric acid, there is no obvious appearance of sulfur-containing functional groups in the obtained precursor. The typical infrared absorption peak of potassium carbonate appears due to the reaction between potassium hydroxide and carbon dioxide in the air during the evaporation to dryness process. In Comparative Example 2, by adding a sulfur-containing modifier (carbon disulfide) externally, obvious stretching vibrations of carbon-sulfur double bonds and carbon-sulfur single bonds appear in the infrared spectrum. In Example 1, phosphorus and sulfur elements are in-situ introduced through high-sulfur wet-process phosphoric acid, and -C-O-P and P=S functional groups are successfully generated to achieve the protection of carbon during the pyrolysis process.

[0082] The carbon yields of the biochars obtained in Example 1, Comparative Example 2, and Comparative Example 3 were measured, and the calculation formula for the carbon yield is as follows:

[0083] Carbon yield (%) = precursor * carbon content of the precursor / (biochar * carbon content in the biochar)

[0084] The measurement results are as Figure 3 shown. It can be seen that compared with Comparative Example 2 and Comparative Example 3 with externally added sulfur-containing modifiers, the carbon yield of Example 1 increased by about 10%, effectively reducing carbon emissions during the pyrolysis process.

[0085] Experimental Example 4: Pore parameters and morphological structure of biochar

[0086] The pore parameters of the biochars prepared in Example 1 and Comparative Examples 1-3 were measured, and the results are shown in Table 3. According to the comparative analysis of the pore parameters in Table 3, the biochar prepared in Example 1 achieved an approximately 45% increase in the total specific surface area compared with Comparative Examples 2-3 with externally added sulfur-containing modifiers on the basis of the increased carbon yield. The optimization of this pore structure indicates that sulfur-phosphorus synergistic modification can significantly enhance the adsorption performance of biochar.

[0087] Table 3 Pore parameters of biochar products

[0088]

[0089] Experimental Example 5: Adsorption effects on enramycin wastewater and tylosin wastewater

[0090] At 25 °C, 0.02 g (±0.001 g) of the biochar products obtained in Example 1, Comparative Example 1, and Comparative Example 2, as well as commercial activated carbon, were respectively added to centrifuge tubes containing 20 ml of pharmaceutical wastewater, and continuously adsorbed on a constant-temperature air shaker at a rotation speed of 250 rpm for 180 min. After reaching the specified time, the biochar samples were separated from the pharmaceutical wastewater by filtering through a 0.22 μm microporous filter.

[0091] Enramycin and tiamulin are determined by high performance liquid chromatography, and the detection limit is 1 μg / ml; the chemical oxygen demand content is determined according to the standard of HJ828-2017; the ammonia nitrogen content is determined according to the standard of HJ 537-2009.

[0092] The adsorption effects of enramycin wastewater and tiamulin wastewater are shown in Table 4 and Table 5 respectively. Based on the comparison of the adsorption experiments of enramycin and tiamulin pharmaceutical wastewater, it can be seen that the phosphorus-sulfur synergistic antibiotic residue biochar prepared in Example 1 shows significant advantages: the removal rate of the two antibiotics reaches 100%, the COD removal rate is increased to 96%, and the ammonia nitrogen removal rate reaches 71%. It fully demonstrates the advantages of phosphorus-sulfur synergistic antibiotic residue biochar in practical applications.

[0093] Table 4 Contents of antibiotics, COD and ammonia nitrogen in enramycin wastewater before and after adsorption

[0094]

[0095] Table 5 Contents of antibiotics, COD and ammonia nitrogen in tiamulin wastewater before and after adsorption

[0096]

[0097] Although the specific implementation manners of the present invention have been described in detail in conjunction with the embodiments, it should not be construed as a limitation on the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative work still fall within the protection scope of this patent.

Claims

1. A method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar, characterized in that: The following steps are involved: S1: mixing penicillin residue with wet-process phosphoric acid produced by sulfuric acid method, and then performing hydrothermal reaction; filtering after the reaction is completed, collecting the filter residue, and obtaining acid hydrolysis residue; the sulfur content in the wet-process phosphoric acid is 5-15wt%; S2: Disperse the acid hydrolysis residue and alkali in water, heat to 35-45°C in a closed condition, and stir for 90-150 minutes to obtain an impregnation system; S3: drying and grinding the impregnation system to obtain a precursor; S4: Heat the precursor to 500-800°C under a protective gas flow, keep it warm for 1-4 hours, then air-cool it to room temperature, wash it, and dry it.

2. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The content of phosphorus pentoxide in the wet-process phosphoric acid is 30-46wt%, and the mass ratio of the penicillin residue to the wet-process phosphoric acid is 1:

20.

3. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The temperature of the hydrothermal reaction in S1 is 120~180℃, and the hydrothermal reaction time is 1~6h.

4. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The mass ratio of acid hydrolysis slag, alkali and water in S2 is 8~16:15~30:100~300.

5. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1 or 4, characterized in that: The base is potassium hydroxide.

6. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The drying temperature in S3 is 110°C.

7. The method for preparing phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The protective gas flow is nitrogen flow, and the flow rate of the nitrogen flow is 60 mL min -1 .

8. The method for preparing porous biochar from antibiotic waste residue according to claim 1, characterized in that: The heating rate in S4 is 5~15℃·min -1 ; Drying temperature is 80℃.

9. A phosphorus-sulfur synergistic antibiotic bacterial residue biochar, characterized in that: The method is prepared by any one of claims 1 to 8.

10. The use of the phosphorus-sulfur synergistic antibiotic bacterial residue biochar according to claim 9, characterized in that: Phosphorus-sulfur synergistic antibiotic bacterial residue biochar is used to purify enramycin wastewater or tylosin wastewater.

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