Phosphorus-sulfur synergistic antibiotic bacterial residue biochar, and preparation method and application thereof

Abstract

The application discloses a phosphorus-sulfur synergistic antibiotic bacterial residue biochar, a preparation method and application thereof, and belongs to the technical field of biochar. The application takes penicillin bacterial residue and high-sulfur wet-process phosphoric acid as raw materials, and prepares biochar through phosphorus-sulfur synergistic modification and applies the biochar to adsorption of antibiotic wastewater, so that efficient purification of the antibiotic wastewater and full-resource utilization of the bacterial residue are realized. The method innovatively uses cheap high-sulfur wet-process phosphoric acid to replace traditional strong acid (hydrochloric acid, sulfuric acid, etc.) for pretreatment, and the obtained acid hydrolysis solution can be directly used for preparing fertilizer, thereby simultaneously reducing pyrolysis cost and improving nitrogen utilization rate. The phosphorus-sulfur in-situ modification process makes the carbon yield of the biochar increase by 10%, the specific surface area increase by 45%, and the resistant genes in the bacterial residue are completely eliminated. The prepared biochar has an antibiotic removal rate of more than 99% for antibiotic wastewater such as enrofloxacin and tylosin, and the wastewater COD and ammonia nitrogen removal rates reach 96% and 71% respectively, so that the high-value utilization of antibiotic bacterial residue is realized while the environmental safety is ensured.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of biochar, and particularly relates to a phosphorus-sulfur synergistic antibiotic fungus residue biochar, a preparation method thereof and application thereof. BACKGROUND

[0002] Antibiotic mycelium residue is a large amount of solid waste produced in the process of antibiotic fermentation production. 8-10 tons of antibiotic fungus residue will be produced for every ton of antibiotic. The antibiotic fermentation process generally uses corn syrup, glucose, starch, etc. as carbon source, uses soybean, peanut powder, etc. as nitrogen source, and uses calcium sulfate, ammonium sulfate, potassium phosphate, magnesium sulfate, etc. to provide the necessary metal ions for microbial growth. Therefore, the addition of various sulfates and phosphates and the protein (such as sulfur-containing amino acids) in the fungus make the phosphorus content and sulfur content of the antibiotic fungus residue itself relatively high (6%-8%). If the antibiotic fungus residue is not properly treated, it will also cause serious environmental problems, such as serious secondary fermentation pollution, foul odor generated by autolysis of solid substances in the fungus residue, and serious environmental hazards to the atmosphere, water body and soil; and due to the presence of a small amount of antibiotic residues and intermediate metabolites in the antibiotic fermentation process in the antibiotic fungus residue, it is easy to cause the massive reproduction of drug-resistant microorganisms, so that the antibiotic fungus residue inevitably contains a large amount of antibiotic resistance genes. Therefore, how to efficiently and safely treat the antibiotic in the wastewater and the fungus residue produced in the antibiotic production process has become a difficult problem to be solved in the field of environmental protection and resource recycling.

[0003] At present, the main methods for treating antibiotic fungus residue are pyrolysis, incineration, anaerobic digestion and aerobic composting. Among them, pyrolysis has obvious advantages as a relatively efficient treatment method. Under typical pyrolysis conditions, antibiotics and antibiotic resistance genes in antibiotic fungus residue can be completely eliminated, and biochar generally has a high specific surface area and good adsorption performance, which can be used as an adsorbent for wastewater treatment, further improving its added value. The removal of antibiotics in antibiotic wastewater mainly focuses on the application and optimization of activated sludge, physical adsorption, advanced oxidation, membrane bioreactor and other technologies. Among them, the physical adsorption method is considered to be the most promising method for antibiotic wastewater treatment because of its high removal efficiency, convenient treatment and low operation cost. Among the many adsorbents currently used, carbon materials with high specific surface area, rich pore structure and excellent chemical stability are widely welcomed in the removal of organic pollutants in water. However, for traditional carbon-based materials, due to high production cost, limited adsorption capacity, poor regeneration after adsorption saturation, and easy influence by other solutes in complex water quality environment, it is difficult for carbon materials to realize large-scale, economically effective industrial application in actual wastewater treatment. Therefore, it is essential to find cheap raw materials, consider the balance between cost, yield and performance, and ensure the sustainable application and market acceptance of carbon-based adsorbent materials for the current development of carbon-based adsorbent materials.

[0004] The sulfur content in the wet-process phosphoric acid prepared by decomposing phosphate ore with sulfuric acid is high due to the composition of raw materials, process characteristics and other reasons. The sulfides (such as FeS2) and sulfates (such as CaSO4) associated with the raw material phosphate ore are converted into sulfate ions in the sulfuric acid decomposition process, plus the addition of excess sulfuric acid, the residue of gypsum filtration and the sulfur enrichment in the concentration process, forming a high-sulfur phosphoric acid system. The present application fully utilizes the phosphorus and sulfur elements in the wet-process phosphoric acid prepared by the sulfuric acid method through a phosphorus-sulfur synergistic modification strategy, achieving the dual goals of resource utilization of antibiotic residue and wastewater purification. SUMMARY

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

[0006] To achieve the above purpose, the technical scheme adopted by the present application is to provide a preparation method of a phosphorus-sulfur synergistic antibiotic residue biochar, comprising the following steps:

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

[0008] S2: dispersing the acidolysis residue and alkali in water, heating to 35-45℃ under airtight conditions, and stirring for 90-150min to obtain an impregnation system;

[0009] S3: drying the impregnation system, and grinding to obtain a precursor;

[0010] S4: heating the precursor to 500-800℃ under a protective gas flow, and keeping warm for 1-4h, then air cooling to room temperature, and then washing and drying to obtain the phosphorus-sulfur synergistic antibiotic residue biochar.

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

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

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

[0014] Further, the mass ratio of 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℃.

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

[0018] Further, the rate of the temperature rise in S4 is 5~15℃·min -1 ; the drying temperature is 80℃.

[0019] The application further discloses the phosphorus-sulfur synergistic antibiotic residue biochar prepared by the preparation method.

[0020] The application further discloses application of the phosphorus-sulfur synergistic antibiotic residue biochar in purifying enrofloxacin wastewater or tylosin wastewater.

[0021] The application has the following beneficial effects:

[0022] 1. The application uses antibiotic residue (penicillin residue) and wet-process phosphoric acid produced by the sulfuric acid method as raw materials, does not need to introduce a sulfur-containing modifier subsequently, enriches sulfur elements in the residue and the wet-process phosphoric acid through a hydrothermal reaction, in-situ introduces phosphorus elements to realize organic combination of phosphorus and sulfur through a chemical reaction, and finally prepares biochar with higher specific surface area and adsorption performance.

[0023] 2. The application uses cheap wet-process phosphoric acid to mediate acidolysis of antibiotic residue, and compared with hydrochloric acid and sulfuric acid, the organic wet-process phosphoric acid obtained after filtration has more advantages in avoiding secondary pollution and resource integration due to its fertilizerization characteristics.

[0024] 3. The application uses a phosphorus-sulfur synergistic in-situ modification technology, in an excessive acid environment of phosphoric acid, preferentially forms C-P=O, C-O-P and other phosphorus-containing functional groups on the surface of the residue, and then under strong alkali conditions, breaks the phosphorus-oxygen double bond to combine with sulfur components in the system to generate P-S and P=S bonds; in the pyrolysis stage, the sulfur element dynamically escapes to produce a surface etching effect, and a high specific surface area pore structure is constructed. At the same time, the carbon sequestration characteristics of phosphorus elements below 850 DEG C effectively inhibit carbon loss, and the double effects significantly improve carbon yield and adsorption performance.

[0025] 4. The phosphorus-sulfur synergistic antibiotic residue biochar obtained in the application has good practical application adsorption effect, good metal ion impurity resistance effect, and wide application range. Through adsorption on enrofloxacin wastewater and tylosin wastewater with high chemical oxygen demand (COD) of a certain pharmaceutical enterprise, the COD is efficiently reduced, and complete adsorption of residual antibiotics is realized. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The amino acid and polypeptide contents in the acidolysis solution in Example 1 are as follows:

[0027] Figure 2Infrared spectrum of the precursor in Example 1, Comparative Example 1 and Comparative Example 2;

[0028] Figure 3 Carbon yield for preparing the biochar in Example 1, Comparative Example 2 and Comparative Example 3. DETAILED DESCRIPTION

[0029] The specific embodiments of the present application will be described in detail below with reference to the examples.

[0030] Example 1

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

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

[0033] S2: The liner is loaded into a hydrothermal reaction kettle, and after being sealed, hydrothermal reaction is carried out at 150℃ for 120min. After the reaction is completed, the reaction liquid is cooled to room temperature, filtered, and the filter residue is collected to obtain acidolysis residue;

[0034] S3: 100 parts by mass of the acidolysis residue, 230 parts by mass of potassium hydroxide are added into 2000 parts by mass of deionized water, and the temperature is raised to 40℃ under sealed conditions, and the mixture is stirred for 2h 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℃. After being fully ground, a precursor is obtained;

[0036] S5: The precursor is transferred to a tube furnace, and nitrogen is used as the protective gas (gas speed is 60mL·min -1 ), the tube furnace is heated at a rate of 5℃·min -1 , and the temperature is raised to 800℃, and the mixture is kept at this temperature for 2h. Then, the mixture is air-cooled to room temperature, and the pyrolysis obtained solid is washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain a biochar product.

[0037] Example 2

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

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

[0040] S2: The liner is loaded into a hydrothermal reaction kettle, and after being sealed, hydrothermal reaction is carried out at 120℃ for 6h. After the reaction is completed, the reaction liquid is cooled to room temperature, filtered, and the filter residue is collected to obtain acidolysis residue;

[0041] S3: 80 parts by mass of the acidolysis residue, 150 parts by mass of potassium hydroxide were added into 1000 parts by mass of deionized water, and the temperature was raised to 35℃ under a sealed condition, and the mixture was stirred for 150 min to obtain an impregnation system;

[0042] S4: The impregnation system was transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110℃, and then ground thoroughly to obtain a precursor;

[0043] S5: The precursor was transferred to a tube furnace, and nitrogen was used as the protective gas (the gas speed was 60 mL·min -1 ), the tube furnace was heated at a rate of 5℃·min -1 to 500℃, and then kept for 4 h; then air-cooled to room temperature, and the pyrolysis obtained solid was washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain a biochar product.

[0044] Example 3

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

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

[0047] S2: The liner was loaded into a hydrothermal reaction kettle, and after sealing, hydrothermal reaction was carried out at 180℃ for 1 h, and after the reaction was completed, the reaction liquid was cooled to room temperature, and the filter residue was collected to obtain an acidolysis residue;

[0048] S3: 160 parts by mass of the acidolysis residue, 300 parts by mass of potassium hydroxide were added into 3000 parts by mass of deionized water, and the temperature was raised to 45℃ under a sealed condition, and the mixture was stirred for 90 min to obtain an impregnation system;

[0049] S4: The impregnation system was transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110℃, and then ground thoroughly to obtain a precursor;

[0050] S5: The precursor was transferred to a tube furnace, and nitrogen was used as the protective gas (the gas speed was 60 mL·min -1 ), the tube furnace was heated at a rate of 5℃·min -1 to 800℃, and then kept for 1 h; then air-cooled to room temperature, and the pyrolysis obtained solid was washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain a biochar product.

[0051] Comparative Example 1

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

[0053] S1: The same batch of penicillin residue (dry basis) as in Example 1 was added to a 100ml polytetrafluoroethylene liner at a mass ratio of 1:20 with deionized water, and stirred at room temperature for 0.5h;

[0054] S2: The liner was placed in a hydrothermal reaction kettle, and after sealing, hydrothermal reaction was carried out at 150℃ for 120min. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered, and the filter residue was collected to obtain the hydrolysis residue;

[0055] S3: 100 parts by mass of the hydrolysis residue, 230 parts by mass of potassium hydroxide were added to 2000 parts by mass of deionized water, and heated to 40℃ under sealed conditions, and stirred for 2h to obtain an impregnation system;

[0056] S4: The impregnation system was transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110℃, and then ground thoroughly to obtain a precursor;

[0057] S5: The precursor was transferred to a tube furnace with nitrogen as the protective gas (gas speed was 60mL·min -1 ), the tube furnace was heated at a rate of 5℃·min -1 , and heated to 800℃, and kept for 2h. Then air-cooled to room temperature, and the pyrolysis obtained solid was washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain a biochar product.

[0058] Comparative Example 2

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

[0060] S1: The same batch of penicillin residue (dry basis) as in Example 1 was added to a 100ml polytetrafluoroethylene liner at a mass ratio of 1:20 with wet phosphoric acid (concentration of P2O5% was 35.05wt%), and stirred at room temperature for 0.5h;

[0061] S2: The liner was placed in a hydrothermal reaction kettle, and after sealing, hydrothermal reaction was carried out at 150℃ for 120min. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered, and the filter residue was collected to obtain the acidolysis residue;

[0062] S3: 100 parts by mass of the acidolysis residue, 230 parts by mass of potassium hydroxide and 25 parts by mass of carbon disulfide were added to 2000 parts by mass of deionized water, and heated to 40℃ under sealed conditions, and stirred for 2h to obtain an impregnation system;

[0063] S4: The impregnation system was transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110℃, and then ground thoroughly to obtain a precursor;

[0064] S5: The precursor was transferred to a tube furnace for pyrolysis under the protection of nitrogen (gas velocity was 60 mL·min -1 ), the tube furnace was heated at a rate of 5℃·min -1 , and heated to 800℃, and kept for 2h; then air-cooled to room temperature, and the pyrolysis obtained solid was washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain the biochar product.

[0065] Comparative Example 3

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

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

[0068] S2: The liner was loaded into a hydrothermal reaction kettle, and after sealing, hydrothermal reaction was carried out at 150℃ for 120min, and after the reaction was completed, the reaction liquid was cooled to room temperature, and the filter residue was collected to obtain the hydrolysis residue;

[0069] S3: 100 parts by mass of the hydrolysis residue, 230 parts by mass of potassium hydroxide and 50 parts by mass of sodium sulfide were added to 2000 parts by mass of deionized water, and heated to 40℃ under sealed conditions, and kept stirring for 2h to obtain an impregnation system;

[0070] S4: The impregnation system was transferred to an evaporating dish, and then evaporated and dried in an oven at a temperature of 110℃, and then ground thoroughly to obtain a precursor;

[0071] S5: The precursor was transferred to a tube furnace for pyrolysis under the protection of nitrogen (gas velocity was 60 mL·min -1 ), the tube furnace was heated at a rate of 5℃·min -1 , and heated to 800℃, and kept for 2h; then air-cooled to room temperature, and the pyrolysis obtained solid was washed with water and ethanol until neutral, and then dried in an oven at 80℃ to obtain the biochar product.

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

[0073] The phosphorus and sulfur contents of the antibiotic bacterial residues and wet-process phosphoric acid produced by the sulfuric acid method used in Examples 1-3 were determined by X-ray fluorescence spectrometry, and the results are shown in Table 1. Table 1 shows that the three types of antibiotic bacterial residues selected in Examples 1-3 all contain high levels of phosphorus and sulfur. Furthermore, through hydrothermal acid hydrolysis of wet-process phosphoric acid with a high sulfur content (8%-13%), phosphorus and sulfur elements are introduced in situ onto the surface of the antibiotic bacterial residue using an acidic, high-temperature, and pressurized reaction environment. This fully utilizes the phosphorus and sulfur elements in the bacterial residue and wet-process phosphoric acid, eliminating the need for additional sulfur-containing modifiers.

[0074] Table 1. Phosphorus and sulfur content (expressed in oxide form) in antibiotic bacterial residue and wet-process phosphoric acid from Examples 1-3

[0075]

[0076] Experimental Example 2: Determination of nitrogen content in antibiotic bacterial residue before and after hydrothermal reaction in Example 1 and Comparative Example 1, and determination of the content of 18 amino acids and peptides in acid hydrolysate.

[0077] Nitrogen content and the contents of amino acids and peptides were determined using an elemental analyzer and an amino acid analyzer, respectively. The nitrogen content results are shown in Table 2, and the amino acid and peptide content results are shown in Table 3. Figure 1 As shown in Table 2 and Figure 1 As can be seen, using high-sulfur wet-process phosphoric acid as the hydrothermal medium can effectively reduce the nitrogen content in penicillin bacterial residue. This is because the crude protein in the antibiotic bacterial residue (accounting for more than 90% of the nitrogen in the residue) decomposes into amino acids and polypeptides. Figure 1 The phosphoric acid is then added to the acid hydrolysis solution. Compared to medium-strong acids such as hydrochloric acid and sulfuric acid, wet-process phosphoric acid can be used for the preparation of subsequent fertilizers, which avoids secondary pollution and introduces fertilizer-enhancing substances at low cost.

[0078] Table 2. Nitrogen content of antibiotic bacterial residue before and after hydrothermal treatment in Example 1 and Comparative Example 1

[0079]

[0080] Experimental Example 3: Infrared Spectroscopic Analysis and Carbon Yield Calculation of Precursor

[0081] Infrared spectroscopy analysis was performed on the precursors obtained in Example 1, Comparative Example 1, and Comparative Example 2, and the results are as follows: Figure 2 As shown. From Figure 2As can be seen, Comparative Example 1 did not have a high-sulfur content wet-process phosphoric acid added, and no obvious sulfur-containing functional groups appeared in the precursor obtained, and the typical infrared absorption peak of potassium carbonate appeared due to the reaction of potassium hydroxide and carbon dioxide in the air during the evaporation process. Comparative Example 2 added a sulfur-containing modifier (carbon disulfide) exogenously, and obvious carbon-sulfur double bond and carbon-sulfur single bond stretching vibrations appeared in the infrared spectrum. Example 1 successfully generated -C-O-P and P=S functional groups by introducing phosphorus and sulfur elements in situ through high-sulfur content wet-process phosphoric acid, to achieve protection of carbon during pyrolysis.

[0082] The carbon yield of the biochar obtained in Example 1, Comparative Example 2 and Comparative Example 3 was determined, and the calculation formula of the carbon yield was as follows:

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

[0084] The hand green determination results are shown in Table 2. Figure 3 As can be seen, the carbon yield of Example 1 was increased by about 10% compared to Comparative Examples 2 and 3 in which a sulfur-containing modifier was added exogenously, effectively reducing carbon emissions during pyrolysis.

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

[0086] The pore parameters of the biochar prepared in Example 1 and Comparative Examples 1-3 were determined, 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 had an increase of about 45% in total specific surface area on the basis of an increase in carbon yield compared to Comparative Examples 2-3 in which a sulfur-containing modifier was added exogenously. The optimization of the 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 effect on enramycin wastewater and tylosin wastewater

[0090] At 25°C, 0.02 g (±0.001 g) of the biochar products prepared in Example 1, Comparative Example 1 and Comparative Example 2 and a commercial activated carbon were added to centrifuge tubes containing 20 ml of pharmaceutical wastewater, and adsorption was continued for 180 min in a constant-temperature air shaking box at a rotation speed of 250 rpm. After the specified time, the biochar samples were separated from the pharmaceutical wastewater by filtration through a 0.22 μm microporous filter.

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

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

[0093] Table 4 Antibiotic, COD and ammonia nitrogen contents before and after adsorption of enrofloxacin wastewater

[0094]

[0095] Table 5 Antibiotic, COD and ammonia nitrogen contents before and after adsorption of tylosin wastewater

[0096]

[0097] Although the specific embodiments of the present application are described in detail in combination with the embodiments, it should not be understood as limiting the protection scope of the patent. Various modifications and changes made by those skilled in the art within the scope described in the claims are still within the protection scope of the patent.

Claims

1. The use of phosphorus-sulfur synergistic antibiotic bacterial residue biochar, characterized in that, The phosphorus-sulfur synergistic antibiotic bacteria residue biochar is used for purifying enramycin wastewater or tylosin wastewater; a preparation method of the phosphorus-sulfur synergistic antibiotic bacteria residue biochar comprises the following steps: S1: mixing penicillin bacteria residue and wet-process phosphoric acid produced by a sulfuric acid method, and then performing a hydrothermal reaction; after the reaction is completed, filtration is performed, and the filter residue is collected to obtain acidolysis residue; the sulfur content in the wet-process phosphoric acid is 5-15 wt%; S2: dispersing the acidolysis residue and alkali in water, heating to 35-45 DEG C under a sealed condition, and stirring and keeping warm for 90-150 min to obtain an impregnation system; S3: drying the impregnation system, grinding, and obtaining a precursor; S4: under a protective gas flow, heating the precursor to 500-800 DEG C, keeping warm for 1-4 h, then air cooling to room temperature, and then washing and drying, and the phosphorus-sulfur synergistic antibiotic bacteria residue biochar is obtained.

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

20.

3. The use of the phosphosulfur synergistic antibiotic bacteria residue biochar according to claim 1, characterized in that: The temperature of the hydrothermal reaction in S1 is 120-180 DEG C, and the hydrothermal reaction time is 1-6 h.

4. The phosphosulfur synergistic antibiotic bacterial residue biochar for use according to claim 1, characterized in that: In S2, the mass ratio of the acidolysis residue, alkali and water is 8-16:15-30:100-300.

5. The use of the phosphosulfur synergistic antibiotic bacterial residue biochar according to claim 1 or 4, characterized in that: The alkali is potassium hydroxide.

6. The use of the phosphosulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The drying temperature in S3 is 110 DEG C.

7. The use of the phosphosulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The protective gas flow is a nitrogen flow, the flow rate of the nitrogen flow is 60 mL·min -1 .

8. The use of the phosphosulfur synergistic antibiotic bacterial residue biochar according to claim 1, characterized in that: The rate of temperature rise in S4 is 5-15 °C·min -1 ; the drying temperature is 80 °C.

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