Co-hydrothermal resourceful treatment method for chlorine-containing ammonia-nitrogen wastewater and antibiotic mushroom dregs

Abstract

The invention belongs to the technical field of wastewater and solid waste treatment and resource utilization, and particularly relates to a co-hydrothermal resource treatment method for chlorine-containing ammonia nitrogen wastewater and antibiotic mushroom dregs. The method comprises the following treatment steps: uniformly stirring and mixing the antibiotic mushroom dregs and the chlorine-containing ammonia nitrogen wastewater, and adjusting the pH value to 0.2-0.6 by using an acid solution; feeding the mixed bacterial liquid obtained after pretreatment into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-200 DEG C, controlling the pressure to be 0.5-1.0 Mpa through a pressure stabilizing system, and after the reaction is completed, cooling, relieving the pressure and discharging; and carrying out solid-liquid separation on the mixed solution obtained by the hydrothermal reaction to obtain reduced and harmless micromolecule complex liquid and solid slag. According to the method disclosed by the invention, synchronous reduction, harmless and resourceful treatment of the high-ammonia-nitrogen wastewater and the antibiotic mushroom dregs in the antibiotic production process is synergistically realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater and solid waste treatment and resource utilization, and specifically relates to a method for the co-hydrothermal resource utilization treatment of chlorine-ammonia nitrogen-containing wastewater and antibiotic bacterial residue. Background Art

[0002] The production of antibiotics can generate large amounts of wastewater and bacterial residue (approximately 150-200 tons of wastewater and 8-10 tons of bacterial residue per ton of antibiotics). During the fermentation process of antibiotics, many bacteria or fungi metabolize nitrogen-containing organic substances (such as amino acids and urea) to produce ammonia or amino compounds, resulting in high ammonia nitrogen and low biodegradability. Antibiotic bacterial residue is a solid waste generated during the production of antibiotics. It is mainly composed of microbial cells, incompletely fermented raw materials, residual antibiotics, and other metabolic byproducts. In addition, it contains large amounts of organic matter, antibiotic residues, and heavy metals, posing a high environmental risk. If not properly treated, indiscriminate discharge may lead to soil and water pollution and the spread of antibiotic resistance, endangering human health and ecological safety.

[0003] The current treatment method for antibiotic fermentation broth mainly adopts solid-liquid separation treatment: first, the fermentation broth is frozen by freezing equipment, and then the solid and liquid are separated by centrifugation or filtration, and then the wastewater and bacterial residue generated by the production process are treated separately. For wastewater treatment, a variety of process combinations are mainly used: first, the vast majority of macromolecular compounds and organic matter are decomposed into low-toxic small molecules and short-chain organic matter by adding strong oxidants, and then biological treatment is carried out. However, the high toxicity and high ammonia nitrogen in the wastewater will inhibit the activity of microorganisms, resulting in a decrease in treatment efficiency, resulting in incomplete nitrification and denitrification processes, making it difficult to degrade ammonia nitrogen. At the same time, the mutual competition and survival of the fittest between autotrophic bacteria and heterotrophic microorganisms make it difficult to control the effective microbial dominant flora, and the effluent indicators fluctuate, seriously affecting the normal operation of the sewage treatment system.

[0004] Currently, the main treatment methods for antibiotic residue include incineration, pyrolysis composting, and anaerobic digestion. However, due to the high moisture content (>70%) and bound water content of residue, mechanical dehydration is ineffective, increasing energy consumption. Incineration can also lead to incomplete combustion due to the high moisture content, potentially generating harmful substances such as SOx, NOx, and dioxins, causing secondary pollution. Pyrolysis, which heats residue at high temperatures in the absence of oxygen, recovers combustible gas, bio-oil, or biochar. However, this is also limited by the residue's high moisture content, resulting in high energy consumption. Furthermore, the high nitrogen and sulfur content in the residue easily generates precursors of hydrocyanic acid and isocyanic acid. Composting and anaerobic digestion are primarily limited by difficulties in mycelium destruction, resulting in poor degradation of antibiotics, the toxicity of high antibiotic concentrations, and the resulting spread of bacterial resistance, which can lead to ecological safety issues.

[0005] Given these challenges, there is an urgent need to develop a green, environmentally friendly treatment technology that is efficient, energy-efficient, highly resource-efficient, and minimally polluting. This technology can effectively detoxify and reduce the amount of high-ammonia nitrogen wastewater and antibiotic residue produced during antibiotic production. This technology is crucial for the treatment and disposal of antibiotic production wastewater and residue, and for the health and sustainability of pharmaceutical companies.

[0006] Patent publication number CN 115672951 B discloses a highly efficient and harmless treatment method for antibiotic bacterial residues. The method employs a mixed solution of nitric acid and sulfuric acid to hydrothermally degrade the antibiotic residues, which can completely degrade the antibiotics and facilitate the dissolution of the residues to generate a water-soluble small-molecule organic complex solution. However, the introduction of sulfate radicals has an adverse effect on subsequent anaerobic digestion, and the method does not disclose the simultaneous treatment of high-ammonia nitrogen wastewater. Furthermore, for antibiotic bacterial residues with a high solid content or after dehydration (solid content 10%-30%), re-adjusting the moisture content for hydrothermal treatment not only wastes water resources but also fails to effectively utilize energy.

[0007] Patent publication number CN 119430349 A discloses a method for treating high-concentration ammonia nitrogen wastewater. This method utilizes acid in conjunction with sodium nitrite to regulate hydrothermal treatment of high-concentration ammonia nitrogen wastewater, promoting the removal of ammonia nitrogen and the generation of nitrogen gas. However, this prior art does not disclose the synergistic treatment of high-concentration ammonia nitrogen wastewater with antibiotic bacterial residue to achieve a synergistic effect in reducing the amount of antibiotic bacterial residue. Summary of the Invention

[0008] The highly toxic bacterial residue produced during the production of antibiotics has poor dehydration, difficulty in reducing the volume, and low biodegradability, which makes it impossible to effectively utilize it as a resource. In addition, the existing "solid-liquid separation + separate treatment" process route has problems such as high cost, high energy consumption and unstable treatment effect. The purpose of the present invention is to provide a method for the hydrothermal resource treatment of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue. The method of the present invention mixes antibiotic bacterial residue with chlorine-containing ammonia nitrogen wastewater for hydrothermal treatment. On the one hand, the solid content is adjusted by using ammonia nitrogen wastewater while supplementing the nitrogen source, and Cl in the ammonia nitrogen wastewater is reduced. - It can accelerate the dissolution of the cell walls of antibiotic residue mycelium and promote the release of organic matter into the liquid phase, synergizing high-temperature hydrolysis to prepare a small molecule carbon source. While reducing water waste and reusing nitrogen resources, it also improves the antibiotic removal rate and solid reduction rate. On the other hand, the synergistic reaction of organic nitrogen in the organic matter of antibiotic residue is utilized to effectively promote the conversion and removal of nitrate nitrogen in ammonia nitrogen wastewater, thereby improving the total nitrogen removal rate. The method of the present invention can effectively reduce the toxicity and ammonia nitrogen in mixed residue wastewater, while achieving antibiotic residue reduction and antibiotic removal.

[0009] The purpose of the present invention is achieved through the following technical solutions:

[0010] A method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue, comprising the following steps:

[0011] (1) The antibiotic residue and the chlorine-containing ammonia nitrogen wastewater are stirred and mixed evenly, and then the pH is adjusted to 0.2-0.6 with an acidic solution;

[0012] (2) feeding the mixed bacterial liquid obtained after the pretreatment in step (1) into a hydrothermal reactor, performing a hydrothermal reaction at 150-200° C., and controlling the pressure at 0.5-1.0 MPa by a pressure stabilizing system. After the reaction is completed, cooling and releasing the pressure to discharge the material;

[0013] (3) subjecting the mixed liquid obtained from the hydrothermal reaction in step (2) to solid-liquid separation to obtain a small molecule composite liquid and solid residue after being reduced and harmless.

[0014] Furthermore, the antibiotic bacterial residue in step (1) is daptomycin bacterial residue, having a moisture content of 65% to 90%, a COD concentration of 60,000 to 80,000 mg / L, an ammonia nitrogen concentration of 400 to 600 mg / L, a total phosphorus concentration of 300 to 500 mg / L, a total nitrogen concentration of 500 to 1,000 mg / L, and a daptomycin concentration of 30 to 1,000 mg / L.

[0015] Furthermore, the COD concentration of the chlorine-containing ammonia nitrogen wastewater in step (1) is 5000-8000 mg / L, Cl -The concentration is 25,000-35,000 mg / L, the ammonia nitrogen concentration is 10,000-15,000 mg / L, the total phosphorus concentration is 10-20 mg / L, and the total nitrogen concentration is 12,000-18,000 mg / L.

[0016] Furthermore, the volume ratio of the mixture of the antibiotic bacterial residue and the chlorine-containing ammonia nitrogen wastewater is 1:2 to 1:5.

[0017] Preferably, the solid content of the antibiotic bacterial residue and the chlorine-ammonia nitrogen-containing wastewater after mixing is 3% to 8% (wt.%).

[0018] Furthermore, the acidic solution in step (1) is a nitric acid solution with a mass concentration of 60% to 70%.

[0019] Furthermore, the pressure stabilizing system in step (2) is an adjustable air release pressure stabilizing valve, and the exhaust gas is collected and then passed into the alkali washing tower for treatment.

[0020] Furthermore, the hydrothermal reaction time in step (2) is 2 to 4 hours.

[0021] Furthermore, the cooling method in step (2) is a water cooling system.

[0022] Furthermore, after the reaction in step (2) is completed, the COD removal rate of the material is 51.61% to 55.75%, the ammonia nitrogen removal rate is 75.07% to 89.45%, the total nitrogen removal rate is 55.43% to 72.84%, the antibiotic removal rate is 96.59% to 100%, and the solid reduction rate is 87.78% to 93.35%.

[0023] Furthermore, the small molecule composite solution obtained in step (3) is further adjusted in pH value and element ratio to obtain a small molecule carbon source for anaerobic digestion or composting.

[0024] Preferably, the method for adjusting the pH value is to use sodium hydroxide or calcium hydroxide to adjust the pH value of the small molecule composite liquid to 6.8-7.5; the method for adjusting the element ratio is to use sodium acetate and potassium dihydrogen phosphate to adjust the ratio of carbon, nitrogen and phosphorus in the small molecule composite liquid to 100:5:1.

[0025] The process flow chart of the treatment method of the present invention is as follows Figure 1 shown.

[0026] The principle of the present invention is that the present invention realizes water-slag synchronous treatment by hydrothermal treatment of high-concentration ammonia nitrogen wastewater and antibiotic bacterial residue, adopts hydrothermal technology to create high-temperature and low-pressure hydrothermal conditions, and under high-temperature acidic environment, the Cl in the mixed solution is -Promote the rupture of flocculent structures and cell walls in bacterial residues, thereby releasing macromolecular organic substances such as lipids, polysaccharides, and proteins in the cells, followed by hydrolysis and redox reactions to generate amino acids, CO2, H2O, and NO x The ester and amide bonds of daptomycin also undergo hydrolysis and ring opening in a high temperature and acidic environment to generate small molecule carboxylic acid, CO2 and nitrogen-containing fragments. At the same time, NH4 + and reduced organic nitrogen react with nitric acid at high temperature to generate N2 and NO x and water to achieve the purpose of simultaneous treatment of high-solid content antibiotic slag and high-concentration high-ammonia nitrogen wastewater.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The method of the present invention solves the problems of the existing separate treatment of antibiotic bacterial residue and wastewater, high cost, high energy consumption and resource waste caused by difficulty in resource utilization, and simultaneously achieves the purpose of harmlessness, resource utilization and reduction of high-concentration ammonia nitrogen wastewater (ammonia nitrogen concentration is 10,000-15,000 mg / L) and high-solid content antibiotic bacterial residue (solid content is 10%-35%).

[0029] (2) The present invention uses a pressure-stabilized exhaust method to stabilize the pressure in the reactor at 0.5-1.0 MPa, which can promote the forward reaction and reduce the safety risks caused by excessive pressure. The exothermic reaction in the reactor can maintain the temperature required for the reaction process, which only requires appropriate heating. At the same time, the lower pressure requirement also greatly reduces equipment costs, enabling large-scale industrial production.

[0030] (3) The harmless and reduced-volume small molecule composite liquid obtained by the present invention can be used for anaerobic digestion or composting after adjusting the pH to 6.8-7.5 and adjusting the carbon, nitrogen and phosphorus ratio to close to 100:5:1, which has broad application prospects and important environmental significance. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The present invention is a process flow chart of the method for co-hydrothermal resource treatment of ammonia nitrogen wastewater and antibiotic residue.

[0032] Figure 2 This is a picture of the actual morphology of the slurry-like antibiotic residue to be treated in the embodiment.

[0033] Figure 3 This is a picture of the actual morphology of the mixed solution of high-concentration ammonia nitrogen wastewater and antibiotic bacterial residue in the example.

[0034] Figure 4 This is a physical morphology diagram of the harmless and reduced solid slag and small molecule composite liquid in the examples. DETAILED DESCRIPTION

[0035] The present invention will be described in further detail below with reference to the embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0036] Example 1

[0037] A method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue, comprising the following steps:

[0038] (1) The antibiotic residue (daptomycin residue from the antibiotic pharmaceutical factory, the physical form is as shown in the attached Figure 2 As shown, COD: 72500mg / L, ammonia nitrogen: 400mg / L, total nitrogen: 856mg / L, total phosphorus: 360mg / L, daptomycin concentration 256mg / L, solid content: 21.83%) and high concentration ammonium chloride wastewater (COD: 5578mg / L, Cl - : 31579mg / L, ammonia nitrogen: 13100mg / L, total nitrogen: 15060mg / L, total phosphorus: 16mg / L) in a volume ratio of 1:2 and stirred to form a mixed bacterial solution (the actual form is as shown in the attached Figure 3 The mixture was purified by centrifugation and then adjusted to pH 0.6 using 68 wt % nitric acid.

[0039] (2) The pretreated mixed bacterial liquid obtained in step (1) is fed into a hydrothermal reactor equipped with an adjustable air release and pressure regulating valve, heated to 160°C in an oil bath, and maintained at a pressure of 0.6 MPa for 2 hours by means of pressure regulation and exhaust by the air release and pressure regulating valve. After the reaction is completed, the water cooling system is turned on to reduce the temperature in the reactor to 80°C, and the air release and pressure regulating valve is opened to release the gas. The gas is collected through the exhaust pipe and then passed into the alkaline washing tower for treatment. The discharge is opened when the pressure in the reactor drops to zero.

[0040] (3) The mixed liquid after the treatment in step (2) is discharged into the discharge tank, and after static solid-liquid separation, the small molecule composite liquid and solid residue after reduction and harmlessness are obtained (the actual form is as shown in the attached Figure 4 A small amount of solid residue is collected and transported for disposal. The ratio of carbon, nitrogen, and phosphorus in the liquid phase of the small molecule organic composite liquid is approximately 121:44:1. The pH of the liquid phase is adjusted to 6.8 using sodium hydroxide, and the ratio of carbon, nitrogen, and phosphorus is adjusted to approximately 100:5:1 using sodium acetate and potassium dihydrogen phosphate, thereby obtaining a small molecule carbon source for anaerobic digestion or composting.

[0041] After the mixed hydrothermal treatment in step (2) of this embodiment, the COD in the mixed solution was reduced to 12151 mg / L, the ammonia nitrogen was reduced to 2171 mg / L, the total nitrogen was reduced to 4433 mg / L, and the daptomycin was reduced to 3 mg / L, and the corresponding removal rates were 55.75%, 75.07%, 55.43% and 96.59%, respectively (the determination methods of COD, ammonia nitrogen, total nitrogen and daptomycin were rapid digestion spectrophotometry (HJT399-2007), Nessler's reagent spectrophotometry (HJ 535-2009), alkaline potassium persulfate digestion ultraviolet spectrophotometry (HJ 636-2012) and high performance liquid chromatography (USP) 43-NF38); total phosphorus content was 109 mg / L, and solid reduction rate was 87.78% (solid reduction rate was calculated by differential weight method: 50 mL of mixed post-treatment sample was taken and filtered through a 0.22 μm organic filter membrane to obtain a filter residue. The filter residue was vacuum dried for 8 hours, and the mass of the dried sludge was weighed using a balance. The conversion unit is g / L. The sample before treatment is recorded as m1, and the sample after treatment is recorded as m2. ).

[0042] Example 2

[0043] A method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue, comprising the following steps:

[0044] (1) Antibiotic bacterial residue (same as in Example 1) and high-concentration ammonium chloride wastewater (same as in Example 1) were stirred and mixed at a volume ratio of 1:3 to form a mixed bacterial solution (COD: 21654 mg / L, ammonia nitrogen: 9948 mg / L, total nitrogen: 12974 mg / L, total phosphorus: 98 mg / L, daptomycin: 71 mg / L, solid content: 5.42%). The pH of the mixed bacterial solution was then adjusted to 0.3 using 68 wt% nitric acid.

[0045] (2) The pretreated mixed bacterial liquid obtained in step (1) is fed into a hydrothermal reactor equipped with an adjustable air release and pressure regulating valve, heated to 200°C in an oil bath, and maintained at a pressure of 1.0 MPa for 4 hours by means of pressure regulation and exhaust by the air release and pressure regulating valve. After the reaction is completed, the water cooling system is turned on to reduce the temperature in the reactor to 80°C, and the air release and pressure regulating valve is opened to release the gas. The gas is collected through the exhaust pipe and then passed into the alkaline washing tower for treatment. The discharge is opened when the pressure in the reactor drops to zero.

[0046] (3) The mixed liquid after the treatment in step (2) is discharged into a discharge tank, and after static solid-liquid separation, a small molecule composite liquid and solid residue are obtained after being reduced and harmless. A small amount of solid residue is collected and transported for disposal. The carbon, nitrogen, and phosphorus ratio of the liquid phase small molecule organic composite liquid is about 99:43:0.8. The pH of the liquid phase is adjusted to 7.2 using sodium hydroxide, and the carbon, nitrogen, and phosphorus ratio is adjusted to about 100:5:1 using sodium acetate and potassium dihydrogen phosphate, thereby obtaining a small molecule carbon source for anaerobic digestion or composting.

[0047] After the mixed hydrothermal treatment in step (2) of this embodiment, the COD in the mixed liquid was reduced to 9942 mg / L, the ammonia nitrogen was reduced to 1838 mg / L, the total nitrogen was reduced to 4285 mg / L, and the daptomycin was reduced to below the detection line. The corresponding removal rates were 54.09%, 81.52%, 66.97% and 100%, respectively; the total phosphorus content was 84 mg / L, and the solid reduction rate was 91.64%.

[0048] Example 3

[0049] A method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue, comprising the following steps:

[0050] (1) Antibiotic bacterial residue (same as in Example 1) and high-concentration ammonium chloride wastewater (same as in Example 1) were stirred and mixed at a volume ratio of 1:5 to form a mixed bacterial solution (COD: 17612 mg / L, ammonia nitrogen: 11654 mg / L, total nitrogen: 13183 mg / L, total phosphorus: 75 mg / L, daptomycin concentration: 48 mg / L, solid content: 3.46%). The pH of the mixed bacterial solution was then adjusted to 0.4 using 68 wt% nitric acid.

[0051] (2) The pretreated mixed bacterial liquid obtained in step (1) is fed into a hydrothermal reactor equipped with an adjustable air release and pressure regulating valve, heated to 180°C in an oil bath, and maintained at a pressure of 0.8 MPa for 3 hours by means of pressure regulation and exhaust through the air release and pressure regulating valve. After the reaction is completed, the water cooling system is turned on to reduce the temperature in the reactor to 80°C, and the air release and pressure regulating valve is opened to release the gas. The gas is collected through the exhaust pipe and then passed into the alkaline washing tower for treatment. The discharge is opened when the pressure in the reactor drops to zero.

[0052] (3) The mixed liquid after the treatment in step (2) is discharged into a discharge tank, and after static solid-liquid separation, a small molecule composite liquid and solid residue are obtained after being reduced and harmless. A small amount of solid residue is collected and transported for disposal. The carbon, nitrogen, and phosphorus ratio of the liquid phase small molecule organic composite liquid is about 85:12:0.7. The pH of the liquid phase is adjusted to 7.4 using sodium hydroxide, and the carbon, nitrogen, and phosphorus ratio is adjusted to about 100:5:1 using sodium acetate and potassium dihydrogen phosphate, thereby obtaining a small molecule carbon source for anaerobic digestion or composting.

[0053] After the mixed hydrothermal treatment in step (2) of this embodiment, the COD in the mixed solution was reduced to 8522 mg / L, the ammonia nitrogen was reduced to 1229 mg / L, the total nitrogen was reduced to 3581 mg / L, and the daptomycin was reduced to the detection line. The corresponding removal rates were 51.61%, 89.45%, 72.84% and 100%, respectively; the total phosphorus content was 71 mg / L, and the solid reduction rate was 93.35%.

[0054] Comparative Example 1

[0055] Compared with Example 1, this comparative example only treats high-concentration ammonium chloride wastewater alone, and the other conditions are the same.

[0056] After treatment in this comparative example, the COD in the solution dropped to 3153 mg / L, ammonia nitrogen dropped to 6491 mg / L, total nitrogen dropped to 12782 mg / L, and total phosphorus was 14 mg / L, with corresponding removal rates of 43.47%, 50.45%, 15.13% and 12.5%, respectively.

[0057] Although this comparative example only treated high-ammonia nitrogen wastewater, it still had a certain removal effect on COD and ammonia nitrogen, but the removal rate of total nitrogen was only 15.12%. The reaction process lacked the synergistic reaction of organic nitrogen in the organic matter of antibiotic bacterial residue, resulting in a portion of nitrogen still existing in the wastewater in the form of nitrate nitrogen and unable to be directly converted into N2 and NO. x removed, so the total nitrogen content remains high.

[0058] Comparative Example 2

[0059] Compared with Example 1, this comparative example only replaced the high-concentration ammonium chloride wastewater with ordinary tap water and mixed it with the antibiotic bacterial residue in a volume ratio of 2:1 (the mixed solution was measured to have COD: 24651 mg / L, ammonia nitrogen: 142 mg / L, total nitrogen: 268 mg / L, total phosphorus: 126 mg / L, daptomycin: 82 mg / L, and solid content: 7.24%), and the other conditions were the same.

[0060] After treatment in this comparative example, the COD in the mixed liquor was reduced to 15947 mg / L, the ammonia nitrogen was reduced to 85 mg / L, the total nitrogen was reduced to 134 mg / L, and the daptomycin was reduced to 8 mg / L, with corresponding removal rates of 35.31%, 40.14%, 50.00% and 90.24%, respectively; the total phosphorus content was 122 mg / L, and the solid reduction rate was 74.79%.

[0061] In this comparative example, when treating antibiotic bacterial residue alone, the removal effect of various indicators was generally reduced, especially the removal rate of solid content was only 74.79%, and there was still a high content of daptomycin residue. The reason may be that the Cl in the high ammonium chloride wastewater is lacking. - The ions destroy the biofilm and cell wall in the antibiotic bacterial residue, and the organic matter cannot be fully degraded. The daptomycin contained in it is not completely released into the liquid phase for full oxidation and decomposition, resulting in low removal efficiency of solid content and daptomycin.

[0062] The above embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for treating chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue by hydrothermal resource recovery, characterized in that: The following processing steps are included: (1) The antibiotic residue and the chlorine-containing ammonia nitrogen wastewater are stirred and mixed uniformly, and then the pH is adjusted to 0.2-0.6 with an acidic solution; (2) feeding the mixed bacterial liquid obtained after the pretreatment in step (1) into a hydrothermal reactor, performing a hydrothermal reaction at 150-200° C., and controlling the pressure at 0.5-1.0 MPa by a pressure stabilizing system. After the reaction is completed, cooling and releasing the pressure to discharge the material; (3) subjecting the mixed liquid obtained from the hydrothermal reaction in step (2) to solid-liquid separation to obtain a small molecule composite liquid and solid residue after being reduced and harmless.

2. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: The antibiotic bacterial residue in step (1) is daptomycin bacterial residue, which has a moisture content of 65% to 90%, a COD concentration of 60,000 to 80,000 mg / L, an ammonia nitrogen concentration of 400 to 600 mg / L, a total phosphorus concentration of 300 to 500 mg / L, a total nitrogen concentration of 500 to 1,000 mg / L, and a daptomycin concentration of 30 to 1,000 mg / L.

3. The method for treating chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue by hydrothermal resource recovery according to claim 1, characterized in that: The COD concentration of the chlorine-containing ammonia nitrogen wastewater in step (1) is 5000-8000 mg / L, Cl - The concentration is 25,000-35,000 mg / L, the ammonia nitrogen concentration is 10,000-15,000 mg / L, the total phosphorus concentration is 10-20 mg / L, and the total nitrogen concentration is 12,000-18,000 mg / L.

4. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: The volume ratio of the mixture of the antibiotic bacterial residue and the chlorine-containing ammonia nitrogen wastewater is 1:2 to 1:

5.

5. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 4, characterized in that: The solid content of the antibiotic bacterial residue and the chlorine-containing ammonia nitrogen wastewater after mixing is 3% to 8%.

6. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: The acidic solution in step (1) is a nitric acid solution with a mass concentration of 60% to 70%.

7. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: The pressure stabilizing system in step (2) is an adjustable air release pressure stabilizing valve, and the exhaust gas is collected and then passed into an alkali washing tower for treatment; the time of the hydrothermal reaction is 2 to 4 hours; and the cooling method is a water cooling system.

8. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: After the reaction in step (2) is completed, the COD removal rate of the material is 51.61% to 55.75%, the ammonia nitrogen removal rate is 75.07% to 89.45%, the total nitrogen removal rate is 55.43% to 72.84%, the antibiotic removal rate is 96.59% to 100%, and the solid reduction rate is 87.78% to 93.35%.

9. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 1, characterized in that: The small molecule composite solution obtained in step (3) is further adjusted in pH value and element ratio to obtain a small molecule carbon source for anaerobic digestion or composting.

10. The method for co-hydrothermal resource recovery of chlorine-containing ammonia nitrogen wastewater and antibiotic bacterial residue according to claim 9, characterized in that: The method for adjusting the pH value is to use sodium hydroxide or calcium hydroxide to adjust the pH value of the small molecule composite liquid to 6.8-7.5; the method for adjusting the element ratio is to use sodium acetate and potassium dihydrogen phosphate to adjust the ratio of carbon, nitrogen and phosphorus in the small molecule composite liquid to 100:5:1.

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