Process method for treating pollutants in tetracycline hydrochloride wastewater

Abstract

The invention relates to the technical field of biological treatment, in particular to a process method for treating pollutants in tetracycline hydrochloride wastewater. Comprising the following steps: S1, removing suspended matters and part of tetracycline hydrochloride in the wastewater by a physical adsorption method and a membrane filtration technology to reduce the concentration of pollutants; and S2, carrying out biodegradation by utilizing specific microorganisms and the constructed wetland, and converting tetracycline hydrochloride into low-toxicity or non-toxic substances by utilizing the metabolism of the microorganisms. According to the invention, pretreatment is carried out through the adsorbent and the membrane module according to the characteristics of the wastewater, the concentration of pollutants is reduced, the pollutants are converted synergistically by virtue of specific microorganisms and the constructed wetland, advanced oxidation deep degradation is matched, and finally, the tetracycline hydrochloride wastewater is ensured to reach the standard through secondary treatment and water quality monitoring and adjustment, so that efficient degradation and low-consumption stable standard reaching of the tetracycline hydrochloride wastewater are realized comprehensively; and meanwhile, the risk of secondary pollution is reduced, and the method has both environmental friendliness and economic feasibility.

Description

Technical Field

[0001] The invention relates to the technical field of biological treatment, in particular to a process for treating pollutants in tetracycline hydrochloride wastewater. Background Art

[0002] The composition of wastewater containing antibiotics is complex and diverse. Not only are there many types of pollutants with high concentrations, but they are also difficult to remove efficiently. Once antibiotic wastewater enters natural water bodies, it will cause damage to the structure of microbial communities, adversely affect the growth and development of plants and animals, and threaten the stability and integrity of the ecosystem. What is more worrying is that the long-term use of antibiotics to inhibit the development of pathogens has led to the proliferation of drug-resistant bacteria, while weakening the efficacy of the antibiotics themselves. This situation not only poses a serious threat to the ecological environment, but also poses a huge risk to human health. Faced with this severe challenge, it is particularly urgent to develop an efficient, economical and environmentally friendly process for treating antibiotic wastewater poisoning. Taking tetracycline hydrochloride as an example, as an antibiotic drug with typical broad-spectrum antibacterial activity, it is widely used in medical, animal husbandry and aquaculture. Tetracycline hydrochloride has a strong lipophilic characteristic, which enables it to easily penetrate biological cell membranes, enter the body or be discharged into the environment through the excretion system. Therefore, if wastewater containing high concentrations of tetracycline hydrochloride is directly discharged into natural water bodies without treatment, it will cause serious damage to the environmental ecology. Specifically, tetracycline hydrochloride is difficult to degrade effectively in the natural environment. It can be converted into dihydrotetracycline derivatives through photochemical decomposition. This conversion process requires specific conditions and catalyst support. However, without effective catalytic assistance, this degradation pathway is very slow or even difficult to achieve. In addition, tetracycline hydrochloride forms large suspended matter in water or adsorbs on organic carbon nanoparticles in water, further exacerbating the complexity of pollution. In response to the above problems, researchers have proposed a variety of technical routes, including traditional biodegradation technology, physical adsorption purification technology and chemical conversion methods.

[0003] In the existing technology, the traditional technology has low treatment efficiency and cannot meet the treatment needs of high-concentration tetracycline hydrochloride wastewater. The treatment cost is high and it is difficult to promote in large-scale applications.

[0004] Based on this, the present invention provides a process for treating pollutants in tetracycline hydrochloride wastewater to solve the above-mentioned technical problems. Summary of the invention

[0005] The object of the present invention is to provide a process method for treating pollutants in tetracycline hydrochloride wastewater. The present invention selects adsorbents and membrane components for pretreatment according to wastewater characteristics to reduce pollutant concentrations, then uses specific microorganisms and artificial wetlands to synergistically transform pollutants, cooperates with advanced oxidation for deep degradation, and finally ensures compliance with standards through secondary treatment and water quality monitoring and adjustment. The present invention achieves efficient degradation of tetracycline hydrochloride wastewater, stable compliance with standards with low consumption, reduces treatment costs, and reduces the risk of secondary pollution, and has both environmental friendliness and economic feasibility.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a process for treating pollutants in tetracycline hydrochloride wastewater, comprising the following steps:

[0008] S1: Remove suspended solids and part of tetracycline hydrochloride in wastewater through physical adsorption and membrane filtration technology to reduce pollutant concentration;

[0009] S2: Biodegradation using specific microorganisms and artificial wetlands, using the metabolism of microorganisms to convert tetracycline hydrochloride into low-toxic or non-toxic substances;

[0010] S3: Use advanced oxidation methods to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives, and select appropriate methods and determine corresponding operating parameters based on the wastewater quality characteristics and treatment requirements;

[0011] S4: Ensure that the effluent quality meets the standard through secondary physical adsorption or membrane filtration, and conduct water quality monitoring and adjustment.

[0012] In S1, the specific steps of removing suspended solids and part of tetracycline hydrochloride in the wastewater by physical adsorption and membrane filtration technology to reduce the concentration of pollutants are as follows:

[0013] S1.1: First, select the adsorbent according to the characteristics of the wastewater and perform pretreatment. At the same time, select the appropriate membrane module according to the wastewater treatment requirements, install the membrane module and ensure that the connection is well sealed;

[0014] S1.2: Add the pretreated adsorbent to the wastewater in proportion, stir and mix for 30-120 minutes to allow the adsorbent to fully contact the wastewater, and then let it stand for 1-2 hours;

[0015] S1.3: Separate the adsorbent from the preliminarily treated wastewater by filtration or centrifugation, and use the wastewater as the membrane filtration feed water for later use;

[0016] S1.4: Rinse the membrane components with clean water to remove impurities, adjust the water inlet pressure and flow rate to ensure stable operation of the membrane filtration system, pump the pretreated wastewater into the system, control the parameters for filtration, and regularly monitor the membrane flux and retention rate during operation;

[0017] S1.5: When the membrane flux decreases, backwashing should be performed first. If the effect is not good, chemical cleaning should be performed with a suitable chemical cleaning agent. If the membrane performance cannot be restored after multiple cleanings, the membrane assembly should be replaced in time.

[0018] The wastewater characteristics in S1.1 include pH and pollutant concentration; the adsorbent includes activated carbon, hydrogel, ceramic, resin and mesoporous molecules; the membrane assembly includes microfiltration membrane and ultrafiltration membrane.

[0019] The pretreatment in S1.1 includes washing, activating, screening and calcining the adsorbent.

[0020] The specific microorganisms in S2 include Sphingobacterium mizutaii strains; the artificial wetland includes a matrix, aquatic plants, and a microbial community.

[0021] The specific steps of biodegrading S2 using specific microorganisms and artificial wetlands and converting tetracycline hydrochloride into low-toxic or non-toxic substances using the metabolism of microorganisms are as follows:

[0022] S2.1: First, screen the highly efficient degradation bacteria Sphingobacterium mizutaii from the soil or water contaminated with tetracycline hydrochloride, and expand the culture in the laboratory until the activity is stable;

[0023] S2.2: Inoculate the cultured microorganisms into the bioreactor and control the reaction conditions;

[0024] S2.3: The pretreated wastewater is pumped into the bioreactor, where microorganisms decompose tetracycline hydrochloride into low-toxic intermediates through enzymatic reactions;

[0025] S2.4: Construct an artificial wetland system, lay gravel and sand substrates on the bottom, plant pollution-tolerant wetland plants including reeds and cattails, and form a plant-microorganism-substrate synergistic degradation system;

[0026] S2.5: Introduce the effluent from the bioreactor into the artificial wetland to promote the attachment of microorganisms through the secretion of organic matter by plant roots, and further degrade the residual tetracycline hydrochloride and its metabolites;

[0027] S2.6: Finally, regularly test the residual concentration and toxicity of tetracycline hydrochloride in the water, and adjust the hydraulic retention time or supplement microbial agents based on the results.

[0028] The S3 intermediate and advanced oxidation methods include Fenton oxidation, ozone oxidation, and photocatalytic oxidation; the operating parameters include optimizing the dosage of the oxidant, the reaction time, and the pH value.

[0029] The specific steps of using advanced oxidation process to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives in S3, and selecting a suitable method and determining corresponding operating parameters according to the wastewater quality characteristics and treatment requirements are as follows:

[0030] S3.1: First, detect the concentration of tetracycline hydrochloride, COD, pH, salinity and types of coexisting pollutants in the wastewater, and select the efficient degradation method of Fenton oxidation, ozone oxidation or photocatalytic oxidation based on the results;

[0031] S3.2: Set key parameters based on the selected method;

[0032] S3.3: Start the reaction equipment and monitor the ORP and free radical concentration in real time, and dynamically adjust the oxidant dosage or reaction time to ensure thorough degradation;

[0033] S3.4: Treatment of by-products including precipitation of iron sludge by Fenton method, adsorption of tail gas by ozone method, recovery of catalyst and avoidance of secondary pollution;

[0034] S3.5: Finally, HPLC-MS or GC-MS is used to detect the degradation intermediates of tetracycline hydrochloride, including tetracycline ketone and small molecule carboxylic acids, to verify that COD, TOC and toxicity indicators meet the standards and ensure the safety of effluent.

[0035] The specific steps of ensuring that the effluent water quality meets the standard through secondary physical adsorption or membrane filtration and performing water quality monitoring and adjustment in S4 are as follows:

[0036] S4.1: Based on the water quality after primary treatment and the requirements for reaching the standard, determine activated carbon adsorption or nanofiltration membrane or reverse osmosis membrane filtration as the deep treatment method;

[0037] S4.2: The wastewater treated in the previous step is introduced into the secondary treatment stage, and adsorbent is added for stirring or the wastewater is processed through the membrane module by a pressure pump according to the selected method;

[0038] S4.3: With the help of water quality monitoring system, various indicators of effluent after secondary treatment, including COD and tetracycline hydrochloride concentration, are tested in real time;

[0039] S4.4: Based on the water quality monitoring results, if the indicators do not meet the standards, adjust the parameters of the secondary treatment process to ensure that the effluent quality is stable and meets the standards.

[0040] The adjustment of the parameters of the secondary treatment process includes increasing or decreasing the amount of adsorbent, and changing the membrane filtration time or pressure.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The present invention selects adsorbents and membrane components for pretreatment based on wastewater characteristics to reduce pollutant concentrations, then uses specific microorganisms and artificial wetlands to synergistically transform pollutants, cooperates with advanced oxidation to deeply degrade them, and finally performs secondary treatment and water quality monitoring and adjustment to ensure compliance with standards. This fully realizes efficient degradation of tetracycline hydrochloride wastewater, low-consumption and stable compliance with standards, reduces treatment costs, and reduces the risk of secondary pollution, thereby being both environmentally friendly and economically feasible. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The present invention is a flow chart of the overall process of treating pollutants in tetracycline hydrochloride wastewater. DETAILED DESCRIPTION

[0044] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0045] Example:

[0046] like Figure 1 As shown, this embodiment provides a process for treating pollutants in tetracycline hydrochloride wastewater, comprising the following steps:

[0047] S1: Remove suspended solids and part of tetracycline hydrochloride in wastewater through physical adsorption and membrane filtration technology to reduce pollutant concentration;

[0048] S2: Biodegradation using specific microorganisms and artificial wetlands, using the metabolism of microorganisms to convert tetracycline hydrochloride into low-toxic or non-toxic substances;

[0049] S3: Use advanced oxidation methods to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives, and select appropriate methods and determine corresponding operating parameters based on the wastewater quality characteristics and treatment requirements;

[0050] S4: Ensure that the effluent quality meets the standard through secondary physical adsorption or membrane filtration, and conduct water quality monitoring and adjustment.

[0051] In S1, suspended solids and part of tetracycline hydrochloride in wastewater are removed by physical adsorption and membrane filtration technology. The specific steps to reduce the concentration of pollutants are as follows:

[0052] S1.1: First, select the adsorbent according to the characteristics of the wastewater and perform pretreatment. At the same time, select the appropriate membrane module according to the wastewater treatment requirements, install the membrane module and ensure that the connection is well sealed;

[0053] S1.2: Add the pretreated adsorbent to the wastewater in proportion, stir and mix for 30-120 minutes to allow the adsorbent to fully contact the wastewater, and then let it stand for 1-2 hours;

[0054] S1.3: Separate the adsorbent from the preliminarily treated wastewater by filtration or centrifugation, and use the wastewater as the membrane filtration feed water for later use;

[0055] S1.4: Rinse the membrane components with clean water to remove impurities, adjust the water inlet pressure and flow rate to ensure stable operation of the membrane filtration system, pump the pretreated wastewater into the system, control the parameters for filtration, and regularly monitor the membrane flux and retention rate during operation;

[0056] S1.5: When the membrane flux decreases, backwashing should be performed first. If the effect is not good, chemical cleaning should be performed with a suitable chemical cleaning agent. If the membrane performance cannot be restored after multiple cleanings, the membrane assembly should be replaced in time.

[0057] The wastewater characteristics in S1.1 include pH and pollutant concentration; the adsorbent includes activated carbon, hydrogel, ceramic, resin and mesoporous molecules; the membrane assembly includes microfiltration membrane and ultrafiltration membrane.

[0058] The specific microorganisms in S2 include Sphingobacterium mizutaii strains; the artificial wetland includes a matrix, aquatic plants, and a microbial community.

[0059] S2 uses specific microorganisms and artificial wetlands for biodegradation. The specific steps of using the metabolism of microorganisms to convert tetracycline hydrochloride into low-toxic or non-toxic substances are as follows:

[0060] S2.1: First, screen the highly efficient degradation bacteria Sphingobacterium mizutaii from the soil or water contaminated with tetracycline hydrochloride, and expand the culture in the laboratory until the activity is stable;

[0061] S2.2: Inoculate the cultured microorganisms into the bioreactor and control the reaction conditions;

[0062] S2.3: The pretreated wastewater is pumped into the bioreactor, where microorganisms decompose tetracycline hydrochloride into low-toxic intermediates through enzymatic reactions;

[0063] S2.4: Construct an artificial wetland system, lay gravel and sand substrates on the bottom, plant pollution-tolerant wetland plants including reeds and cattails, and form a plant-microorganism-substrate synergistic degradation system;

[0064] S2.5: Introduce the effluent from the bioreactor into the artificial wetland to promote the attachment of microorganisms through the secretion of organic matter by plant roots, and further degrade the residual tetracycline hydrochloride and its metabolites;

[0065] S2.6: Finally, regularly test the residual concentration and toxicity of tetracycline hydrochloride in the water, and adjust the hydraulic retention time or supplement microbial agents based on the results.

[0066] S3 medium and high-level oxidation methods include Fenton oxidation, ozone oxidation, and photocatalytic oxidation; operating parameters include optimizing the dosage of oxidant, reaction time, and pH value.

[0067] In S3, the advanced oxidation process is used to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives, and the specific steps of selecting a suitable method and determining the corresponding operating parameters according to the wastewater quality characteristics and treatment requirements are as follows:

[0068] S3.1: First, detect the concentration of tetracycline hydrochloride, COD, pH, salinity and types of coexisting pollutants in the wastewater, and select the efficient degradation method of Fenton oxidation, ozone oxidation or photocatalytic oxidation based on the results;

[0069] S3.2: Set key parameters based on the selected method;

[0070] S3.3: Start the reaction equipment and monitor the ORP and free radical concentration in real time, and dynamically adjust the oxidant dosage or reaction time to ensure thorough degradation;

[0071] S3.4: Treatment of by-products including precipitation of iron sludge by Fenton method, adsorption of tail gas by ozone method, recovery of catalyst and avoidance of secondary pollution;

[0072] S3.5: Finally, HPLC-MS or GC-MS is used to detect the degradation intermediates of tetracycline hydrochloride, including tetracycline ketone and small molecule carboxylic acids, to verify that COD, TOC and toxicity indicators meet the standards and ensure the safety of effluent.

[0073] In S4, the specific steps of ensuring that the effluent quality meets the standards through secondary physical adsorption or membrane filtration and conducting water quality monitoring and adjustment are as follows:

[0074] S4.1: Based on the water quality after primary treatment and the requirements for reaching the standard, determine activated carbon adsorption or nanofiltration membrane or reverse osmosis membrane filtration as the deep treatment method;

[0075] S4.2: The wastewater treated in the previous step is introduced into the secondary treatment stage, and adsorbent is added for stirring or the wastewater is processed through the membrane module by a pressure pump according to the selected method;

[0076] S4.3: With the help of water quality monitoring system, various indicators of effluent after secondary treatment, including COD and tetracycline hydrochloride concentration, are tested in real time;

[0077] S4.4: Based on the water quality monitoring results, if the indicators do not meet the standards, adjust the parameters of the secondary treatment process to ensure that the effluent quality is stable and meets the standards.

[0078] Adjusting the parameters of the secondary treatment process includes increasing or decreasing the amount of adsorbent, changing the membrane filtration time or pressure.

[0079] like Figure 1As shown, this embodiment provides a process for treating pollutants in tetracycline hydrochloride wastewater, and the specific method is as follows: First, S1: remove suspended matter and part of tetracycline hydrochloride in wastewater by physical adsorption and membrane filtration technology to reduce the concentration of pollutants; the specific steps are as follows: S1.1: first select adsorbent according to the characteristics of wastewater and perform pretreatment, and at the same time select suitable membrane components according to the requirements of wastewater treatment, install membrane components and ensure good connection and sealing; wastewater characteristics include pH and pollutant concentration. Membrane components include microfiltration membranes and ultrafiltration membranes; the pore size of microfiltration membranes is generally between 0.1-10 microns, and is mainly used to remove larger suspended particles in wastewater; the pore size of ultrafiltration membranes is between 0.001-0.1 microns, which can effectively intercept colloids, macromolecular organic matter and some viruses; pretreatment includes cleaning, activating, screening and calcining the adsorbent. S1.2: Add the pretreated adsorbent to the wastewater in proportion, 5-10 grams of adsorbent per liter of wastewater, stir and mix for 30-120 minutes to make the adsorbent fully contact with the wastewater, and then let it stand for 1-2 hours; the adsorbent includes activated carbon, hydrogel, ceramic, resin and mesoporous molecules; S1.3: Use filtration or centrifugation to separate the adsorbent from the preliminarily treated wastewater, and use the wastewater as membrane filtration water for standby; S1.4: Rinse the membrane assembly with clean water to remove impurities, adjust the water inlet pressure and flow rate to make the membrane filtration system run stably, pump the pretreated wastewater into the system, control the parameters for filtration, and regularly monitor the membrane flux and retention rate during operation; the operating pressure of the microfiltration membrane is generally 0.05-0.2MPa, and the operating pressure of the ultrafiltration membrane is 0.1-0.5MPa; S1.5: When the membrane flux decreases, backwash first. If the effect is not good, use a suitable chemical cleaning agent for chemical cleaning. If the membrane performance cannot be restored after multiple cleanings, replace the membrane assembly in time. S2: Biodegradation is carried out using specific microorganisms and artificial wetlands, and tetracycline hydrochloride is converted into low-toxic or non-toxic substances using the metabolism of microorganisms; the specific microorganisms include Sphingobacterium mizutaii strains; the artificial wetland includes a matrix, aquatic plants, and a microbial community.The specific steps are as follows: S2.1: First, select the efficient degradation bacteria Sphingobacterium mizutaii strain from the soil or water body contaminated by tetracycline hydrochloride, and expand the culture in the laboratory until the activity is stable; S2.2: Inoculate the cultured microorganisms into the bioreactor and control the reaction conditions; S2.3: Pump the pretreated wastewater into the bioreactor, and the microorganisms decompose the tetracycline hydrochloride into low-toxic intermediates through enzymatic reactions; S2.4: Construct an artificial wetland system, lay gravel and sand matrix on the bottom, and plant pollution-resistant wetland plants including reeds and cattails to form a plant-microorganism-matrix synergistic degradation system; S2.5: Introduce the effluent from the bioreactor into the artificial wetland, promote the attachment of microorganisms through the secretion of organic matter by the plant roots, and further degrade the residual tetracycline hydrochloride and its metabolites; S2.6: Finally, regularly detect the residual concentration and toxicity of tetracycline hydrochloride in the effluent, and adjust the hydraulic retention time or supplement microbial agents according to the results. S3: Use advanced oxidation methods to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives, and select appropriate methods and determine corresponding operating parameters based on the wastewater quality characteristics and treatment requirements; advanced oxidation methods include Fenton oxidation, ozone oxidation, and photocatalytic oxidation; operating parameters include optimizing the dosage of oxidant, reaction time, and pH value. The specific steps are as follows: S3.1: First, detect the concentration of tetracycline hydrochloride, COD, pH, salinity and types of coexisting pollutants in the wastewater, and select the efficient degradation method of Fenton oxidation, ozone oxidation or photocatalytic oxidation based on the results; Fenton oxidation: Under acidic conditions, Fe2+ and H2O2 are added to generate strongly oxidizing hydroxyl radicals (·OH), which can completely degrade tetracycline hydrochloride and its derivatives. After the reaction, the pH value needs to be adjusted to neutral to precipitate Fe3+; Ozone oxidation: Using the strong oxidizing property of ozone (O3), tetracycline hydrochloride molecules are directly oxidized and decomposed to generate small molecular organic matter or mineralize them into CO2 and H2O; Photocatalytic oxidation: Using photocatalysts such as TiO2, strong oxidizing free radicals are generated under ultraviolet light to degrade difficult-to-treat organic matter.S3.2: Set key parameters according to the selected method; Fenton oxidation method: According to the water quality and treatment requirements of the wastewater, determine the dosage of Fe2+ and H2O2 (generally the molar ratio of Fe2+ to H2O2 is 1:5-1:10), the reaction time is 30-120 minutes and the pH value is controlled at 3-5; Photocatalytic oxidation method: Select suitable photocatalysts and light sources including ultraviolet lamps and visible light LED lamps, determine the dosage of photocatalysts to be 0.1-1 g / L and the illumination time (determined according to the concentration of the wastewater and the treatment effect); Ozone oxidation method: Control The dosage and reaction time of ozone production are 15-60 minutes; S3.3: Start the reaction equipment and monitor ORP and free radical concentration in real time, dynamically adjust the dosage of oxidant or reaction time to ensure the thoroughness of degradation; S3.4: Treat byproducts including iron sludge precipitation by Fenton method, tail gas adsorption by ozone method, recover catalyst and avoid secondary pollution; S3.5: Finally, HPLC-MS or GC-MS is used to detect the intermediate products of tetracycline hydrochloride degradation including tetracycline ketone and small molecule carboxylic acid, verify that COD, TOC and toxicity indicators meet the standards, and ensure the safety of effluent. S4: Ensure that the effluent water quality meets the standards through secondary physical adsorption or membrane filtration, and conduct water quality monitoring and adjustment. The specific steps are as follows: S4.1: According to the water quality status and compliance requirements after the primary treatment, determine activated carbon adsorption or nanofiltration membrane, reverse osmosis membrane filtration as the deep treatment method; S4.2: The wastewater treated in the previous step is introduced into the secondary treatment link, and adsorbent is added for stirring or the wastewater is treated through the membrane assembly by a pressure pump according to the selected method; S4.3: With the help of the water quality monitoring system, various indicators of the effluent after the secondary treatment, including COD, tetracycline hydrochloride concentration, etc., are tested in real time; S4.4: According to the water quality monitoring results, if the indicators do not meet the standards, the parameters of the secondary treatment link are adjusted to ensure that the effluent water quality is stable and meets the standards. Adjusting the parameters of the secondary treatment link includes increasing or decreasing the amount of adsorbent, changing the membrane filtration time or pressure.

[0080] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0081] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A process for treating pollutants in tetracycline hydrochloride wastewater, characterized in that: The following steps are involved: S1: Remove suspended solids and part of tetracycline hydrochloride in wastewater through physical adsorption and membrane filtration technology to reduce pollutant concentration; S2: Biodegradation using specific microorganisms and artificial wetlands, using the metabolism of microorganisms to convert tetracycline hydrochloride into low-toxic or non-toxic substances; S3: Use advanced oxidation methods to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives, and select appropriate methods and determine corresponding operating parameters based on the wastewater quality characteristics and treatment requirements; S4: Ensure that the effluent water quality meets the standard through secondary physical adsorption or membrane filtration, and conduct water quality monitoring and adjustment.

2. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 1, characterized in that: In S1, the specific steps of removing suspended solids and part of tetracycline hydrochloride in the wastewater by physical adsorption and membrane filtration technology to reduce the concentration of pollutants are as follows: S1.1: First, select the adsorbent according to the characteristics of the wastewater and perform pretreatment. At the same time, select the appropriate membrane module according to the wastewater treatment requirements, install the membrane module and ensure that the connection is well sealed; S1.2: Add the pretreated adsorbent to the wastewater in proportion, stir and mix for 30-120 minutes to allow the adsorbent to fully contact the wastewater, and then let it stand for 1-2 hours; S1.3: Separate the adsorbent from the preliminarily treated wastewater by filtration or centrifugation, and use the wastewater as the membrane filtration feed water for later use; S1.4: Rinse the membrane components with clean water to remove impurities, adjust the water inlet pressure and flow rate to ensure stable operation of the membrane filtration system, pump the pretreated wastewater into the system, control the parameters for filtration, and regularly monitor the membrane flux and retention rate during operation; S1.5: When the membrane flux decreases, backwashing should be performed first. If the effect is not good, chemical cleaning should be performed with a suitable chemical cleaning agent. If the membrane performance cannot be restored after multiple cleanings, the membrane assembly should be replaced in time.

3. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 2, characterized in that: The wastewater characteristics in S1.1 include pH and pollutant concentration; the adsorbent includes activated carbon, hydrogel, ceramic, resin and mesoporous molecules; the membrane assembly includes microfiltration membrane and ultrafiltration membrane.

4. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 2, characterized in that: The pretreatment in S1.1 includes washing, activating, screening and calcining the adsorbent.

5. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 1, characterized in that: The specific microorganisms in S2 include Sphingobacterium mizutaii strains; the artificial wetland includes a matrix, aquatic plants, and a microbial community.

6. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 5, characterized in that: The specific steps of biodegrading S2 using specific microorganisms and artificial wetlands and converting tetracycline hydrochloride into low-toxic or non-toxic substances using the metabolism of microorganisms are as follows: S2.1: First, select the highly efficient degradation bacteria Sphingobacterium mizutaii from the soil or water contaminated by tetracycline hydrochloride, and expand the culture in the laboratory until the activity is stable; S2.2: Inoculate the cultured microorganisms into the bioreactor and control the reaction conditions; S2.3: The pretreated wastewater is pumped into the bioreactor, where microorganisms decompose tetracycline hydrochloride into low-toxic intermediates through enzymatic reactions; S2.4: Construct an artificial wetland system, lay gravel and sand substrates on the bottom, plant pollution-tolerant wetland plants including reeds and cattails, and form a plant-microorganism-substrate synergistic degradation system; S2.5: Introduce the effluent from the bioreactor into the artificial wetland to promote the attachment of microorganisms through the secretion of organic matter by plant roots, and further degrade the residual tetracycline hydrochloride and its metabolites; S2.6: Finally, regularly test the residual concentration and toxicity of tetracycline hydrochloride in the water, and adjust the hydraulic retention time or supplement microbial agents based on the results.

7. The process for treating pollutants in tetracycline hydrochloride wastewater according to claim 1, characterized in that: The S3 intermediate and advanced oxidation methods include Fenton oxidation, ozone oxidation, and photocatalytic oxidation; the operating parameters include optimizing the dosage of the oxidant, the reaction time, and the pH value.

8. A process for treating pollutants in tetracycline hydrochloride wastewater according to claim 7, characterized in that: The specific steps of using advanced oxidation process to completely degrade the difficult-to-treat tetracycline hydrochloride and its derivatives in S3, and selecting a suitable method and determining corresponding operating parameters according to the wastewater quality characteristics and treatment requirements are as follows: S3.1: First, detect the concentration of tetracycline hydrochloride, COD, pH, salinity and types of coexisting pollutants in the wastewater, and select the efficient degradation method of Fenton oxidation, ozone oxidation or photocatalytic oxidation based on the results; S3.2: Set key parameters based on the selected method; S3.3: Start the reaction equipment and monitor the ORP and free radical concentration in real time, and dynamically adjust the oxidant dosage or reaction time to ensure thorough degradation; S3.4: Treatment of by-products including precipitation of iron sludge by Fenton method, adsorption of tail gas by ozone method, recovery of catalyst and avoidance of secondary pollution; S3.5: Finally, HPLC-MS or GC-MS is used to detect the degradation intermediates of tetracycline hydrochloride, including tetracycline ketone and small molecule carboxylic acids, to verify that COD, TOC and toxicity indicators meet the standards and ensure the safety of effluent.

9. The process for treating pollutants in tetracycline hydrochloride wastewater according to claim 1, characterized in that: The specific steps of ensuring that the effluent water quality meets the standard through secondary physical adsorption or membrane filtration and performing water quality monitoring and adjustment in S4 are as follows: S4.1: Based on the water quality after primary treatment and the requirements for reaching the standard, determine activated carbon adsorption or nanofiltration membrane or reverse osmosis membrane filtration as the deep treatment method; S4.2: The wastewater treated in the previous step is introduced into the secondary treatment stage, and adsorbent is added for stirring or the wastewater is processed through the membrane module by a pressure pump according to the selected method; S4.3: With the help of water quality monitoring system, various indicators of effluent after secondary treatment, including COD and tetracycline hydrochloride concentration, are tested in real time; S4.4: Based on the water quality monitoring results, if the indicators do not meet the standards, adjust the parameters of the secondary treatment process to ensure that the effluent quality is stable and meets the standards.

10. The process for treating pollutants in tetracycline hydrochloride wastewater according to claim 1, characterized in that: The adjustment of the parameters of the secondary treatment process includes increasing or decreasing the amount of adsorbent, and changing the membrane filtration time or pressure.

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