Process for harmlessly treating penicillin wastewater

Abstract

The invention relates to the technical field of wastewater treatment, in particular to a process for harmlessly treating penicillin wastewater, which comprises the following steps: S1, adsorption and degradation: adding goethite-loaded modified cellulose into penicillin wastewater for degradation, and performing primary filtration; s2, biodegradation: adding phycomycete composite capsules into the penicillin wastewater subjected to primary filtration under an anaerobic condition for degradation, and then performing secondary filtration to complete degradation; according to the method, firstly, goethite-loaded modified cellulose is adopted for adsorption and degradation, so that active sites on the surface of the goethite-loaded modified cellulose are in full contact with penicillin molecules, and the penicillin molecules are more easily subjected to interaction such as electrostatic attraction with an adsorption material to be adsorbed; then biodegradation is carried out, the phycomycete composite capsule can grow and metabolize by taking residual penicillin in the wastewater as a nutrient source, and penicillin molecules are further decomposed into harmless small molecular substances through an enzyme system in microorganisms.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, in particular to a process for harmlessly treating penicillin wastewater. Background Art

[0002] In addition to penicillin, the main pollutant, there are also a large number of organic by-products produced during the production process. For example, in the production of penicillin fermentation, some unused sugars (such as glucose), nitrogen-containing compounds (such as amino acids) and other metabolic intermediates are produced. These organic substances are mixed with penicillin, increasing the complexity of the wastewater composition.

[0003] Penicillin itself is an antibiotic that has a strong inhibitory and bactericidal effect on microorganisms. Even at low concentrations, it will inhibit the growth and metabolism of microorganisms. This makes it impossible to directly use conventional biological treatment methods for penicillin-containing wastewater, because the microorganisms in the wastewater will be poisoned by penicillin, resulting in low treatment efficiency.

[0004] In order to solve the above problems, the present invention decides to combine adsorption and biological treatment methods to solve the problems. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a process for harmlessly treating penicillin wastewater.

[0006] A process for harmlessly treating penicillin wastewater comprises the following steps:

[0007] S1. Adsorption degradation:

[0008] Adding goethite-loaded modified cellulose to penicillin wastewater at 80-90° C., pressure 0.07-0.09 MPa, dissolved oxygen concentration 0.5-0.7 mg / L, wherein the concentration of penicillin in the penicillin wastewater is 3-8 mM, the pH is 2-4, the amount of goethite-loaded modified cellulose added is 50-150 mg / L, degraded for 1.5-2.5 hours, and filtered once more;

[0009] S2. Biodegradation:

[0010] Under anaerobic conditions, algae-bacteria composite capsules are added to the penicillin wastewater after primary filtration at 40-60°C, pressure 0.01-0.03MPa, and vacuum degree 0.02-0.04MPa. The addition amount of the algae-bacteria composite capsules is 25-45g / L. The degradation is carried out for 3-3.5h, and then secondary filtration is performed to complete the degradation.

[0011] Furthermore, the preparation method of the goethite-loaded modified cellulose is: mixing goethite, modified cellulose and buffer for 1.5 to 2 hours to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.05 to 0.4 g / L, and the concentration of modified cellulose in the mixed solution is 10 to 40 μM, and then solid-liquid separation and washing and drying are performed to obtain goethite-loaded modified cellulose.

[0012] Description: Modified cellulose has good dispersibility and can prevent goethite from agglomerating. Goethite particles tend to aggregate in water, which reduces their specific surface area and the availability of active sites. Modified cellulose can act as a dispersant to evenly disperse goethite particles in the system.

[0013] Furthermore, the buffer solution is selected from any one of a phosphate solution, an acetate solution, and a borate solution, and the concentration of the buffer solution is 0.01 to 0.05 mol / L.

[0014] Note: In the process of loading modified cellulose with goethite, phosphate solution can maintain the pH stability of the system; in an acidic environment, modified cellulose will expose more active sites, and acetate solution will facilitate its combination with goethite loading; in an alkaline environment, the nucleophilicity of the functional groups (such as amine groups) on the modified cellulose will be enhanced, which is more conducive to chemical reactions with the active sites on the surface of goethite.

[0015] Furthermore, the preparation method of the modified cellulose is as follows: under the action of an electric field, immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 20 to 25% for a first immersion time of 20 to 30 minutes; after the first immersion is completed, immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 10 to 15% for a second immersion time of 5 to 10 minutes under the action of an electric field, and then washing and drying the cellulose after the second immersion to obtain the modified cellulose;

[0016] The current of the first immersion is 60-80 mA, and the potential gradient is 0.7-1.0 V / cm; the current of the second immersion is 30-40 mA, and the potential gradient is 0.2-0.5 V / cm.

[0017] Description: After polyethylene glycol activated ester modifies cellulose, more active functional groups can be introduced on the cellulose surface. These functional groups can interact with penicillin molecules in various ways. For example, penicillin can be adsorbed through hydrogen bonds and van der Waals forces. During the first soaking process, the higher concentration of polyethylene glycol activated ester solution and the relatively long soaking time allow cellulose to fully contact and bind to a large amount of activated esters, while the second soaking further increases the loading amount of active functional groups, making the adsorption sites of modified cellulose more abundant; after two soaking modification processes assisted by the electric field, a relatively stable chemical bond is formed between polyethylene glycol activated ester and cellulose.

[0018] Furthermore, the preparation method of the bacteria-algae composite capsule is:

[0019] The Myriophyllum extract is magnetized at a magnetic induction intensity of 40 to 60 mT for 10 to 30 minutes to obtain a magnetized Myriophyllum extract powder;

[0020] The magnetized foxtail algae extract powder and the anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:10-15ml. The number of viable bacteria in the anaerobic bacteria solution was 1-1.5×10 9 CFU / mL to obtain a mixed solution; then the sodium alginate solution, Tween-80 and the mixed solution are sheared and homogenized at 12000-18000 rpm for 10-25 minutes at a mass ratio of 1:0.3:1-1.4 to obtain an emulsion;

[0021] The emulsion is subjected to electrostatic spraying at 30-50° C., a voltage of 10-20 KV, an emulsion flow rate of 0.2-0.8 mL / h, and a distance from the needle tip to the dichloromethane solidified liquid of 5-15 cm to obtain bacteria-algae composite capsules.

[0022] Description: Under the action of magnetic field, the activity of some functional groups (such as hydroxyl, carboxyl, etc.) in foxtail algae extract is enhanced, and these functional groups can be adsorbed with penicillin molecules through hydrogen bonding, ion exchange, etc. At the same time, the anaerobic bacteria in the bacteria-algae composite capsule also produce some substances that can bind to penicillin during metabolism. Moreover, the capsule wall formed by sodium alginate can enrich the bacteria and algae components inside, so that the bacteria-algae composite capsule can more effectively adsorb penicillin when it comes into contact with penicillin in wastewater.

[0023] Furthermore, the preparation method of the foxtail algae extract is as follows: placing the foxtail algae residue in water at a solid-liquid ratio of 1g:15-25ml, extracting at 90-100°C for 1.5-2.5h, filtering to obtain a primary filtrate and a filter residue; placing the filter residue in 90-95vt% ethanol at a solid-liquid ratio of 1g:1-1.2ml, ultrasonically extracting at 150-250W and 75-85°C for 0.4-0.8h, filtering to obtain a secondary filtrate, combining the primary filtrate and the secondary filtrate to obtain a mixed filtrate, and then concentrating and drying the mixed filtrate in turn to obtain the foxtail algae extract.

[0024] Description: In the hot water extraction process, macromolecular substances such as polysaccharides and proteins in foxtail algae can be dissolved into the primary filtrate. These macromolecular substances contain rich functional groups, such as hydroxyl groups in polysaccharides, which can be adsorbed with penicillin molecules through hydrogen bonds and other interactions. In the process of ultrasonic extraction of filter residues with ethanol, the solubility characteristics of ethanol and the cavitation effect of ultrasound can be used to extract small molecular active ingredients such as flavonoids and phenols in foxtail algae, thereby enhancing the processing capacity of penicillin.

[0025] Furthermore, the anaerobic bacteria solution contains methanogens and / or Citrobacter freundii.

[0026] Note: When treating wastewater containing penicillin, methanogens mainly degrade penicillin through co-metabolism. Citrobacter freundii can secrete some extracellular enzymes, such as β-lactamase. Penicillin belongs to the β-lactam antibiotics. β-lactamase can hydrolyze the β-lactam ring in the penicillin molecule, thereby making penicillin lose its antibacterial activity and achieving the purpose of degradation.

[0027] Furthermore, in step S1, the filter membrane for the primary filtration is selected from any one of cellulose acetate membrane, polyacrylonitrile membrane and polyamide membrane, and the filter diameter is 0.05-0.1 μm.

[0028] Description: Cellulose acetate membrane has good permeability and anti-pollution properties; polyacrylonitrile membrane has high mechanical strength and chemical stability, and is suitable for various harsh environments; polyamide membrane has high desalination rate and good chemical stability, and polyamide membrane has good resistance to strong alkali, oil esters and organic solvents.

[0029] Furthermore, in step S2, the filter membrane for the secondary filtration is selected from a polycarbonate membrane or a sulfonated polysulfone membrane, and the filter diameter is 1.5 to 2 nm.

[0030] Description: The main advantages of polycarbonate membranes are their high transparency, high strength and high impact resistance, while sulfonated polysulfone membranes have stability under high pressure and excellent water permeability.

[0031] Compared with the existing process for treating penicillin wastewater, the beneficial effects of the present invention are:

[0032] (1) The treatment process of the present invention first uses goethite-loaded modified cellulose for adsorption and degradation. Under a specific dissolved oxygen concentration, this material can exert good adsorption performance. High temperature and certain pressure conditions are conducive to improving the reaction rate, so that the active sites on the surface of goethite-loaded modified cellulose (such as functional groups on modified cellulose and surface hydroxyl groups of goethite, etc.) are fully in contact with penicillin molecules. At the same time, the lower pH value environment is conducive to protonation, making it easier for penicillin molecules to interact with the adsorption material such as electrostatic attraction and be adsorbed; then the biodegradation step is carried out. The algae-bacteria composite capsule works under anaerobic conditions. The anaerobic environment is suitable for the anaerobic bacteria in the capsule to exert its biodegradation function. Within this temperature and pressure range, the metabolic activity of the microorganism is relatively high, and the penicillin residual in the wastewater can be used as a nutrient source for growth and metabolism. The enzyme system in the microorganism further decomposes the penicillin molecules into harmless small molecules.

[0033] (2) The treatment process of the present invention uses a bacterial-algae composite capsule. Under the action of a magnetic field, the activity of some functional groups (such as hydroxyl, carboxyl, etc.) in the foxtail algae extract is enhanced, and these functional groups can be adsorbed with penicillin molecules through hydrogen bonds, ion exchange, etc. At the same time, the anaerobic bacteria in the bacterial-algae composite capsule also produce some substances that can bind to penicillin during the metabolic process. Moreover, the capsule wall formed by sodium alginate can enrich the bacterial-algae components inside, so that the bacterial-algae composite capsule can more effectively adsorb penicillin when it comes into contact with penicillin in wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a comparison chart of the results of the research 1 of the treatment process of the present invention;

[0035] Figure 2 It is a comparison chart of the results of the investigation 2 of the treatment process of the present invention;

[0036] Figure 3 It is a comparison chart of the results of the investigation 3 of the treatment process of the present invention;

[0037] Figure 4 It is a comparison chart of the results of the investigation of the treatment process of the present invention. DETAILED DESCRIPTION

[0038] In order to further illustrate the method adopted by the present invention and the effect achieved, the technical solution of the present invention will be clearly and completely described in combination with experiments below.

[0039] Embodiment 1: A process for harmlessly treating penicillin wastewater comprises the following steps:

[0040] S1. Adsorption degradation:

[0041] Adding goethite-loaded modified cellulose to penicillin wastewater at 85°C, a pressure of 0.08 MPa, and a dissolved oxygen concentration of 0.6 mg / L, wherein the concentration of penicillin in the penicillin wastewater is 6 mM, the pH is 3, and the amount of goethite-loaded modified cellulose added is 100 mg / L. Degrade for 2 hours, and then filter once, wherein the filter membrane for the first filtration is selected from a cellulose acetate membrane, and the filter diameter is 0.08 μm;

[0042] The preparation method of the goethite-loaded modified cellulose is as follows: goethite, modified cellulose and a 0.03 mol / L potassium dihydrogen phosphate solution are mixed for 1.8 hours to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.2 g / L, and the concentration of modified cellulose in the mixed solution is 25 μM, then solid-liquid separation is performed, the mixture is washed with pure water, and dried at 80° C. for 10 minutes to obtain the goethite-loaded modified cellulose;

[0043] The preparation method of the modified cellulose comprises: immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 23% under the action of an electric field for a first immersion time of 25 minutes; after the first immersion is completed, immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 12% under the action of an electric field for a second immersion time of 8 minutes, and then washing the cellulose after the second immersion with pure water and drying at 80° C. for 10 minutes to obtain the modified cellulose;

[0044] The current of the first immersion was 70 mA, and the potential gradient was 0.8 V / cm; the current of the second immersion was 35 mA, and the potential gradient was 0.4 V / cm;

[0045] S2. Biodegradation:

[0046] Under anaerobic conditions, the algae-bacteria composite capsules were added to the penicillin wastewater after primary filtration at 50°C, a pressure of 0.02MPa, and a vacuum degree of 0.03MPa. The addition amount of the algae-bacteria composite capsules was 35g / L. The water was degraded for 3.2h, and then a secondary filtration was performed. The filter membrane of the secondary filtration was selected from a polycarbonate membrane with a filter diameter of 1.8nm. The degradation was completed.

[0047] The preparation method of the bacteria-algae composite capsule is as follows:

[0048] First, the foxtail algae is crushed and ground to obtain foxtail algae residue with a particle size of less than 3 mm, the foxtail algae residue is placed in water at a solid-liquid ratio of 1g:20ml, extracted at 95°C for 2h, and filtered to obtain a primary filtrate and a filter residue; the filter residue is placed in 93vt% ethanol at a solid-liquid ratio of 1g:1.1ml, ultrasonically extracted at 200W and 80°C for 0.6h, filtered to obtain a secondary filtrate, the primary filtrate and the secondary filtrate are combined to obtain a mixed filtrate, and the mixed filtrate is concentrated by 1.2 times and then dried at 80°C for 10min to obtain a foxtail algae extract;

[0049] The Myriophyllum extract was magnetized at a magnetic induction intensity of 50 mT for 20 min to obtain a magnetized Myriophyllum extract powder;

[0050] The magnetized foxtail algae extract powder and the anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:12ml. The number of viable Citrobacter freundii in the anaerobic bacteria solution was 1.2×10 9 CFU / mL, and a mixed solution was obtained; the sodium alginate solution, Tween-80 and the mixed solution were sheared and homogenized at 15000 rpm for 15 min at a mass ratio of 1:0.3:1.2 to obtain an emulsion;

[0051] The emulsion was electrostatically sprayed at 30-50° C., with a voltage of 15 KV, an emulsion flow rate of 0.5 mL / h, and a distance of 10 cm from the needle tip to the dichloromethane solidified liquid to obtain bacteria-algae composite capsules.

[0052] Example 2: This example is different from Example 1 in that goethite-loaded modified cellulose is added to penicillin wastewater at 80° C., pressure 0.07 MPa, and dissolved oxygen concentration 0.5 mg / L and degraded for 1.5 h.

[0053] Example 3: This example is different from Example 1 in that goethite-loaded modified cellulose is added to penicillin wastewater at 90° C., pressure 0.09 MPa, and dissolved oxygen concentration 0.7 mg / L and degraded for 2.5 hours.

[0054] Example 4: This example is different from Example 1 in that the concentration of penicillin in the penicillin wastewater is 3 mM, the pH is 2, and the addition amount of the goethite-loaded modified cellulose is 150 mg / L.

[0055] Example 5: This example is different from Example 1 in that the concentration of penicillin in the penicillin wastewater is 8 mM, the pH is 4, and the addition amount of the goethite-loaded modified cellulose is 50 mg / L.

[0056] Example 6: This example is different from Example 1 in that goethite, modified cellulose and a 0.01 mol / L sodium acetate solution are mixed for 1.5 h to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.05 g / L, and the concentration of modified cellulose in the mixed solution is 40 μM.

[0057] Example 7: This example is different from Example 1 in that goethite, modified cellulose and 0.05 mol / L borax buffer are mixed for 2 hours to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.4 g / L, and the concentration of modified cellulose in the mixed solution is 10 μM.

[0058] Example 8: The difference between this example and Example 1 is that, under the action of an electric field, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 25% for a first immersion for 30 minutes; after the first immersion is completed, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 10% for a second immersion for 5 minutes under the action of an electric field.

[0059] Example 9: The difference between this example and Example 1 is that, under the action of an electric field, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 20% for a first immersion for 20 minutes; after the first immersion is completed, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 15% for a second immersion for 10 minutes under the action of an electric field.

[0060] Example 10: This example is different from Example 1 in that the current of the first immersion is 60 mA, and the potential gradient is 0.7 V / cm; the current of the second immersion is 30 A, and the potential gradient is 0.2 V / cm.

[0061] Example 11: This example is different from Example 1 in that the current of the first immersion is 80 mA, and the potential gradient is 1.0 V / cm; the current of the second immersion is 40 mA, and the potential gradient is 0.5 V / cm.

[0062] Example 12: This example is different from Example 1 in that the algae-bacteria composite capsule is added to the once filtered penicillin wastewater at 40°C, pressure 0.01 MPa, and vacuum degree 0.02 MPa for degradation for 3 hours.

[0063] Example 13: This example is different from Example 1 in that the algae-bacteria composite capsule is added to the once filtered penicillin wastewater at 60°C, pressure 0.03MPa, and vacuum degree 0.04MPa for degradation for 3.5h.

[0064] Example 14: This example is different from Example 1 in that the addition amount of the algae-fungus composite capsule is 25 g / L.

[0065] Example 15: This example is different from Example 1 in that the addition amount of the algae-fungus composite capsule is 45 g / L.

[0066] Example 16: This example is different from Example 1 in that the filter membrane for the first filtration is selected from a cellulose acetate membrane with a filter diameter of 0.05 μm; the filter membrane for the second filtration is selected from a polycarbonate membrane with a filter diameter of 1.5 nm.

[0067] Example 17: This example is different from Example 1 in that the filter membrane for the first filtration is selected from a cellulose acetate membrane with a filter diameter of 0.1 μm; the filter membrane for the second filtration is selected from a polycarbonate membrane with a filter diameter of 2 nm.

[0068] Example 18: This example is different from Example 1 in that the foxtail algae residue is placed in water at a solid-liquid ratio of 1 g:25 ml, extracted at 90°C for 1.5 h, and filtered to obtain a primary filtrate and a residue.

[0069] Example 19: This example is different from Example 1 in that the foxtail algae residue is placed in water at a solid-liquid ratio of 1 g:15 ml, extracted at 100°C for 2.5 hours, and filtered to obtain a primary filtrate and a residue.

[0070] Example 20: This example is different from Example 1 in that the filter residue is placed in 90vt% ethanol at a solid-liquid ratio of 1g:1.2ml, and ultrasonic extraction is carried out at 150W and 75°C for 0.4h.

[0071] Example 21: This example is different from Example 1 in that the filter residue is placed in 95vt% ethanol at a solid-liquid ratio of 1g:1ml, and ultrasonic extraction is carried out at 250W and 85°C for 0.8h.

[0072] Example 22: This example is different from Example 1 in that the Myriophyllum extract is magnetized at a magnetic induction intensity of 40 mT for 10 min.

[0073] Example 23: This example is different from Example 1 in that the Myriophyllum extract is magnetized at a magnetic induction intensity of 60 mT for 30 min.

[0074] Example 24: This example is different from Example 1 in that the magnetized foxtail algae powder and the anaerobic bacteria solution are mixed evenly at a solid-liquid ratio of 1 g:10 ml, and the number of viable Citrobacter freundii in the anaerobic bacteria solution is 1.5×10 9 CFU / mL.

[0075] Example 25: This example is different from Example 1 in that the magnetized foxtail algae powder and the anaerobic bacteria solution are mixed evenly at a solid-liquid ratio of 1 g:15 ml, and the number of viable Citrobacter freundii in the anaerobic bacteria solution is 1×10 9 CFU / mL.

[0076] Example 26: This example is different from Example 1 in that the sodium alginate solution, Tween-80 and the mixed solution are shear homogenized at a mass ratio of 1:0.3:1 at 12000 rpm for 10 min.

[0077] Example 27: This example is different from Example 1 in that the sodium alginate solution, Tween-80 and the mixed solution are shear homogenized at a mass ratio of 1:0.3:1.4 at 18000 rpm for 25 minutes.

[0078] Example 28: This example is different from Example 1 in that the emulsion is electrostatically sprayed at 30°C, the voltage is 10KV, the emulsion flow rate is 0.2mL / h, and the distance from the needle tip to the dichloromethane solidifying liquid is 5cm.

[0079] Example 29: This example is different from Example 1 in that the emulsion is electrostatically sprayed at 50°C, the voltage is 20KV, the emulsion flow rate is 0.8mL / h, and the distance from the needle tip to the dichloromethane solidifying liquid is 15cm.

[0080] Experimental Example: The description of this experimental example is based on the scheme described in Example 1, and is intended to illustrate the practical application effect of the present invention.

[0081] The treatment effect of each embodiment on penicillin wastewater was explored, and the changes in penicillin and ammonia nitrogen concentrations before and after the treatment of each embodiment were taken as the degradation rate of the method of the present invention, and the degradation rate of each embodiment was taken as the average value of three experiments as the result.

[0082] 1. To explore the effect of adsorption degradation parameters on the degradation rate of penicillin wastewater.

[0083] The difference between Control Example 1 and Example 1 is that the adsorption process is carried out under anaerobic conditions;

[0084] Depend on Figure 1 The comparison results show that the dissolved oxygen concentration of Control Example 1 is different, and under aerobic conditions, goethite-loaded modified cellulose can more effectively adsorb and remove penicillin, so that the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 1 are both reduced compared with Examples 1 to 5;

[0085] Comparing Examples 1 to 5, it can be seen that if the parameters of aerobic adsorption are too small or too large, and the amount of goethite-loaded modified cellulose added is too small or too large, the degradation rate of penicillin and ammonia nitrogen will be reduced. Therefore, in comprehensive comparison, the parameter effect of Example 1 is relatively better.

[0086] 2. Investigate the effect of preparation parameters of adsorption materials on the degradation rate of penicillin wastewater.

[0087] The difference between Control Example 2 and Example 1 is that the cellulose is not modified;

[0088] Depend on Figure 2The comparison results show that the cellulose in Control Example 2 is not modified, and the adsorption capacity of unmodified cellulose is weaker than that of modified cellulose, and it lacks stability, so the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 2 are both lower than those of Examples 6 to 11;

[0089] By comparing Examples 1 and 6 to 11, it can be seen that if the concentration of modified cellulose in the goethite-loaded modified cellulose is too small or too large, if the parameter changes of the two cellulose soakings are too small or too large, and if the parameter changes of the two electric field actions are too small or too large, the penicillin degradation rate and the ammonia nitrogen degradation rate will be reduced. Therefore, in comprehensive comparison, the parameter effect of Example 1 is relatively better.

[0090] 3. To explore the effect of biodegradation parameters on the degradation rate of penicillin wastewater.

[0091] The difference between Control Example 3 and Example 1 is that the biodegradation process is carried out under aerobic conditions;

[0092] Depend on Figure 3 The comparison results show that the biodegradation process of Control Example 3 increases the dissolved oxygen concentration, and the bacteria-algae composite capsule containing anaerobic bacteria cannot effectively play a biodegradation role, so that the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 3 are both lower than those of Examples 12 to 17;

[0093] By comparing Examples 12 to 17, it can be seen that if the biodegradation parameters are too small or too large, the amount of bacteria-algae composite capsules added is too small, and the filtration diameter is too small or too large, the penicillin degradation rate and the ammonia nitrogen degradation rate will be reduced. After the amount of bacteria-algae composite capsules added in Example 15 reaches a certain level, the effect cannot be further enhanced. Therefore, from an economic perspective, the parameter effect of Example 1 is relatively better.

[0094] 4. Investigate the effect of preparation parameters of bacteria-algae composite capsules on the degradation rate of penicillin wastewater.

[0095] The difference between Control Example 4 and Example 1 is that the Myriophyllum extract is not magnetized;

[0096] Depend on Figure 4 The comparison results show that the control example 4 lacks the magnetic activation of the foxtail extract, so the binding performance of the foxtail extract and the anaerobic bacteria solution is reduced, so the penicillin degradation rate and the ammonia nitrogen degradation rate are reduced compared with Examples 18 to 29;

[0097] By comparing Examples 18 to 29, it can be seen that the parameters of water extraction that are too small or too large, the parameters of alcohol extraction that are too small or too large, the magnetization parameters that are too small or too large, the anaerobic bacteria concentration that are too small or too large, the shear mean parameters that are too small or too large, and the electrostatic spray parameters that are too small or too large will all reduce the penicillin degradation rate and the ammonia nitrogen degradation rate. Therefore, in comprehensive comparison, the parameter effect of Example 1 is relatively better.

Claims

1. A process for harmlessly treating penicillin wastewater, characterized in that: The following steps are involved: S1. Adsorption degradation: Adding goethite-loaded modified cellulose to penicillin wastewater at 80-90° C., pressure 0.07-0.09 MPa, dissolved oxygen concentration 0.5-0.7 mg / L, wherein the concentration of penicillin in the penicillin wastewater is 3-8 mM, the pH is 2-4, the amount of goethite-loaded modified cellulose added is 50-150 mg / L, degraded for 1.5-2.5 hours, and filtered once more; S2. Biodegradation: Under anaerobic conditions, algae-bacteria composite capsules are added to the penicillin wastewater after primary filtration at 40-60°C, pressure 0.01-0.03MPa, and vacuum degree 0.02-0.04MPa. The addition amount of the algae-bacteria composite capsules is 25-45g / L. The degradation is carried out for 3-3.5h, and then secondary filtration is performed to complete the degradation.

2. A process for harmlessly treating penicillin wastewater as claimed in claim 1, characterized in that: The preparation method of the goethite-loaded modified cellulose is as follows: mixing goethite, modified cellulose and buffer for 1.5 to 2 hours to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.05 to 0.4 g / L, and the concentration of modified cellulose in the mixed solution is 10 to 40 μM, and then solid-liquid separation, washing and drying are performed to obtain the goethite-loaded modified cellulose.

3. A process for harmlessly treating penicillin wastewater as claimed in claim 2, characterized in that: The buffer solution is selected from any one of a phosphate solution, an acetate solution, and a borate solution, and the concentration of the buffer solution is 0.01 to 0.05 mol / L.

4. A process for harmlessly treating penicillin wastewater as claimed in claim 2, characterized in that: The preparation method of the modified cellulose comprises: immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 20 to 25% under the action of an electric field for a first immersion time of 20 to 30 minutes; after the first immersion is completed, immersing the cellulose in a polyethylene glycol activated ester solution with a mass concentration of 10 to 15% under the action of an electric field for a second immersion time of 5 to 10 minutes, and then washing and drying the cellulose after the second immersion to obtain the modified cellulose; The current of the first immersion is 60-80 mA, and the potential gradient is 0.7-1.0 V / cm; the current of the second immersion is 30-40 mA, and the potential gradient is 0.2-0.5 V / cm.

5. A process for harmlessly treating penicillin wastewater as claimed in claim 1, characterized in that: The preparation method of the bacteria-algae composite capsule is as follows: The Myriophyllum extract is magnetized at a magnetic induction intensity of 40 to 60 mT for 10 to 30 minutes to obtain a magnetized Myriophyllum extract powder; The magnetized foxtail algae extract powder and the anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:10-15ml. The number of viable bacteria in the anaerobic bacteria solution was 1-1.5×10 9 CFU / mL to obtain a mixed solution; then the sodium alginate solution, Tween-80 and the mixed solution are sheared and homogenized at 12000-18000 rpm for 10-25 minutes at a mass ratio of 1:0.3:1-1.4 to obtain an emulsion; The emulsion is subjected to electrostatic spraying at 30-50° C., a voltage of 10-20 KV, an emulsion flow rate of 0.2-0.8 mL / h, and a distance from the needle tip to the dichloromethane solidified liquid of 5-15 cm to obtain bacteria-algae composite capsules.

6. A process for harmlessly treating penicillin wastewater as claimed in claim 5, characterized in that: The preparation method of the foxtail algae extract is as follows: placing foxtail algae residue in water at a solid-liquid ratio of 1g:15-25ml, extracting at 90-100°C for 1.5-2.5h, filtering to obtain a primary filtrate and a filter residue; placing the filter residue in 90-95vt% ethanol at a solid-liquid ratio of 1g:1-1.2ml, ultrasonically extracting at 150-250W and 75-85°C for 0.4-0.8h, filtering to obtain a secondary filtrate, combining the primary filtrate and the secondary filtrate to obtain a mixed filtrate, and then sequentially concentrating and drying the mixed filtrate to obtain the foxtail algae extract.

7. A process for harmlessly treating penicillin wastewater as claimed in claim 1, characterized in that: The anaerobic bacteria solution contains methanogens and / or Citrobacter freundii.

8. A process for harmlessly treating penicillin wastewater as claimed in claim 1, characterized in that: In step S1, the filter membrane for the primary filtration is selected from any one of cellulose acetate membrane, polyacrylonitrile membrane and polyamide membrane, and the filter diameter is 0.05-0.1 μm.

9. A process for harmlessly treating penicillin wastewater as claimed in claim 1, characterized in that: In step S2, the filter membrane for the secondary filtration is selected from a polycarbonate membrane or a sulfonated polysulfone membrane, and the filter diameter is 1.5 to 2 nm.

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