A process for harmless treatment of penicillin wastewater

Abstract

This invention relates to the field of wastewater treatment technology, specifically to a process for the harmless treatment of penicillin wastewater, comprising the following steps: S1, adsorption degradation: goethite-loaded modified cellulose is added to the penicillin wastewater for degradation, followed by a first filtration; S2, biodegradation: under anaerobic conditions, algae-bacterial composite capsules are added to the first-filtered penicillin wastewater for degradation, followed by a second filtration, completing the degradation process; The method of this invention first uses goethite-loaded modified cellulose for adsorption degradation, allowing the active sites on the surface of the goethite-loaded modified cellulose to fully contact penicillin molecules, making it easier for penicillin molecules to be adsorbed by electrostatic attraction and other interactions with the adsorption material; then, biodegradation is carried out, where the algae-bacterial composite capsules can utilize the residual penicillin in the wastewater as a nutrient source for growth and metabolism, and further decompose penicillin molecules into harmless small molecules through the enzyme system within the microorganisms.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a process for the harmless treatment of penicillin wastewater. Background Technology

[0002] In addition to penicillin, the main pollutant, the wastewater also contains a large amount of organic byproducts generated during the production process. For example, penicillin fermentation produces unused sugars (such as glucose), nitrogenous compounds (such as amino acids), and other metabolic intermediates. These organic substances mix with penicillin, increasing the complexity of the wastewater composition.

[0003] Penicillin itself is an antibiotic with strong inhibitory and bactericidal effects on microorganisms. Even at low concentrations, it can inhibit the growth and metabolism of microorganisms. This makes conventional biological treatment methods unsuitable for penicillin-containing wastewater, as the microorganisms in the wastewater would be toxic to penicillin, resulting in low treatment efficiency.

[0004] To address the aforementioned problems, this invention combines adsorption and biological treatment methods. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a process for the harmless treatment of penicillin wastewater.

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

[0007] S1, Adsorption and Degradation:

[0008] Goethite-loaded modified cellulose was added to penicillin wastewater at 80–90°C, 0.07–0.09 MPa, and dissolved oxygen concentration of 0.5–0.7 mg / L. The concentration of penicillin in the wastewater was 3–8 mM, the pH was 2–4, and the amount of goethite-loaded modified cellulose added was 50–150 mg / L. The degradation process lasted 1.5–2.5 hours, followed by filtration.

[0009] S2, Biodegradation:

[0010] Under anaerobic conditions, algae-bacterial composite capsules were added to penicillin wastewater after one filtration at 40–60°C, 0.01–0.03 MPa pressure, and 0.02–0.04 MPa vacuum. The amount of algae-bacterial composite capsules added was 25–45 g / L. The degradation process lasted 3–3.5 h, followed by a second filtration to complete the degradation.

[0011] Further, the preparation method of the goethite-loaded modified cellulose is as follows: goethite, modified cellulose and buffer solution are mixed 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. Then, solid-liquid separation, washing and drying are performed to obtain goethite-loaded modified cellulose.

[0012] Note: Modified cellulose exhibits excellent dispersibility and can prevent goethite agglomeration. 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, uniformly dispersing goethite particles within the system.

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

[0014] Note: During the process of modifying cellulose with goethite loading, phosphate solution can maintain the pH stability of the system; in an acidic environment, the modified cellulose will expose more active sites, and the acetate solution is conducive to its binding with the 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 reaction with the active sites on the surface of goethite.

[0015] Further, the method for preparing the modified cellulose is as follows: under the action of an electric field, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 20-25% for a first soaking time of 20-30 minutes; after the first soaking, the cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 10-15% for a second soaking time of 5-10 minutes under the action of an electric field; the cellulose after the second soaking is then washed and dried to obtain the modified cellulose.

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

[0017] Explanation: Modifying cellulose with polyethylene glycol (PEG) activated esters introduces more active functional groups onto the cellulose surface. These functional groups can interact with penicillin molecules in various ways, such as through hydrogen bonds and van der Waals forces. In the first soaking process, the high concentration of PEG activated ester solution and the relatively long soaking time allow cellulose to fully contact and bind a large amount of activated ester. The second soaking further increases the loading of active functional groups, enriching the adsorption sites of the modified cellulose. Through the two-stage electric field-assisted soaking modification process, a relatively stable chemical bond is formed between the PEG activated ester and cellulose.

[0018] Furthermore, the preparation method of the fungal-algae composite capsule is as follows:

[0019] The extract of Myriophyllum spicatum was magnetized at a magnetic induction intensity of 40-60 mT for 10-30 min to obtain magnetized Myriophyllum spicatum extract powder.

[0020] The magnetized *Myriophyllum spicatum* extract powder and anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:10-15ml. The viable bacteria count in the anaerobic bacteria solution was 1-1.5 × 10⁻⁶. 9 CFU / mL, to obtain a mixture; then, the sodium alginate solution, Tween-80 and the mixture are sheared and homogenized at 12000-18000 rpm for 10-25 min at a mass ratio of 1:0.3:1-1.4 to obtain an emulsion;

[0021] The emulsion was electrostatically sprayed at 30–50°C with a voltage of 10–20 KV and an emulsion flow rate of 0.2–0.8 mL / h. The distance from the needle tip to the dichloromethane curing liquid was 5–15 cm, resulting in a bacterial-algae composite capsule.

[0022] Note: Under the influence of a magnetic field, the activity of some functional groups (such as hydroxyl and carboxyl groups) in the *Myriophyllum spicatum* extract is enhanced. These functional groups can adsorb penicillin molecules through hydrogen bonding, ion exchange, and other mechanisms. Simultaneously, the anaerobic bacteria in the bacterial-algae composite capsules also produce substances that can bind to penicillin during their metabolism. Furthermore, the capsule wall formed by sodium alginate can enrich the internal bacterial and algae components, enabling the bacterial-algae composite capsules to more effectively adsorb penicillin when in contact with wastewater.

[0023] Further, the preparation method of the *Myriophyllum spicatum* extract is as follows: *Myriophyllum spicatum* residue is placed in water at a solid-liquid ratio of 1g:15-25ml, and extracted at 90-100℃ for 1.5-2.5h, then filtered to obtain a primary filtrate and a residue; the residue is placed in 90-95 wt% ethanol at a solid-liquid ratio of 1g:1-1.2ml, and ultrasonically extracted at 150-250W and 75-85℃ for 0.4-0.8h, then filtered to obtain a secondary filtrate; the primary and secondary filtrates are combined to obtain a mixed filtrate, which is then concentrated and dried sequentially to obtain the *Myriophyllum spicatum* extract.

[0024] Explanation: During hot water extraction, large molecules such as polysaccharides and proteins from *Myriophyllum spicatum* dissolve into the primary filtrate. These large molecules contain abundant functional groups, such as the hydroxyl groups in polysaccharides, which can adsorb penicillin molecules through interactions such as hydrogen bonds. During the ultrasonic extraction of the filter residue with ethanol, the dissolving properties of ethanol and the cavitation effect of ultrasound can extract small molecule active ingredients such as flavonoids and phenols from *Myriophyllum spicatum*, thereby enhancing the penicillin-removing capacity.

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

[0026] Note: In treating penicillin-containing wastewater, methanogenic bacteria primarily degrade penicillin through cometabolism. *Citrobacter freundii* can secrete extracellular enzymes, such as β-lactamases. Penicillin belongs to the β-lactam antibiotic class, and β-lactamases can hydrolyze the β-lactam ring in the penicillin molecule, thereby rendering penicillin inactive and achieving degradation.

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

[0028] Note: Cellulose acetate membranes have good permeability and antifouling properties; polyacrylonitrile membranes have high mechanical strength and chemical stability, making them suitable for various harsh environments; polyamide membranes have high desalination rates and good chemical stability, and are highly resistant to strong alkalis, oils, and organic solvents.

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

[0030] Note: 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 existing processes for treating penicillin wastewater, the advantages of this invention are:

[0032] (1) The treatment process of this invention first uses goethite-supported 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 increasing the reaction rate, so that the active sites on the surface of goethite-supported modified cellulose (such as functional groups on modified cellulose and surface hydroxyl groups of goethite) can fully contact penicillin molecules. At the same time, the lower pH environment is conducive to protonation, making it easier for penicillin molecules to be adsorbed by electrostatic attraction and other interactions with the adsorption material. Then, the biodegradation step is carried out. The algae-bacterial composite capsule works under anaerobic conditions. The anaerobic environment is suitable for the anaerobic bacteria in the capsule to perform their biodegradation function. Within this temperature and pressure range, the metabolic activity of microorganisms is high, and they can use the residual penicillin in the wastewater as a nutrient source for growth and metabolism. Through the enzyme system in the microorganisms, penicillin molecules are further decomposed into harmless small molecules.

[0033] (2) The treatment process of this invention uses a bacterial-algae composite capsule. Under the action of a magnetic field, the activity of some functional groups (such as hydroxyl and carboxyl groups) in the Myriophyllum spicatum extract is enhanced. These functional groups can adsorb penicillin molecules through hydrogen bonding, ion exchange, and other means. At the same time, the anaerobic bacteria in the bacterial-algae composite capsule also produce some substances that can bind to penicillin during metabolism. Moreover, the capsule wall formed by sodium alginate can play a certain enrichment role for the bacterial and algae components inside, so that the bacterial-algae composite capsule can more effectively adsorb penicillin when it comes into contact with wastewater. Attached Figure Description

[0034] Figure 1 This is a comparison chart of the results of the investigation 1 of the processing technology of this invention;

[0035] Figure 2 This is a comparison chart of the results of investigation 2 of the processing technology of this invention;

[0036] Figure 3 This is a comparison chart of the results of the investigation of the processing technology of this invention;

[0037] Figure 4 This is a comparison chart of the results of the investigation of the processing technology of this invention. Detailed Implementation

[0038] To further illustrate the methods and effects of this invention, the technical solution of this invention will be clearly and completely described below in conjunction with experiments.

[0039] Example 1: A process for harmlessly treating penicillin wastewater, comprising the following steps:

[0040] S1, Adsorption and Degradation:

[0041] Goethite-loaded modified cellulose was added to penicillin wastewater at 85°C, 0.08 MPa, and 0.6 mg / L dissolved oxygen. The concentration of penicillin in the wastewater was 6 mM and the pH was 3. The amount of goethite-loaded modified cellulose added was 100 mg / L. After degradation for 2 hours, it was filtered once. The filter membrane for the first filtration was selected from cellulose acetate membrane with a filter diameter of 0.08 μm.

[0042] The preparation method of goethite-supported modified cellulose is as follows: goethite, modified cellulose and a 0.03 mol / L potassium dihydrogen phosphate solution are mixed for 1.8 h 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. The mixture is then separated into solid and liquid components, washed with pure water, and dried at 80 °C for 10 min to obtain goethite-supported modified cellulose.

[0043] The modified cellulose is prepared as follows: under the action of an electric field, cellulose is immersed in a 23% (w / w) polyethylene glycol activated ester solution for a first soaking time of 25 min; after the first soaking, under the action of an electric field, cellulose is immersed in a 12% (w / w) polyethylene glycol activated ester solution for a second soaking time of 8 min; after the second soaking, the cellulose is washed with pure water and dried at 80°C for 10 min to obtain modified cellulose;

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

[0045] S2, Biodegradation:

[0046] Under anaerobic conditions, algae-bacterial composite capsules were added to penicillin wastewater after one filtration at 50°C, 0.02 MPa pressure, and 0.03 MPa vacuum. The amount of algae-bacterial composite capsules added was 35 g / L. After degradation for 3.2 h, a second filtration was performed. The filter membrane for the second filtration was selected from polycarbonate membrane with a filter diameter of 1.8 nm. Degradation was then complete.

[0047] The preparation method of the fungal-algae compound capsule is as follows:

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

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

[0050] The magnetized *Myriophyllum spicatum* extract powder and anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:12ml. The viable count of *Citrobacter freundii* in the anaerobic bacteria solution was 1.2 × 10⁻⁶. 9 CFU / mL was used to obtain a mixture; then, sodium alginate solution, Tween-80 and the mixture 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 and an emulsion flow rate of 0.5 mL / h. The distance from the needle tip to the dichloromethane curing liquid was 10 cm, resulting in a bacterial-algae composite capsule.

[0052] Example 2: The difference between this example and Example 1 is that goethite-loaded modified cellulose was added to penicillin wastewater at 80°C, 0.07 MPa, and 0.5 mg / L dissolved oxygen concentration, and degraded for 1.5 h.

[0053] Example 3: The difference between this example and Example 1 is that goethite-loaded modified cellulose was added to penicillin wastewater at 90°C, 0.09 MPa, and 0.7 mg / L dissolved oxygen concentration, and degraded for 2.5 h.

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

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

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

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

[0058] Example 8: This example differs from Example 1 in that, under the action of an electric field, cellulose is immersed in a 25% (w / w) polyethylene glycol activated ester solution for a first soaking time of 30 minutes; after the first soaking, under the action of an electric field, cellulose is immersed in a 10% (w / w) polyethylene glycol activated ester solution for a second soaking time of 5 minutes.

[0059] Example 9: This example differs from Example 1 in that, under the action of an electric field, cellulose is immersed in a 20% (w / w) polyethylene glycol activated ester solution for a first soaking time of 20 minutes; after the first soaking, under the action of an electric field, cellulose is immersed in a 15% (w / w) polyethylene glycol activated ester solution for a second soaking time of 10 minutes.

[0060] Example 10: The difference between this example and Example 1 is that the current for the first immersion is 60mA and the potential gradient is 0.7V / cm; the current for the second immersion is 30A and the potential gradient is 0.2V / cm.

[0061] Example 11: The difference between this example and Example 1 is that the current for the first immersion is 80mA and the potential gradient is 1.0V / cm; the current for the second immersion is 40mA and the potential gradient is 0.5V / cm.

[0062] Example 12: The difference between this example and Example 1 is that the algae-bacteria composite capsules were added to the penicillin wastewater after one filtration at 40°C, 0.01 MPa pressure, and 0.02 MPa vacuum, and degraded for 3 hours.

[0063] Example 13: The difference between this example and Example 1 is that the algae-bacteria composite capsules were added to the penicillin wastewater after one filtration at 60°C, pressure 0.03MPa, and vacuum degree 0.04MPa, and degraded for 3.5 hours.

[0064] Example 14: The difference between this example and Example 1 is that the amount of algae and bacteria compound capsules added is 25g / L.

[0065] Example 15: The difference between this example and Example 1 is that the amount of algae and bacteria compound capsules added is 45g / L.

[0066] Example 16: The difference between this example and Example 1 is that the filter membrane for the primary filtration is selected from cellulose acetate membrane with a filter diameter of 0.05 μm; the filter membrane for the secondary filtration is selected from polycarbonate membrane with a filter diameter of 1.5 nm.

[0067] Example 17: The difference between this example and Example 1 is that the filter membrane for the primary filtration is selected from a cellulose acetate membrane with a filtration diameter of 0.1 μm; the filter membrane for the secondary filtration is selected from a polycarbonate membrane with a filtration diameter of 2 nm.

[0068] Example 18: The difference between this example and Example 1 is that the residue of Myriophyllum spicatum is placed in water at a solid-liquid ratio of 1g:25ml, extracted at 90℃ for 1.5h, and filtered to obtain a primary filtrate and a filter residue.

[0069] Example 19: The difference between this example and Example 1 is that the residue of Myriophyllum spicatum is placed in water at a solid-liquid ratio of 1g:15ml, extracted at 100℃ for 2.5h, and filtered to obtain a primary filtrate and a filter residue.

[0070] Example 20: The difference between this example and Example 1 is that the filter residue was placed in 90 wt% ethanol at a solid-liquid ratio of 1 g: 1.2 ml and ultrasonically extracted at 150 W and 75 °C for 0.4 h.

[0071] Example 21: The difference between this example and Example 1 is that the filter residue was placed in 95% ethanol at a solid-liquid ratio of 1g:1ml and ultrasonically extracted at 250W and 85℃ for 0.8h.

[0072] Example 22: The difference between this example and Example 1 is that the extract of Myriophyllum spicatum was magnetized for 10 minutes at a magnetic induction intensity of 40mT.

[0073] Example 23: The difference between this example and Example 1 is that the extract of Myriophyllum spicatum was magnetized for 30 minutes at a magnetic induction intensity of 60mT.

[0074] Example 24: This example differs from Example 1 in that the magnetized *Myriophyllum spicatum* powder and anaerobic bacteria solution are mixed evenly at a solid-liquid ratio of 1g:10ml, and the viable count of *Citrobacter freundii* in the anaerobic bacteria solution is 1.5 × 10⁻⁶. 9 CFU / mL.

[0075] Example 25: This example differs from Example 1 in that the magnetized Myriophyllum spicatum powder and anaerobic bacteria solution are mixed evenly at a solid-liquid ratio of 1g:15ml, and the viable count of Citrobacter freundii in the anaerobic bacteria solution is 1×10⁻⁶. 9 CFU / mL.

[0076] Example 26: The difference between this example and Example 1 is that the sodium alginate solution, Tween-80 and the mixture were sheared and homogenized at 12000 rpm for 10 min at a mass ratio of 1:0.3:1.

[0077] Example 27: The difference between this example and Example 1 is that the sodium alginate solution, Tween-80 and the mixture were sheared and homogenized at 18000 rpm for 25 min at a mass ratio of 1:0.3:1.4.

[0078] Example 28: The difference between this example and Example 1 is that the emulsion is electrostatically sprayed at 30°C with a voltage of 10KV, the emulsion flow rate is 0.2mL / h, and the distance from the needle tip to the dichloromethane curing liquid is 5cm.

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

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

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

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

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

[0084] Depend on Figure 1 The results show that the dissolved oxygen concentration of Control Example 1 is different. Under aerobic conditions, the modified cellulose supported on goethite can more effectively adsorb and remove penicillin. As a result, the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 1 are lower than those of Examples 1-5.

[0085] Comparing Examples 1 to 5, it can be seen that both excessively small or large aerobic adsorption parameters and excessively small or large amounts of goethite-loaded modified cellulose will reduce the degradation rate of penicillin and ammonia nitrogen. Therefore, in summary, the parameters of Example 1 are relatively better.

[0086] 2. To investigate the effect of the preparation parameters of the adsorption material on the degradation rate of penicillin wastewater.

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

[0088] Depend on Figure 2The comparison results show that the cellulose in Control Example 2 was not modified. The adsorption capacity of unmodified cellulose is weaker than that of modified cellulose, and it lacks stability. As a result, the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 2 were lower than those of Examples 6-11.

[0089] Comparing Examples 1 and 6-11, it can be seen that too low or too high concentration of modified cellulose in goethite-loaded modified cellulose, too low or too high parameter changes in the two cellulose soakings, and too low or too high parameter changes in the two electric field applications will all reduce the degradation rate of penicillin and ammonia nitrogen. Therefore, in summary, the parameter effect of Example 1 is relatively better.

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

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

[0092] Depend on Figure 3 The comparison results show that the biodegradation process of Control Example 3 increased the dissolved oxygen concentration, and the bacterial-algae complex capsule containing anaerobic bacteria could not effectively exert the biodegradation effect. As a result, the penicillin degradation rate and ammonia nitrogen degradation rate of Control Example 3 were lower than those of Examples 12-17.

[0093] Comparing Examples 12-17, it can be seen that too small or too large biodegradation parameters, too small amount of bacterial-algae compound capsules, and too small or too large filter diameter will reduce the degradation rate of penicillin and ammonia nitrogen. In Example 15, the effect could not be further enhanced after the amount of bacterial-algae compound capsules added reached a certain level. Therefore, from an economic point of view, the parameters of Example 1 are relatively better.

[0094] 4. To investigate the degradation rate of penicillin wastewater by the preparation parameters of the bacterial-algae compound capsule.

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

[0096] Depend on Figure 4 The comparison results show that, since the magnetization activation of the Myriophyllum spicatum extract was not performed in Control Example 4, the binding performance of the Myriophyllum spicatum extract with the anaerobic bacteria solution was reduced. Therefore, the degradation rates of penicillin and ammonia nitrogen were lower than those in Examples 18-29.

[0097] Comparing Examples 18-29, it can be seen that excessively small or large parameters for water extraction, alcohol extraction, magnetization, anaerobic bacteria concentration, shear mean, and electrostatic spraying all reduce the degradation rate of penicillin and ammonia nitrogen. Therefore, in summary, the parameters in Example 1 are relatively better.

Claims

1. A process for harmlessly treating penicillin wastewater, characterized in that, Includes the following steps: S1, Adsorption and Degradation: Goethite-loaded modified cellulose was added to penicillin wastewater at 80-90℃, 0.07-0.09 MPa, and dissolved oxygen concentration of 0.5-0.7 mg / L. The concentration of penicillin in the wastewater was 3-8 mM, the pH was 2-4, and the amount of goethite-loaded modified cellulose added was 50-150 mg / L. The degradation was carried out for 1.5-2.5 hours, followed by filtration. The modified cellulose is prepared as follows: under the action of an electric field, cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 20-25% for a first soaking time of 20-30 minutes; after the first soaking, under the action of an electric field, cellulose is immersed in a polyethylene glycol activated ester solution with a mass concentration of 10-15% for a second soaking time of 5-10 minutes; and the cellulose after the second soaking is washed and dried to obtain modified cellulose. The current for the first immersion is 60~80mA, and the potential gradient is 0.7~1.0V / cm; the current for the second immersion is 30~40mA, and the potential gradient is 0.2~0.5V / cm. S2, Biodegradation: Under anaerobic conditions, the bacterial-algae composite capsules were added to the penicillin wastewater after one filtration at 40-60℃, pressure 0.01-0.03MPa, and vacuum degree 0.02-0.04MPa. The amount of bacterial-algae composite capsules added was 25-45g / L. The degradation process lasted for 3-3.5 hours, followed by a second filtration to complete the degradation. The preparation method of the fungal-algae compound capsule is as follows: The extract of Myriophyllum spicatum was magnetized at a magnetic induction intensity of 40~60mT for 10~30min to obtain magnetized Myriophyllum spicatum extract powder. The preparation method of the *Myriophyllum spicatum* extract is as follows: *Myriophyllum spicatum* residue is placed in water at a solid-liquid ratio of 1g:15-25ml, and extracted at 90-100℃ for 1.5-2.5h. The residue is then filtered to obtain a primary filtrate and a secondary filtrate. The secondary filtrate is then placed in 90-95 wt% ethanol at a solid-liquid ratio of 1g:1-1.2ml, and extracted ultrasonically at 150-250W and 75-85℃ for 0.4-0.8h. The residue is then filtered to obtain a secondary filtrate. The primary and secondary filtrates are combined to obtain a mixed filtrate, which is then concentrated and dried sequentially to obtain the *Myriophyllum spicatum* extract. The magnetized *Myriophyllum spicatum* extract powder and anaerobic bacteria solution were mixed evenly at a solid-liquid ratio of 1g:10~15ml. The viable bacteria count in the anaerobic bacteria solution was 1~1.5×10⁻⁶. 9 CFU / mL, to obtain a mixture; then, the sodium alginate solution, Tween-80 and the mixture are sheared and homogenized at 12000~18000 rpm for 10~25 min at a mass ratio of 1:0.3:1~1.4 to obtain an emulsion; The emulsion was electrostatically sprayed at 30-50°C with a voltage of 10-20KV and an emulsion flow rate of 0.2-0.8mL / h. The distance from the needle tip to the dichloromethane curing liquid was 5-15cm, resulting in a bacterial-algae composite capsule.

2. The process for harmlessly treating penicillin wastewater as described in claim 1, characterized in that, The method for preparing goethite-loaded modified cellulose is as follows: goethite, modified cellulose and buffer solution are mixed for 1.5-2 hours to obtain a mixed solution, wherein the concentration of goethite in the mixed solution is 0.05-0.4 g / L and the concentration of modified cellulose in the mixed solution is 10-40 µM. The mixture is then separated into solid and liquid components, washed and dried to obtain goethite-loaded modified cellulose.

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

4. The process for harmlessly treating penicillin wastewater as described in claim 1, characterized in that, The anaerobic bacterial solution contains methanogens and / or Citrobacter freundii.

5. The process for harmlessly treating penicillin wastewater as described in claim 1, characterized in that, In step S1, the filter membrane used for primary filtration is selected from any one of cellulose acetate membrane, polyacrylonitrile membrane, and polyamide membrane, with a filter diameter of 0.05~0.1μm.

6. The process for harmlessly treating penicillin wastewater as described in claim 1, characterized in that, In step S2, the filter membrane for secondary filtration is selected from polycarbonate membrane or sulfonated polysulfone membrane, with a filter diameter of 1.5~2nm.

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