A method for treating cefuroxime sodium production wastewater

Abstract

The present application relates to the technical field of pharmaceutical wastewater treatment, and relates to a treatment method of cefuroxime sodium production wastewater. First, the cefuroxime sodium production wastewater is pretreated, and the pH is adjusted to 5.0-7.5; the porous magnetic catalytic aerogel is put into the pretreated wastewater, and mixed treatment is carried out while sunlight irradiation; the porous magnetic catalytic aerogel is taken out, and the treated water is obtained. The 24-hour degradation rate of the cefuroxime sodium and cefuroxime axetil can reach more than 95%, and the COD removal rate is more than 90%. The present application realizes the efficient degradation treatment of antibiotics and organic matters in the cefuroxime sodium production wastewater by using visible light catalysis and through the synergistic mechanism of 'adsorption-enrichment-degradation'.

Description

Technical Field

[0001] This invention relates to the field of pharmaceutical wastewater treatment technology, and more specifically, to a method for treating wastewater from the production of cefuroxime sodium. Background Technology

[0002] Cefuroxime sodium is a commonly used cephalosporin antibiotic with broad-spectrum antibacterial activity, widely used clinically for the treatment of respiratory, urinary tract, and postoperative infections. However, its stable β-lactam ring structure makes it difficult to degrade in the natural environment. Cefuroxime sodium and its metabolites may enter the aquatic environment through various pathways, existing in water bodies, soil, and even drinking water, thus becoming a new type of environmental pollutant.

[0003] Semiconductor photocatalysis technology has attracted much attention in the field of antibiotic wastewater treatment due to its advantages such as mild reaction conditions and thorough degradation. However, traditional photocatalysts (such as TiO2 and ZnO) suffer from problems such as easy deactivation and difficulty in recovery, which limits their engineering applications. In particular, for cefuroxime sodium wastewater with complex composition, single treatment technologies often fail to achieve simultaneous and efficient removal of pollutants. Therefore, developing wastewater treatment methods with high catalytic activity to achieve the synergistic removal of antibiotics and organic matter, and the harmless treatment of cefuroxime sodium production wastewater, has become a key technical challenge that urgently needs to be solved in the current water treatment field. Summary of the Invention

[0004] To overcome the deficiencies described in the prior art, this invention provides a method for treating wastewater from the production of cefuroxime sodium.

[0005] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:

[0006] A method for treating wastewater from cefuroxime sodium production, the method comprising the following steps:

[0007] S1: Pre-treat the wastewater from cefuroxime sodium production, adjust the pH, and obtain pre-treated wastewater;

[0008] S2: The porous magnetic catalytic aerogel is placed into the pretreated wastewater and mixed with sunlight during the treatment.

[0009] S3: Remove the porous magnetic catalytic aerogel to obtain the treated water.

[0010] Preferably, step S1 involves adjusting the pH to 5.0~7.5.

[0011] More preferably, step S1 involves adjusting the pH to 6.0-7.0.

[0012] Preferably, the mass ratio of the porous magnetic catalytic aerogel to the pretreated wastewater in step S2 is 1~2:1000.

[0013] Preferably, the sunlight exposure in step S2 includes natural sunlight or simulated sunlight, wherein the simulated sunlight intensity is 50~100 mW / cm². 2 .

[0014] Preferably, the mixing in step S2 includes one or more of stirring mixing and aeration mixing.

[0015] Preferably, the sunlight exposure time in step S2 is 12h to 24h.

[0016] Preferably, the porous magnetic catalytic aerogel extraction method in step S3 includes magnetic adsorption separation.

[0017] Furthermore, the porous magnetic catalytic aerogel is prepared by the following method:

[0018] (1) Deionized water, sulfated nanocellulose, cobalt nitrate hexahydrate and nano Fe3O4 are mixed and stirred to form a uniform and stable dispersion; then cellulose acetoacetate powder is added to the dispersion and stirred to ensure that the components are fully mixed and uniform to obtain a mixed solution;

[0019] (2) Add crosslinking agent to the mixed solution obtained in step (1), stir evenly and let stand for 24~48h to form primary hydrogel;

[0020] (3) Take out the primary hydrogel, immerse it completely in the pre-prepared cross-linking strengthening solution, soak it, wash it with deionized water, and freeze-dry it to form a porous magnetic catalytic aerogel.

[0021] Preferably, the nano Fe3O4 particles in step (1) have a particle size of 10~50 nm.

[0022] Preferably, the mass ratio of deionized water, sulfated nanocellulose, cobalt nitrate hexahydrate and nano Fe3O4 in step (1) is 1000 : 2~4 : 1~2 : 0.5~1.

[0023] Preferably, the mass ratio of cellulose acetoacetate powder to deionized water in step (1) is 4~6:1000.

[0024] Preferably, the crosslinking agent in step (2) comprises one of arginine, lysine and polyethyleneimine.

[0025] Preferably, the mass ratio of the crosslinking agent in step (2) to the deionized water in step (1) is 1~2:1000.

[0026] Preferably, the crosslinking agent in step (2) is polyethyleneimine, and the molecular weight of the polyethyleneimine is 300~600.

[0027] Preferably, the crosslinking agent in step (2) is polyethyleneimine, and the molecular weight of the polyethyleneimine is 300.

[0028] Preferably, the mass of the crosslinking strengthening solution in step (3) is 2 times or more the mass of the deionized water in step (1).

[0029] Preferably, the crosslinking strengthening solution in step (3) is obtained by mixing ammonium salt, aldehyde, ethanol and deionized water.

[0030] Preferably, in the crosslinking strengthening solution of step (3), the concentration of ammonium salt is 0.1~0.2 mol / L, the concentration of aldehyde is 0.1~0.2 mol / L, the mass percentage of ethanol is 60~80%, and the remainder is deionized water.

[0031] Preferably, the ammonium salt in the crosslinking strengthening solution in step (3) comprises ammonium acetate or ammonium chloride.

[0032] Preferably, the aldehyde in the crosslinking strengthening solution in step (3) includes one of vanillin, benzaldehyde, and p-hydroxybenzaldehyde.

[0033] Preferably, the soaking temperature in step (3) is 40~60℃ and the soaking time is 6~8 hours.

[0034] In this invention, the mechanical and catalytic properties of porous magnetic catalytic aerogels are enhanced through a dual reaction: some carbonyl groups and amine groups undergo Schiff base reaction (C=N bond formation) to construct additional cross-linking nodes; acetoacetic acid groups, ammonium ions and aldehydes in the system undergo cyclization condensation to further strengthen the cross-linking network and generate nitrogen-containing heterocycles (mainly aromatic pyridine derivatives) in situ to stabilize and enhance cobalt catalytic active sites.

[0035] More preferably, the cellulose acetoacetate powder is prepared by the following steps:

[0036] Cellulose powder was added to a surface-functionalized solvent for reaction; after filtration, the reacted cellulose powder was washed with an aqueous ethanol solution and then dried to obtain cellulose acetoacetate powder.

[0037] The surface-functionalized solvent comprises acetoacetate compounds and N,N-dimethylformamide;

[0038] The mass ratio of the cellulose powder to N,N-dimethylformamide is 1:8-12;

[0039] The mass ratio of acetoacetate compounds to N,N-dimethylformamide in the surface functionalized solvent is 1:8~12.

[0040] Preferably, the cellulose powder has a particle size of 50~65μm.

[0041] Preferably, the cellulose powder has a particle size of 50 μm.

[0042] Preferably, the acetoacetate compound comprises one of tert-butyl acetoacetate and ethyl acetoacetate.

[0043] Preferably, the mass ratio of the cellulose powder to N,N-dimethylformamide is 1:8-12, the reaction temperature is 110-150℃, and the reaction time is 3-5 h.

[0044] Preferably, the mass percentage of ethanol in the aqueous ethanol solution is 60-80%.

[0045] Preferably, the washing includes washing at least three times with an aqueous solution of ethanol at a mass of 5 times that of the cellulose powder.

[0046] In this invention, the sulfate groups of sulfated cellulose nanoparticles form a primary network through electrostatic interactions with amino groups. The β-diketone groups of cellulose acetoacetate powder further crosslink with primary amines. Then, the hydrogel precursor, in an ammonium salt / aldehyde system, utilizes the aldehyde to participate in the Hantzsch pyridine ring formation reaction, forming a cobalt-pyridine coordinated active catalytic center and thus a photocatalytic hydrogel. Fe3O4 can simultaneously participate in the catalytic degradation reaction and also facilitates the recovery of the hydrogel. The catalytic aerogel structure is beneficial for increasing the specific surface area for adsorbing organic pollutants.

[0047] Compared with the prior art, the beneficial effects of the technical solution of the present invention are:

[0048] The magnetic photocatalytic aerogel material provided by this invention and its application in the treatment of cefuroxime sodium production wastewater have the following significant advantages: the degradation rate of cefuroxime sodium can reach over 95% within 12 hours, the degradation rate of cefuroxime axetil can reach over 96% within 12 hours, and the COD removal rate exceeds 90%. The magnetic photocatalytic aerogel material provided by this invention can absorb visible light, effectively utilizing the visible light energy of sunlight. This aerogel material integrates adsorption, catalysis, and magnetic separation functions, achieving highly efficient synergistic removal of antibiotics and organic matter from cefuroxime sodium production wastewater and treating the wastewater through a synergistic mechanism of "adsorption-enrichment-degradation." Detailed Implementation

[0049] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0050] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0051] The raw materials used in the embodiments and comparative examples are described below, but are not limited to these materials:

[0052] Cellulose powder, C434461 Aladdin reagent, powder, particle size: 20μm.

[0053] Cellulose powder, C804601 Maclean's reagent, powder, particle size: 65μm.

[0054] Cellulose powder, C104842 Aladdin reagent, powder, particle size: 50μm.

[0055] Polyethyleneimine, Aladdin Reagent E498552, ≥99%, MW 300.

[0056] Polyethyleneimine, E107077 Aladdin Reagent, ≥99%, MW 600.

[0057] tert-butyl acetoacetate, B802387, Maclean's reagent, 95%.

[0058] N,N-Dimethylformamide, N807505, Maclean's reagent, 99.5%.

[0059] Ammonium acetate, A800998 Maclean's reagent, ≥99%.

[0060] Vanillin, V820371 Maclean's reagent, reagent grade, 99%.

[0061] Aminosulfonic acid, S823797, Maclean's reagent, 99.9%.

[0062] Nano-Fe3O4 (Fe3O4), 1317-61-9, powder, 20nm, Aladdin.

[0063] The sulfated cellulose nanoparticles were prepared by the inventors themselves, and the preparation method includes the following steps:

[0064] N,N-dimethylformamide, cellulose powder (20 μm), and aminosulfonic acid were added to a three-necked flask at a mass ratio of 50:1:1. The mixture was heated to 80°C and reacted for 3 hours with stirring, then cooled to room temperature. The reaction product was then filtered, washed with 70% ethanol aqueous solution, and added to deionized water (mass ratio of reaction product to deionized water 1:500). After ultrasonic dispersion for 30 minutes, a sulfated cellulose nanoparticle suspension was obtained. Finally, the sulfated cellulose nanoparticle suspension was freeze-dried under vacuum to obtain the sulfated cellulose nanoparticles. The degree of substitution of the sulfated cellulose nanoparticles was tested to be 0.2. The ultrasonic power was 800 W.

[0065] Example 1

[0066] 1. Preparation of cellulose acetoacetate powder

[0067] Cellulose powder with a particle size of 50 μm, tert-butyl acetoacetate, and N,N-dimethylformamide were mixed in a mass ratio of 1:1:10 and heated to 130 °C for 4 h. After filtration, the cellulose powder was washed with 70% ethanol aqueous solution and then dried to obtain cellulose acetoacetate powder.

[0068] 2. Preparation of porous magnetic catalytic aerogels

[0069] (1) Add 3 g of sulfated cellulose nanoparticles, 1 g of cobalt nitrate hexahydrate and 1 g of nano Fe3O4 (average particle size 20 nm) sequentially to 1000 g of deionized water. Stir the mixture magnetically at 500 rpm for 3 h at 25 °C to form a uniform dispersion. Then add 6 g of cellulose acetoacetate powder and continue stirring for 1 h to ensure thorough mixing.

[0070] (2) Slowly add 2 g of polyethyleneimine (MW300) as a crosslinking agent to the above mixture and stir at 500 rpm to make it uniform. Then let it stand at room temperature (25℃) for 24 h to allow the system to fully crosslink. It can be observed that the phase state of the reaction system changes significantly, and the initial homogeneous solution gradually transforms into a heterogeneous system to form a primary hydrogel.

[0071] (3) Immerse the primary hydrogel in 2000g of cross-linking strengthening solution (containing 0.1 mol / L ammonium acetate (NH4Ac) and 0.1 mol / L vanillin in ethanol aqueous solution) at 50℃ for 7 h.

[0072] (4) After the cross-linked hydrogel is washed with deionized water, it is freeze-dried for 3-4 days to finally obtain a porous magnetic catalytic aerogel.

[0073] 3. Treatment of wastewater from cefuroxime sodium production:

[0074] Degradation tests of cefuroxime sodium and cefuroxime axetil were conducted using a prepared mixed aqueous solution of cefuroxime containing 5 mg / L of cefuroxime sodium and 0.2 mg / L of cefuroxime axetil. For COD degradation testing, wastewater from the production of cefuroxime sodium was used, and the COD was measured to be 30,000 mg / L. First, the pH of the mixed aqueous solution of cefuroxime sodium or the wastewater from the production of cefuroxime sodium was measured and adjusted to 6.0. The prepared porous magnetic catalytic aerogel was added at a mass ratio of porous magnetic catalytic aerogel to pretreated wastewater of 1.5:1000. A stirring speed of 150-300 rpm was maintained during the treatment. Simulated sunlight irradiation was used, and the reaction time was controlled at 12 hours.

[0075] Then, magnetic adsorption separation is performed. When the magnet is brought close to the reactor wall, the aerogel material is completely adsorbed by the magnet within 3-15 minutes. After washing with water and drying, the dry weight of the recovered aerogel material is measured, and the recovery rate is calculated. The supernatant is then collected, which is the treated effluent. The effluent undergoes final testing.

[0076] Example 2

[0077] This embodiment provides a method for treating wastewater from cefuroxime sodium production. The preparation method is similar to that in Example 1, except that in the porous magnetic catalytic aerogel step (1), 2 g of sulfated nanocellulose, 2 g of cobalt nitrate hexahydrate and 0.5 g of nano Fe3O4 are added to 1000 g of deionized water; 4 g of cellulose acetoacetate powder is added; in step (2), 1 g of polyethyleneimine (MW600) is added as a crosslinking agent, and the system is allowed to stand for 48 h to allow the system to fully crosslink. It can be observed that the phase state of the reaction system changes significantly, and the initial homogeneous solution gradually transforms into a heterogeneous system to form a primary hydrogel; in the treatment step of cefuroxime sodium production wastewater, the pH is adjusted to 7.0 and simulated sunlight is used for irradiation for 24 hours.

[0078] Example 3

[0079] This embodiment provides a method for treating wastewater from the production of cefuroxime sodium. The treatment method is similar to that in Example 1, except that cellulose acetoacetate powder with a particle size of 65 μm is used for its preparation.

[0080] Example 4

[0081] This embodiment provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that 2 g of arginine is added as a crosslinking agent in step (2) of porous magnetic catalytic aerogel; and 0.2 mol / L benzaldehyde and 0.2 mol / L ammonium chloride are used in step (3).

[0082] Example 5

[0083] This embodiment provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that 2 g of lysine is added as a crosslinking agent in the porous magnetic catalytic aerogel step (2); and 0.2 mol / L p-hydroxybenzaldehyde and 0.2 mol / L ammonium acetate are used in step (3).

[0084] Comparative Example 1

[0085] This comparative example provides a method for treating wastewater from the production of cefuroxime sodium. The treatment method is similar to that in Example 1, except that in the porous magnetic catalytic aerogel step (1), cellulose acetoacetate powder is not added, but ordinary cellulose powder is used instead.

[0086] Comparative Example 2

[0087] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that step (3) is omitted in the preparation of porous magnetic catalytic aerogel.

[0088] Comparative Example 3

[0089] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that in the porous magnetic catalytic aerogel preparation step (3), the primary hydrogel is immersed in 2000g of crosslinking strengthening solution (containing 0.4 mol / L ammonium acetate (NH4Ac) and 0.4 mol / L vanillin in 70% ethanol aqueous solution) for 7 h.

[0090] Comparative Example 4

[0091] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that Fe3O4 is not added in the porous magnetic catalytic aerogel step (1).

[0092] Comparative Example 5

[0093] This comparative example provides a method for treating wastewater from the production of cefuroxime sodium. The treatment method is similar to that in Example 1, except that cellulose powder with a particle size of 20 μm is used in the preparation of cellulose acetoacetate powder.

[0094] Comparative Example 6

[0095] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that the pH value is adjusted to 8.5 in the treatment step of cefuroxime sodium production wastewater.

[0096] Comparative Example 7

[0097] This comparative example provides a method for treating wastewater from the production of cefuroxime sodium. The method is similar to that in Example 1, except that the settling time in step (2) of the porous magnetic catalytic aerogel is 12 hours.

[0098] Comparative Example 8

[0099] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that in the porous magnetic catalytic aerogel step (1), 1 g of sulfated nanocellulose, 0.5 g of cobalt nitrate hexahydrate, and 0.1 g of nano Fe3O4 are added sequentially to 1000 g of deionized water. The mixture is magnetically stirred at 500 rpm for 3 h at 25°C to form a uniform dispersion.

[0100] Comparative Example 9

[0101] This comparative example provides a method for treating wastewater from cefuroxime sodium production. The treatment method is similar to that in Example 1, except that in the porous magnetic catalytic aerogel step (1), 5 g of sulfated cellulose nanoparticles, 3 g of cobalt nitrate hexahydrate, and 2 g of nano-Fe3O4 are added sequentially to 1000 g of deionized water. The mixture is magnetically stirred at 500 rpm for 3 h at 25°C to form a uniform dispersion.

[0102] Comparative Example 10

[0103] This comparative example provides a method for treating wastewater from the production of cefuroxime sodium. The method is similar to that in Example 1, except that (1) polyethyleneimine with a molecular weight of 1200 is used.

[0104] Detection methods

[0105] The light source used was a 500W xenon lamp with an AM1.5 standard filter, and the illuminance was measured to be 80mW / cm² using a lux meter. 2 The determination of cefuroxime in water was performed using ultra-high performance liquid chromatography-mass spectrometry. COD was determined according to HJ 828-2017. The mechanical properties of the aerogel were determined according to the aerogel compressive strength test method, characterized using an electronic universal testing machine at a compression rate of 5 mm / min. The mineralization rate was analyzed using a TOC analyzer to determine the TOC content in the samples and calculate the relevant mineralization rate. The formula is: Mineralization rate (%) = (1 - Ct / C0) × 100%, where C0 is the initial TOC concentration in the wastewater sample, and Ct is the TOC concentration in the treated wastewater sample after reaction time t minutes.

[0106] The reusability test involved re-degrading the porous magnetic catalytic aerogel recovered in Example 1 under the conditions of Example 1, repeating the experiment three times to test the removal effect.

[0107] The results are shown in the table below:

[0108] Table 1. Combined data on wastewater treatment results of the examples and comparative examples.

[0109]

[0110] Table 2 Mineralization rate data from examples

[0111]

[0112] Table 3 Reuse data from Example 1

[0113]

[0114] Results analysis:

[0115] As can be seen from Examples 1-5 and Comparative Examples 1-10, the method for treating cefuroxime sodium production wastewater provided by the present invention utilizes porous magnetic photocatalytic aerogel materials. By introducing cellulose acetoacetate powder and employing a dual-reaction process, the overall performance of the wastewater treatment process is significantly improved. This method enhances catalytic degradation activity while also significantly improving the stability of the catalytic structure, exhibiting excellent wastewater treatment capabilities. Specifically, the degradation rate of cefuroxime sodium reaches over 95%, and the degradation rate of cefuroxime axetil reaches over 96%. Within the preferred parameter range, the wastewater treatment effect is good, and the recovery rate of the magnetic photocatalytic aerogel is >95%, with a mineralization rate exceeding 65%, reaching a maximum of 71.2%, indicating that most of the cefuroxime sodium and cefuroxime axetil are mineralized into CO2 and H2O. In particular, the porous magnetic photocatalytic aerogel material in Example 1 can be reused at least 3 times, and the degradation rate of cefuroxime axetil and cefuroxime sodium reaches 95%.

[0116] As can be seen from Examples 1 and 3, the cellulose acetoacetate powder prepared with a particle size of 50 μm (Example 1) has improved degradation rates of cefuroxime sodium, cefuroxime ester, COD, and aerogel mechanical properties compared with the cellulose acetoacetate powder prepared with a particle size of 65 μm (Example 3), exhibiting superior overall performance.

[0117] As can be seen from Example 1 and Comparative Example 1, without the addition of cellulose acetoacetate powder, the structural stability and catalytic performance are significantly reduced, the wastewater treatment effect is poor, the antibiotic degradation rate drops to less than 50%, the COD degradation rate is only 56.2%, and recycling is difficult.

[0118] As can be seen from Example 1 and Comparative Example 2, the aerogel without ammonium salt / aldehyde crosslinking strengthening solution treatment exhibits significantly reduced structural stability and water treatment efficiency, with a mechanical property of 26.2 kPa (compared to 128.5 kPa in Example 1). As can be seen from Example 1 and Comparative Example 3, using a crosslinking strengthening solution with a concentration higher than the preferred range of this invention, the degradation rate of cefuroxime sodium or cefuroxime axetil decreases by more than 30%.

[0119] As can be seen from Example 1 and Comparative Example 4, the degradation rate of cefuroxime sodium or cefuroxime axetil in samples without added Fe3O4 was only 70%~85%, and the catalyst recovery rate decreased significantly, indicating that Fe3O4 exhibits a synergistic catalytic effect. Further, the results of Example 1, Comparative Example 1, and Comparative Example 4 show that the combined use of cellulose acetoacetate powder and nano-Fe3O4 (Example 1) significantly improved the antibiotic degradation efficiency and COD degradation rate compared to the use of cellulose acetoacetate powder (Comparative Example 1) or nano-Fe3O4 (Comparative Example 4), while also increasing the catalyst recovery rate, further demonstrating the synergistic effect of the material composition.

[0120] As can be seen from the results of Example 1 and Comparative Example 5, the particle size of the cellulose powder used to prepare cellulose acetoacetate powder is not within the preferred range of the present invention (Comparative Example 5, 20 μm). Although the structural stability catalyst recovery rate is high, the overall effect of wastewater treatment is poor, and the degradation rate of cefuroxime sodium or cefuroxime ester and the COD degradation rate are less than 85%.

[0121] As can be seen from Example 1 and Comparative Example 6, the wastewater treatment efficiency of wastewater treatment methods with pH outside the preferred range is significantly reduced. When the pH value is adjusted to 8.5 in the treatment step of cefuroxime sodium production wastewater, the degradation rate of cefuroxime sodium or cefuroxime ester drops to below 70%, and the COD degradation rate is less than 80%.

[0122] As can be seen from the results of Example 1 and Comparative Example 7, the settling time after mixing the crosslinking agent in the preparation of porous magnetic catalytic aerogel has a significant impact on the overall performance of wastewater treatment. When the settling time is not within the preferred range of this invention, specifically when the settling time is 12 hours (less than 24 hours), the antibiotic degradation rate drops to below 70%, the COD degradation rate is less than 70%, and the mechanical properties of the aerogel and the catalyst recovery rate also decrease significantly.

[0123] As can be seen from the results of Example 1 and Comparative Examples 8 and 9, the mass ratio of deionized water, sulfated nanocellulose, cobalt nitrate hexahydrate, and nano-Fe3O4 in the preparation of porous magnetic catalytic aerogel has a significant impact on the overall performance of wastewater treatment, showing a significant synergistic effect in terms of antibiotic degradation rate and COD degradation rate. When the ratio is outside the preferred range of this invention, specifically, when the ratio is 1000:0.5:0.5:0.1, the wastewater recovery effect decreases, and the antibiotic degradation rate and COD degradation rate decrease by more than 30%. When the ratio is 1000:5:3:2, increasing the mass ratio of sulfated nanocellulose, cobalt nitrate hexahydrate, and nano-Fe3O4 does not improve the wastewater treatment effect; instead, the antibiotic degradation rate and COD degradation rate decrease by more than 30%.

[0124] As can be seen from Example 1 and Comparative Example 10, the molecular weight of polyethyleneimine has a significant impact on the overall performance of wastewater treatment in the preparation of porous magnetic catalytic aerogel. When polyethyleneimine (Comparative Example 10, MW1200) that is not within the preferred range of this invention is used, the wastewater treatment and wastewater recovery effects decrease, and the antibiotic degradation rate and COD degradation rate decrease by more than 30%.

[0125] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for treating wastewater from cefuroxime sodium production, characterized in that, Includes the following steps: S1: Pre-treat the wastewater from cefuroxime sodium production, adjust the pH, and obtain pre-treated wastewater; S2: The porous magnetic catalytic aerogel is placed into the pretreated wastewater and mixed with sunlight during the treatment. S3: Remove the porous magnetic catalytic aerogel to obtain the treated water; The porous magnetic catalytic aerogel was prepared by the following method: (1) Deionized water, sulfated nanocellulose, cobalt nitrate hexahydrate and nano Fe3O4 are mixed and stirred to form a uniform and stable dispersion; then cellulose acetoacetate powder is added to the dispersion and stirred to ensure that the components are fully mixed and uniform to obtain a mixed solution; (2) Add crosslinking agent to the mixed solution obtained in step (1), stir evenly and let stand for 24~48h to form primary hydrogel; (3) Take out the primary hydrogel, immerse it completely in the pre-prepared cross-linking strengthening solution, soak it, wash it with deionized water, and freeze-dry it to form a porous magnetic catalytic aerogel. The crosslinking agent in step (2) comprises one of arginine, lysine, and polyethyleneimine; The cross-linking strengthening solution in step (3) is obtained by mixing ammonium salt, aldehyde, ethanol and deionized water.

2. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, The pH is adjusted to 5.0~7.5 as described in step S1.

3. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, In step S2, the mass ratio of the porous magnetic catalytic aerogel to the pretreated wastewater is 1~2:1000; the sunlight irradiation time is 12h~24h.

4. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, The mass ratio of deionized water, sulfated nanocellulose, cobalt nitrate hexahydrate and nanoFe3O4 in step (1) is 1000: 2~4: 1~2: 0.5~1; the mass ratio of cellulose acetoacetate powder to deionized water in step (1) is 4~6: 1000.

5. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, The mass ratio of the crosslinking agent in step (2) to the deionized water in step (1) is 1~2:1000.

6. The method for treating cefuroxime sodium production wastewater according to claim 5, characterized in that, The crosslinking agent in step (2) is polyethyleneimine, and the molecular weight of polyethyleneimine is 300~600.

7. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, The soaking temperature in step (3) is 40~60℃, and the soaking time is 6~8 hours.

8. The method for treating cefuroxime sodium production wastewater according to claim 1, characterized in that, The cellulose acetoacetate powder mentioned in step (1) is prepared by the following method: Cellulose powder was added to a surface-functionalized solvent for reaction; after filtration, the reacted cellulose powder was washed with an aqueous ethanol solution and then dried to obtain cellulose acetoacetate powder. The surface-functionalized solvent comprises acetoacetate compounds and N,N-dimethylformamide; The mass ratio of cellulose powder to N,N-dimethylformamide is 1:8 to 12; the mass ratio of acetoacetate compounds to N,N-dimethylformamide in the surface functionalized solvent is 1:8 to 12.

9. The method for treating cefuroxime sodium production wastewater according to claim 8, characterized in that, The cellulose powder has a particle size of 50~65 μm.

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