Device and method for treating antibiotic production wastewater by coupling catalytic hydrolysis and catalytic degradation

Abstract

The invention belongs to the technical field of pharmaceutical wastewater treatment, and particularly relates to a device and a method for treating antibiotic production wastewater by coupling catalytic hydrolysis and catalytic degradation. The device comprises a catalytic hydrolysis reactor and an electro-catalysis reactor, the two reactors are connected in series through a pipeline with a water stop valve, the catalytic hydrolysis reactor is divided into a plurality of compartments by water baffles, and each compartment is filled with a catalytic porous hydrolysis filler; and a cathode, an anode and a stirrer are arranged in the electro-catalytic reactor. By utilizing the porous hydrolysis filler in the device, selective catalytic hydrolysis of high-concentration antibiotics in wastewater is completed by controlling the hydraulic retention time, the anodic oxidation efficiency is improved by virtue of the high contact reaction area of the porous blocky anode, and efficient mineralization degradation of residual antibiotics and hydrolysates thereof is realized. The treatment device and method for the antibiotic production wastewater are good in selective hydrolysis effect, high in mineralization degradation efficiency, easy and convenient to operate and maintain and low in energy consumption.

Description

Technical Field

[0001] The invention belongs to the technical field of pharmaceutical wastewater treatment, and in particular relates to a device and method for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation. Background Art

[0002] Antibiotic production wastewater has the characteristics of high chromaticity and COD, low BOD, etc. It has strong microbial inhibition and induces the production of antibiotic-resistant bacteria (ARBs) and resistance genes (ARGs). Conventional water quality parameters such as COD and ammonia nitrogen are difficult to treat and meet the standards, and residual antibiotics, ARBs and ARGs will enter the surface water with the drainage of sewage treatment plants. Sewage irrigation and agricultural resource utilization of sludge may also lead to soil enrichment of antibiotics. Due to the lack of feasible technical support for pollution prevention and control, it is difficult for pharmaceutical companies that indirectly discharge wastewater to meet the discharge standards. About 44% of chemical synthesis pharmaceutical companies and about 14% of fermentation pharmaceutical companies fail to meet the standard proportion of the management agreement. The "Guidelines for Feasible Technologies for Pollution Prevention and Control in the Pharmaceutical Industry - APIs (Fermentation, Chemical Synthesis, Extraction) and Preparations" (HJ 1305-2023) has not formulated special pollution prevention and control technologies for antibiotics. The hydrolysis rate is an important indicator for predicting the environmental persistence of antibiotics, and the degradation of most antibiotics is based on the principle of hydrolysis. Antibiotics can be degraded by heat, alkali and transition metal ions (Fe 3+ , Cu 2+ The antibiotics can be hydrolyzed by homogeneous catalysis (such as solid alkali, CaO / MgO, MgO / SiO2, etc.), or heterogeneous catalysis (such as solid alkali, CaO / MgO, MgO / SiO2, etc.). In addition, antibiotics can also be hydrolyzed by metal complexes with Lewis acid properties (such as Al2O3, molecular sieve-loaded CuFe2O4, etc.).

[0003] In order to achieve the hydrolysis of high-concentration antibiotics in production wastewater, patent CN106986434A discloses a method for catalyzing the hydrolysis of antibiotics in wastewater by a solid alkali (CaO-MgO, CaO-ZrO2, MgO-ZrO2, K2CO3 / γ-Al2O3, KOH / γ-Al2O3, ZnO / Al2O3, MgO / MCM-41, K2SiO3 / SBA-15, K2SiO3 / Al-SBA-15, strong base styrene anion exchange resin D201-OH), which can completely hydrolyze streptomycin, penicillin, erythromycin, and spiramycin in simulated wastewater and eliminate their titers, but cannot achieve the degradation and mineralization removal of the hydrolysis products. Patent CN114538650A discloses a method for high temperature (85°C) catalytic hydrolysis of fermentation antibiotic production wastewater using an iron-based catalyst (goethite, siderite) loaded with metal (at least one of Zn, Mn, and Cu), which can achieve efficient hydrolysis of oxytetracycline in high-concentration actual production wastewater (oxytetracycline = 876 mg / L, COD = 10860 mg / L, SS = 206 mg / L), but the method has high energy consumption, significantly increases the SS content (800-821 mg / L) after the reaction, and cannot remove COD. Patent CN113213715B proposes a method for pretreating fermentation antibiotic production wastewater by thermal hydrolysis combined with anaerobic biofilm reactor (AnMBR), which can effectively hydrolyze oxytetracycline in oxytetracycline production mother liquor (pH = 4.8, COD = 12000 mg / L, SS = 200 mg / L, oxytetracycline 900 mg / L) and solve the problem of increased SS concentration during enhanced hydrolysis. However, this method requires preheating the waste mother liquor to 60°C and then heating it to 110°C for 1 hour, which consumes a lot of energy; the COD removal efficiency of AnMBR decreases with the increase of organic load, and the COD removal efficiency is only 50.02% to 51.58% when the organic load is 8g COD / L / d.

[0004] Although the existing technology can achieve efficient hydrolysis of high-concentration antibiotics in production wastewater, there are still problems such as high energy consumption, difficulty in recovering hydrolysis catalysts, inability to achieve mineralization and degradation of hydrolysis products, and high organic load in subsequent processes. The research results show that the hydrolysis of antibiotics in production wastewater will produce soluble and difficult-to-biodegrade COD, and the hydrolysis products may still have biological inhibitory activity, which significantly affects the subsequent biological treatment process. Summary of the invention

[0005] The purpose of the present invention is to provide the pharmaceutical industry with a special pollution prevention and control technology for antibiotics, and to propose a device and method for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation, the device comprises a catalytic hydrolysis reactor and an electrocatalytic reactor, the two reactors are connected in series via a pipeline with a water stop valve, wherein the catalytic hydrolysis reactor is divided into a plurality of compartments by a water retaining plate, each compartment is filled with a catalytic porous hydrolysis filler; a cathode, an anode and a stirrer are arranged in the electrocatalytic reactor.

[0008] There is at least one catalytic hydrolysis reactor in the device, and multiple catalytic hydrolysis reactors are arranged in sequence in a step-by-step manner and connected in series through pipelines with water stop valves; wherein, a water inlet pipe is provided at one end of a first-stage catalytic hydrolysis reactor, and a pipeline with a water stop valve is provided at the other end as a drainage pipeline and connected to the next-stage catalytic hydrolysis reactor.

[0009] At least two water retaining plates are arranged in the catalytic hydrolysis reactor, wherein the heights of the water retaining plates are arranged in a stepped manner from the water inlet end to the water outlet end.

[0010] A cathode and an anode are arranged in the electrocatalytic reactor; a plurality of stirrers are arranged between the cathode and the anode, each stirrer is connected to a stirring motor, and the stirring motor is fixed to the electrocatalytic reactor through an electrode bracket; and a reagent injection pipe and a disposal water outlet pipe are respectively arranged on the side walls of the electrocatalytic reactor.

[0011] The cathode and anode are arranged at intervals, and cathodes are arranged on both sides of the device, that is, cathode-anode-cathode-anode-cathode...-cathode.

[0012] A method for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation using the device, utilizing porous hydrolysis fillers in the device to complete selective catalytic hydrolysis of high-concentration antibiotics in the wastewater by controlling the hydraulic retention time, and improving the anodic oxidation efficiency by using the high contact reaction area of ​​the porous block anode to achieve efficient mineralization degradation of residual antibiotics and their hydrolysis products.

[0013] Further speaking

[0014] (1) After the production wastewater is pretreated to remove suspended solids, the pH is adjusted and the wastewater enters the catalytic hydrolysis reactor of the device to complete the catalytic hydrolysis reaction of the antibiotic;

[0015] (2) After the wastewater has been catalytically hydrolyzed, it enters the electrocatalytic reactor, and the peroxide oxidant is injected while the agitator is turned on to fully mix it;

[0016] (3) Continue stirring and turn on the DC power supply to complete the catalytic degradation of residual antibiotics and their hydrolysis products in the wastewater, and discharge them into subsequent treatment process facilities through the external pipeline of the electrocatalytic reactor.

[0017] The compartment in the catalytic hydrolysis reactor of the device is filled with catalytic porous hydrolysis fillers; the porous hydrolysis fillers can be selected from foamed magnesium oxide and / or foamed aluminum oxide, with a filler porosity of 60% to 90% and a pore size of 0.1 to 10 mm (5 to 120 ppi); the total filling volume of the catalytic hydrolysis fillers in the device is 60% to 80% of the volume of the catalytic hydrolysis reactor.

[0018] The magnesium oxide, aluminum oxide or magnesium oxide-aluminum oxide composite foam material is prepared by a foaming method. Magnesium oxide, aluminum oxide or magnesium oxide-aluminum oxide mixed powder with a particle size of 1-10 μm (mass ratio of 100:25-50) is made into a 15-60wt% slurry, 0.1%-2% of sodium dodecyl sulfate (SDS) or sodium dodecylbenzene sulfonate (SDBS) is added, and the mixture is stirred at 1000-2000 r / min for 5-15 minutes. The foamed slurry is poured into a mold, cured at room temperature for 24-48 hours, dried at 110°C for 12-24 hours, and finally sintered at 1200-1600°C for 2-4 hours.

[0019] The cathode in the electrocatalytic reactor can be made of graphite, titanium or boron-doped diamond; the anode material is spinel oxide (MCo2O4, M=Fe, Cu, Zn, Mg) modified titanium foam; the electrode distance between the anode and the cathode is 10 to 50 cm.

[0020] The anode was prepared by in situ deposition method. The foamed titanium was reacted with a precursor aqueous solution (containing 0.5mM Fe(NO3)3·9H2O or Cu(NO3)2·2.5H2O or Zn(NO3)2·6H2O or Mg(NO3)2·6H2O, 1mM Co(NO3)2·6H2O, 1mM NH4F, 2.5mM CO(NH2)2) in a polytetrafluoroethylene-lined stainless steel high-pressure reactor at 120°C for 6 hours, then rinsed with deionized water and anhydrous ethanol, dried at 60°C, and finally calcined at 400°C for 2h.

[0021] In the step (1), the pH value of the wastewater is adjusted to 7-11 with sodium hydroxide; the hydraulic retention time is controlled by the inlet flow rate; the hydraulic retention time is 3-14 hours;

[0022] The peroxide oxidant in step (2) is hydrogen peroxide, peracetic acid, peroxymonosulfate or peroxydisulfate, with a concentration of 10 to 500 g / L; the stirring speed of the stirrer is 50 to 300 r / min.

[0023] The current density of the electrocatalytic reaction in step (3) is 0.1 to 50 mA / cm 2 , reaction time 30 to 180 minutes.

[0024] The pretreatment of production wastewater described in step (1) can refer to the "Guidelines for Feasible Technologies for Pollution Prevention and Control in Pharmaceutical Industry - APIs (Fermentation, Chemical Synthesis, Extraction) and Preparations" (HJ 1305-2023). If the suspended solids concentration is high, coagulation sedimentation or flotation process can be selected; if the suspended solids concentration is low, adsorption filtration and other processes can be selected;

[0025] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0026] This application can be used for the treatment of pharmaceutical industrial wastewater containing high-concentration antibiotics. It can achieve efficient selective hydrolysis and deep mineralization degradation of antibiotics under complex water quality conditions, effectively avoid the induced generation of ARBs and ARGs in the sewage treatment process and block their environmental transmission. The device is simple to manufacture and has low cost and low operating energy consumption. The reactor, catalytic hydrolysis filler, electrode, etc. can all be obtained through market customization and processing. The installation of catalytic hydrolysis filler and electrode is simple and easy to clean and maintain. The disposal method is simple. The catalytic hydrolysis reaction time is controlled by hydraulic retention time. The wastewater enters the secondary hydrolysis reactor and the electrocatalytic reactor in a natural flow from the primary hydrolysis reactor. The input of chemicals in the wastewater disposal process is small. The high pH of the wastewater in the catalytic hydrolysis reaction stage can be reduced to near neutral in the electrocatalytic reaction stage. The high anode contact reaction area can significantly reduce the input of oxidants, avoiding the risk of secondary pollution and the impact on subsequent treatment processes. After the efficiency of catalytic hydrolysis fillers and electrodes decreases after long-term use, they can be simply reused by calcination, which significantly reduces the overall operating cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A schematic diagram of a device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation provided in an embodiment of the present invention;

[0028] Figure 2 The wastewater treatment effect when the foamed magnesium oxide is used as the catalytic hydrolysis filler and the FeCo2O4-modified foamed titanium is used as the electrocatalytic reaction anode provided in the embodiment of the present invention;

[0029] Figure 3 The wastewater treatment effect when using foamed aluminum oxide as a catalytic hydrolysis filler and FeCo2O4-modified foamed titanium as an electrocatalytic reaction anode provided in an embodiment of the present invention;

[0030] Figure 4 The wastewater treatment effect when the foamed magnesium oxide is used as the catalytic hydrolysis filler and the CuCo2O4-modified foamed titanium is used as the electrocatalytic reaction anode provided in the embodiment of the present invention;

[0031] Figure 5The wastewater provided in the embodiment of the present invention directly enters the electrocatalytic reactor (CuCo2O4 modified titanium foam as anode) without pH adjustment or two-stage catalytic hydrolysis treatment. DETAILED DESCRIPTION

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0034] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0035] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0036] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0037] After completing the selective catalytic hydrolysis of high-concentration antibiotics in production wastewater, the treatment method of the present invention uses electrocatalytic reaction to mineralize and degrade residual antibiotics and their hydrolysis products, thereby achieving deep mineralization and detoxification of high-concentration antibiotics in production wastewater, effectively eliminating the induced production of ARBs and ARGs and blocking their environmental spread, thereby solving the current problems of the pharmaceutical industry in terms of the difficulty in mineralization and degradation of antibiotics, strong microbial inhibition and induced production of ARBs and ARGs.

[0038] The equipment, materials and reagents used in the following examples of the present invention are all commercially available.

[0039] In the following embodiments of the present invention, the magnesium oxide powder, aluminum oxide powder, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, Fe(NO3)3·9H2O, Cu(NO3)2·2.5H2O, Zn(NO3)2·6H2O, Mg(NO3)2·6H2O, Co(NO3)2·6H2O, NH4F, CO(NH2)2, and anhydrous ethanol are all analytically pure reagents; plate cathodes such as graphite, titanium, and boron-doped diamond are commercially available materials customized to appropriate sizes; foamed titanium is a commercially available product customized to appropriate sizes, and MCo2O4 (M=Fe, Cu, Zn, Mg) modified foamed titanium can be prepared as described in the following embodiments.

[0040] The following examples serve as further illustrations of the technical solutions of the present invention.

[0041] Example 1

[0042] A device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation comprises a catalytic hydrolysis reactor and an electrocatalytic reactor. The two reactors are connected in series via a pipeline with a water stop valve. The catalytic hydrolysis reactor is divided into a plurality of compartments by a water retaining plate, and each compartment is filled with a catalytic porous hydrolysis filler. A cathode, an anode and a stirrer are arranged in the electrocatalytic reactor.

[0043] There is at least one catalytic hydrolysis reactor in the device, and multiple catalytic hydrolysis reactors are arranged in sequence in a step-by-step manner and connected in series through pipelines with water stop valves; wherein, a water inlet pipe is provided at one end of a first-stage catalytic hydrolysis reactor, and a pipeline with a water stop valve is provided at the other end as a drainage pipeline and connected to the next-stage catalytic hydrolysis reactor.

[0044] At least two water retaining plates are arranged in the catalytic hydrolysis reactor, wherein the heights of the water retaining plates are arranged in a stepped manner from the water inlet end to the water outlet end.

[0045] A cathode and an anode are arranged in the electrocatalytic reactor; a plurality of stirrers are arranged between the cathode and the anode, each stirrer is connected to a stirring motor, and the stirring motor is fixed to the electrocatalytic reactor through an electrode bracket; and a reagent injection pipe and a disposal water outlet pipe are respectively arranged on the side walls of the electrocatalytic reactor.

[0046] The cathode and anode are arranged at intervals, and cathodes are arranged on both sides of the device, that is, cathode-anode-cathode-anode-cathode...-cathode.

[0047] Example 2

[0048] See the schematic diagram of the device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation for details. Figure 1 The catalytic hydrolysis reactor is made of glass fiber reinforced plastic. The volume of the first-stage catalytic hydrolysis reactor is 1m 3(length 1m*width 1m*height 1m), the heights of the two water retaining plates are 0.9m and 0.85m respectively (thickness is 2cm), and the effective wastewater treatment capacity is about 0.8m 3 The designed hydraulic retention time is 4h; the volume of the secondary catalytic hydrolysis reactor is 0.8m 3 (length 1m*width 1m*height 0.8m), the heights of the two water retaining plates are 0.7m and 0.65m respectively (thickness is 2cm), and the effective wastewater treatment capacity is about 0.6m 3 , the hydraulic retention time is designed to be 3h; the size of the foamed magnesium oxide catalytic hydrolysis filler is 32cm long * 20cm wide * 20cm thick (porosity is about 70%, average pore size is 5mm), the filling volume in the first-stage catalytic hydrolysis reactor is 80%, and the filling volume in the second-stage catalytic hydrolysis reactor is 75%; the preparation method of foamed magnesium oxide: magnesium oxide powder with an average particle size of about 5μm is made into a 40wt% slurry, 0.5% mass fraction of sodium dodecylbenzene sulfonate is added, and stirred at 1500r / min for 10min, the foamed slurry is poured into the mold, cured at room temperature for 48h, dried at 110℃ for 12h, and finally sintered at 1400℃ for 2h.

[0049] The electrocatalytic reactor is also made of fiberglass and has a volume of 0.6m 3 (length 1m*width 1m*height 0.6m), effective wastewater treatment capacity 0.5m 3 ; The cathode is a porous titanium metal plate (length 80cm*width 2cm*height 50cm) welded with a terminal, and the anode is welded by FeCo2O4 modified block foam titanium, welded with a terminal, and the overall size is length 80cm*width 20cm*height 50cm; The preparation method of the anode: block foam titanium (length 16cm*width 20cm*height 10cm) and a precursor aqueous solution (containing 0.5mM Fe(NO3)3·9H2O, 1mM Co(NO3)2·6H2O, 1mM NH4F, 2.5mM CO(NH2)2) was reacted at 120°C for 6 hours in a stainless steel autoclave lined with polytetrafluoroethylene, then rinsed with deionized water and anhydrous ethanol, dried at 60°C, and finally calcined at 400°C for 2 hours; the distance between the anode and the cathode was 10 cm; the paddle stirrer was equipped with a steel-lined polytetrafluoroethylene stirring paddle (stirring diameter 10 cm), a vertical cycloidal pinwheel reducer (power 0.37 kW, speed adjustable from 0 to 300 r / min); the DC power supply input voltage was AC380V, and the output current was adjustable from 0 to 600A.

[0050] Method for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation: (1) After coagulation and sedimentation pretreatment, the production wastewater (see Table 1) is adjusted to pH 11 and pumped into the catalytic hydrolysis reactor. The hydraulic retention time of the wastewater in the two-stage catalytic hydrolysis reactor is controlled to be 7 h; (2) After the catalytic hydrolysis is completed, the wastewater enters the electrocatalytic reactor with an injection volume of 0.5 m3 ; Turn on the stirrer at a stirring speed of 150 r / min; Simultaneously inject 0.1 m of a 100 g / L peroxymonosulfate aqueous solution 3 After being fully mixed, the oxidant concentration in the wastewater is 20 g / L; turn on the DC power supply and set the output current to 21.6 A (the anode current density is about 0.2 mA / cm 2 ); electrocatalytic reaction time 180min.

[0051] Streptomycin was determined by high performance liquid chromatography (Shimadzu LC-20AT) equipped with an Agilent ZORBAXSB Aq (4.6×250mm, 5μm) column, the mobile phase was 0.05% phosphoric acid and acetonitrile (72:28, v:v), the flow rate was 1mL / min, the injection volume was 20μL, and the detection wavelength was 278nm.

[0052] The toxicity of the treated water is expressed as the inhibitory effect on the standard bacterial strain. The specific test method is: the Gram-positive bacteria Staphylococcus aureus (S. aureus) is used for the antibacterial activity test. The bacteria are cultured in sterile LB medium (37°C, 120r / min) for 12h, and 0.2mL of culture solution and 1mL of treated water (the control group is sterile deionized water) are added to 24mL of sterile LB medium and cultured (37°C, 120r / min) for 24h. The S. aureus culture solution is collected regularly, and the absorbance of the culture solution is tested at a wavelength of 450nm using an ultraviolet spectrophotometer. S. aureus growth inhibition rate (I R )Calculation formula:

[0053]

[0054] In the formula, A0 is the OD value of the control group, A E It is the average OD value of the culture medium with added treatment water.

[0055] The effluent from the coagulation and sedimentation pretreatment facility of an actual streptomycin production enterprise was taken as the treatment object, and the physical and chemical properties of the wastewater are shown in Table 1.

[0056] Table 1 Physical and chemical properties of actual streptomycin production wastewater

[0057]

[0058] The results show that ( Figure 2 ), after the catalytic hydrolysis reaction, the concentration of streptomycin in the wastewater decreased from the initial 8.6 mg / L to 1.8 mg / L; the electrocatalytic oxidation reaction can effectively remove COD in the wastewater Cr(residual concentration 1239mg / L, removal rate 92.0%), BOD5 (residual concentration 667mg / L, removal rate 84.5%), NH3-N (residual concentration 6.6mg / L, removal rate 88.4%), and streptomycin removal efficiency reached 100%. At the same time, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.28 to 0.54. In addition, the S. aureus inhibition rate of the effluent treated by the catalytic hydrolysis reaction decreased from the initial 65% to 13.6%, and further decreased to 0.3% after the electrocatalytic oxidation reaction, almost completely eliminating the biological activity inhibition of the wastewater.

[0059] Example 3

[0060] The device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation is the same as that in Example 1, except that the catalytic hydrolysis filler is foamed alumina, and the pH of the pretreated effluent is adjusted to 8. Preparation method of foamed alumina: Alumina powder with an average particle size of about 5 μm is made into a 40wt% slurry, 0.5% by mass of sodium dodecylbenzene sulfonate is added, and stirred at 1500r / min for 10min, the foamed slurry is poured into a mold, cured at room temperature for 48h, dried at 110°C for 12h, and finally sintered at 1400°C for 2h.

[0061] The results show that ( Figure 3 ), after the catalytic hydrolysis reaction, the concentration of streptomycin in the wastewater decreased from the initial 8.6 mg / L to 1.6 mg / L; the electrocatalytic oxidation reaction can effectively remove COD in the wastewater Cr (residual concentration 1147mg / L, removal rate 92.6%), BOD5 (residual concentration 578mg / L, removal rate 86.6%), NH3-N (residual concentration 8.1mg / L, removal rate 85.8%), streptomycin removal efficiency reached 100%. At the same time, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.28 to 0.51. In addition, the S. aureus inhibition rate of the effluent treated by the catalytic hydrolysis reaction decreased from the initial 65% to 11.3%, and further decreased to 0.12% after the electrocatalytic oxidation reaction, almost completely eliminating the biological activity inhibition of the wastewater.

[0062] Example 4

[0063] The device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation is the same as that in Example 1, except that the anode material is CuCo2O4-modified foam titanium. The preparation method is as follows: blocky foam titanium (length 16 cm*width 20 cm*height 10 cm) and a precursor aqueous solution (containing 0.5 mM Cu(NO3)2·2.5H2O, 1 mM Co(NO3)2·6H2O, 1 mM NH4F, 2.5 mM CO(NH2)2) are reacted at 120°C in a polytetrafluoroethylene-lined stainless steel high-pressure reactor for 6 hours, and then rinsed with deionized water and anhydrous ethanol, dried at 60°C, and finally calcined at 400°C for 2 hours.

[0064] The results show that ( Figure 4 ), after the catalytic hydrolysis reaction, the concentration of streptomycin in the wastewater decreased from the initial 8.6 mg / L to 1.5 mg / L; the electrocatalytic oxidation reaction can effectively remove COD in the wastewater Cr (residual concentration 1368mg / L, removal rate 91.2%), BOD5 (residual concentration 827mg / L, removal rate 80.8%), NH3-N (residual concentration 9.4mg / L, removal rate 83.5%), streptomycin removal efficiency reached 100%. At the same time, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.28 to 0.60. In addition, the S. aureus inhibition rate of the effluent treated by the catalytic hydrolysis reaction decreased from the initial 65% to 14.2%, and further decreased to 0.31% after the electrocatalytic oxidation reaction, almost completely eliminating the biological activity inhibition of the wastewater.

[0065] Comparative Example 1

[0066] The device for catalytic degradation of antibiotic production wastewater directly uses the electrocatalytic reactor described in Example 1. The wastewater enters the electrocatalytic reactor directly without pH adjustment or two-stage catalytic hydrolysis treatment. The results show that ( Figure 5 ), the absence of catalytic hydrolysis reaction will not significantly affect COD Cr (residual concentration 1304 mg / L, removal rate 91.6%), BOD5 (residual concentration 531 mg / L, removal rate 87.7%), NH3-N (residual concentration 7.2 mg / L, removal rate 87.4%), the biodegradability of wastewater was also significantly improved, BOD5 / COD Cr The value increased from the initial 0.28 to 0.41. However, the antibiotic residue in the treated water (1.7 mg / L) and the inhibition rate of S. aureus (17.9%) increased significantly.

[0067] In summary, the catalytic hydrolysis reaction using the device and equipment of the present invention is beneficial to the mineralization removal of antibiotics and their hydrolysis products by catalytic degradation reaction, and catalytic hydrolysis + catalytic degradation can effectively eliminate the biological activity inhibition of wastewater.

Claims

1. A device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation, characterized in that: The device comprises a catalytic hydrolysis reactor and an electrocatalytic reactor, the two reactors are connected in series through a pipeline with a water stop valve, wherein the catalytic hydrolysis reactor is divided into a plurality of compartments by a water retaining plate, each compartment is filled with a catalytic porous hydrolysis filler; a cathode, an anode and a stirrer are arranged in the electrocatalytic reactor.

2. The device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation according to claim 1 is characterized in that: There is at least one catalytic hydrolysis reactor in the device, and multiple catalytic hydrolysis reactors are arranged in sequence in a step-by-step manner and connected in series through pipelines with water stop valves; wherein, a water inlet pipe is provided at one end of a first-stage catalytic hydrolysis reactor, and a pipeline with a water stop valve is provided at the other end as a drainage pipeline and connected to the next-stage catalytic hydrolysis reactor.

3. The device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation according to claim 1 or 2, characterized in that: At least two water retaining plates are arranged in the catalytic hydrolysis reactor, wherein the heights of the water retaining plates are arranged in a stepped manner from the water inlet end to the water outlet end.

4. The device for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation according to claim 1 is characterized in that: A cathode and an anode are arranged in the electrocatalytic reactor; a plurality of stirrers are arranged between the cathode and the anode, each stirrer is connected to a stirring motor, and the stirring motor is fixed to the electrocatalytic reactor through an electrode bracket; and a reagent injection pipe and a disposal water outlet pipe are respectively arranged on the side walls of the electrocatalytic reactor.

5. A method for treating antibiotic production wastewater by catalytic hydrolysis coupled with catalytic degradation using the device of claim 1, characterized in that: By utilizing the porous hydrolysis filler in the device described in claim 1, the selective catalytic hydrolysis of high-concentration antibiotics in wastewater is completed by controlling the hydraulic retention time, and the high contact reaction area of ​​the porous block anode is used to improve the anodic oxidation efficiency, thereby achieving efficient mineralization degradation of residual antibiotics and their hydrolysis products.

6. The method according to claim 5, characterized in that: (1) The production wastewater is pretreated to remove suspended solids and then the pH is adjusted before entering the catalytic hydrolysis reactor of the device of claim 1 to complete the catalytic hydrolysis reaction of the antibiotic; (2) After the wastewater is catalytically hydrolyzed, it enters the electrocatalytic reactor, and the peroxide oxidant is injected while the agitator is turned on to fully mix it; (3) Continue stirring and turn on the DC power supply to complete the catalytic degradation of residual antibiotics and their hydrolysis products in the wastewater, and discharge them into subsequent treatment process facilities through the external pipeline of the electrocatalytic reactor.

7. The method according to claim 5 or 6, characterized in that: The compartment in the catalytic hydrolysis reactor of the device is filled with catalytic porous hydrolysis fillers; the porous hydrolysis fillers can be selected from foamed magnesium oxide and / or foamed aluminum oxide, with a filler porosity of 60% to 90% and a pore size of 0.1 to 10 mm (5 to 120 ppi); the total filling volume of the catalytic hydrolysis fillers in the device is 60% to 80% of the volume of the catalytic hydrolysis reactor.

8. The method according to claim 7, characterized in that: The magnesium oxide, aluminum oxide or magnesium oxide-aluminum oxide composite foam material is prepared by a foaming method. Magnesium oxide, aluminum oxide or magnesium oxide-aluminum oxide mixed powder with a particle size of 1-10 μm (mass ratio of 100:25-50) is made into a 15-60wt% slurry, 0.1%-2% of sodium dodecyl sulfate (SDS) or sodium dodecylbenzene sulfonate (SDBS) is added, and the mixture is stirred at 1000-2000 r / min for 5-15 minutes. The foamed slurry is poured into a mold, cured at room temperature for 24-48 hours, dried at 110°C for 12-24 hours, and finally sintered at 1200-1600°C for 2-4 hours.

9. The method according to claim 8, characterized in that: The anode was prepared by in situ deposition method. The foamed titanium was reacted with a precursor aqueous solution (containing 0.5mM Fe(NO3)3·9H2O or Cu(NO3)2·2.5H2O or Zn(NO3)2·6H2O or Mg(NO3)2·6H2O, 1mM Co(NO3)2·6H2O, 1mM NH4F, 2.5mM CO(NH2)2) in a polytetrafluoroethylene-lined stainless steel high-pressure reactor at 120°C for 6 hours, then rinsed with deionized water and anhydrous ethanol, dried at 60°C, and finally calcined at 400°C for 2h.

10. The method according to claim 6, characterized in that: In the step (1), the pH value of the wastewater is adjusted to 7-11 with sodium hydroxide; the hydraulic retention time is controlled by the inlet flow rate; the hydraulic retention time is 3-14 hours; The peroxide oxidant in step (2) is hydrogen peroxide, peracetic acid, peroxymonosulfate or peroxydisulfate, with a concentration of 10 to 500 g / L; the stirring speed of the stirrer is 50 to 300 r / min; The current density of the electrocatalytic reaction in step (3) is 0.1 to 50 mA / cm 2 , reaction time 30 to 180 minutes.

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