Ultrasonic coupling electrochemical pretreatment device and method for high-concentration antibiotic production wastewater

Abstract

The invention belongs to the technical field of pharmaceutical wastewater treatment, and particularly relates to an ultrasonic coupling electrochemical pretreatment device and method for high-concentration antibiotic production wastewater. According to the device, a first ultrasonic treatment reactor, a second electrochemical reactor and a third flocculating settling reactor are sequentially connected in series through pipelines; wherein a wall-mounted ultrasonic vibration plate is arranged in the first reactor, a stable electrode and a sacrificial electrode are arranged in the second reactor, a plurality of disc aerators are arranged at the bottom of the second reactor, and an overflow groove, inclined tube filler and an electromagnet are arranged in the third reactor. According to the invention, efficient desorption and mineralization degradation of suspended matter adsorption state antibiotics in production wastewater can be realized, residues of antibiotics and degradation products thereof in floccules are reduced, and toxic effects on subsequent biological treatment sections are eliminated.

Description

Technical Field

[0001] The invention belongs to the technical field of pharmaceutical wastewater treatment, and in particular relates to an ultrasonically coupled electrochemical pretreatment device and method for high-concentration antibiotic production wastewater. Background Art

[0002] Wastewater produced by fermentation antibiotics has the characteristics of complex composition, high suspended solids, high salinity, high COD and strong biological toxicity. The pretreatment technologies for wastewater from fermentation pharmaceutical industries in my country mainly include multi-effect evaporation and steam mechanical recompression technology for high-salt wastewater, air stripping and steam stripping technology for high NH3-N (>1000mg / L) wastewater, and coagulation sedimentation and flotation technology for high suspended solids (>500mg / L) wastewater; the main treatment technologies are anaerobic and aerobic biological treatment technologies; deep treatment technologies include coagulation sedimentation, flotation, Fenton oxidation, ozone oxidation + aerated biological filter, ozone oxidation + membrane bioreactor, etc. In addition to the above-mentioned treatment technologies for high-salt and high-NH3-N wastewater, the pretreatment of wastewater from chemical synthesis pharmaceutical industries also includes treatment technologies for wastewater with poor biodegradability (BOD5 / COD Cr <0.3) Iron-carbon micro-electrolysis and Fenton oxidation of wastewater, COD Cr The removal rate can reach 20% to 50%, BOD5 / COD Cr >0.3; the main treatment technology and deep treatment technology are not much different from those of fermentation pharmaceutical wastewater. Since it is difficult to achieve efficient mineralization and removal of residual antibiotics in wastewater with pretreatment technology, the subsequent biological treatment effect is extremely unstable and induces the production of antibiotic-resistant bacteria (ARBs) and resistance genes (ARGs). Electroflocculation is a method of treating wastewater using alternating current or direct current. The metal cations generated by sacrificial anodes (materials such as stainless steel, iron and aluminum) are used to flocculate pollutants and precipitate them into sludge. Pollutants can also be removed through the oxidation / reduction effect of electrodes. It has been applied to the treatment of wastewater containing antibiotics.

[0003] Patent CN114212862A discloses an integrated electro-flocculation oxidation method for treating antibiotic-containing wastewater, using an inert material (one of BDD, RuO2, TiO2, SnO2 and titanium-coated ruthenium electrode) as the anode, and a cathode material of one of aluminum, magnesium and zinc, and using anode oxidation and cathode indirect electro-flocculation to simultaneously remove the turbidity, chloramphenicol and sulfamethoxazole of the wastewater. However, due to the high cost of removing the inert anode and the weak flocculant (metal ion) precipitation ability of the sacrificial cathode, the scope of application of this technology is also unclear. Patent CN114835205A discloses a method for treating copper-ciprofloxacin complex (Cu-CIP) by heterogeneous electro-Fenton-electro-flocculation, using N-doped cobalt-iron bimetallic porous carbon as the cathode and aluminum sheet as the anode, using the active oxygen free radicals generated by the cathode to break the Cu-CIP complex and degrade CIP into small molecules, and removing Cu by electro-flocculation. The pH application range of this method is relatively narrow (weakly acidic to neutral), the cathode preparation method is complex and costly, and it is not suitable for large-scale treatment of high-concentration antibiotic production wastewater. Patent CN115959745A discloses a method using an iron plate or an iron-containing metal plate as an anode and a graphene-based Fe n+ (GO@Fe n+ ) as a particle electrode to synergistically activate persulfate and utilize Fe 3+ The flocculation precipitation method did not completely degrade the antibiotic (tetracycline hydrochloride, TCH). However, this technology is greatly affected by organic load (COD) and wastewater pH value. n+ The catalytic activity is weak, the TCH degradation rate is not significantly improved, and it is difficult to recycle.

[0004] Although the existing electrocoagulation and its coupling technology can achieve efficient pretreatment of antibiotic-containing wastewater under certain conditions, there are still disadvantages such as high electrode manufacturing cost, high reaction conditions, and high antibiotic residual concentration in flocculation precipitation. The high surface area of ​​the plate electrode is prone to cause concentration polarization and electrochemical polarization, resulting in a large amount of electrical energy being consumed on the electrode surface, and the installation spacing of the electrodes is small (1 to 5 cm), which leads to inconvenience in cleaning and maintenance. In addition, suspended matter will adsorb more antibiotics, and higher temperatures, neutral to weakly alkaline environments, and high ionic strengths will promote the transfer of antibiotics to suspended matter, resulting in a higher risk of secondary pollution in the resource utilization of sludge. Summary of the invention

[0005] The purpose of the present invention is to solve the problems of strong adsorption of antibiotics by high-content suspended solids in production wastewater, poor subsequent biological treatment effect of wastewater due to difficulty in mineralization and degradation of antibiotics, high antibiotic content in sludge and high ecological risks caused by this, and proposes an ultrasonically coupled electrochemical pretreatment device and method for high-concentration antibiotic production wastewater.

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

[0007] An ultrasonically coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater comprises an ultrasonic treatment first reactor, an electrochemical second reactor and a flocculation sedimentation third reactor which are sequentially connected in series through pipelines; wherein a wall-mounted ultrasonic vibration plate is arranged in the first reactor, a stabilizing electrode and a sacrificial electrode are arranged in the second reactor, a plurality of disc aerators are arranged at the bottom, and an overflow tank, an inclined tube filler and an electromagnet are arranged in the third reactor.

[0008] The three reactors are connected in series via a pipeline, and a pipeline pump is provided on the pipeline.

[0009] The second reactor is provided with stable electrodes and sacrificial electrodes arranged in a staggered and symmetrical manner, with a distance between two adjacent electrodes of 6 to 30 cm; and a liquid injection pipe is provided along one side wall of the reactor.

[0010] The third reactor is divided into an overflow trough and a sedimentation tank by a water retaining plate; the overflow trough is arranged on one side of the third reactor adjacent to the second reactor, and the pipeline connected to the second reactor is connected through the bottom of the overflow trough; a sludge discharge port is arranged at the bottom of the sedimentation tank and is connected to a slurry pump through a pipeline, a wall-mounted electromagnet is arranged in the sedimentation tank, and an inclined tube filler fixed by a bracket is arranged, and at the same time, a toothed drainage groove is arranged above the inclined tube filler, which is fixed to the side wall of the reactor by bolts and is connected to the water outlet located at the top of the third reactor.

[0011] There are three reactors in total, made of PVC or fiberglass, with a volume of 0.1 to 10 m 3 , connected in series via pipeline pumps, with a flow rate of 1 to 10 m 3 / h; the first reactor performs ultrasonic treatment, the second reactor simultaneously performs electrochemically enhanced heterogeneous catalytic reaction and electro-flocculation + electro-catalytic reaction, and the third reactor performs particle electrode recovery and flocculent precipitation.

[0012] The wall-mounted ultrasonic vibration plate is made of acid-alkali resistant stainless steel or titanium, installed in the first reactor and connected to an ultrasonic power supply, and the output frequency of the ultrasonic power supply is adjustable within a range of 0.1 to 200 kHz.

[0013] The DC power supply for the stabilizing electrode and the sacrificial electrode has an output voltage adjustment range of 0 to 60V; the disc aerator is made of acid- and alkali-resistant materials such as rubber, PP or ABS nylon, and has a working ventilation volume of 0.05 to 0.2m 3 / h·pcs, service area 0.2~0.5m 2 / piece; the injection tube is made of PVC or PBDE, with a diameter of 25 to 50 mm.

[0014] The water retaining plate is made of PVC or FRP (consistent with the reactor material), the inclined tube filler is made of PP, PVC, FRP or EPDM, with a tube diameter of 30-80 mm; the electromagnet is an insulating structure, waterproof and acid-resistant, with an initial suction of 1000-8000 N; the mud pump is self-priming, with a flow rate of 1-5 m 3 / h.

[0015] The invention discloses an ultrasonic coupled electrochemical pretreatment method for high-concentration antibiotic production wastewater using the device, wherein the device is used to desorb adsorbed antibiotics in wastewater suspension through ultrasonic water oxidation and mechanical shearing, and then the wastewater is passed through electrodes to realize the stages of electrically enhanced heterogeneous catalytic oxidation reaction, electrocoagulation and electrocatalytic reaction during the switching of electrodes, thereby realizing deep mineralization and degradation of high-concentration antibiotics in the wastewater, reducing the residual antibiotics and their degradation products in the flocculent body and eliminating the toxicity of the wastewater.

[0016] The stabilizing electrode can be made of graphite, titanium, titanium alloy, or boron-doped diamond; the sacrificial electrode can be made of iron, aluminum, or their alloys; the disc aerator has a working ventilation volume of 0.05 to 0.2 m 3 / h·pcs, service area 0.2~0.5m 2 / indivual.

[0017] The wastewater enters the first reactor for ultrasonic treatment; then enters the second reactor, where granular electrodes and oxidants are added. First, an electrically enhanced heterogeneous catalytic oxidation reaction is carried out with a stable electrode as the anode and a sacrificial electrode as the cathode, and then the electrode polarity is switched to use the stable electrode as the cathode and the sacrificial electrode as the anode for electrocoagulation and electrocatalytic reaction; after electrochemical treatment, the wastewater enters the bottom of the overflow tank of the third reactor, and the granular electrodes are recovered by magnetic adsorption. The suspended matter is precipitated in an inclined tube and then discharged by a mud pump for subsequent treatment. The clarified wastewater after treatment is collected through a toothed drainage trough and discharged from the sedimentation tank for subsequent biological treatment.

[0018] The ultrasonic treatment time of the first reactor is 10 to 120 minutes;

[0019] The particle electrode in the second reactor can be selected from one or more of cobalt trioxide (Co3O4), cobalt ferrite (CoFe2O4), manganese ferrite (MnFe2O4), nickel cobalt ferrite (CoNiFe2O4), and cobalt zinc ferrite (CoZnFe2O4); the particle electrode dosage is 0.1-10 g / L; the oxidant can be selected from one or more of permonosulfate (PMS), peroxydisulfate (PDS), hydrogen peroxide (H2O2), and peracetic acid (PAA); the oxidant dosage is 0.5-50 g / L.

[0020] In the second reactor, the stable electrode is used as the anode and the sacrificial electrode is used as the cathode to carry out the electrically enhanced heterogeneous catalytic oxidation reaction for 15 to 180 minutes; then the electrode polarity is switched to carry out the electrocoagulation and electrocatalytic reaction for 15 to 180 minutes.

[0021] The wastewater is deposited in the inclined tube of the third reactor for 60 to 240 minutes.

[0022] There are three reactors in total, made of PVC or fiberglass, with a volume of 0.1 to 10 m 3 , connected in series via pipeline pumps, with a flow rate of 1 to 10 m 3 / h; the first reactor performs ultrasonic treatment, the second reactor simultaneously performs electrochemically enhanced heterogeneous catalytic reaction and electro-flocculation + electro-catalytic reaction, and the third reactor performs particle electrode recovery and flocculent precipitation.

[0023] The wall-mounted ultrasonic vibration plate is made of acid-alkali resistant stainless steel or titanium, installed in the first reactor and connected to an ultrasonic power supply, and the output frequency of the ultrasonic power supply is adjustable within a range of 0.1 to 200 kHz.

[0024] The DC power supply for the stabilizing electrode and the sacrificial electrode has an output voltage adjustment range of 0 to 60V; the disc aerator is made of acid- and alkali-resistant materials such as rubber, PP or ABS nylon, and has a working ventilation volume of 0.05 to 0.2m 3 / h·pcs, service area 0.2~0.5m 2 / piece; the injection tube is made of PVC or PBDE, with a diameter of 25 to 50 mm.

[0025] The inclined tube filler is made of PP, PVC, glass fiber reinforced plastic or ethylene-propylene copolymer, with a tube diameter of 30 to 80 mm; the electromagnet is an insulating structure, waterproof and acid-resistant, with an initial suction force of 1000 to 8000 N; the mud pump is self-priming, with a flow rate of 1 to 5 m 3 / h.

[0026] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0027] (1) The present application can be used for the pretreatment of antibiotic production wastewater with high suspended solids content, and can achieve the desorption of suspended solid adsorbed antibiotics and their deep mineralization degradation, reduce antibiotic residues in flocs and achieve wastewater detoxification, significantly improve the biodegradability of wastewater, improve the overall wastewater treatment efficiency and avoid the induced production of ARBs and ARGs.

[0028] (2) The manufacturing cost of the device of the present application is low, and all supporting equipment, components and materials can be obtained through market purchase or simple custom processing. The operating energy consumption of the device is low, the use cost of the method is low, and the effective detoxification and biodegradability of wastewater can significantly reduce the overall disposal time and cost of wastewater.

[0029] (3) The electrochemical system of the present application can realize the staged occurrence of electrically enhanced heterogeneous catalytic oxidation and electrocoagulation + electrocatalytic reaction based on a set of electrode reaction systems, which significantly improves the space utilization rate of the device and saves construction costs. The columnar electrodes avoid concentration polarization and electrochemical polarization and the energy loss caused by them. The installation spacing of the electrodes is large, which is convenient for cleaning and maintenance.

[0030] (4) The method provided in the present application is not affected by the pH value, COD content and conductivity of the wastewater, and is applicable to a wider range of water quality. In addition, the particle electrodes can be recovered by magnetic adsorption and can be reused after calcination and resurrection. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0032] Figure 1 A schematic diagram of the structure of an ultrasonically coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater provided by an embodiment of the present invention; in the figure: 1-first reactor, 2-wall hanging, 3-ultrasonic vibration plate, 4-pipeline pump, 5-sacrificial electrode, 6-stable electrode, 7-disc aerator, 8-liquid injection pipe, 9-overflow tank, 10-inclined tube filler, 11-electromagnet, 12-toothed drainage tank, 13-water outlet, 14-sludge outlet, 15-mud pump;

[0033] Figure 2 A schematic diagram of the principle of the ultrasonic coupled electrochemical pretreatment method for high-concentration antibiotic production wastewater provided by an embodiment of the present invention;

[0034] Figure 3 The effect of the ultrasonically coupled electrochemical pretreatment device provided by the embodiment of the present invention on the actual treatment of penicillin production wastewater;

[0035] Figure 4 The effect of the ultrasonically coupled electrochemical pretreatment device provided by the embodiment of the present invention on the actual treatment of erythromycin production wastewater;

[0036] Figure 5 The effect of the ultrasonically coupled electrochemical pretreatment device provided by the embodiment of the present invention on the actual treatment of streptomycin production wastewater;

[0037] Figure 6 This is the effect of using the ultrasonically coupled electrochemical pretreatment device provided in the embodiment of the present invention for actual norfloxacin production wastewater treatment. DETAILED DESCRIPTION

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0043] The treatment method of the present invention, based on effectively breaking the adsorption of antibiotics by suspended matter, simultaneously realizes efficient mineralization degradation of desorbed antibiotics and efficient flocculation of suspended matter through a low-cost electrochemical reaction system. It can not only reduce the antibiotic residues in the flocculent body during the pretreatment process and achieve detoxification of wastewater, but also significantly improve the biodegradability of wastewater, improve the overall treatment efficiency of wastewater and avoid the induced production of ARBs and ARGs.

[0044] The equipment, materials and reagents used in the following examples of the present invention are all commercially available.

[0045] In the following examples of the present invention, the nanocatalysts (Co3O4, CoFe2O4, MnFe2O4, CoNiFe2O4, CoZnFe2O4) and oxidants (PMS, PDS, H2O2, PAA) are all commercially available products.

[0046] The following examples serve as further illustrations of the technical solutions of the present invention.

[0047] Example 1

[0048] The ultrasonically coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater comprises an ultrasonic treatment first reactor, an electrochemical second reactor and a flocculation sedimentation third reactor which are connected in series in sequence through pipelines; wherein a wall-mounted ultrasonic vibration plate is arranged in the first reactor, a stabilizing electrode and a sacrificial electrode are arranged in the second reactor, a plurality of disc aerators are arranged at the bottom, and an overflow tank, an inclined tube filler and an electromagnet are arranged in the third reactor.

[0049] The three reactors are connected in series via a pipeline, and a pipeline pump is provided on the pipeline.

[0050] The second reactor is provided with stable electrodes and sacrificial electrodes arranged in a staggered and symmetrical manner, with a distance between two adjacent electrodes of 6 to 30 cm; and a liquid injection pipe is provided along one side wall of the reactor.

[0051] The third reactor is divided into an overflow trough and a sedimentation tank by a water retaining plate; the overflow trough is arranged on one side of the third reactor adjacent to the second reactor, and the pipeline connected to the second reactor is connected through the bottom of the overflow trough; a sludge discharge port is arranged at the bottom of the sedimentation tank and is connected to a slurry pump through a pipeline, a wall-mounted electromagnet is arranged in the sedimentation tank, and an inclined tube filler fixed by a bracket is arranged, and at the same time, a toothed drainage groove is arranged above the inclined tube filler, which is fixed to the side wall of the reactor by bolts and is connected to the water outlet located at the top of the third reactor.

[0052] Treatment method: wastewater enters the first reactor for ultrasonic treatment; then enters the second reactor, adds particle electrodes and oxidants, first uses the stable electrode as the anode and the sacrificial electrode as the cathode to perform an electrically enhanced heterogeneous catalytic oxidation reaction, and then switches the electrode polarity to perform electro-flocculation and electro-catalytic reaction; finally, the wastewater enters the third reactor, the particle electrodes are recovered by magnetic adsorption, the suspended matter is precipitated in an inclined tube and then led out by a mud pump for subsequent treatment, and the effluent enters the subsequent biological treatment section. The present invention can achieve efficient desorption and mineralization degradation of suspended adsorbed antibiotics in production wastewater, reduce the residual antibiotics and their degradation products in the flocculent, and eliminate the toxic effects on the subsequent biological treatment section.

[0053] Specifically, the wastewater enters the first reactor for ultrasonic treatment; and then enters the second reactor, where granular electrodes and oxidants are added, and first, an electrically enhanced heterogeneous catalytic oxidation reaction is carried out with a stable electrode as the anode and a sacrificial electrode as the cathode, and then the electrode polarity is switched to use the stable electrode as the cathode and the sacrificial electrode as the anode for electrocoagulation and electrocatalytic reaction; after electrochemical treatment, the wastewater enters the bottom of the overflow tank of the third reactor, and the granular electrodes are recovered by magnetic adsorption. The suspended matter is precipitated in an inclined tube and then discharged by a mud pump for subsequent treatment. The clarified wastewater after treatment is collected through a toothed drainage trough and discharged from the sedimentation tank for subsequent treatment.

[0054] Example 2

[0055] The ultrasonic coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater was built as described above. Figure 1 The three reactors of the device are all made of fiberglass. The first reactor performs ultrasonic treatment, and the second reactor performs electrochemical enhanced heterogeneous catalytic reaction and electrocoagulation + electrocatalytic reaction at the same time. The first and second reactors have the same size (volume 1.5m 3 , length 1.5m*width 1m*height 1m), the third reactor (volume 2.5m 3 ) performs particle electrode recovery and floc sedimentation.

[0056] Other components include pipeline pump (flow rate 1~10m 3 / h), ultrasonic power supply (output frequency adjustment range 0.1 ~ 200kHz), wall-mounted ultrasonic vibration plate (titanium material, length 1m * width 0.5m), DC power supply (constant voltage output, 0 ~ 60V adjustable), cylindrical titanium electrode (diameter 30mm, length 0.8m), cylindrical iron electrode (diameter 30mm, length 0.8m), ABS nylon disc aerator (0.1m 3 / h·pcs), PVC injection pipe (pipe diameter 32mm), PVC inclined pipe filler (pipe diameter 50mm), electromagnet (initial suction force 4000N), self-priming mud pump (flow rate 1m 3 / h) etc.

[0057] The ultrasonic coupled electrochemical pretreatment method for high-concentration antibiotic production wastewater includes the following steps: the production wastewater enters the first reactor for ultrasonic treatment, and the treatment time is 60 minutes; the wastewater after ultrasonic treatment enters the second reactor, and 5g / L cobalt ferrite (CoFe2O4) granular electrode and 25g / L permonosulfate (PMS) oxidant are added; the titanium electrode is used as the anode and the iron electrode is used as the cathode for electrically enhanced heterogeneous catalytic oxidation reaction, and the reaction time is 120 minutes; the electrode polarity is switched, and the titanium electrode is used as the cathode and the iron electrode is used as the anode for electrocoagulation + electrocatalytic reaction, and the reaction time is 90 minutes; the wastewater after electrochemical treatment enters the overflow tank of the third reactor, and the granular electrode is recovered by magnetic adsorption, and the wastewater is precipitated for 120 minutes. The principle of ultrasonic coupled electrochemical pretreatment method can be found in Figure 2 .

[0058] Penicillin, erythromycin, streptomycin and norfloxacin were determined by high performance liquid chromatography (Shimadzu LC-20AT) equipped with an Agilent ZORBAX SB Aq (4.6×250mm, 5μm) column and a column temperature of 35℃. When testing penicillin, the mobile phase was 0.1% formic acid and acetonitrile (35:65, v:v), the flow rate was 0.8 mL / min, the injection volume was 20 μL, and the detection wavelength was 210 nm; when testing erythromycin, the mobile phase was dipotassium hydrogen phosphate ((0.03 mol / L, pH=10)) and acetonitrile (45:55, v:v), the flow rate was 1 mL / min, the injection volume was 20 μL, and the detection wavelength was 215 nm; when testing streptomycin, the mobile phase was 0.05% phosphoric acid and acetonitrile (72:28, v:v), the flow rate was 1 mL / min, the injection volume was 20 μL, and the detection wavelength was 278 nm; when testing norfloxacin, the mobile phase was 0.1% formic acid and methanol (40:60, v:v), the flow rate was 1 mL / min, the injection volume was 20 μL, and the detection wavelength was 286 nm.

[0059] The penicillin production wastewater of an actual pharmaceutical company was taken as a representative of the β-lactam antibiotic production process wastewater for treatment. The physical and chemical properties of the wastewater are shown in Table 1.

[0060] Table 1 Physical and chemical properties of actual penicillin production wastewater

[0061]

[0062] The results show that ( Figure 3 ), with the extension of ultrasonic treatment time, the adsorbed penicillin in the suspended matter gradually desorbed, and the concentration of penicillin in the wastewater increased from the initial 11.3 mg / L to 14.2 mg / L; the electrically enhanced heterogeneous catalytic oxidation reaction and the electrocoagulation + electrocatalytic reaction could effectively remove COD Cr(residual concentration 1411mg / L, removal rate 91.3%), BOD5 (residual concentration 757mg / L, removal rate 85.4%), NH3-N (residual concentration 57mg / L, removal rate 71.6%), SS (residual concentration 320mg / L, removal rate 96.3%), penicillin removal efficiency reached 100%, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.32 to 0.54.

[0063] Example 3

[0064] The ultrasonically coupled electrochemical pretreatment device is the same as in Example 1. The erythromycin production wastewater of an actual pharmaceutical company is treated as a representative of the macrolide antibiotic production process wastewater. The physical and chemical properties of the wastewater are shown in Table 2.

[0065] Table 2 Physical and chemical properties of actual erythromycin production wastewater

[0066]

[0067] The results show that ( Figure 4 ), with the extension of ultrasonic treatment time, the suspended adsorbed erythromycin gradually desorbed into the wastewater, and the concentration increased from the initial 1.3 mg / L to 2.2 mg / L; the electrically enhanced heterogeneous catalytic oxidation reaction and electrocoagulation + electrocatalytic reaction can effectively remove COD Cr (residual concentration 372mg / L, removal rate 95.7%), BOD5 (residual concentration 213mg / L, removal rate 91.5%), NH3-N (residual concentration 14mg / L, removal rate 82.3%), SS (residual concentration 21mg / L, removal rate 98.7%), erythromycin removal efficiency reached 100%, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.29 to 0.57.

[0068] Example 4

[0069] The ultrasonically coupled electrochemical pretreatment device is the same as in Example 1. The streptomycin production wastewater of an actual pharmaceutical company is treated as a representative of the aminoglycoside antibiotic production process wastewater. The physical and chemical properties of the wastewater are shown in Table 3.

[0070] Table 3 Physical and chemical properties of actual streptomycin production wastewater

[0071]

[0072] The results show that ( Figure 5), with the extension of ultrasonic treatment time, the suspended adsorbed streptomycin gradually desorbed into the wastewater, and the concentration increased from the initial 17.6 mg / L to 19.4 mg / L; the electrically enhanced heterogeneous catalytic oxidation reaction and electrocoagulation + electrocatalytic reaction can effectively remove COD Cr (residual concentration 641mg / L, removal rate 94.5%), BOD5 (residual concentration 324mg / L, removal rate 90.9%), NH3-N (residual concentration 26mg / L, removal rate 79.2%), SS (residual concentration 51mg / L, removal rate 98.0%), erythromycin removal efficiency reached 100%, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.31 to 0.51.

[0073] Example 5

[0074] The ultrasonically coupled electrochemical pretreatment device is the same as in Example 1. The norfloxacin production wastewater of an actual pharmaceutical company is treated as a representative of quinolone antibiotic production process wastewater. The physical and chemical properties of the wastewater are shown in Table 4.

[0075] Table 4 Physical and chemical properties of actual norfloxacin production wastewater

[0076]

[0077] The results show that ( Figure 6 ), with the extension of ultrasonic treatment time, the adsorbed norfloxacin in the suspended matter gradually desorbed into the wastewater, and the concentration increased from the initial 5.7 mg / L to 8.4 mg / L; the electrically enhanced heterogeneous catalytic oxidation reaction and electrocoagulation + electrocatalytic reaction can effectively remove COD Cr (residual concentration 721mg / L, removal rate 94.9%), BOD5 (residual concentration 417mg / L, removal rate 84.6%), NH3-N (residual concentration 16mg / L, removal rate 76.8%), SS (residual concentration 37mg / L, removal rate 97.2%), erythromycin removal efficiency reached 100%, the biodegradability of wastewater was significantly improved, BOD5 / COD Cr The value increased from the initial 0.19 to 0.58.

[0078] Example 6

[0079] The ultrasonic coupled electrochemical pretreatment device is the same as that in Example 1, except that the wastewater does not enter the first reactor for ultrasonic treatment, but only performs electrochemical enhanced heterogeneous catalytic reaction and electroflocculation + electrocatalytic reaction in the second reactor, and performs particle electrode recovery and flocculent precipitation in the third reactor. The residual conditions of penicillin, erythromycin, streptomycin and norfloxacin in wastewater and precipitated sludge are shown in Table 5. Compared with wastewater not subjected to ultrasonic treatment, ultrasonic treatment can avoid antibiotic residues in sludge and promote electrocatalytic degradation of antibiotics.

[0080] Table 5 Antibiotic residues in sludge and treated water under different treatment conditions

[0081]

Claims

1. An ultrasonic coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater, characterized in that: The device comprises an ultrasonic treatment first reactor, an electrochemical second reactor and a flocculation sedimentation third reactor which are connected in series in sequence through pipelines; wherein a wall-mounted ultrasonic vibration plate is arranged in the first reactor, a stabilizing electrode and a sacrificial electrode are arranged in the second reactor, a plurality of disc aerators are arranged at the bottom, and an overflow tank, an inclined tube filler and an electromagnet are arranged in the third reactor.

2. The ultrasonic coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater according to claim 1, characterized in that: The three reactors are connected in series via a pipeline, and a pipeline pump is provided on the pipeline.

3. The ultrasonic coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater according to claim 1, characterized in that: The second reactor is provided with stable electrodes and sacrificial electrodes arranged in a staggered and symmetrical manner, with a distance between two adjacent electrodes of 6 to 30 cm; and a liquid injection pipe is provided along one side wall of the reactor.

4. The ultrasonic coupled electrochemical pretreatment device for high-concentration antibiotic production wastewater according to claim 1, characterized in that: The third reactor is divided into an overflow trough and a sedimentation tank by a water retaining plate; the overflow trough is arranged on one side of the third reactor adjacent to the second reactor, and the pipeline connected to the second reactor is connected through the bottom of the overflow trough; a sludge discharge port is arranged at the bottom of the sedimentation tank and is connected to a slurry pump through a pipeline, a wall-mounted electromagnet is arranged in the sedimentation tank, and an inclined tube filler fixed by a bracket is arranged, and at the same time, a toothed drainage groove is arranged above the inclined tube filler, which is fixed to the side wall of the reactor by bolts and is connected to the water outlet located at the top of the third reactor.

5. A method for ultrasonically coupled electrochemical pretreatment of high-concentration antibiotic production wastewater using the device of claim 1, characterized in that: The device described in claim 1 is used to desorb adsorbed antibiotics in wastewater suspension through ultrasonic water oxidation and mechanical shearing, and then the wastewater passes through electrodes to achieve the stages of electrically enhanced heterogeneous catalytic oxidation reaction, electrocoagulation and electrocatalytic reaction during the switching of electrodes, thereby achieving deep mineralization and degradation of high-concentration antibiotics in the wastewater, reducing the residual antibiotics and their degradation products in the flocs and eliminating the toxicity of the wastewater.

6. The method according to claim 5, characterized in that: The stabilizing electrode may be made of graphite, titanium, titanium alloy, or boron-doped diamond; the sacrificial electrode may be made of iron, aluminum, or an alloy thereof; Disc aerator working ventilation volume 0.05~0.2m 3 / h·pcs, service area 0.2~0.5m 2 / indivual.

7. The method according to claim 5, characterized in that: The wastewater enters the first reactor for ultrasonic treatment; then enters the second reactor, where granular electrodes and oxidants are added. First, an electrically enhanced heterogeneous catalytic oxidation reaction is carried out with a stable electrode as the anode and a sacrificial electrode as the cathode, and then the electrode polarity is switched to use the stable electrode as the cathode and the sacrificial electrode as the anode for electrocoagulation and electrocatalytic reaction; after electrochemical treatment, the wastewater enters the bottom of the overflow tank of the third reactor, and the granular electrodes are recovered by magnetic adsorption. The suspended matter is precipitated in an inclined tube and then discharged by a mud pump for subsequent treatment. The clarified wastewater after treatment is collected through a toothed drainage trough and discharged from the sedimentation tank for subsequent treatment.

8. The method according to claim 6, characterized in that: The ultrasonic treatment time of the first reactor is 10 to 120 minutes; The particle electrode in the second reactor can be selected from one or more of cobalt trioxide (Co3O4), cobalt ferrite (CoFe2O4), manganese ferrite (MnFe2O4), nickel cobalt ferrite (CoNiFe2O4), and cobalt zinc ferrite (CoZnFe2O4); the particle electrode dosage is 0.1-10 g / L; the oxidant can be selected from one or more of permonosulfate (PMS), peroxydisulfate (PDS), hydrogen peroxide (H2O2), and peracetic acid (PAA); the oxidant dosage is 0.5-50 g / L.

9. The method according to claim 6, characterized in that: In the second reactor, the stable electrode is used as the anode and the sacrificial electrode is used as the cathode to carry out the electrically enhanced heterogeneous catalytic oxidation reaction for 15 to 180 minutes; then the electrode polarity is switched to carry out the electrocoagulation and electrocatalytic reaction for 15 to 180 minutes.

10. The method according to claim 6, characterized in that: The wastewater is deposited in the inclined tube of the third reactor for 60 to 240 minutes.

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