CN114715982A - Method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate - Google Patents

Method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate Download PDF

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CN114715982A
CN114715982A CN202210462746.9A CN202210462746A CN114715982A CN 114715982 A CN114715982 A CN 114715982A CN 202210462746 A CN202210462746 A CN 202210462746A CN 114715982 A CN114715982 A CN 114715982A
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antibiotic wastewater
peroxymonosulfate
antibiotic
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wastewater
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CN114715982B (en
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周元臻
党媛
张瑞瑞
于莎
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Xian University of Architecture and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
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    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract

The invention discloses a method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate, which comprises the following steps: taking a rare earth metal oxide modified titanium-based lead dioxide electrode as an anode and a stainless steel electrode as a cathode to carry out electrochemical treatment on the antibiotic wastewater; when the antibiotic wastewater is electrochemically treated, peroxymonosulfate is added into the antibiotic wastewater and continuously stirred. The invention combines EAOP and PMS-AOP, utilizes rare earth metal oxide to modify a titanium-based lead dioxide anode, and improves the titanium-based PbO by optimizing the appearance and composition2Self-fouling of the anodeElectrocatalytic oxidation characteristics and cycle stability of the dye; meanwhile, the rare earth metal oxide modified titanium-based lead dioxide anode can electrochemically activate persulfate, further enhance the degradation effect on pollutants, play a role in electrocatalytic degradation and the synergistic degradation of the electrochemically activated persulfate, and realize the efficient treatment of single and mixed antibiotic wastewater. In addition, the degradation efficiency is almost unchanged after the cyclic use for many times.

Description

Method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate.
Background
The rapid development of the pharmaceutical industry has resulted in an increasing content of toxic and refractory antibiotics remaining in water bodies, constituting a potential threat to ecosystem and human safety. The traditional wastewater treatment process is not ideal in antibiotic removal efficiency, and therefore, development of an efficient and feasible treatment process for improving the treatment effect of antibiotic wastewater is urgently needed. Advanced Oxidation Processes (AOPs) and Electrochemical Advanced Oxidation Processes (EAOP) based on Peroxymonosulfate (PMS) exhibit high mineralization efficiency for organic pollutants due to the generation of highly reactive species, such as sulfate radicals and reactive oxygen species. However, the existing PMS-AOP system still has the defects of circulation stability check, difficult catalyst recovery, easy generation of secondary pollution, high energy consumption and the like when used for activating PMS; when the EAOP is applied to the treatment of high-concentration organic wastewater which is difficult to degrade, the limited degradation efficiency limits the practical application of the EAOP.
Disclosure of Invention
Aiming at the defects of the existing PMS-AOP and EAOP technologies, the invention aims to provide a method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate, and the method can realize high-efficiency treatment of single and mixed antibiotic wastewater.
The technical scheme adopted by the invention is as follows:
a method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate comprises the following processes:
taking a rare earth metal oxide modified titanium-based lead dioxide electrode as an anode and a stainless steel electrode as a cathode to carry out electrochemical treatment on the antibiotic wastewater;
when the antibiotic wastewater is electrochemically treated, peroxymonosulfate is added into the antibiotic wastewater and continuously stirred.
Preferably, when the antibiotic wastewater is electrochemically treated, the external power supply is a direct current power supply, and the current is controlled to be 10-30mA/cm2。
Preferably, the treatment is carried out on antibiotic wastewaterIn the electrochemical treatment, the supporting electrolyte is sulfate Na2SO4。
Preferably, the antibiotics in the antibiotic wastewater comprise one or more of cefadroxil, levofloxacin and tetracycline.
Preferably, the concentration of the antibiotics in the antibiotic wastewater is not higher than 30 mg/L.
Preferably, when the antibiotic wastewater is subjected to electrochemical treatment, the concentration of the peroxymonosulfate in the electrolyte is 3-7 mM.
Preferably, the pH of the antibiotic wastewater is 3.0-9.0.
Preferably, the rare earth metal oxide modified titanium-based lead dioxide electrode is Ti/La prepared by adopting a codeposition method2O3-PbO2And an electrode.
Preferably, the Ti/La is prepared by adopting a codeposition method2O3-PbO2The process of the electrode comprises:
la2O3Adding nanoparticles to an acidic solution and allowing La to form2O3Dispersing the nano particles uniformly, then performing electrodeposition on the titanium mesh electrode in the acid solution to obtain the Ti/La after the electrodeposition is finished2O3-PbO2An electrode;
wherein the acidic solution comprises: 0.05M Pb (NO)3)20.1M HNO3And 0.05g of cetyltrimethylammonium bromide;
La2O3the concentration of the nanoparticles in the acidic solution was 0.03M;
during electrodeposition: the temperature is kept at 60 +/-5 ℃, and the current density is 40 +/-5 mA/cm2The time of electrodeposition is 1-2 h.
Preferably, the Ti/La is prepared by adopting a codeposition method2O3-PbO2The electrode process also comprises a process of pretreating the titanium mesh electrode, wherein the pretreatment process can remove an oxide layer on the surface of the titanium mesh.
The invention has the following beneficial effects:
the invention electrochemically activates the peroxy monosulfurThe method for treating the antibiotic wastewater by the acid salt combines EAOP and PMS-AOP, on one hand, utilizes rare earth metal oxide to modify a titanium-based lead dioxide anode, and improves titanium-based PbO by optimizing morphology and composition2The anode per se has the electrocatalytic oxidation characteristic on pollutants; meanwhile, the rare earth metal oxide modified titanium-based lead dioxide anode can electrochemically activate persulfate, so that the degradation effect on pollutants is further enhanced, the effects of electrocatalytic degradation and the synergistic degradation of the electrochemically activated persulfate are achieved, and the high-efficiency treatment of single and mixed antibiotic wastewater is realized. In addition, the degradation efficiency is almost unchanged after the cyclic use for many times.
Drawings
FIG. 1 is a schematic view of an apparatus for degrading antibiotic wastewater used in example 1 of the present invention;
the device comprises a direct current power supply 1, a modified anode 2, a stainless steel cathode 3, a beaker 4 and a constant-temperature magnetic stirrer 5.
FIG. 2 shows Ti/La employed in the present invention2O3-PbO2Scanning electron micrographs of the anode;
FIG. 3 shows (Ti/La)2O3-PbO2) A reuse degradation diagram of the EA-PMS system;
FIG. 4 shows (Ti/La)2O3-PbO2) A degradation comparison graph of an EA-PMS system on different antibiotics;
FIG. 5 is a graph showing the degradation of antibiotic wastewater by different systems under optimal conditions.
Detailed Description
The invention will be further described with reference to the drawings and the embodiments, but the scope of the invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
The method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate utilizes modified titanium-based PbO2The antibiotic wastewater is treated by an anodic electrochemical activation peroxymonosulfate system, referring to FIG. 1, the water treatment system comprisesThe reactor comprises a power supply and a reactor; the reactor comprises a reaction chamber and a stirrer, wherein the upper end of the reaction chamber is provided with an electrode fixer and a charging hole, a modified anode stainless steel plate and a modified cathode stainless steel plate are fixed in the reaction chamber in parallel, and the anode and the cathode are both rectangular thin plates; the cathode and the anode are connected with an external power supply through a lead; the persulfate is put into a reaction chamber, and the antibiotic wastewater is degraded in a reactor; the anode is titanium-based PbO modified by rare earth metal oxide2. In the invention, rare earth metal oxide is modified titanium-based PbO2The combination of the anode-mediated electrocatalytic oxidation and the anode electrochemical activation of persulfate realizes the high-efficiency treatment of mixed wastewater of one or more of cefadroxil, levofloxacin and tetracycline. Compared with the electrochemical water treatment technology of the same type, the combination of the two technologies ensures that the degradation efficiency is higher and the energy consumption is reduced; compared with the persulfate activation technology of the same type, the rare earth metal oxide-based modified titanium-based PbO2The persulfate technology of anode activation obviously improves the circulation stability when degrading antibiotic wastewater, and can be widely applied to the treatment process of various single and mixed antibiotic wastewater.
In the invention, Ti/La is prepared by a codeposition method2O3-PbO2The preparation method of the anode specifically comprises the following steps: preparing a co-deposition solution to contain 0.05M Pb (NO)3)2、0.1M HNO30.05g of cetyltrimethylammonium bromide (CTAB), and La were added to the solution2O3Stirring the solution for 5min, and performing ultrasonic treatment for 40min to ensure uniform dispersion of the solution in the deposited solution, wherein La is added2O3The concentration of the nanoparticles was 0.03M. And then, immersing the pretreated titanium mesh electrode into the deposition solution to perform electrodeposition. The temperature is kept at 60 +/-5 ℃ during electrodeposition, and the current density is 40 +/-5 mA/cm2The time of electrodeposition is 1-2 h, and the Ti/La is obtained2O3-PbO2And an anode. The unit "M" mentioned above means "mol/L".
The method for treating the antibiotic wastewater by electrochemically activating the peroxymonosulfate comprises the following specific process steps: is connected toAnd (3) adding a power supply, adding persulfate from a feed inlet, starting the stirrer, and purifying the antibiotic wastewater in the reactor. The upper fixer of the reactor is provided with small holes along the horizontal direction, the cathode and the anode are fixed by fixing the electrode clamps in the small holes, and the distance between the electrodes is kept to be 30 mm. The anode and cathode used should be equal in size and placed in parallel, each 20X 50mm in size2. And immersing the cathode and the anode fixed by the electrode clamp in the solution for 2-4 cm. The anode and the cathode are connected with a direct current stabilized voltage power supply which can be linearly regulated and controlled through a lead; the anode is a rare earth metal oxide modified titanium-based lead dioxide electrode (Ti/La)2O3-PbO2) And the cathode is a stainless steel electrode. The water treatment system also comprises stirring and temperature control, and the water temperature in the reactor is controlled to be 20-30 ℃ by heating the magnetic stirrer.
The pretreatment process of the anode titanium mesh substrate is as follows: cutting the titanium mesh into a size of 20mm multiplied by 50mm, and sequentially putting the titanium mesh into distilled water, acetone and ethanol for ultrasonic cleaning for 15min to remove surface impurities. And then washing the titanium mesh with distilled water, and then adding hydrogen fluoride: nitric acid: h2O is 1: 5: and (5) performing acid etching in the 10 mixed solution for 10-15s, and finally repeatedly washing the solution clean by using distilled water. After pretreatment, the titanium mesh is dried and packed into a sealed bag for standby.
Anode Ti/La2O3-PbO2The preparation process of the electrode is as follows: the pretreated titanium mesh substrate is put into an acidic deposition solution for electrodeposition, and the acidic solution is composed of 0.05M Pb (NO)3)2、0.1M HNO30.05g of cetyltrimethylammonium bromide (CTAB) and well dispersed 0.03M La2O3And (4) nano particles. The temperature is kept at 60 +/-5 ℃ during electrodeposition, and the current density is 40 +/-5 mA/cm2The electrodeposition time is 1-2 h, and Ti/La is obtained2O3-PbO2And an anode.
In the method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate, an external power supply is a direct current power supply, and the current is controlled to be 10-40mA/cm2. The supporting electrolyte in the electrolyte solution is sulfate (Na)2SO4). The antibiotic is cefadroxilLevofloxacin and tetracycline are dissolved in sodium sulfate solution to prepare single and mixed antibiotic wastewater.
The invention provides a rare earth metal oxide modified titanium-based lead dioxide anode and composite La2O3After nanoparticles, the Ti/La obtained2O3-PbO2The specific surface area of the anode electrochemistry is increased, and the electrocatalytic activity and the generation efficiency of active free radicals are obviously improved; the surface is more compact, and the electrochemical corrosion resistance and the service life of the electrode are improved. Thus, Ti/La2O3-PbO2Anode liftable titanium-based PbO2The electrocatalytic oxidation performance of the anode itself on the contaminants.
The method for treating the antibiotic wastewater by electrochemically activating the peroxymonosulfate can not only carry out electrocatalytic degradation on the anode, but also pass Ti/La2O3-PbO2PMS is electrochemically activated by the anode, so that the effects of electrocatalytic degradation and persulfate synergistic degradation through electrochemical activation are achieved, and the treatment effects on single and mixed antibiotic wastewater of cefadroxil, levofloxacin and tetracycline are further enhanced. In addition, the degradation system ((Ti/La) is established by the method2O3-PbO2) EA-PMS system) also solves the problem of limited mass transfer of pure electrocatalytic degradation, and after PMS is added, activated free radicals can be diffused into a solution to react with pollutants, so that the reaction range is expanded, and the degradation efficiency of antibiotics is improved; the system has good degradation effect and good circulation stability to antibiotic wastewater with different pH values, and can stably operate. Ti/La of the invention2O3-PbO2The anode electrochemical activation PMS system has the advantages of good stability, high treatment efficiency on single and mixed antibiotics, stable effluent quality, simple flow, small occupied area, easy realization of automatic control and convenient operation and management.
Example 1
The experimental apparatus used in this example is shown in fig. 1, and includes a power supply 1, a modified anode 2, a stainless steel cathode 3, a beaker 4, and a constant temperature magnetic stirrer 5.
Wherein the anode and the cathode are arranged in parallelThe interval is 30mm, and the cathode electrode is connected with a linearly-adjustable DC stabilized voltage power supply through a lead, wherein the cathode electrode is made of stainless steel, and the anode electrode is made of Ti/La2O3-PbO2And an electrode.
Ti/La2O3-PbO2The preparation method of the anode comprises the following steps:
(1) pretreatment of a titanium mesh substrate: cutting a purchased titanium net with the purity of 99.9 percent into the size of 20mm multiplied by 50mm, and sequentially putting the titanium net into distilled water, acetone and ethanol for ultrasonic cleaning for 15min respectively to remove surface impurities. The titanium mesh was then rinsed clean with distilled water and charged with hydrogen fluoride: nitric acid: h2O is 1: 5: and (5) performing acid etching in the 10 mixed solution for 10 s. And after the etching is finished, repeatedly washing the titanium net by using distilled water and drying for later use.
(2) Preparation of electrodeposition acidic solution: 0.05M Pb (NO)3)2、0.1M HNO30.05g of cetyltrimethylammonium bromide (CTAB) and 0.03M of La2O3Dissolving the nano particles in deionized water to form an acidic solution, stirring the solution for 5min, and then performing ultrasonic treatment for 40min to ensure that the nano particles are uniformly dispersed in the deposition solution.
(3) Finally, the pretreated titanium mesh electrode is put into the prepared electro-deposition acidic solution for electro-deposition, the temperature is kept at 60 +/-5 ℃ during electro-deposition, and the current density is 40mA/cm2After the electrodeposition time is 1.5h, Ti/La can be obtained2O3-PbO2And an anode. As shown in FIG. 2, with Ti/PbO2Anode ratio, resulting Ti/La2O3-PbO2The surface of the anode is rougher and the structure is more compact, which shows that the electrochemical specific surface area is increased, and the electrocatalytic activity and the generation efficiency of active free radicals are obviously improved; the compact surface structure endows the electrode with more excellent electrochemical corrosion resistance and longer service life of the electrode.
The antibiotic wastewater treatment process comprises the following steps: the external direct current power supply is connected, and the current density is 30mA/cm2When the pH is 3, the temperature is 25 +/-5 ℃ and the initial pollutant concentration is 30mg/L, placing the wastewater to be treated in a pollutant container, adding 5mM PMS, starting stirringAnd (4) a stirrer, and sampling to determine the antibiotic content after reacting for a certain time.
In this example, the removal rate of the antibiotic (cefadroxil) is determined to be 98.07% at 60 min. In addition, as shown in fig. 3, after the operation is repeatedly performed for 5 cycles under the same conditions (after 60min of cefadroxil wastewater is treated, the anode is cleaned by using anhydrous ethanol and ionized water, and then the next batch of wastewater is treated, and the operation is repeated for 5 times), the antibiotic removal rate is hardly changed (95.31%), which indicates that the method effectively realizes the degradation of cefadroxil antibiotic, the degradation performance is stable, the operation can be stable, and the quality of the effluent is stable.
Example 2
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process step, the degradation current density is 10mA/cm2And sampling after the reaction is finished to determine the content of cefadroxil.
Through determination, the cefadroxil removal rate in the embodiment is 83%; the removal rate is high, which shows that the method can effectively realize the degradation of cefadroxil antibiotic under low current density.
Example 3
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the processing steps, the on-state current density is 20mA/cm2And sampling after the reaction is finished to determine the cefadroxil content.
Through determination, the cefadroxil removal rate in the embodiment is 89.21%; the removal rate is high, which shows that the method effectively realizes the degradation of cefadroxil antibiotic, the degradation performance is stable, the operation can be stable, and the effluent quality is stable.
Example 4
This example of a process for treating antibiotic wastewater with electrochemically activated peroxymonosulfate is as in example 1, except that: in the treatment process, the pH value of the antibiotic wastewater is 7.0, and after the reaction is finished, a sample is taken to determine the antibiotic content.
Through determination, the cefadroxil removal rate in the method of the embodiment is 94.46 percent; the method can still effectively degrade antibiotics when the pH value of the degradation medium is increased, has stable degradation performance, can stably operate, and has stable effluent quality.
Example 5
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process, the pH value of the antibiotic wastewater is 9.0, and after the reaction is finished, a sample is taken to determine the antibiotic content.
The determination result shows that the removal rate of the antibiotics in the embodiment is 87.19 percent; the method can still effectively degrade antibiotics in a slightly alkaline environment, has stable degradation performance, can stably operate, and has stable effluent quality.
Example 6
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process, the addition of PMS is 3mM, and sampling is carried out after the reaction is finished to determine the antibiotic content.
Through determination, the antibiotic removal rate of the method is 86.56 percent; the removal rate of antibiotics is slightly reduced, which shows that the method effectively realizes the degradation of cefadroxil antibiotics, the degradation performance is stable, the operation can be stable, and the effluent quality is stable.
Example 7
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process, the addition of PMS is 7mM, and sampling is carried out after the reaction is finished to determine the antibiotic content.
The antibiotic removal rate of the embodiment is 93.76% by measurement; the removal rate of the antibiotics is stable, which shows that the method effectively realizes the degradation of the pollutant antibiotics, the degradation performance is stable, the operation can be stable, and the effluent quality is stable.
Example 8
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process, the used antibiotic is 30mg/L tetracycline.
According to the determination, as shown in fig. 4, the removal rate of tetracycline in the present example is 99.59% >; the removal rate of the antibiotics is stable, which shows that the method can effectively realize the degradation of the tetracycline antibiotics, and has stable degradation performance, stable operation and stable effluent quality.
Example 9
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process, the used antibiotic is 30mg/L levofloxacin.
Through measurement, as shown in fig. 4, the removal rate of levofloxacin in this example is 99.77%; the removal rate of antibiotics is stable, which shows that the method can effectively degrade levofloxacin antibiotics, has stable degradation performance, can stably operate and has stable effluent quality.
Example 10
This example of a process for the electrochemical activation of peroxymonosulfate for the treatment of antibiotic wastewater is as in example 1, except that: in the treatment process steps, the used antibiotics are mixed solution of cefadroxil, tetracycline and levofloxacin, the concentration of the three is 10mg/L, and the total concentration of the antibiotics in the solution is 30 mg/L.
Through determination, the removal rates of cefadroxil, tetracycline and levofloxacin in the embodiment are all more than 95%; the method can realize the simultaneous high-efficiency degradation of various antibiotics, has stable degradation performance, can stably operate, and has stable effluent quality.
Comparative example 1
The overall procedure of this comparative example is as in example 1, except that: and (4) not connecting a direct current power supply, and sampling to determine the content of the antibiotics after the reaction is finished.
It was determined that the antibiotic removal rate of this comparative example was only 19.97% at 60min (as shown in fig. 5), the antibiotic removal rate decreased and the reaction rate slowed. The comparison of the data shows that the importance of electrochemistry on the action of activating peroxymonosulfate to degrade antibiotics, the method established by the invention can realize the synergistic efficient degradation of the antibiotic wastewater by electrochemically activating PMS while the antibiotics are degraded by the self-electrocatalysis of the anode.
Comparative example 2
The overall procedure of this comparative example is as in example 1, except that: PMS is not added, and sampling is carried out after the reaction is finished to determine the content of the antibiotics.
As a result of the measurement, the method of this comparative example showed that the removal rate of antibiotics was only 80.22% within 60min, the removal rate of antibiotics was decreased and the reaction rate was slowed down in fig. 5. As can be seen from the comparison of the data, PMS plays an important role in electrochemically degrading antibiotics, and PMS is Ti/La2O3-PbO2A great deal of sulfate radical (SO) is generated after the anode is electrochemically activated4 ·-) Thereby realizing the high-efficiency degradation of the antibiotic pollutants.
Compared with the electrochemical water treatment technology, the technical scheme of the invention has the advantages of higher degradation efficiency and lower energy consumption; compared with persulfate activation technology, the method provided by the invention has the advantages that the circulation stability is obviously improved, and the method can be widely applied to treatment of various single and mixed antibiotic wastewater.

Claims (10)

1. A method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate is characterized by comprising the following steps:
taking a rare earth metal oxide modified titanium-based lead dioxide electrode as an anode and a stainless steel electrode as a cathode to carry out electrochemical treatment on the antibiotic wastewater;
when the antibiotic wastewater is subjected to electrochemical treatment, peroxymonosulfate is added into the antibiotic wastewater and is continuously stirred.
2. The method for treating antibiotic wastewater by using electrochemically activated peroxymonosulfate according to claim 1, wherein the applied power source is DC power source, and the current is controlled to be 10-30mA/cm2。
3. The method of claim 1The method for treating the antibiotic wastewater by electrochemically activating the peroxymonosulfate is characterized in that when the antibiotic wastewater is electrochemically treated, the supporting electrolyte is sulfate Na2SO4。
4. The method for treating antibiotic wastewater by electrochemically activating peroxymonosulfate according to claim 1, wherein the antibiotic in the antibiotic wastewater comprises one or more of cefadroxil, levofloxacin and tetracycline.
5. The method for treating antibiotic wastewater by using electrochemically activated peroxymonosulfate as claimed in claim 1 or 4, wherein the concentration of the antibiotic in the antibiotic wastewater is not higher than 30 mg/L.
6. The method of claim 1, wherein the concentration of peroxymonosulfate in the electrolyte is 3 to 7mM when the antibiotic wastewater is electrochemically treated.
7. The method for treating antibiotic wastewater by using electrochemically activated peroxymonosulfate as claimed in claim 1, wherein the pH of the antibiotic wastewater is 3.0-9.0.
8. The method for treating antibiotic wastewater by using electrochemically activated peroxomonosulfate as claimed in claim 1, wherein the electrode of rare earth metal oxide modified titanium-based lead dioxide is Ti/La prepared by co-deposition method2O3-PbO2And an electrode.
9. The method for treating antibiotic wastewater by using electrochemically activated peroxymonosulfate according to claim 8, wherein the co-deposition method is used to prepare Ti/La2O3-PbO2The process of the electrode comprises:
la2O3Nanoparticles of a compound of formula (I) and (II)Into an acidic solution and allowing La2O3Dispersing the nano particles uniformly, then carrying out electrodeposition on the titanium mesh electrode in the acidic solution to obtain the Ti/La2O3-PbO2An electrode;
wherein the acidic solution contains: 0.05M Pb (NO)3)20.1M HNO3And 0.05g of cetyltrimethylammonium bromide;
La2O3the concentration of the nanoparticles in the acidic solution was 0.03M;
during electrodeposition: the temperature is kept at 60 +/-5 ℃, and the current density is 40 +/-5 mA/cm2The time of electrodeposition is 1-2 h.
10. The method for treating antibiotic wastewater by using the electrochemically activated peroxymonosulfate according to claim 9, further comprising a pretreatment process of the titanium mesh electrode, wherein the pretreatment process can remove an oxide layer on the surface of the titanium mesh.
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