CN114262068A - Photoelectric biological Fenton reactor, preparation process thereof and ribavirin wastewater treatment process - Google Patents

Abstract

The invention relates to a photoelectric biological Fenton reactor, a preparation process thereof and a ribavirin wastewater treatment process, and belongs to the technical field of sewage purification and wastewater resource utilization. The preparation process comprises the following steps: 1. preparing an S-MFO catalyst; 2. preparing an S-MFO electrode slice; 3. culturing an anode microorganism; 4. constructing a Fenton reaction system; 5. and (3) taking the S-MFO electrode slice obtained in the step (2) as a cathode, putting the microorganism cultured in the step (3) into an anode chamber, taking a carbon brush as an anode, putting the carbon brush into a reactor, connecting the cathode and the anode by using a lead and externally connecting a resistor to form a closed loop, and putting an aeration pump below the S-MFO electrode to provide oxygen required in the Fenton reaction. The S-MFO catalytic cathode coupled biological photoelectric Fenton optimization treatment process realizes effective removal of antibiotic ribavirin, and effectively treats and recovers refractory ribavirin wastewater.

Description

Photoelectric biological Fenton reactor, preparation process thereof and ribavirin wastewater treatment process

Technical Field

The invention relates to a photo-biological electro-Fenton reactor, a preparation process and application thereof, and belongs to the technical field of sewage purification and wastewater resource utilization.

Background

Since the outbreak of a new coronavirus (COVID-19), the world has entered a severe and challenging period. The popularity of COVID-19 poses a great hazard to the health of people. According to the COVID-19 diagnosis and treatment scheme, antiviral drugs such as ribavirin and the like are widely used for treating COVID-19. The large scale use of ribavirin during COVID-19 resulted in a large increase in ribavirin concentration in wastewater, especially pharmaceutical factory wastewater and hospital wastewater. Ribavirin has a great influence on human health and ecology. In vitro bioassays using human induced pluripotent stem cells indicate that ribavirin may cause DNA damage and accumulation of reactive oxygen species. Release of large quantities of antiviral drugs and their metabolites into the environmental waters causes the development of resistant viral strains in wild animals, where the viruses may develop resistance through rapid mutation.

Ribavirin wastewater belongs to refractory wastewater. The traditional method for treating the organic wastewater difficult to degrade mostly adopts common methods such as air floatation, adsorption, filtration, ozone oxidation, chlorination, micro-electrolysis and the like, and the processes generally have the defects of low treatment efficiency, high cost and the like.

Therefore, there is a need for a ribavirin wastewater purification device which can solve the above technical problems.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a novel photoelectric biological Fenton reactor, and a preparation process and application thereof.

In order to achieve the purpose, the invention provides the following technical scheme:

one of the purposes of the invention is to provide a photoelectric biological Fenton reaction device for efficiently treating ribavirin antibiotic wastewater, which comprises a cathode chamber 1 and an anode chamber 2, and is characterized in that: an S-MFO electrode 3 is used as a cathode in a cathode chamber 1, a carbon brush 4 is used as an anode in an anode chamber 2, an activated carbon biological electrode 9 for providing microorganism attachment points is filled in the anode chamber 2, the cathode chamber 1 and the anode chamber 2 are separated by a proton exchange membrane 10, the S-MFO electrode 3 and the carbon brush 4 are connected by a lead 5 and are connected with an external resistor 6 in series, a xenon lamp 7 for simulating sunlight is arranged above the cathode chamber 1, and an aeration pump 8 for providing oxygen is arranged in the cathode chamber 1.

The invention also aims to provide a preparation process of the photoelectric biological Fenton reaction device, which is characterized by comprising the following steps of:

1) preparation of S-MFO particles

1.69g of MnSO₄·H₂O,5.56g of FeSO₄·7H₂O, 4.936g of Na₂S₂O₃Putting the mixture into 50mL of deionized water, uniformly stirring the mixture, pouring the mixture into 50mL of oxalic acid aqueous solution containing 3.78g of the mixture, heating the mixture for 20 minutes in a water bath at the temperature of between 60 and 80 ℃, washing and drying generated orange precipitate;

preferably, the generated orange precipitate is washed for three times by deionized water and ethanol respectively, and then is dried in an oven at 60 ℃;

2) preparation of S-MFO cathode

Adding PVDF, PVP and DMF into the S-MFO particles prepared in the step 1), wherein the mass ratio of the S-MFO particles to the PVDF to the PVP to the DMF is 20%: 5%: 3%: 72 percent, uniformly stirring the solution to obtain an S-MFO solution, putting a carbon felt into the prepared S-MFO solution, putting the carbon felt which is fully absorbed into a tubular furnace after the carbon felt fully absorbs the S-MFO solution, and firing for 2 hours at 500 ℃ to finally obtain an S-MFO electrode 3;

preferably, the solution is stirred uniformly by placing the solution on a magnetic stirrer and stirring for 12 hours;

3) cultivation of electrogenic microbial anodes

Mixing anaerobic sludge and activated carbon for culturing for a week to make microorganisms completely attached to the surface of the activated carbon, and adding a manually prepared nutrient medium during culturing to obtain an activated carbon bioelectrode;

4) operation of microbial anodes

Putting the activated carbon bioelectrode into the anode chamber 2 of the reaction device, inserting the carbon brush 4 as an anode electrode, and simultaneously continuously adding the nutrient medium in the step 3);

5) the S-MFO electrode 3 and the carbon brush 4 are connected by a lead 5, and are externally connected with a resistor to form a closed loop, an aeration pump 8 is arranged below the S-MFO electrode 3 to provide oxygen required in Fenton reaction, and a xenon lamp 7 is used for irradiating simulated visible light above the cathode chamber 1.

The invention also aims to provide a process for treating ribavirin antibiotic wastewater by using a photoelectric biological Fenton reactor, which is characterized by comprising the following steps of:

1) leading the ribavirin waste water into a regulating tank from a water inlet, and adding 0.5mol/L H into the regulating tank₂SO₄Adjusting the pH value of the wastewater to 3, and adding 0.5mol/L Na₂SO₄The conductive electrolyte is used as an electrolyte of a photo-biological electro-Fenton reaction to improve the conductivity of the ribavirin wastewater;

2) adding the ribavirin wastewater treated in the step 1) into a cathode chamber 1 of the photo-biological electro-Fenton reaction device, wherein the ribavirin wastewater passes through an S-MFO electrode 3, and simulating visible light irradiation by using a xenon lamp 7 above the photo-biological electro-Fenton cathode chamber to perform an oxidation-reduction reaction;

3) under the irradiation of visible light and the action of electric field provided by microbe, H generated by cathode₂O₂With Fe in the cathode solution²⁺The reaction is carried out to generate OH with strong oxidation performance and non-selectivity, and the opening and the breaking action are carried out on the ribavirin, so that the ribavirin wastewater is effectively treated and recovered.

The invention adopts the improved photobiological electro-Fenton technology to treat the ribavirin wastewater without additionally adding a power supply, and H generated in the cathode chamber is irradiated by electrochemical action and visible light₂O₂And Fe present in the solution²⁺The two react with each other to generate OH, has strong oxidation performance and nonselectivity, and can treat various organic pollutants which are difficult to degrade. The invention introduces electrogenesis microorganisms as an anode and provides Fenton reactionThe required electrical energy. Visible light (xenon lamp) is also introduced as energy to catalyze the degradation of pollutants, so that not only can the redox performance and the degradation efficiency of the pollutants be improved, but also the energy consumption is saved, and the cost is reduced.

The invention has the following beneficial effects:

1. the S-MFO electrode has larger specific surface area, more active sites, low cost and easy preparation;

2. the S-MFO electrode has sustainable utilization and can realize efficient degradation of pollutants repeatedly;

3. compared with the traditional method for producing the organic polluted wastewater difficult to degrade, the experiment utilizes the electrogenesis microorganism coupled Fenton system to produce H in the cathode chamber under the irradiation of visible light₂O₂With Fe in solution²⁺OH is generated by the reaction to degrade the organic pollutants which are difficult to degrade by ribavirin.

4. In the experiment, the xenon lamp is placed above the cathode chamber to simulate visible light, so that the oxidation-reduction performance of the reaction is improved, and the generation of H by Fenton is obviously improved₂O₂And OH activity.

In conclusion, the photo-biological electro-Fenton reactor effectively improves the degradation efficiency of ribavirin, and effectively recycles ribavirin wastewater.

Drawings

FIG. 1 is a cyclic voltammogram of an S-MFO cathode;

in the figure: the abscissa indicates the voltage in V, the ordinate indicates the current in A, the scanning rate is 0.01V/s at 1mol/L Na₂SO₄Medium scan cyclic voltammograms.

FIG. 2 is a polarization curve of an S-MFO cathode;

in the figure: the abscissa represents the current density in units of A/m²On the left of the ordinate, the voltage is indicated, on the right of the ordinate, the power density is indicated, in mW/m²。

FIG. 3 is a diagram showing the processing performance of the photoelectric biological Fenton reaction device for degrading ribavirin.

In the figure, the abscissa represents time in units h; the left side of the ordinate represents the removal efficiency.

Fig. 4 is a schematic structural diagram of the photoelectric biological fenton reactor.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The photoelectric biological fenton reactor of the embodiment, referring to fig. 4, includes a cathode chamber 1 and an anode chamber 2, and is characterized in that: an S-MFO electrode 3 is used as a cathode in the cathode chamber 1, a carbon brush 4 is used as an anode in the anode chamber 2, an activated carbon biological electrode 9 for providing microorganism attachment points is filled in the anode chamber 2, the cathode chamber 1 and the anode chamber 2 are separated by a proton exchange membrane 10, the anode electrode and the cathode electrode are connected by a lead 5 and are connected with an external resistor 6(200 ohms) in series, a xenon lamp 7 for simulating sunlight is arranged above the cathode chamber 1, and an aeration pump 8 for providing oxygen is arranged in the cathode chamber 1.

The preparation process of the photoelectric biological Fenton reaction device for efficiently treating ribavirin antibiotic wastewater comprises the following steps:

1) preparation of S-MFO cathode

1.69g of MnSO₄·H₂O,5.56g of FeSO₄·7H₂O and 4.936g of Na₂S₂O₃Putting the mixture into 50mL of deionized water, stirring the mixture evenly, pouring the mixture into 50mL of oxalic acid aqueous solution containing 3.78g of oxalic acid, heating the mixture for 20 minutes in a water bath at 60-80 ℃, washing the generated orange precipitate for three times by the deionized water and ethanol respectively, and putting the orange precipitate into an oven to dry at 60 ℃. And adding PVDF, PVP and DMF into the prepared S-MFO particles, wherein the mass ratios of the S-MFO, the PVDF, the PVP and the DMF are respectively 20%, 5%, 3% and 72%. The solution was placed on a magnetic stirrer and stirred for 12 hours. Putting the carbon felt into the prepared S-MFO solution, and after the carbon felt fully absorbs the S-MFO solution, fully absorbing carbonThe felt is put into a tube furnace and fired at 500 ℃ for 2 hours to finally obtain the S-MFO electrode 3.

2) Cultivation of electrogenic microbial anodes

Anaerobic sludge and activated carbon are mixed and cultured for one week to ensure that microorganisms are completely attached to the surface of the activated carbon, and artificially prepared nutrient media (1g/L sodium acetate solution, 50mM phosphate buffer solution, 12.5mL/L mineral solution and 5mL/L vitamin solution) are added during culture. The cultured activated carbon biological anode is placed in the anode chamber 2 of the reaction device, and the carbon brush 4 is inserted as an anode electrode.

3) Installation of a reaction device: adding 0.5mol/LH into ribavirin wastewater₂SO₄Adjusting the pH value of the wastewater to 3, and adding 0.5mol/L Na₂SO₄The prepared anode and cathode electrodes are fixed and are respectively connected with an external resistor 6 in series by leads, and the cathode chamber 1 is placed in an aeration pump 8.

The process for treating ribavirin antibiotic wastewater by using the photoelectric biological Fenton reactor comprises the following steps:

1) leading the ribavirin waste water into a regulating tank from a water inlet, and adding 0.5mol/L H into the regulating tank₂SO₄Adjusting the pH value of the wastewater to 3, and adding 0.5mol/L Na₂SO₄The conductive electrolyte is used as an electrolyte of a photo-biological electro-Fenton reaction to improve the conductivity of the ribavirin wastewater;

2) adding the ribavirin wastewater treated in the step 1) into a cathode chamber 1 of the photo-biological electro-Fenton reaction device, wherein the ribavirin wastewater passes through an S-MFO electrode 3, and simulating visible light irradiation by using a xenon lamp 7 above the photo-biological electro-Fenton cathode chamber to perform an oxidation-reduction reaction;

3) under the irradiation of visible light and the action of the electric field provided by the microbe, H is generated at the cathode₂O₂With Fe in the cathode solution²⁺The reaction is carried out to generate OH with strong oxidation performance and non-selectivity, and the opening and the breaking action are carried out on the ribavirin, so that the ribavirin wastewater is effectively treated and recovered.

Comparative example 1

(1) Preparing an S-MFO electrode: the S-MFO electrode was fired in a tube furnace at 450 ℃ for 2 hours.

(2) Culturing the electrogenesis microorganism anode: the same as in example 1.

(3) Installation of a reaction device: the same as in example 1.

Comparative example 2

(1) Preparing an S-MFO electrode: the S-MFO electrode was placed in a tube furnace and fired at 550 ℃ for 2 hours.

(2) Culturing the electrogenesis microorganism anode: the same as in example 1.

(3) Installation of a reaction device: the same as in example 1.

Comparative example 3

(1) MFO electrode preparation: no Na is added in the preparation of the electrode₂S₂O₂。

(2) Culturing the electrogenesis microorganism anode: the same as in example 1.

(3) Installation of a reaction device: the same as in example 1.

Test 1

The redox properties of the catalytic cathodes obtained in example 1 and comparative examples 1-2 were examined.

The redox test of the catalytic cathode is carried out by adopting cyclic voltammetry, the scanning speed is 0.01V/s, and the scanning speed is 1mol/L of Na₂SO₄Cyclic voltammetry characterization was performed on catalytic cathodes with different sintering temperatures in the solution, and the results are shown in fig. 1. As can be seen from FIG. 1, the S-MFO-fired 500-degree catalytic cathode has a distinct redox peak compared with the cyclic voltammetry curves of S-MFO-fired 450 degrees and S-MFO-fired 550 degrees, which shows that the redox performance of the S-MFO-fired 500-degree catalytic cathode is stronger than that of the other two catalytic cathodes, and the redox potential is closer to 0 potential, which is more favorable for promoting the degradation of ribavirin pollutants, and shows that the redox reaction of the S-MFO-fired 500-degree catalytic cathode has a distinct promoting effect.

Test 2

The relationship between the polarization potential or overpotential in the reaction and the passing current density of the S-MFO electrode and the MFO electrode obtained in example 1 and comparative example 3 was examined.

And connecting the cathode and the anode in the reaction device by using a lead, connecting an adjustable resistance box in series, connecting a voltmeter in parallel, adjusting the size of an external resistor to obtain a test voltage value, and drawing a polarization curve. In the photo-biological electro-reaction system, the S-MFO electrode has larger voltage than the MFO electrode, and the power density generated by the S-MFO electrode is far larger than that generated by the MFO electrode.

Test 3

The performance test of treating ribavirin wastewater was carried out on the S-MFO catalytic cathode photo-electro-biological fenton reaction apparatus prepared in example 1.

And fixing the prepared S-MFO cathode and the carbon brush anode, connecting the S-MFO cathode and the carbon brush anode by using a lead, and connecting the S-MFO cathode and the carbon brush anode in series with an external resistor. An aeration pump device is arranged in the cathode chamber. With 0.5M Na₂SO₄The aqueous solution is taken as electrolyte, ribavirin wastewater with different concentrations (the concentrations are respectively 2mg/L,4mg/L,6mg/L,8mg/L and 10mg/L) is regulated, and the performance of the system for treating ribavirin is tested. The results are shown in FIG. 3. Therefore, the photobioreactor disclosed by the invention can effectively remove the ribavirin wastewater with the concentration of 2mg-10mg/L under the condition that the S-MFO is used as an electrode, so that the ribavirin wastewater is effectively purified.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. The utility model provides a biological fenton reaction unit of photoelectricity, includes cathode chamber and anode chamber, its characterized in that: the cathode chamber is internally provided with an S-MFO electrode as a cathode, the anode chamber is internally provided with a carbon brush as an anode, the anode chamber is internally filled with an activated carbon biological electrode for providing microorganism attachment points, the cathode chamber and the anode chamber are separated by a proton exchange membrane, the S-MFO electrode and the carbon brush are connected by a lead and are connected with an external resistor in series, a xenon lamp for simulating sunlight is arranged above the cathode chamber, and the cathode chamber is internally provided with an aeration pump for providing oxygen.

2. The process for preparing a photo-electric biological Fenton reaction device according to claim 1, comprising the steps of:

1) preparation of S-MFO particles

1.69g of MnSO₄·H₂O,5.56g of FeSO₄·7H₂O, 4.936g of Na₂S₂O₃Putting the mixture into 50mL of deionized water, uniformly stirring the mixture, pouring the mixture into 50mL of oxalic acid aqueous solution containing 3.78g of the mixture, heating the mixture for 20 minutes in a water bath at the temperature of between 60 and 80 ℃, washing and drying generated orange precipitate;

2) preparation of S-MFO cathode

Adding PVDF, PVP and DMF into the S-MFO particles prepared in the step 1), wherein the mass ratio of the S-MFO particles to the PVDF to the PVP to the DMF is 20%: 5%: 3%: 72 percent, uniformly stirring the solution to obtain an S-MFO solution, putting a carbon felt into the prepared S-MFO solution, putting the carbon felt which is fully absorbed into a tubular furnace after the carbon felt fully absorbs the S-MFO solution, and firing for 2 hours at 500 ℃ to finally obtain an S-MFO electrode;

3) cultivation of electrogenic microbial anodes

Mixing anaerobic sludge and activated carbon for culturing for a week to make microorganisms completely attached to the surface of the activated carbon, and adding a manually prepared nutrient medium during culturing to obtain an activated carbon bioelectrode;

4) operation of microbial anodes

Putting an activated carbon bioelectrode into an anode chamber of the reaction device, inserting a carbon brush as an anode, and simultaneously continuously adding the nutrient medium in the step 3);

5) the S-MFO electrode and the carbon brush are connected by a lead 5, and are externally connected with a resistor to form a closed loop, an aeration pump is arranged below the S-MFO electrode to provide oxygen required in Fenton reaction, and a xenon lamp is used for irradiating simulated visible light above the cathode chamber.

3. The process for preparing a photo-electric biological Fenton reaction device according to claim 1, wherein the orange precipitate generated in step 1) is washed with deionized water and ethanol three times respectively, and then dried in an oven at 60 ℃.

4. The process for preparing a photo-electro-biological Fenton reaction device according to claim 1, wherein said step 2) of uniformly stirring said solution is to place said solution on a magnetic stirrer and stir said solution for 12 hours.

5. The process for treating ribavirin antibiotic wastewater by using the photoelectric biological Fenton reactor as claimed in claim 1, which is characterized by comprising the following steps of:

1) leading the ribavirin waste water into a regulating tank from a water inlet, and adding 0.5mol/L H into the regulating tank₂SO₄Adjusting the pH value of the wastewater to 3, and adding 0.5mol/L Na₂SO₄The conductive electrolyte is used as an electrolyte of a photo-biological electro-Fenton reaction to improve the conductivity of the ribavirin wastewater;

2) adding the ribavirin wastewater treated in the step 1) into a cathode chamber of the photo-biological electro-Fenton reaction device, wherein the ribavirin wastewater passes through an S-MFO electrode, and simulating visible light irradiation by using a xenon lamp above the cathode chamber of the photo-biological electro-Fenton reaction device to perform an oxidation-reduction reaction;

3) under the irradiation of visible light and the action of electric field provided by microbe, H generated by cathode₂O₂With Fe in the cathode solution²⁺The reaction is carried out to generate OH with strong oxidation performance and non-selectivity, and the opening and the breaking action are carried out on the ribavirin, so that the ribavirin wastewater is effectively treated and recovered.

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