CN115340245A - Dye wastewater degradation treatment system and method for treating dye wastewater by using same - Google Patents
Dye wastewater degradation treatment system and method for treating dye wastewater by using same Download PDFInfo
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- CN115340245A CN115340245A CN202210150074.8A CN202210150074A CN115340245A CN 115340245 A CN115340245 A CN 115340245A CN 202210150074 A CN202210150074 A CN 202210150074A CN 115340245 A CN115340245 A CN 115340245A
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Images
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
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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
- C02F1/467—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
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a dye wastewater degradation treatment system and a method for treating dye wastewater by using the same, and belongs to the technical field of organic dye wastewater treatment. The invention integrates the functions of magnetic adsorption, enrichment and separation, visible light photoelectrocatalysis and hydrogen peroxide synergistic degradation, and is used for degradation treatment of high-concentration dye wastewater, and the data of the embodiment shows that compared with the independent H 2 O 2 Degradation by illumination, electrochemical oxidation, degradation by Fe 3 O 4 @SiO 2 @TiO 2 Photocatalytic degradation of Fe 3 O 4 @SiO 2 @TiO 2 The degradation rates of photoelectrocatalysis degradation are respectively 13%/120min, 22%/120min, 25%/120min and 61.5%/40min, and the invention provides a dye wastewater degradation treatment system, fe 3 O 4 @SiO 2 @TiO 2 photoelectrocatalysis/H 2 O 2 The degradation rate of the synergistic degradation is close to 100%/5min.
Description
Technical Field
The invention relates to the technical field of organic dye wastewater treatment, in particular to a dye wastewater degradation treatment system and a method for treating dye wastewater by using the same.
Background
The dye wastewater has the obvious characteristics of large discharge amount, high chroma, poor biodegradability, difficult degradation, high toxicity and the like, and is one of industrial wastewater which is difficult to treat at present. Even if the organic dye with low concentration still has very high chroma, the lower light transmittance in the water body can influence the photosynthesis of aquatic plants and the growth of aquatic animals, and the organic dye has carcinogenicity, teratogenicity and mutagenicity. The traditional sewage biochemical treatment process cannot completely remove the dye, and once the dye is discharged into a natural water body, certain ecological environment risk is caused. The prior dye wastewater treatment method mainly comprises an adsorption method, a coagulation method, an oxidation method (biological oxidation, chemical oxidation and photocatalysis methods), an electrochemical method and the like.
Conventional wastewater treatment methods, such as biological treatment, adsorption and coagulation, do not completely remove pollutants from wastewater. But also has the defects of high cost, large dosage, low efficiency and secondary pollution. Therefore, the development of a low-carbon and green dye wastewater treatment technology with low cost and high degradation efficiency is very necessary.
The photoelectrocatalysis technology is considered to be a promising advanced oxidation water treatment technology which meets the increasing energy requirements and provides effective wastewater treatment, and the photoelectrocatalysis technology combines a photocatalysis oxidation method and an electrochemical oxidation method to generate a synergistic effect, effectively inhibits the recombination of photogenerated electron hole pairs, obviously improves the photocatalysis activity of a semiconductor photocatalyst and can efficiently oxidize and degrade organic pollutants. The method not only can solve the electrode passivation phenomenon frequently occurring in electrochemical oxidation, but also overcomes the problem that the powder photocatalyst needs to be subsequently separated.
However, the heterogeneous photoelectrocatalysis reaction is affected by mass transfer limitation, low amount of generated active free radicals and other factors, and the efficiency of removing pollutants by photoelectrocatalysis oxidation needs to be further improved. H 2 O 2 Can be irradiated by catalyst or ultraviolet lightCan generate strong oxidizing hydroxyl free radical OH to oxidize and degrade organic pollutants. Reported in the literature, in TiO 2 Adding H in ultraviolet light catalytic system 2 O 2 A large amount of OH can be generated in a mode of combining heterogeneous photocatalysis and homogeneous oxidation, so that the degradation effect of organic pollutants is improved. In g-C 3 N 4 Adding H into a visible photoelectrocatalysis degradation methylene blue system 2 O 2 The degradation rate of the methylene blue can be improved from 35.92% to 53.43% within 2h. Thus, addition of H to the photoelectrocatalytic system 2 O 2 The defect of low active free radical quantity in the photoelectrocatalysis process can be overcome, and thus the degradation rate of pollutants is effectively improved.
Disclosure of Invention
The invention aims to provide a dye wastewater degradation treatment system and a method for treating dye wastewater by using the same. The invention integrates the magnetic adsorption, enrichment and separation, visible light photoelectrocatalysis and hydrogen peroxide synergistic degradation, and is used for degradation treatment of high-concentration dye wastewater, thereby improving the degradation rate of organic matters in the dye wastewater.
The invention provides a dye wastewater degradation treatment system, which comprises an adsorption tank (1), a three-way valve (2), a peristaltic pump (3), a magnetic separation system (4), a three-way valve (5), a photoelectrocatalysis degradation system (6), a flushing tank (7), a peristaltic pump (8), a receiving tank (9) and a receiving tank outlet (10), wherein the magnetic separation system (4) comprises a power supply (44) and a hose (41), and an iron pipe (42) outside the hose (41) is wrapped by a magnetic coil (43); the photoelectrocatalytic degradation system (6) comprises: the device comprises a photoelectric reaction cell cover (61), a photoelectric reaction cell (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a xenon lamp light source (68) and an electrochemical workstation (69), wherein the photoelectric reaction cell (62) has a double-layer structure, the inner layer is the reaction cell, and a quartz light window (623) is arranged on one side of the reaction cell; the outer layer is a cooling water bath and comprises a water inlet (621) and a water outlet (622), five holes are formed in a photoelectric reaction cell cover (61) and used for fixing a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66) and a working electrode (67), wherein the mercury/mercurous sulfate reference electrode (63), the Pt sheet auxiliary electrode (66) and the working electrode (67) are connected with an electrochemical workstation (69) through electrode wires, and a xenon lamp light source (68) is opposite to a quartz light window (623) and is 10cm away from the quartz light window.
Preferably, the working electrode (67) is made of ITO conductive glass with a surface fixed with a magnetic mesoporous nano material.
Preferably, the feed tube (64) contains a filling material comprising H 2 O 2 And (3) solution.
The invention also provides a method for treating dye wastewater by using the dye wastewater degradation treatment system, which comprises the following steps:
adding the dye wastewater and the magnetic mesoporous nano material into an adsorption tank (1) respectively, and stirring to enable the nano material to fully adsorb the enriched pollutants to obtain a suspension;
opening the peristaltic pump (3), enabling the suspension to enter the magnetic separation system (4), simultaneously switching on a power supply (44), enabling the suspension to flow through a hose (41) of the magnetic separation system (4), wrapping an iron pipe (42) outside the hose (41) by a magnetic coil (43), and attaching the magnetic nano material enriched with pollutants in the suspension to the wall of the hose due to an electromagnetic effect;
the residual pollutant suspension enters a photoelectrocatalysis degradation system (6); wherein the water inlet (621) and the water outlet (622) form circulating condensed water for cooling the system; the working electrode (67) is made of ITO conductive glass with the surface fixed with magnetic nano materials; visible light provided by a xenon lamp light source (68) is irradiated on the surface of the working electrode (67) through a quartz light window (623);
na is added from a feeding pipe (64) 2 SO 4 Solution, H 2 O 2 After the solution and the pH regulator are mixed, an aeration port (65) aerates to uniformly mix the solution;
the photoelectrocatalysis/H is generated in the photoelectrocatalysis degradation system (6) by applying potential to the working electrode (67) through the electrochemical work station (69) 2 O 2 The dye pollutants are subjected to degradation and mineralization reaction under the synergistic effect;
after the degradation reaction is finished, the three-way valve (2) and the three-way valve (5) are opened, the peristaltic pump (3) and the peristaltic pump (8) are started, flushing liquid in the flushing pool (7) enters the hose (41), the power supply (44) is in a closed state at the moment, and the magnetic mesoporous nano material flows into the receiving pool (9) along with the flushing liquid and is finally discharged through the receiving pool outlet (10).
Preferably, the magnetic mesoporous nanomaterial comprises Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
Preferably, the Fe 3 O 4 @SiO 2 @TiO 2 The preparation method of the magnetic mesoporous nano material comprises the following steps:
preparation of Fe by coprecipitation method 3 O 4 Nanoparticles: feCl 3 Solution with Fe 3 O 4 Uniformly mixing the solution in a beaker, simultaneously heating in a water bath for heat preservation, slowly dripping NaOH solution under the stirring condition, then dripping concentrated ammonia water until the solution is completely black, measuring the pH, centrifugally separating the reaction mixture after the reaction is finished, respectively washing the black solid obtained by separation with absolute ethyl alcohol and deionized water, and obtaining Fe after magnetic separation and vacuum drying 3 O 4 A nanoparticle;
preparation of magnetic SiO 2 And (3) core: subjecting said Fe to 3 O 4 Dispersing nano particles in absolute ethyl alcohol, ultrasonically oscillating, sequentially adding the absolute ethyl alcohol, deionized water and concentrated ammonia water, adjusting the pH of the solution to obtain a turbid liquid, uniformly stirring the turbid liquid, then dropwise adding tetraethoxysilane, carrying out reflux reaction, centrifuging the reacted solution to obtain a solid product, respectively washing with the absolute ethyl alcohol and the deionized water, carrying out magnetic separation and vacuum drying to obtain magnetic SiO 2 A core;
preparing Fe by using polypropylene glycol as template agent and adopting hydrothermal method 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material: under vigorous stirring, butyl titanate was added dropwise to the aqueous acetic acid solution, followed by addition of magnetic SiO 2 Stirring under sealed condition to obtain solution A, dissolving polypropylene glycol in ethanol under vigorous stirring to obtain solution B containing polypropylene glycol, dropwise adding solution B into solution A, sealing the mixed solution, stirring, transferring into polytetrafluoroethylene reaction kettle, performing hydrothermal reaction, cooling, centrifuging to separate reaction solution, and solidifyingWashing the product with absolute ethyl alcohol and deionized water, drying overnight, calcining in a muffle furnace, grinding, and magnetically separating to obtain Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
Preferably, said FeCl 3 Solution with FeSO 4 The molar ratio of the solution was 2.
Preferably, the polypropylene glycol has a molecular weight of 1000.
Preferably, the preparation method of the working electrode (67) comprises the following steps:
dispersing the magnetic mesoporous nano particles in ethanol, and performing ultrasonic dispersion to obtain a magnetic photoelectrocatalysis material suspension;
ultrasonically cleaning conductive glass in acetone, ethanol and deionized water in sequence, and drying for later use;
connecting one end of the conductive glass with a conductive silver adhesive to a lead, drying overnight, sealing the connection part of the conductive glass and the lead by using an epoxy resin adhesive, coating a magnetic photoelectrocatalysis material suspension on the working surface of the conductive glass, and airing at room temperature;
and adhering the other neodymium iron boron magnet to the back surface of the working surface of the conductive glass to obtain the working electrode (67).
Preferably, the neodymium iron boron magnet is coated with a layer of polyvinyl chloride film.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The invention adds H to a photoelectrocatalysis system 2 O 2 The defect of low active free radical quantity in the photoelectrocatalysis process can be overcome, so that the degradation rate of pollutants is effectively improved;
(2) The invention integrates the magnetic adsorption enrichment separation, visible light photoelectrocatalysis and hydrogen peroxide synergistic degradation, is used for degradation treatment of high-concentration dye wastewater, and can obviously improve the degradation rate;
(3) Fe in the invention 3 O 4 The material has magnetism, can carry out magnetic separation of pollutants, and is directly adsorbed on the surface of conductive glass by utilizing the magnetism when the working electrode is prepared, and the fixing method is simpleFirm, reusable and SiO 2 Can protect Fe 3 O 4 The magnetic core is prevented from being eroded by acid environment, the magnetic property is ensured to be reused, and simultaneously, the mesoporous TiO is 2 Mesoporous in (C) increases TiO 2 The specific surface area of the material is increased, the adsorption performance of the material is enhanced, the adsorption capacity of the nano material to pollutants is increased, the material compounds three semiconductor materials, and Fe 3 O 4 And SiO 2 By adding of titanium oxide to reduce TiO 2 Forbidden band width of (2) to make TiO 2 The light absorption of (2) is expanded to a visible light area, and when the photoelectrocatalysis is degraded, sunlight can be utilized to provide light energy, ultraviolet light is not needed to be used like the traditional photocatalysis, photoelectrocatalysis and photo-Fenton methods, so that the energy is saved, and the method has higher practicability.
(4) Fe in photoelectrocatalytic degradation of dyes of the present application 3 O 4 @SiO 2 @TiO 2 The magnetic mesoporous nano material can generate O with strong oxidizing property 2 - OH, after bias voltage is applied to the working electrode, photoproduction electrons can circulate along the external electric field under the action of the external electric field, so that the recombination rate of electron-hole pairs is reduced, the photoelectric coupling effect is realized, the degradation efficiency of pollutants is improved, and H is added 2 O 2 Then, fe 3 O 4 @SiO 2 @TiO 2 The photo-generated electrons generated by the visible light excitation of the mesoporous catalyst can be excited by H 2 O 2 Trapping to finally generate OH, increasing the amount of substances with strong oxidizing property, further reducing the recombination of electron-hole pairs, and further improving the degradation efficiency of the dye due to synergistic effect;
(5) According to the invention, the neodymium iron boron magnet is coated with the polyvinyl chloride film, the polyvinyl chloride film can prevent the contact between the magnet and a reaction solution and is adhered to the back of the working surface of the conductive glass, meanwhile, the magnet plays a role in fixing the magnetic photoelectric catalytic material, the method is simple, the manufactured working electrode can be repeatedly used, other adhesives are not needed when the nano material is fixed, the effective working area of the material is not influenced, and the problems of high cost, complex operation and easy peeling of the material of other fixing methods are solved.
(6) Table of results of examplesMing, H 2 O 2 Degradation by light, electrochemical oxidation, fe 3 O 4 @SiO 2 @TiO 2 Photocatalytic degradation of Fe 3 O 4 @SiO 2 @ mesoporous TiO 2 The degradation rates of photoelectrocatalysis degradation are respectively 13%/120min, 22%/120min, 25%/120min and 61.5%/40min, and the Fe-based catalyst provided by the invention is prepared from Fe 3 O 4 @SiO 2 @TiO 2 photoelectrocatalysis/H 2 O 2 The degradation rate of the synergistic degradation is close to 100%/5min.
Drawings
FIG. 1 is a system diagram of the dye wastewater degradation treatment of the invention, which comprises an adsorption tank (1), a three-way valve (2), a peristaltic pump (3), a magnetic separation system (4), a three-way valve (5), a photoelectrocatalysis degradation system (6), a flushing tank (7), a peristaltic pump (8), a receiving tank (9), a receiving tank outlet (10), a hose (41), an iron pipe (42), a magnetic coil (43), a power supply (44), a photoelectricity reaction tank cover (61), a photoelectricity reaction tank (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a xenon lamp light source (68), an electrochemical work station (69), a water inlet (621), a water outlet (622) and a quartz light window (623);
FIG. 2 is a cross-sectional view of the cover (61) of the photoelectric reaction cell of the present invention; the device comprises a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66) and a working electrode (67);
FIG. 3 is a graph of a dye wastewater degradation treatment system of the present invention for degrading rhodamine B;
FIG. 4 is a graph of a dye wastewater degradation treatment system of the present invention for degrading methyl orange;
FIG. 5 is a bar graph of a repetitive experiment of degradation of the dye wastewater degradation treatment system of the present invention;
FIG. 6 is a graph showing the results of treatment of printing and dyeing wastewater by the dye wastewater degradation treatment system according to the present invention;
FIG. 7 is a bar graph of the degradation results of methylene blue in a methylene blue solution subjected to a radical quenching experiment of the present invention;
FIG. 8 shows direct photolysis and photocatalysis of methylene blue as a model contaminantChemical method, electrochemical oxidation method, photoelectrocatalysis/H 2 O 2 Degradation result graph of methylene blue by a synergistic method, wherein a curve is only H 2 O 2 Direct photodegradation results when present; curve b is without addition of H 2 O 2 Adding Fe into methylene blue solution 3 O 4 @SiO 2 @TiO 2 The subsequent photodegradation results; curve c is addition of H 2 O 2 Adding Fe into methylene blue solution 3 O 4 @SiO 2 @TiO 2 The subsequent photodegradation results; curves d-f represent experimental results under electrochemical conditions, wherein curve d is a result curve under electrochemical + magnetic material conditions, and curve e is electrochemical + H 2 O 2 Graph of results under the conditions, curve f electrochemical + magnetic material + H 2 O 2 Results plot under conditions; the curve g-H represents the experimental result under the condition of photoelectrocatalysis, wherein g is the result curve graph under the conditions of illumination, electrochemistry and magnetic materials, and H is the conditions of illumination, electrochemistry and H 2 O 2 The result curve under the condition is that the curve i is illumination, electrochemistry, magnetic materials and H 2 O 2 Results under the conditions are plotted.
Detailed Description
The invention provides a dye wastewater degradation treatment system, which comprises an adsorption tank (1), a three-way valve (2), a peristaltic pump (3), a magnetic separation system (4), a three-way valve (5), a photoelectrocatalysis degradation system (6), a flushing tank (7), a peristaltic pump (8), a receiving tank (9) and a receiving tank outlet (10), wherein the magnetic separation system (4) comprises a power supply (44) and a hose (41), and an iron pipe (42) outside the hose (41) is wrapped by a magnetic coil (43); the photoelectrocatalysis degradation system (6) comprises a photoelectricity reaction cell cover (61), a photoelectricity reaction cell (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a xenon lamp light source (68) and an electrochemical workstation (69), wherein the photoelectricity reaction cell (62) has a double-layer structure, the inner layer is the reaction cell, and one side of the photoelectricity reaction cell is provided with a quartz light window (623); the outer layer is a cooling water bath and comprises a water inlet (621) and a water outlet (622), five holes are formed in a photoelectric reaction cell cover (61) and used for fixing a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66) and a working electrode (67), wherein the mercury/mercurous sulfate reference electrode (63), the Pt sheet auxiliary electrode (66) and the working electrode (67) are connected with an electrochemical workstation (69) through electrode wires, and a xenon lamp light source (68) is opposite to a quartz light window (623) and is 10cm away from the quartz light window.
In the present invention, the working electrode (67) is preferably made of ITO conductive glass with a magnetic mesoporous nano material fixed on the surface, and the magnetic mesoporous nano material preferably comprises Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
In the present invention, the feed tube (64) is preferably provided with a gas containing H 2 O 2 The solution is preferably also filled with Na 2 SO 4 Solution and pH regulator, said H 2 O 2 The mass-to-volume ratio of the solution is preferably 2.5%, and the Na 2 SO 4 The concentration of (b) is preferably 0.5mol/L, and the pH after adjustment by the pH adjustor is preferably 3.
In the invention, the adsorption tank (1) is communicated with the left and right openings of the three-way valve (2), and suspension is pumped into one end of a hose (41) by controlling the peristaltic pump (3);
the flushing pool (7) is connected with a lower outlet of the three-way valve (2), and the nano particles are flushed into one end of the hose (41) by controlling the peristaltic pump (3), flow into the receiving pool (9) and finally are discharged through the receiving pool outlet (10).
The other end of the hose (41) is connected with the photoelectrocatalysis degradation system (6) through a left through hole and a right through hole of the three-way valve (5), a lower outlet of the three-way valve (5) is connected with the receiving pool (9), and a peristaltic pump (8) for controlling flushing liquid is arranged in the middle of the hose.
The invention also provides a method for treating dye wastewater by using the dye wastewater degradation treatment system, which comprises the following steps:
adding the dye wastewater and the magnetic mesoporous nano material into an adsorption tank (1) respectively, and stirring to enable the nano material to fully adsorb the enriched pollutants to obtain a suspension;
opening the peristaltic pump (3), enabling the suspension to enter the magnetic separation system (4), simultaneously switching on a power supply (44), enabling the suspension to flow through a hose (41) of the magnetic separation system (4), wrapping an iron pipe (42) outside the hose (41) by a magnetic coil (43), and attaching magnetic nano materials enriched with pollutants in the suspension to the wall of the hose due to an electromagnetic effect;
the residual pollutant suspension enters a photoelectrocatalysis degradation system (6); wherein the water inlet (621) and the water outlet (622) form circulating condensed water for cooling the system; the working electrode (67) is made of ITO conductive glass with the surface fixed with magnetic nano materials; visible light provided by a xenon lamp light source (68) is irradiated on the surface of the working electrode (67) through a quartz light window (623);
na is added from a feeding pipe (64) 2 SO 4 Solution, H 2 O 2 After the solution and the pH regulator are mixed, an aeration port (65) aerates to uniformly mix the solution;
photoelectrocatalysis/H occurs in a photoelectrocatalysis system by applying an electric potential to a working electrode (67) through an electrochemical workstation (69) 2 O 2 The synergistic effect enables the dye pollutants to generate degradation and mineralization reaction;
after the degradation reaction is finished, the three-way valve (2) and the three-way valve (5) are opened, the peristaltic pump (3) and the peristaltic pump (8) are started, flushing liquid in the flushing pool (7) enters the hose (41), the power supply (44) is in a closed state at the moment, the magnetic mesoporous nano material flows into the receiving pool (9) along with the flushing liquid, and finally the magnetic mesoporous nano material is discharged through the receiving pool outlet (10).
In one embodiment of the present invention, the method for treating dye wastewater by using the dye wastewater degradation treatment system preferably comprises the following steps:
100mg/L dye wastewater and magnetic nano material (adding 100mg Fe per liter wastewater solution) 3 O 4 @SiO 2 @ mesoporous TiO 2 The ratio) are respectively added into the adsorption tank (1) and stirred for 20min to ensure that the nano material fully adsorbs the enriched pollutants. The peristaltic pump (3) is started, the suspension in the mixing and stirring tank enters the magnetic separation system (4), meanwhile, the power supply (44) is switched on, the suspension flows through the hose (41) of the magnetic separation system (4), the iron pipe (42) outside the hose (41) is wrapped by the magnetic coil (43), due to the electromagnetic effect, the magnetic nano material enriched with pollutants in the suspension can be attached to the pipe wall of the hose, and the residual pollutant solution enters the photoelectrocatalytic degradation system (6). Photoelectricity catalysisThe chemical degradation system (6) comprises: the device comprises a water inlet (61), a water outlet (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a quartz light window (68) and a xenon lamp light source (69); wherein the water inlet (61) and the water outlet (62) form circulating condensed water for cooling the system; the working electrode (67) has Fe fixed on the surface 3 O 4 @SiO 2 @ mesoporous TiO 2 ITO conductive glass of magnetic nano material; visible light provided by a xenon lamp light source (69) is transmitted through a quartz light window (68) to irradiate the surface of the working electrode (67). Na is added from a feeding pipe (64) 2 SO 4 (concentration 0.5 mol/L), H 2 O 2 (mass/volume ratio: 2.5%) and a pH adjusting agent (pH adjusted to 3.0), and then aerating the aeration port (65) to uniformly mix the solution. A potential (+ 0.6V) is applied to the working electrode (67), and photoelectrocatalysis/H occurs in the photoelectrocatalysis system 2 O 2 The synergistic effect makes the dye pollutant produce degradation and mineralization reaction. After the degradation reaction is finished, the three-way valve (2 and 5) is opened, the peristaltic pump (3 and 8) is started, flushing liquid in the flushing tank (7) enters the hose (41), the power supply (44) is in a closed state at the moment, the nano particles flow into the receiving tank (9) along with the flushing liquid, and are finally discharged through the outlet (10) of the receiving tank, so that the nano particles adsorbed with pollutants can be fixed on the surface of conductive glass to be made into working electrodes, and secondary photoelectrocatalysis treatment is carried out.
In the present invention, the magnetic mesoporous nanomaterial preferably includes Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
In the present invention, the Fe 3 O 4 @SiO 2 @TiO 2 The preparation method of the magnetic mesoporous nano material preferably comprises the following steps:
preparation of Fe by coprecipitation 3 O 4 Nanoparticles: feCl 3 Solution with Fe 3 O 4 Mixing the solution in a beaker uniformly, heating in water bath and keeping the temperature, slowly dripping NaOH solution under the stirring condition, dripping concentrated ammonia water until the solution is completely black, measuring the pH, centrifugally separating the reaction mixture after the reaction is finished, and respectively separating the black solid obtained by separation by using absolute ethyl alcohol and deionized waterWashing, magnetic separating and vacuum drying to obtain Fe 3 O 4 A nanoparticle;
preparation of magnetic SiO 2 And (3) nucleus: subjecting said Fe to 3 O 4 Dispersing nano particles in absolute ethyl alcohol, ultrasonically oscillating, sequentially adding the absolute ethyl alcohol, deionized water and concentrated ammonia water, adjusting the pH of the solution to obtain a turbid liquid, uniformly stirring the turbid liquid, then dropwise adding tetraethoxysilane, carrying out reflux reaction, centrifuging the reacted solution to obtain a solid product, and respectively washing the solid product with the absolute ethyl alcohol and the deionized water to obtain the magnetic SiO 2 A core;
preparing Fe by using polypropylene glycol as template agent and adopting hydrothermal method 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material: under vigorous stirring, butyl titanate was added dropwise to the aqueous acetic acid solution, followed by addition of magnetic SiO 2 Stirring under a closed condition to obtain a solution A, dissolving polypropylene glycol in ethanol under vigorous stirring to obtain a solution B containing polypropylene glycol, dropwise adding the solution B into the solution A, sealing and mixing the solution, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, cooling after the reaction is finished, centrifugally separating the reaction solution, drying overnight after centrifugation, and calcining in a muffle furnace to obtain Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
In the present invention, the FeCl 3 Solution with Fe 3 O 4 The molar ratio of the solution is preferably 2.
In the present invention, the molecular weight of the polypropylene glycol is preferably 1000.
In the present invention, the method for preparing the working electrode (67) preferably comprises the steps of:
dispersing the magnetic mesoporous nano particles in ethanol, and performing ultrasonic dispersion to obtain a magnetic photoelectrocatalysis material suspension;
ultrasonically cleaning conductive glass in acetone, ethanol and deionized water in sequence, and drying for later use;
connecting one end of the conductive glass with a conductive silver adhesive to a lead, drying overnight, sealing the connection part of the conductive glass and the lead by using an epoxy resin adhesive, coating a magnetic photoelectrocatalysis material suspension on the working surface of the conductive glass, and airing at room temperature;
and adhering the other neodymium iron boron magnet to the back surface of the working surface of the conductive glass to obtain the working electrode (67).
In the invention, the neodymium iron boron magnet is coated with a layer of polyvinyl chloride film.
In order to further illustrate the present invention, the following will describe the dye wastewater degradation treatment system and the method for treating dye wastewater in detail with reference to the examples, which should not be construed as limiting the scope of the present invention.
Example 1
Fe 3 O 4 @SiO 2 @TiO 2 Preparation of
Firstly, preparing Fe by adopting a coprecipitation method 3 O 4 The nano-particles specifically operate as follows: 25mL of 1.00mol/L FeCl are respectively taken 3 The solution was mixed with 0.50mol/LFeSO 4 The solution was mixed well in a beaker while heating with a water bath and maintaining at 30 ℃. Slowly dripping 50mL of 1.00mol/LNaOH solution under the stirring condition, then dripping 10mL of concentrated ammonia water until the solution is completely blackened, measuring the pH value to be 10.0, and stirring and preserving the temperature for 2h at 30 ℃. After the reaction was completed, the reaction mixture was centrifuged. Washing the black solid with anhydrous ethanol and deionized water for 3 times, magnetically separating, and vacuum drying at 80 deg.C to obtain Fe 3 O 4 And (3) nanoparticles.
Second, preparing magnetic SiO 2 And (3) nucleus: taking the Fe prepared in the last step 3 O 4 0.5g of nano particles are dispersed in 100mL of absolute ethyl alcohol, and the particles are uniformly dispersed by ultrasonic oscillation. 100mL of absolute ethyl alcohol, 50mL of deionized water and 2.5mL of concentrated ammonia water were added in this order, and the pH of the solution was 9.0. Stirring the suspension at 80 ℃ for 0.5h, slowly and dropwise adding 0.5g of tetraethoxysilane, and stirring at 80 ℃ for reflux reaction for 2h. Centrifuging the reacted solution to obtain a solid product, and respectively washing the solid product with absolute ethyl alcohol and the separated water for three times to obtain the magnetic SiO 2 A core.
Thirdly, taking polypropylene glycol (PPG) as a template agent, and preparing F by adopting a hydrothermal methode 3 O 4 @SiO 2 @TiO 2 And (3) nanoparticles. 5g of butyl titanate was added dropwise to 20mL of a 20% (v/v) aqueous acetic acid solution (acetic acid as a hydrolysis inhibitor and a catalyst) under vigorous stirring, and 0.4g of magnetic SiO 2 And (4) a core. The resulting mixture was stirred under sealed conditions for 4h to obtain solution a. A liquid PPG of known molecular weight 1000 (designated PPG 1000) was dissolved in 20mL of ethanol under vigorous stirring to give a solution B containing 20% (v/v) PPG 1000. And dropwise adding the solution B into the solution A, sealing the mixed solution, stirring at room temperature for 24 hours, transferring into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 48 hours. Cooling, centrifugally separating reaction liquid, drying the centrifuged colloid at 80 ℃ overnight, and calcining the dried colloid in a muffle furnace at 400 ℃ for 2 hours to obtain Fe 3 O 4 @SiO 2 @TiO 2 Nano mesoporous particles.
Preparation of working electrode
Mixing 30mg of the above Fe 3 O 4 @SiO 2 @TiO 2 The nanometer mesoporous particles are dispersed in 1mL of ethanol, and 30mg/mL of magnetic photoelectrocatalysis material suspension is obtained through ultrasonic dispersion.
Conducting glass (ITO 2.2cm multiplied by 2.2 cm) is cleaned by ultrasonic in acetone, ethanol and deionized water for 5 minutes and dried for standby.
Connecting one end of the conductive glass with a conductive silver adhesive, drying at 60 ℃ overnight, and sealing the connection part of the conductive glass and the lead by using epoxy resin adhesive. Then coating 30mg/mL magnetic photoelectrocatalysis material suspension on the conductive glass working surface, and airing at room temperature. A neodymium iron boron magnet with the thickness of 2.2cm multiplied by 0.3cm is coated with a polyvinyl chloride film (the polyvinyl chloride film can avoid the contact of the magnet and a reaction solution), and is adhered to the back of the working surface of the conductive glass, so that the working electrode is obtained.
Mixing the dye wastewater of 100mg/L with the Fe obtained above 3 O 4 @SiO 2 @TiO 2 Nano mesoporous particles (per liter of wastewater solution 100mg Fe 3 O 4 @SiO 2 @TiO 2 The ratio) are respectively added into the adsorption tank (1) and stirred for 20min to ensure that the nano material fully adsorbs the enriched pollutants. Opening peristaltic motionPump (3), the suspension in the mixing stirring pond gets into magnetic separation system (4), switch on power (44) simultaneously, the hose (41) of magnetic separation system (4) is flowed through to the suspension, and iron pipe (42) outside hose (41) are wrapped up by magnetic coil (43), because electromagnetic effect, the magnetism nano-material that has enriched the pollutant in the suspension can be attached to the hose pipe wall, and remaining pollutant solution gets into photoelectrocatalysis degradation system (6), photoelectrocatalysis degradation system (6) includes: a photoelectric reaction cell cover (61), a photoelectric reaction cell (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a xenon lamp light source (68) and an electrochemical workstation (69); wherein the water inlet (621) and the water outlet (622) form circulating condensed water for cooling the system; the working electrode (67) has Fe fixed on the surface 3 O 4 @SiO 2 @TiO 2 ITO conductive glass of magnetic nano material; visible light provided by a xenon lamp light source (68) is transmitted through a quartz light window (623) and irradiates the surface of the working electrode (67). Na is added from a feed pipe (64) 2 SO 4 (concentration 0.5 mol/L), H 2 O 2 (mass/volume ratio: 2.5%) and a pH adjusting agent (pH adjusted to 3.0), and then aerating the aeration port (65) to uniformly mix the solution. The potential (+ 0.6V) is applied to the working electrode (67) through the electrochemical workstation (69), and photoelectrocatalysis/H occurs in the photoelectrocatalysis system 2 O 2 The synergistic effect makes the dye pollutant produce degradation and mineralization reaction. After the degradation reaction is finished, the three-way valve (2 and 5) is opened, the peristaltic pump (3 and 8) is started, flushing liquid in the flushing tank (7) enters the hose (41), the power supply (44) is in a closed state at the moment, the nano particles flow into the receiving tank (9) along with the flushing liquid, and are finally discharged through the outlet (10) of the receiving tank, so that the nano particles adsorbed with pollutants can be fixed on the surface of conductive glass to be made into working electrodes, and secondary photoelectrocatalysis treatment is carried out.
FIG. 1 is a diagram of a system for dye wastewater degradation treatment; the electrochemical measurement uses CHI electrochemical workstation (Shanghai Chenghua instruments, inc. in China), and xenon lamp light source H8X-F300 (Beijing Newbit technology, inc.) is used as the light source. The concentration of the contaminant was determined by measuring the absorbance at the maximum absorption wavelength (methylene blue maximum absorption wavelength λ =664nm, rhodamine B maximum absorption wavelength λ =554nm, methyl orange maximum absorption wavelength λ =463 nm) with a UV-5800 ultraviolet-visible spectrophotometer (UNICO instruments ltd, shanghai). The photoelectrocatalytic degradation rate Y is calculated according to the following formula:
Y＝1-C/C 0 。
in the formula, C 0 And C is the initial concentration of the dye solution and the concentration at a certain moment during the catalytic reaction, respectively.
The dye wastewater degradation treatment system is used for degrading methylene blue
Wherein the working electrode fixes Fe 3 O 4 @SiO 2 @TiO 2 Magnetic nanomaterial using photoelectrocatalysis/H 2 O 2 Synergistic degradation of methylene blue, H 2 O 2 The concentration is 2.5% (mass to volume ratio), the solution pH is 3.0, the working electrode potential is +0.6V, and the experimental result is shown in a curve i of figure 8, which can be seen that: the removal rate of methylene blue after 1min is 77.2%, and the removal rate after 5min is close to 100%.
The dye wastewater degradation treatment system is used for degrading rhodamine B
Wherein the working electrode fixes Fe 3 O 4 @SiO 2 @TiO 2 Magnetic nanomaterial using photoelectrocatalysis/H 2 O 2 Synergistic degradation of rhodamine B, H 2 O 2 The concentration is 2.5% (mass to volume ratio), the pH of the solution is 3.0, the potential of the working electrode is +0.6V, the experimental result is shown in figure 3, and the following can be seen: 2min of rhodamine B is degraded by 87%, and 6min of rhodamine B is degraded by 96%.
The dye wastewater degradation treatment system is used for degrading methyl orange
Wherein the working electrode fixes Fe 3 O 4 @SiO 2 @TiO 2 Magnetic nanomaterial using photoelectrocatalysis/H 2 O 2 Synergistic degradation of methyl orange dye, H 2 O 2 The concentration is 2.5% (mass to volume ratio), the solution pH is 3.0, the working electrode potential +0.6V, the experimental results are shown in FIG. 4, and it can be seen that: methyl orange was degraded by 63% in 3min and by 97% in 7 min.
The dye wastewater degradation treatment system is subjected to repeatability experiment
The same is usedThe degradation experiment is repeated for 5 times on one working electrode, and the degradation rate of methylene blue is still kept above 99% (see figure 5), which indicates that Fe 3 O 4 @SiO 2 @TiO 2 The magnetic nano material catalyst has good catalytic stability, and the system and the method have high repeatability and strong practicability.
The dye wastewater degradation treatment system treats the printing and dyeing wastewater
From photoelectrocatalysis/H 2 O 2 Starting from the practical application of a synergistic system, the degradation effect of printing and dyeing wastewater generated in the practical production process of a certain dye company Limited is researched. Selecting the COD of 39000mg/L, the pH =7.2 and the NH 4 - Red powder wastewater with N =46mg/L and BOD =11523mg/L, and photoelectrocatalysis/H is carried out under the optimal conditions 2 O 2 And (3) performing a synergistic system degradation experiment on red pink wastewater. As shown in FIG. 6, the COD removal rate of the red-pink wastewater reaches 54.71% in 40 min. The results show that the photoelectrocatalysis/H 2 O 2 The synergistic system has better treatment effect on red-pink wastewater with complex components, high COD and high toxicity, and has great potential in the aspect of dye wastewater treatment.
Analysis of degradation mechanism
To verify photoelectrocatalysis/H 2 O 2 The synergistic system is used for generating active free radicals in degradation reaction and carrying out a free radical quenching experiment in methylene blue solution. To photoelectrocatalysis/H 2 O 2 Adding tert-butyl alcohol (TBA), benzoquinone (BQ), ethylene diamine tetraacetic acid disodium salt (EDTA-2 Na) and silver nitrate (AgNO) into the synergistic system respectively 3 ) Respectively as OH and O 2 - 、h + And e - The capturing agent of (1). The degradation effect of methylene blue is shown in fig. 7. For photoelectrocatalysis/H 2 O 2 Synergistic system, addition of. OH (t-butanol) scavenger significantly suppressed the degradation reaction, indicating that. OH is the main species for photocatalysis, since in this reaction system, the. OH comes not only from. O 2 - H generated by reaction with photo-generated electrons 2 O 2 Also from added H 2 O 2 . The degradation performance of methylene blue is slightly reduced after Benzoquinone (BQ) is added,shows. O 2 - The degradation effect of (B) is not obvious, and the addition of benzoquinone inhibits O to a certain extent 2 - But additionally H 2 O 2 Can still generate OH with photo-generated electrons so as to degrade methylene blue. The addition of EDTA-2Na has a slight influence on the degradation efficiency of methylene blue. In addition, agNO is introduced 3 As photo-generated electrons (e) - ) The scavenger has a strong influence on the performance of degrading methylene blue. Because of AgNO 3 The addition of (2) eliminates photogenerated electrons, thereby inhibiting recombination of photogenerated charges, indicating that e - Is also the main species for degrading methylene blue.
Thus, can obtain Fe 3 O 4 @SiO 2 @TiO 2 Photo-generated electrons generated under irradiation of visible light can react with O 2 Formation of O 2 - Then, next, O 2 - And H + Reacts with photo-generated electrons to generate H 2 O 2 And finally H 2 O 2 Reacts with photo-generated electrons to generate OH. When H is added to the system 2 O 2 Of (i) Fe 3 O 4 @SiO 2 @TiO 2 Can be generated by generating photo-generated electrons e - Direct activation of H 2 O 2 OH is generated to degrade methylene blue. Demonstration of the present System photoelectrocatalysis and H 2 O 2 Synergistic effect between them.
Comparative example
Methylene blue is used as a model pollutant, and direct photolysis, photocatalysis, electrochemical oxidation, photoelectrocatalysis and photoelectrocatalysis/H are compared 2 O 2 The effect of the synergy method (invention) on the degradation of methylene blue (see fig. 8). In direct photolysis, photocatalysis, and photoelectrocatalysis, light is visible light provided by a xenon lamp light source. The applied voltage in the electrochemical and photoelectrocatalysis process is +0.6V. Curve a in FIG. 8 represents H alone 2 O 2 Direct photodegradation in the presence of H added to methylene blue solution 2 O 2 And then the product shows stability under the irradiation of visible light, and the degradation rate is less than 13 percent after 120min irradiation. Curve b represents no addition of H 2 O 2 Adding Fe into methylene blue solution 3 O 4 @SiO 2 @TiO 2 Then, visible light is used for photocatalysis, and the dye removal rate is slightly improved and can reach about 25 percent at most. Curve c represents H 2 O 2 With the assistance of photocatalysis, the removal rate of the dye is obviously improved, and 93 percent of methylene blue in the solution is removed after the visible light irradiation for 120 min. Curves d-f represent the results of experiments under electrochemical conditions, whether with H alone 2 O 2 、Fe 3 O 4 @SiO 2 @TiO 2 Or both of them are added simultaneously, methylene blue shows stability when H is added 2 O 2 And Fe 3 O 4 @SiO 2 @TiO 2 The removal rate is slightly improved, but the degradation rate is less than 22 percent after 120 min. The curve g-h represents the experimental results under photoelectrocatalysis conditions, in which only Fe is added 3 O 4 @SiO 2 @TiO 2 The removal rate of methylene blue can reach 61.5 percent after 40 min; in the presence of only H 2 O 2 The removal rate of methylene blue can reach 96.1% after 10min, and is close to 100% after 20 min. Curve i represents the photoelectrocatalysis/H 2 O 2 The experimental result under the condition of synergistic degradation is that H is simultaneously added under the condition of photoelectrocatalysis 2 O 2 And Fe 3 O 4 @SiO 2 @TiO 2 The degradation speed of the methylene blue is greatly improved, the degradation rate is 77.2% in 1min, and the degradation rate is close to 100% after 5min. Evidence of Fe 3 O 4 @SiO 2 @TiO 2 Photoelectrocatalysis and H 2 O 2 Has good synergistic effect and can quickly remove dye pollutants.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the present invention, and should be considered as within the scope of the present invention.
Claims (10)
1. The dye wastewater degradation treatment system is characterized by comprising an adsorption tank (1), a three-way valve (2), a peristaltic pump (3), a magnetic separation system (4), a three-way valve (5), a photoelectrocatalysis degradation system (6), a flushing tank (7), a peristaltic pump (8), a receiving tank (9) and a receiving tank outlet (10), wherein the magnetic separation system (4) comprises a power supply (44) and a hose (41), and an iron pipe (42) outside the hose (41) is wrapped by a magnetic coil (43); the photoelectrocatalytic degradation system (6) comprises: the device comprises a photoelectric reaction cell cover (61), a photoelectric reaction cell (62), a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66), a working electrode (67), a xenon lamp light source (68) and an electrochemical workstation (69), wherein the photoelectric reaction cell (62) has a double-layer structure, the inner layer is the reaction cell, and a quartz light window (623) is arranged on one side of the reaction cell; the outer layer is a cooling water bath and comprises a water inlet (621) and a water outlet (622), five holes are formed in a photoelectric reaction cell cover (61) and used for fixing a mercury/mercurous sulfate reference electrode (63), a feeding pipe (64), an aeration port (65), a Pt sheet auxiliary electrode (66) and a working electrode (67), wherein the mercury/mercurous sulfate reference electrode (63), the Pt sheet auxiliary electrode (66) and the working electrode (67) are connected with an electrochemical workstation (69) through electrode wires, and a xenon lamp light source (68) is opposite to a quartz light window (623) and is 10cm away from the quartz light window.
2. The dye wastewater degradation treatment system according to claim 1, wherein the working electrode (67) is made of ITO conductive glass with a magnetic mesoporous nanomaterial fixed on the surface.
3. The dye wastewater degradation treatment system according to claim 1, wherein the feed pipe (64) contains H 2 O 2 And (3) solution.
4. The method for treating dye wastewater by using the dye wastewater degradation treatment system as claimed in claim 1, comprising the steps of:
adding the dye wastewater and the magnetic mesoporous nano material into an adsorption tank (1) respectively, and stirring to enable the nano material to fully adsorb the enriched pollutants to obtain a suspension;
opening the peristaltic pump (3), enabling the suspension to enter the magnetic separation system (4), simultaneously switching on a power supply (44), enabling the suspension to flow through a hose (41) of the magnetic separation system (4), wrapping an iron pipe (42) outside the hose (41) by a magnetic coil (43), and attaching the magnetic nano material enriched with pollutants in the suspension to the wall of the hose due to an electromagnetic effect;
the residual pollutant suspension enters a photoelectrocatalysis degradation system (6); wherein the water inlet (621) and the water outlet (622) form circulating condensed water for cooling the system; the working electrode (67) is made of ITO conductive glass with the surface fixed with magnetic nano materials; visible light provided by a xenon lamp light source (68) is irradiated on the surface of the working electrode (67) through a quartz light window (623);
na is added from a feeding pipe (64) 2 SO 4 Solution, H 2 O 2 After the solution and the pH regulator are mixed, an aeration port (65) is aerated to uniformly mix the solution;
photoelectrocatalysis/H occurs in a photoelectrocatalysis system by applying an electric potential to a working electrode (67) through an electrochemical workstation (69) 2 O 2 The synergistic effect enables the dye pollutants to generate degradation and mineralization reaction;
after the degradation reaction is finished, the three-way valve (2) and the three-way valve (5) are opened, the peristaltic pump (3) and the peristaltic pump (8) are started, flushing liquid in the flushing pool (7) enters the hose (41), the power supply (44) is in a closed state at the moment, the magnetic mesoporous nano material flows into the receiving pool (9) along with the flushing liquid, and finally the magnetic mesoporous nano material is discharged through the receiving pool outlet (10).
5. The method for treating dye wastewater by using the dye wastewater degradation treatment system according to claim 4, wherein the magnetic mesoporous nano material comprises Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
6. The method for treating dye wastewater by using the dye wastewater degradation treatment system according to claim 5, wherein the Fe is Fe 3 O 4 @SiO 2 @TiO 2 The preparation method of the magnetic mesoporous nano material comprises the following steps:
preparation of Fe by coprecipitation method 3 O 4 Nanoparticles: feCl is added 3 Solution with FeSO 4 The solution is mixed evenly in a beaker, and simultaneously the water bath is heated and the temperature is kept inSlowly dropping NaOH solution under the condition of stirring, then dropping concentrated ammonia water until the solution is completely black, measuring pH, after the reaction is finished, centrifugally separating the reaction mixture, respectively washing the black solid obtained by separation with absolute ethyl alcohol and deionized water, and obtaining Fe after magnetic separation and vacuum drying 3 O 4 A nanoparticle;
preparation of magnetic SiO 2 And (3) nucleus: subjecting said Fe to 3 O 4 Dispersing nano particles in absolute ethyl alcohol, carrying out ultrasonic oscillation, sequentially adding the absolute ethyl alcohol, deionized water and concentrated ammonia water, adjusting the pH of the solution to obtain a turbid liquid, uniformly stirring the turbid liquid, then dropwise adding tetraethoxysilane, carrying out reflux reaction, centrifuging the reacted solution to obtain a solid product, respectively washing with the absolute ethyl alcohol and the deionized water, carrying out magnetic separation and vacuum drying to obtain the magnetic SiO 2 A core;
preparing Fe by using polypropylene glycol as template agent and adopting hydrothermal method 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material: under vigorous stirring, butyl titanate was added dropwise to the aqueous acetic acid solution, followed by addition of magnetic SiO 2 Stirring under a closed condition to obtain a solution A, dissolving polypropylene glycol in ethanol under vigorous stirring to obtain a solution B containing polypropylene glycol, dropwise adding the solution B into the solution A, sealing and mixing the solution, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, cooling after the reaction is finished, centrifugally separating reaction liquid, respectively washing solid products by absolute ethyl alcohol and deionized water, drying the solid products overnight, calcining the solid products in a muffle furnace, and grinding and magnetically separating the products to obtain Fe 3 O 4 @SiO 2 @TiO 2 Magnetic mesoporous nano material.
7. The method for treating dye wastewater by using the dye wastewater degradation treatment system according to claim 6, wherein the FeCl is 3 Solution with FeSO 4 The molar ratio of the solution is 2.
8. The method for treating dye wastewater in the dye wastewater degradation treatment system according to claim 6, wherein the molecular weight of the polypropylene glycol is 1000.
9. The method for treating dye wastewater by using the dye wastewater degradation treatment system according to claim 4, wherein the preparation method of the working electrode (67) comprises the following steps:
dispersing the magnetic mesoporous nano particles in ethanol, and performing ultrasonic dispersion to obtain a magnetic photoelectrocatalysis material suspension;
ultrasonically cleaning conductive glass in acetone, ethanol and deionized water in sequence, and drying for later use;
connecting one end of the conductive glass with a conductive silver adhesive to a lead, drying overnight, sealing the connection part of the conductive glass and the lead by using an epoxy resin adhesive, coating a magnetic photoelectrocatalysis material suspension on the working surface of the conductive glass, and airing at room temperature;
and adhering the other neodymium iron boron magnet to the back surface of the working surface of the conductive glass to obtain the working electrode (67).
10. The method for treating dye wastewater by using the dye wastewater degradation treatment system according to claim 9, wherein the neodymium iron boron magnet is coated with a polyvinyl chloride film.
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