CN111675417A - Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method - Google Patents
Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method Download PDFInfo
- Publication number
- CN111675417A CN111675417A CN202010390584.3A CN202010390584A CN111675417A CN 111675417 A CN111675417 A CN 111675417A CN 202010390584 A CN202010390584 A CN 202010390584A CN 111675417 A CN111675417 A CN 111675417A
- Authority
- CN
- China
- Prior art keywords
- electrode
- magnetic
- water
- power supply
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
-
- 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
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F2001/46133—Electrodes characterised by the material
-
- 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
-
- 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
-
- 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 discloses a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system and a water treatment method, wherein the water treatment system comprises a liquid storage tank, a degradation tank, a particle filter plate arranged at a water outlet of the liquid storage tank and connected to the degradation tank through a circulating pipeline, and the degradation tank comprises an electrochemical degradation module, a magnetic particle module and a photocatalytic degradation module; the motion state of the magnetic particles is controlled through an electromagnetic field, the magnetic particles adsorb organic matters to the surface of an electrode to promote mass transfer, photocatalysis is coupled with electrocatalysis, and the speed of degrading organic molecules is accelerated by generating hydrogen peroxide through oxygen generated by electrocatalysis side reaction. The invention realizes the high-efficiency degradation of organic matters in water by the cooperation of electrochemical catalysis, photocatalysis and magnetic adsorption.
Description
Technical Field
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and a water treatment method, belonging to the technical field of environment-friendly water treatment.
Background
In recent years, the problem of water pollution in China is still a great problem to be solved, and how to thoroughly degrade high-concentration organic wastewater is a hotspot of research. The traditional water treatment method comprises a biological method, a physical method and a chemical method, wherein the biological method is to convert organic matters into harmless substances by means of metabolism of microorganisms, but the microorganisms lose activity in high-concentration organic wastewater; the physical method is to achieve the effect of wastewater treatment by means of adsorption, separation, concentration and the like, and generally requires higher cost and more complex treatment process to achieve the ideal water treatment effect; the high-grade oxidation method in the chemical method, such as an electrochemical oxidation method, a photocatalysis method and a Fenton method, is widely applied to wastewater treatment due to the characteristics of simple process, wide application range, thorough reaction and the like.
The Chinese invention patent CN201620938735.8 discloses an in-situ adsorption-electrocatalysis coupled organic wastewater treatment system and method. The waste water treatment system comprises an electrolytic tank, an electro-catalytic anode and an electro-catalytic cathode electro-catalytic anode which are hollow rod-shaped, the electro-catalytic anode is arranged in the center of the electrolytic tank, a conductor wound with a lead is placed in a cavity of the electro-catalytic anode, two ends of the lead are connected with an electromagnetic field power supply, the electro-catalytic anode and the electro-catalytic cathode are connected with a cathode and an anode electro-catalytic cathode of the electro-catalytic power supply, the cathode and the anode electro-catalytic cathode are cylindrical and arranged on the inner wall of the electrolytic tank, the electro-catalytic anode is surrounded between the electro-catalytic anode and the electro-catalytic cathode of the electrolytic tank, a solution containing organic matter molecules to. The device can control the position of magnetic adsorbent particles in a solution by using the magnetic adsorbent particles and an electromagnetic field for control, accelerates the mass transfer in the electrocatalytic oxidation process, realizes the improvement of the organic matter enrichment capacity, and then improves the electrocatalytic degradation performance.
However, since the electrocatalytic anode in the device is a carbon electrode, a noble metal electrode or a metal oxide electrode, and the cathode is made of a material capable of playing a role of electric conduction, alternating current cannot be used when the system works, and only a direct current power supply can be used, so that the current utilization rate is reduced, and the operation cost is increased; the impurities are electrodeposited on the surface of the electrocatalytic cathode, which can cause the service life of the electrode plate to be reduced, the conductivity to be reduced, and the water treatment effect and the energy consumption cost to be influenced. In addition, the magnetic particles are used for adsorbing organic matters to promote mass transfer, the surface of the device has good synergistic effect, and actually when the electromagnetic field is disconnected, the magnetic particles return to the solution to be treated to adsorb organic molecules, so that a competitive relationship is generated between the magnetic particles and the organic matters adsorbed and degraded on the surface of the electrode, and the degradation efficiency of the device is restricted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system which can efficiently treat water containing high-concentration organic pollutants difficult to degrade.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, which comprises a liquid storage tank and a degradation tank, wherein the liquid storage tank is provided with a liquid inlet and a liquid outlet; a particle filter plate is arranged at a water outlet of the liquid storage tank and is connected to the degradation tank through a circulating pipeline, and the degradation tank comprises an electrochemical degradation module, a magnetic particle module and a photocatalytic degradation module;
the electrochemical degradation module consists of a plurality of processing units, and any one processing unit comprises; the electrode A and the electrode B are connected with an alternating current power supply through leads;
the magnetic particle module comprises magnetic particles dispersed between an electrode A and an electrode B, a magnetic power supply C positioned above the electrode A and a magnetic power supply D positioned above the electrode B, solenoid wound magnetic cores are arranged in the magnetic power supply C and the magnetic power supply D, and the photocatalytic degradation module comprises a photocatalyst dispersed in front of the electrode A and the electrode B.
In the invention, the magnetic power supply C and the magnetic power supply D are both internally provided with solenoid wound magnetic cores, and the magnetic power supply C and the magnetic power supply D apply electric fields to the solenoid wound magnetic cores to enable the solenoid wound magnetic cores to generate magnetic fields, thereby controlling the positions of magnetic particles in the degradation tank.
The invention relates to a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, wherein a particle filter plate is at least one selected from a quartz sand filter plate, a PP (polypropylene) cotton filter plate and a microporous foam ceramic plate with porosity of more than 35 PPI.
The microporous foamed ceramic plate with the porosity of more than 35PPI is preferably microporous foamed Al with the porosity of more than 35PPI2O3Ceramic plate, microporous foam ZrO with porosity greater than 35PPI2Ceramic plate, microporous foam SiC ceramic plate with porosity larger than 35PPI, and microporous foam Si with porosity larger than 35PPI3N4One of the ceramic plates.
The invention relates to a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, wherein an electrode A and an electrode A are formed by matching cylindrical electrodes and cylindrical electrodes which are coaxial in centers but do not contact with each other, or formed by matching two groups of coaxial cylindrical electrode arrays with different diameters, or formed by matching a honeycomb briquette structure and a cylindrical array, or formed by matching a three-dimensional continuous network structure and a two-dimensional continuous network structure, or formed by matching a two-dimensional closed flat plate structure and a two-dimensional continuous network structure.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein an electrode A and an electrode B are hollow cylinders, and the distance between the electrode A and an electric plate B is 10-60 mm.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein an electrode A and an electrode B are both selected from at least one of a boron-doped diamond electrode, a noble metal electrode, a stainless steel electrode and a carbon material electrode.
Preferably, the electrode A and the electrode B are both boron-doped diamond electrodes, and an electrode working layer of each boron-doped diamond electrode is a boron-doped diamond layer with micropores and/or pointed cones distributed on the surface.
Preferably, the wetting angle theta of the boron-doped diamond electrode is less than 40 degrees; the electrode working layer of the boron-doped diamond electrode is a gradient boron-doped diamond layer; the gradient boron-doped diamond layer sequentially comprises a gradient boron-doped diamond bottom layer, a gradient boron-doped diamond middle layer and a gradient boron-doped diamond top layer from bottom to top, wherein the boron content of the gradient boron-doped diamond bottom layer is increased in a gradient manner;
in the gradient boron-doped diamond bottom layer, the B/C is 3333-33333 ppm in terms of atomic ratio; preferably 3333-10000 ppm; in the gradient boron-doped diamond middle layer, B/C is 10000-33333 ppm by atomic ratio; preferably 13332-20000 ppm; in the top layer of the gradient boron-doped diamond, the B/C is 16666-50000 ppm in terms of atomic ratio; preferably 26664-50000 ppm.
The degradation mechanism of the electrochemical oxidative degradation module is generally divided into two ways, namely direct oxidation of organic pollutants on the surface of an electrode and indirect oxidation of pollutants by active substances with strong oxidizing property (such as hydroxyl radicals, active chlorine, active sulfate groups and the like) generated on the surface of the electrode, wherein the indirect oxidation is dominant. The degradation efficiency is therefore greatly influenced by the intrinsic properties of the electrode material (specific surface area, sp3/sp2, boron doping concentration, etc.), since the intrinsic properties of the electrode material determine the active substance yield. The invention integrates the advantages of the electrode material by adopting the gradient boron-doped electrode material with high specific surface area, and can greatly improve the degradation and mineralization efficiency of the electrochemical degradation module.
In the invention, the boron doping content is gradually increased from the bottom to the top of the film, and the bottom high-adhesion layer adopts the extremely low boron doping concentration to ensure the film associativity and stability, because the bottom layer is directly contacted with the electrode substrate, the diamond phase nucleation is easy in the early deposition stage, the defects are fewer, and the sp2 phase carbon is fewer. The sp3 content and the lattice stability of the nucleation surface can be further improved, so that the adhesion with an electrode substrate is enhanced, the middle layer is corrosion-resistant, the middle boron content (namely, the boron content is higher than that of the bottom layer and lower than that of the top layer) is adopted, the boron content in the middle layer is still lower, so that the sp3 phase purity (namely, the diamond is dense and continuous) can be ensured, and meanwhile, the conductivity of the layer can be ensured due to certain boron doping amount. The doping content of boron in the top layer is high, so that the conductivity and the electrochemical activity of the material can be improved, the potential window of the top layer is wide, the oxygen evolution potential is high, the background current is low, and the electrocatalytic activity and the degradation efficiency of the electrode can be greatly improved by the diamond top layer; meanwhile, the hydrophilicity is improved along with the increase of the boron content, and the oxidation efficiency of the electrode in the electrochemical oxidation process can be greatly improved by the improvement of the hydrophilicity. In a word, the electrode material with high catalytic activity and long service life, which is composed of the bottom high-adhesion layer, the middle high-density corrosion-resistant layer and the top high-boron doping concentration catalyst layer, can effectively reduce the degradation efficiency and the maintenance cost in the practical application process of the system.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein the thickness of a gradient boron-doped diamond layer is 5 mu m-2 mm; the thickness of the middle layer of the gradient boron-doped diamond accounts for 50% -90% of the thickness of the gradient boron-doped diamond layer; the thickness of the gradient boron-doped diamond top layer accounts for less than or equal to 40% of that of the gradient boron-doped diamond layer.
Because the gradient boron-doped diamond bottom layer, the gradient boron-doped diamond middle layer and the gradient boron-doped diamond top layer have different work division, the bottom layer and the top layer respectively play roles in improving the substrate/film associativity, having high electrochemical activity (high catalytic performance) and improving the hydrophilicity. Therefore, the main body part of the film material is the middle corrosion-resistant layer, and plays roles of conducting electricity, resisting corrosion and the like in the service process, so the thickness of the film material needs to account for more than half of the thickness of the gradient boron-doped diamond layer, and the thickness of the top layer is controlled to account for the thickness of the gradient boron-doped diamond layer to be less than or equal to 40 percent, because the sp2 phase carbon (graphite phase carbon) is introduced and increased along with the increase of the boron content, the invention can avoid introducing excessive sp2 phase carbon by controlling the thickness of the top layer within 40 percent, so the hydrophilicity can be improved, and the hydrophilicity and high catalytic activity of the material can be ensured.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein micropores and/or pointed cones are distributed on the surface of a gradient boron-doped diamond layer, the diameter of each micropore is 500 nm-0.5 mm, and the diameter of each pointed cone is 1 mu m-30 mu m. The boron-doped diamond layer with the surface distributed with micropores and/or pointed cones can improve the adsorption effect on magnetic particles.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system.A boron-doped diamond electrode directly takes a substrate as an electrode substrate; or the surface of the substrate is provided with a transition layer to be used as an electrode matrix, and then the surface of the electrode matrix is provided with a gradient boron-doped diamond layer. Wherein the gradient boron-doped diamond layer is an electrode working layer.
In the present invention, there is no limitation on the choice of substrate materials, and any substrate materials reported in the prior art are suitable as the substrate of the present invention.
Preferably, the substrate material is selected from one of metal nickel, niobium, tantalum, copper, titanium, cobalt, tungsten, molybdenum, chromium, iron or one of metal alloys; or the electrode substrate material is selected from ceramic A12O3、ZrO2、SiC、Si3N4、BN、B4C、AlN、WC、Cr7C3、Ti2GeC、Ti2AlC and Ti2AlN、Ti3SiC2、Ti3GeC2、Ti3AlC2、Ti4AlC3、BaPO3One or a doped ceramic therein; or the electrode substrate material is selected from one of the composite materials consisting of the metal and the ceramic, or the substrate material is selected from diamond or Si.
Further preferably, the substrate material is selected from one of titanium, nickel and silicon.
The transition layer is made of at least one of titanium, tungsten, molybdenum, chromium, tantalum, platinum, silver, aluminum, copper and silicon, and the thickness of the transition layer is 50 nm-10 mu m.
Further preferably, when the substrate material is nickel, the transition layer material is titanium.
The invention relates to an electric-membrane coupling organic wastewater treatment system with clean energy, wherein a preparation method of a boron-doped diamond electrode comprises the following steps:
step one, pretreatment of an electrode substrate
Placing the electrode substrate in a suspension containing mixed nano-crystalline and/or micro-crystalline diamond particles; ultrasonic treatment and drying; obtaining an electrode substrate with the surface adsorbing nano-crystal and/or micro-crystal diamond;
step two, depositing a gradient boron-doped diamond layer
Placing the electrode substrate obtained in the step one in a chemical deposition furnace, sequentially carrying out three-stage deposition on the surface of the electrode substrate to obtain a gradient boron-doped diamond layer, and controlling the mass flow of carbon-containing gas accounting for 1-5% of the total gas in the furnace in the first-stage deposition process; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005-0.05%; controlling the mass flow percentage of the carbon-containing gas in the furnace to be 1-5% in the second-stage deposition process; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.015-0.05%; controlling the mass flow percentage of the carbon-containing gas in the third stage of deposition process to be 1-5 percent of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.025-0.075%;
step three, high temperature treatment
Carrying out heat treatment on the electrode substrate with the deposited gradient boron-doped diamond layer, wherein the heat treatment temperature is 400-1200 ℃, and the treatment time is 5-110 min; the pressure in the furnace is 10Pa to 10Pa5Pa。
In the actual operation process, when the substrate is directly used as an electrode base body, the substrate is firstly placed in acetone for ultrasonic treatment for 5-20 min to remove oil stains on the surface of the substrate material, then deionized water and/or absolute ethyl alcohol are used for washing the substrate material, drying is carried out for later use, when the substrate surface is provided with a transition layer, the substrate is used as the electrode base body, and the treatment is carried out before the transition layer is arranged on the substrate surface.
In the first step, the mass fraction of the diamond mixed particles in the suspension containing the nanocrystalline and/or microcrystalline diamond mixed particles is 0.01-0.05%.
In the first step, the particle size of the diamond mixed particles is 5-30 nm, and the purity is more than or equal to 97%.
In the first step, the ultrasonic treatment time is 5-30 min. And after the ultrasonic treatment is finished, taking out the electrode substrate, washing the electrode substrate by using deionized water and/or absolute ethyl alcohol, and drying the electrode substrate.
In the second step, the furnace gas comprises boron-containing gas, carbon-containing gas and hydrogen.
In the actual operation process, after three-section deposition is finished, firstly closing the boron-containing gas and the boron-containing gas, and continuously introducing the hydrogen gas for a period of time to etch the graphite phase on the surface of the gradient boron-doped diamond.
The boron source can be selected from one of solid, gas and liquid boron sources, and the gasification treatment is carried out when the solid or liquid boron source is selected.
Preferably, the boron-containing gas is B2H6The carbon-containing gas is CH4。
In the second step; the temperature of the first stage deposition is 600-1000 ℃, and the air pressure is 103～104Pa, the time is 1-3 h; the temperature of the second stage deposition is 600-1000 ℃, and the air pressure is 103～104Pa, the time is 3-48 h; the temperature of the third stage deposition is 600-1000 ℃, and the air pressure is 103～104Pa; the time is 1-12 h.
In the third step, the heat treatment temperature is 500-800 ℃, and the treatment time is 15-40 min.
Through the doping and heat treatment of the top layer with high boron content, the oxygen evolution potential of the boron-doped diamond layer is larger than 2.3V, the potential window is larger than 3.0V, the electrocatalytic oxidation performance of the surface of the electrode is improved, and meanwhile, the electrode has excellent hydrophilicity (the wetting angle theta is smaller than 40 degrees)
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein any one treatment unit further comprises a stirring device.
The invention relates to a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, wherein an alternating current power supply is selected from a square wave alternating current power supply or a square wave pulse power supply, the voltage of the alternating current power supply is 3-30V, and the frequency of the pulse power supply is 50-100 KHz.
The invention relates to a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, wherein magnetic particles are selected from Fe3O4Particles of Fe2O3Particles, CoFe2O4At least one of particles, the magnetic particles having a size of 0.01 to 100 μm. The magnetic particles have adsorption-desorption characteristics for organic molecules.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, wherein a photocatalyst is selected from TiO2Composite photocatalyst, ZnO composite photocatalyst, ZrO2Composite photocatalyst g-C3N4At least one of photocatalysts.
The invention relates to a magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system, which also comprises a water quality online detection module and a water flow control module; the water quality online detection module and the water flow control module are both arranged at an outlet of the degradation tank. The COD and TOC indexes of the water quality are tested on line, and the flow of circulating water in the pipeline is intelligently controlled, so that the treated water reaches the discharge standard.
The invention relates to a method for treating water by a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system, which comprises the following steps: the water to be treated enters a liquid storage tank, is filtered by a particle filter plate in the liquid storage tank, then enters a degradation tank through a circulating pipeline, is treated by the combined action of electrochemical catalysis of an electrochemical degradation module, magnetic particle magnetic adsorption in a magnetic particle module and photocatalysis in a photocatalysis degradation module to obtain degraded water, and the degraded water is detected by a water quality online detection module and then is discharged after reaching the standard or returns to the liquid storage tank for next circulation treatment;
in the electrochemical catalysis process, after an alternating current power supply is switched on, an electrode A is taken as an anode; the electrode B is a cathode, the magnetic power supply C is powered on, the magnetic power supply D is powered off, and the magnetic particles move and gather around the electrode A; then alternating current power supply changes the current direction, and the electrode B is used as an anode; the electrode a is the cathode, at which time the magnetic power supply D is energized and the magnetic power supply C is de-energized and the magnetic particles move and gather around the electrode B.
Principles and advantages
In the invention, the degradation tank comprises an electrochemical degradation module, a magnetic particle module and a photocatalytic degradation module; the efficient degradation of organic matters in water is realized by the cooperation of electrochemical catalysis, photocatalysis and magnetic adsorption.
In the invention, both electrocatalysis and photocatalysis take free radicals as main oxidants to react with organic matters, but the side reaction of electrolytic water can be unavoidably existed in the electrocatalysis process to generate hydrogen and oxygen, and oxygen is used as a good electron carrier in the photocatalysis process to well capture photoproduction electrons, reduce the recombination velocity of the photoproduction electrons and holes, generate hydrogen peroxide with oxidability, and promote the photocatalysis process. The on-off of the electromagnetic field and the direction of the electrocatalytic current are changed synchronously, so that the electromagnetic field at the electrode (anode) where the oxidation reaction occurs is ensured to be on, and the electromagnetic field at the electrode (cathode) where the reduction reaction occurs is ensured to be off; the magnetic particles adsorb certain organic matters, move to the electrode for oxidation reaction under the action of a magnetic field to promote the degradation of the organic matters, and intelligently control the disconnection of the electromagnetic field at the position for reduction reaction, so that the magnetic particles adsorbing the organic matters can periodically move on the two electrode plates to promote the mass transfer process, and when the current direction is changed, the positions of the electrochemical cathode and the electrochemical anode are changed; the magnetic particles adsorb organic molecules to move from the water to the anode under the control of an electromagnetic field, and leave the anode to return to the water when desorbing the organic molecules, so that the organic molecules are enriched at the interface of the electrode/the water body, and the degradation process of the organic compounds is promoted and enhanced.
The power supply adopts alternating current, and the alternating current can prevent ionic substances from being accumulated on the surface of the electrode plate in the electrolytic process and has certain capacity of preventing cathode scaling; the change of the current direction can lead the two electrode plates to degrade organic matters, thereby not only improving the utilization rate of the electrode plates and prolonging the service life of the electrode plates, but also ensuring the uniformity of mineralization reaction of the organic matters in the degradation tank. The photocatalysis utilizes the photocatalyst responding to visible light to accelerate the speed of degrading organic molecules, and the electrochemical oxidation degradation efficiency is improved by the aid of the magnetic particles for adsorbing organic matters, so that the organic pollutants in water are efficiently degraded. The current can be combined and configured by taking time as a square wave function according to data provided by the water quality online detection module, so that the comprehensive degradation energy consumption is reduced, and the current efficiency in electrochemical degradation of organic pollutants in water is improved. The water quality on-line detection module detects COD and TOC indexes of the water quality at the water outlet of the degradation tank, and the water flow control module controls the flow of circulating water in the pipeline, so that the treated water reaches the discharge standard.
Drawings
FIG. 1 is a schematic structural diagram of a magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system of the present invention; in the figure: 1. a liquid storage tank; 2. a particle filter plate; 3. a circulation pipe; 4. a degradation tank; 5. a magnetic power source; 6. an alternating current power supply; 7. an electrode; 8. magnetic particles; 9. a photocatalyst; 10. a stirring device; 11. a water quality online detection module; 12. a water flow control module; 13. and (4) a valve.
Detailed Description
As shown in fig. 1, the magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system comprises a liquid storage tank 1 and a degradation tank 4; a particle filter plate 2 is arranged at the water outlet of the liquid storage tank 1; and connected to a degradation tank 4 through a circulation pipe 3; the particle filter plate 2 is selected from quartz sand filter plate, PP cotton filter plate, and microporous foam ceramic plate with porosity of more than 35PPI (Al)2O3、ZrO2SiC ceramic foam). The degradation tank 4 contains electrochemical degradation modules (only 1 treatment unit is shown in the figure); any one of the processing units comprises an electrode 7 (an electrode A or an electrode B), the electrode A or the electrode B is made of the same material with catalytic activity, the electrodes are hollow cylinders, and the distance between the electrode plates is 10-60 mm. The electrode A and the electrode B) are connected with an alternating current power supply 6 through leads, the alternating current power supply can be a square wave alternating current power supply or a square wave pulse power supply, the voltage of alternating current is 3-30V, and the frequency of the pulse power supply is 50-100 KHz. Magnetic particles 8 dispersed between the electrodes A and B, Fe in the present invention3O4、Fe2O3Or CoFe2O4Is a magnetic particleParticles dispersed between the solutions of the electrocatalytic electrodes, the particle size is 0.01-100 μm, the particles have adsorption-desorption characteristics to the pretreated organic matter, the magnetic particles are controlled to be distributed at specific positions by a magnetic power supply 5 (a magnetic power supply C above an electrode A and a magnetic power supply D above an electrode B) positioned above the electrodes, and a photocatalyst 9 is dispersed between the electrode A or the electrode B2Composite photocatalyst, ZnO composite photocatalyst, ZrO2Composite photocatalyst g-C3N4The catalyst has the size of 0.01-10 mu m, and an additional light source is not needed; a water flow control module 12 and a water quality on-line detection module 11 which are arranged on a circulating pipeline at the outlet of the degradation tank 4.
The treatment method of the magnetic adsorption auxiliary photoelectric water treatment system comprises the following steps:
firstly, water in the storage tank passes through the particle filtering module to remove solid particles in the water. Then the filtered water flows into a degradation tank through a circulating pipeline for photoelectrocatalysis degradation. The electrode A or the electrode B of the degradation tank is made of the same material, and the electrode is provided with a power supply module; in addition, dispersed magnetic particles and photocatalyst are arranged between the electrode A or the electrode B, and the magnetic particles can be controlled to move by a magnetic power supply arranged in the electrode cavity; in the electrochemical catalysis process, after an alternating current power supply is switched on, an electrode A is taken as an anode; the electrode B is a cathode, the magnetic power supply C is powered on, the magnetic power supply D is powered off, and the magnetic particles move and gather around the electrode A; then alternating current power supply changes the current direction, and the electrode B is taken as an anode; the electrode A is a cathode, the magnetic power supply D is powered on at the moment, the magnetic power supply C is powered off, the magnetic particles move and gather around the electrode B, organic molecules in water in the degradation tank are directly oxidized at the anode or by a photocatalyst, redox substances generated by electrochemical reaction and photocatalytic reaction are indirectly oxidized, or reduction and dehalogenation are carried out at the cathode, so that high-toxicity organic molecules in the water are converted into low-toxicity substances.
For organic matters in high-concentration refractory water, electrocatalysis occupies the main body, and magnetic particles adsorb organic molecules to move to the anode, so that the mass transfer process is accelerated; the photoelectric coupling degradation of organic molecules shows that the photocatalyst can utilize oxygen generated by an anode side reaction to carry out redox decomposition on low-concentration and difficultly-degraded high-toxicity small molecular compounds in a water body so as to convert the compounds into nontoxic and harmless substances.
The degraded water is discharged after reaching the standard after being detected by the water quality online detection module, or is returned to the liquid storage tank again for next cycle treatment; the water flow control module arranged on the circulating pipeline at the outlet of the degradation tank controls the circulating flow and flow velocity, and the water quality online detection module detects COD (chemical oxygen demand) and TOC (total organic carbon) indexes of the treated water, so that the treated water reaches the sewage discharge standard.
Example 1
In this embodiment 1, both the electrode a and the electrode B are boron-doped diamond electrodes (BDD electrodes), and the preparation method of the boron-doped diamond electrodes includes:
1.1 pretreatment of the substrate Material
Firstly, taking cylindrical foam Ti as a substrate, and polishing the cylindrical foam Ti by using 600#, 800#, 1000# metallographic abrasive paper; the polished foamed Ti substrate was then immersed in acetone (CH)3COCH3) Anhydrous ethanol (C)2H5OH) ultrasonic oscillation for 10 min; and then placing the Ti substrate in the nano-diamond suspension, and planting seed crystals for 30min by ultrasonic to enhance the nucleation effect. Finally, washing with deionized ultrapure water and drying for later use.
1.2BDD thin film deposition
(1) As used herein, a hot wire is
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (10mm) is adjusted. After the installation is finished, the cabin door is closed, the cabin door is vacuumized, then hydrogen, methane and borane (diborane used in the experiment is mixed gas of B2H6: H2: 5: 95) are introduced according to the concentration ratio of the gas source set in the experiment, after the reaction gas source is uniformly mixed, the air extraction valve is closed, and the fine adjustment valve is adjusted to adjust the air pressure in the cavity to the set pressure. Then turning on the power supply to regulate current, heating the hot wire to a set temperature, observing the air pressure in the deposition chamber, and if the air pressure changes, using micro-meterAnd adjusting the valve to continue adjustment, and finally beginning to deposit the boron-doped diamond film. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled by regulating the current to reduce the temperature, and CH is required to be closed at the moment4And B2H6Using only H2To etch the graphite phase of the diamond surface. The BDD electrode material deposition parameters used in this example were three deposition runs: the first stage gas flow rate ratio is H2:B2H6:CH4The deposition pressure was 2kPa, the deposition time was 4h, and the deposition temperature was 850 ℃. Second stage gas flow ratio H2:B2H6:CH4The deposition pressure was 2kPa, the deposition time was 8h, and the deposition temperature was 850 ℃. Third stage gas flow Rate H2:B2H6:CH497sccm:1.0sccm:3.0sccm, a deposition pressure of 2kPa, a deposition time of 12h, and a deposition temperature of 850 ℃. Stopping introducing borane and methane after the deposition is finished, etching with hydrogen at 850 ℃ for 30min to remove a graphite phase formed on the surface, cooling along with the furnace, taking out, cleaning the surface with absolute ethyl alcohol, and then putting into the furnace to continuously deposit the other surface according to the operation;
high temperature oxidation treatment of 1.3BDD films
The BDD electrode material obtained after deposition was placed in a crucible. Setting a temperature rise program of the tube furnace, wherein the temperature rise rate is 10 ℃/min, the atmosphere is air, the temperature is raised to 800 ℃, and the temperature is kept for 35 min. Pushing the crucible containing the BDD material into the resistance heating area, starting timing, enabling the processing time to reach 30 minutes, pushing the crucible to the outer side of the tube furnace, and cooling at room temperature to obtain a BDD electrode finished product. The wetting angle of the BDD electrode was 33.4 °.
The system is used for treating landfill leachate at a certain position of Nanjing, 1L of water sample is treated, two pairs of electrodes are arranged, the distance between every two electrodes is 10mm, the voltage of alternating current is 5, and no electrolyte is added; with Fe3O4、Fe2O3The magnetic particles are dispersed among the solutions of the electrocatalytic electrodes, and the particle size is 0.1-1 mu m; in g-C3N4The size of the photocatalyst is 0.2-2 μm; treatment process in degradation tankIn the process, the magnetic power supply is correspondingly disconnected and connected with the alternating current, and after the treatment is carried out for 24 hours under the treatment condition of the flow rate of 150mL/min, the TOC is reduced from 3375mg/L to 1577mg/L, the COD value is reduced from 18643mg/L to 1054mg/L, and the color of water is changed from dark brown to nearly clear.
Comparative example 1
The other conditions were the same as example 1 except that the magnetic power source was not provided, the magnetic particles were dispersed between the electrode A and the electrode B, and the TOC was reduced from 3375mg/L to 1944mg/L, the COD value was reduced from 18643mg/L to 4471mg/L, and the color of the water was changed from dark brown to clear after treating at a flow rate of 150mL/min for 24 hours.
Comparative example 2
The other conditions are the same as example 1, except that the electrode A and the electrode B are connected with a direct current power supply, no magnetic power supply is arranged, magnetic particles are distributed around the electrode as an anode, and after the treatment is carried out for 24 hours under the treatment condition of the flow rate of 150mL/min, the TOC is reduced from 3375mg/L to 2056mg/L, the COD value is reduced from 18643mg/L to 5366mg/L, and the color of water is changed from dark brown to nearly clear.
Comparative example 3
The other conditions are the same as the example 1, except that no photocatalytic module is arranged, the TOC is reduced from 3375mg/L to 2213mg/L, the COD value is reduced from 18643mg/L to 6337mg/L after the treatment is carried out for 24 hours under the treatment condition of the flow rate of 150mL/min, and the color of the water is changed from dark brown to nearly clear.
Example 2
The system is used for treating the actual chemical pharmaceutical wastewater, the water composition is complex, and the wastewater contains antibiotic residues, antibiotic intermediates, unreacted raw materials, organic solvents and the like. Treating a water sample 1L, and setting 3 pairs of point electrodes, wherein both the electrode A and the electrode B are boron-doped diamond electrodes; the distance between the electrodes is 12mm, the voltage of alternating current is 6V, and no electrolyte is added; with Fe3O4、Fe2O3The magnetic particles are dispersed among the solutions of the electrocatalytic electrodes, and the particle size is 0.1-1 mu m; with TiO2/g-C3N4The size of the photocatalyst is 0.2-2 μm; during the treatment of the degradation tank, following the alternating current transformationAnd correspondingly disconnecting and connecting the magnetic power supply, and after treating for 24 hours under the treatment condition of the flow rate of 150mL/min, reducing the TOC of the water from 5691mg/L to 766mg/L, reducing the COD value from 20639mg/L to 2915mg/L, and changing the color of the water from dark brown to colorless.
Comparative example 4
The other conditions were the same as example 1 except that the magnetic power source was not provided, and the magnetic particles were dispersed between the electrode A and the electrode B, and the TOC was reduced from 5691mg/L to 1651mg/L, the COD value was reduced from 20639mg/L to 3544mg/L, and the color of the water was changed from dark brown to colorless after the treatment at a flow rate of 150mL/min for 24 hours.
Comparative example 5
The other conditions are the same as example 1, except that the electrode A and the electrode B are connected with a direct current power supply, no magnetic power supply is arranged, magnetic particles are distributed around the electrode as an anode, and after the treatment is carried out for 24 hours under the treatment condition of the flow rate of 150mL/min, the TOC is reduced from 5691mg/L to 1907mg/L, the COD value is reduced from 20639mg/L to 7418mg/L, and the color of water is changed from dark brown to colorless.
Comparative example 6
The other conditions were the same as example 1 except that no photocatalytic module was provided, and the TOC was reduced from 5691mg/L to 2341mg/L, the COD was reduced from 20639mg/L to 8913mg/L, and the color of water was changed from dark brown to colorless after treating for 24 hours under the treatment condition of the flow rate of 150 mL/min.
Example 3
The system is used for treating actual biological pharmaceutical wastewater which mainly contains mycelium, residual nutrient substances, metabolites, organic solvents and the like. Treating a water sample 1L, and arranging 4 pairs of point electrodes, wherein both the electrode A and the electrode B are boron-doped diamond electrodes; the distance between the electrodes is 10mm, the voltage of alternating current is 6V, and no electrolyte is added; with Fe3O4、CoFe2O4The magnetic particles are dispersed among the solutions of the electrocatalytic electrodes, and the particle size is 0.1-1 mu m; in g-C3N4The size of the photocatalyst is 0.2-2 μm; in the treatment process of the degradation tank, the magnetic power supply is correspondingly disconnected and connected along with the conversion of alternating current, and the treatment is carried out for 24 hours under the treatment condition of the flow rate of 150mL/minAfter the reaction, the TOC of the reaction solution was reduced from 11391mg/L to 303mg/L, and the color of the water was changed from light yellow to colorless.
Comparative example 7
The other conditions were the same as example 1 except that the magnetic power source was not provided, the magnetic particles were dispersed between the electrode A and the electrode B, and the TOC was reduced from 11391mg/L to 2217mg/L under the treatment condition of the flow rate of 150mL/min for 24 hours, whereby the color of the water changed from pale yellow to colorless.
Comparative example 8
The other conditions were the same as example 1 except that the electrode A and the electrode B were connected to a DC power supply and no magnetic power supply was provided, and magnetic particles were distributed around the electrode as an anode, and the TOC was reduced from 11391mg/L to 2410mg/L and the color of water was changed from pale yellow to colorless after treatment at a flow rate of 150mL/min for 24 hours.
Comparative example 9
The other conditions were the same as example 1 except that no photocatalytic module was provided, and the TOC was reduced from 11391mg/L to 3977mg/L and the color of water was changed from pale yellow to colorless after 24 hours of treatment at a flow rate of 150 mL/min.
Claims (10)
1. The utility model provides a supplementary photoelectrocatalysis of magnetic adsorption oxidation water processing system which characterized in that: comprises a liquid storage tank and a degradation tank; a particle filter plate is arranged at a water outlet of the liquid storage tank and is connected to the degradation tank through a circulating pipeline, and the degradation tank comprises an electrochemical degradation module, a magnetic particle module and a photocatalytic degradation module;
the electrochemical degradation module consists of a plurality of processing units, and any one processing unit comprises; the electrode A and the electrode B are connected with an alternating current power supply through leads;
the magnetic particle module comprises magnetic particles dispersed between an electrode A and an electrode B, a magnetic power supply C positioned above the electrode A and a magnetic power supply D positioned above the electrode B, wherein solenoid wound magnetic cores are arranged in the magnetic power supply C and the magnetic power supply D,
the photocatalytic degradation module comprises a photocatalyst dispersed between an electrode A and an electrode B.
2. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the particle filter plate is at least one selected from a quartz sand filter plate, a PP (polypropylene) cotton filter plate and a microporous foam ceramic plate with porosity of more than 35 PPI.
3. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the electrode A and the electrode A are formed by matching cylindrical electrodes and cylindrical electrodes which are coaxial in center but do not contact with each other, or formed by matching two groups of coaxial cylindrical electrode arrays with different diameters, or formed by matching a honeycomb briquette structure and a cylindrical array, or formed by matching a three-dimensional continuous network structure and a two-dimensional continuous network structure, or formed by matching a two-dimensional closed flat plate structure and a two-dimensional continuous network structure.
4. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 3, wherein: the electrode A and the electrode B are hollow cylinders, and the distance between the electrode A and the electrode B is 10-60 mm; the electrode A and the electrode B are both selected from at least one of a boron-doped diamond electrode, a noble metal electrode, a stainless steel electrode and a carbon material electrode.
5. The system for treating water by magnetic adsorption assisted photoelectrocatalysis oxidation according to claim 4, which is characterized in that: the electrode A and the electrode B are both boron-doped diamond electrodes, and the wetting angle theta of the boron-doped diamond electrodes is less than 40 degrees; the electrode working layer of the boron-doped diamond electrode is a gradient boron-doped diamond layer; the gradient boron-doped diamond layer sequentially comprises a gradient boron-doped diamond bottom layer, a gradient boron-doped diamond middle layer and a gradient boron-doped diamond top layer from bottom to top, wherein the boron content of the gradient boron-doped diamond bottom layer is increased in a gradient manner;
in the gradient boron-doped diamond bottom layer, the B/C is 3333-33333 ppm in terms of atomic ratio; in the gradient boron-doped diamond middle layer, B/C is 10000-33333 ppm by atomic ratio; in the top layer of the gradient boron-doped diamond, the B/C is 16666-50000 ppm in terms of atomic ratio.
6. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the alternating current power supply is selected from a square wave alternating current power supply or a square wave pulse power supply, the voltage of the alternating current is 3-30V, and the frequency of the pulse power supply is 50-100 KHz.
7. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the magnetic particles are selected from Fe3O4Particles of Fe2O3Particles, CoFe2O4At least one of particles, the magnetic particles having a size of 0.01 to 100 μm.
8. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the photocatalyst is selected from TiO2Composite photocatalyst, ZnO composite photocatalyst, ZrO2Composite photocatalyst g-C3N4At least one of photocatalysts.
9. The water treatment system with magnetic adsorption and auxiliary photoelectrocatalysis oxidation as claimed in claim 1, wherein: the water treatment system also comprises a water quality online detection module and a water flow control module; the water quality online detection module and the water flow control module are both arranged at an outlet of the degradation tank.
10. The method for treating water by using the magnetic adsorption-assisted photoelectrocatalysis oxidation water treatment system according to any one of claims 1 to 9, which is characterized in that: the method comprises the following steps: the water to be treated enters a liquid storage tank, is filtered by a particle filter plate in the liquid storage tank, then enters a degradation tank through a circulating pipeline, is treated by the combined action of electrochemical catalysis of an electrochemical degradation module, magnetic particle magnetic adsorption in a magnetic particle module and photocatalysis in a photocatalysis degradation module to obtain degraded water, and the degraded water returns to the liquid storage tank through the circulating pipeline again to complete a circulating treatment, is detected by a water quality online detection module and then is discharged after reaching the standard, or is subjected to the next circulating treatment;
in the electrochemical catalysis process, after an alternating current power supply is switched on, an electrode A is taken as an anode; the electrode B is a cathode, the magnetic power supply C is powered on, the magnetic power supply D is powered off, and the magnetic particles move and gather around the electrode A; then alternating current power supply changes the current direction, and the electrode B is used as an anode; the electrode a is the cathode, at which time the magnetic power supply D is energized and the magnetic power supply C is de-energized and the magnetic particles move and gather around the electrode B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390584.3A CN111675417B (en) | 2020-05-11 | 2020-05-11 | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390584.3A CN111675417B (en) | 2020-05-11 | 2020-05-11 | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111675417A true CN111675417A (en) | 2020-09-18 |
| CN111675417B CN111675417B (en) | 2022-10-18 |
Family
ID=72433641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010390584.3A Active CN111675417B (en) | 2020-05-11 | 2020-05-11 | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111675417B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960841A (en) * | 2021-02-07 | 2021-06-15 | 郑州航空工业管理学院 | Emergency water treatment method for sudden petroleum pollution of drinking water |
| CN113307335A (en) * | 2021-06-25 | 2021-08-27 | 南京理工大学 | Method for treating organic wastewater by using heterogeneous Fenton coupling tube type membrane electrode |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562795A (en) * | 2004-04-07 | 2005-01-12 | 太原理工大学 | Photoelectrocatalysis and oxidation device for treating organic substance in water |
| CN101555082A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院理化技术研究所 | Wastewater treatment method and device combining electrochemical degradation and photocatalysis oxidation technologies |
| CN101691262A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Optic-electronics integrated device for treating organic wastewater through catalytic oxidation |
| CN101905912A (en) * | 2010-07-08 | 2010-12-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparing organic pollutant-degrading electrode material |
| CN102157353A (en) * | 2010-12-03 | 2011-08-17 | 北京科技大学 | Method for preparing diamond substrate for high-heat-conductivity integrated circuit |
| CN103370765A (en) * | 2010-12-23 | 2013-10-23 | 六号元素有限公司 | Controlling doping of synthetic diamond material |
| CN103643219A (en) * | 2013-11-29 | 2014-03-19 | 吉林大学 | Preparation method of boron-doped diamond film electrode taking porous titanium as matrix |
| CN104230067A (en) * | 2013-06-08 | 2014-12-24 | 中国科学院理化技术研究所 | Processing apparatus and method for wastewater containing organic pollutants |
| CN104496094A (en) * | 2014-12-05 | 2015-04-08 | 无锡普睿生物环保科技有限公司 | High-risk wastewater treatment apparatus and treatment method for laboratory |
| CN106430796A (en) * | 2016-10-25 | 2017-02-22 | 西安交通大学 | In-situ adsorption and electrocatalysis coupled organic wastewater treatment system and method |
| CN106637111A (en) * | 2016-10-21 | 2017-05-10 | 中南大学 | Niobium-base boron doped diamond foam electrode and preparing method and application thereof |
| CN106986482A (en) * | 2017-05-05 | 2017-07-28 | 孝感双华应用科技开发有限公司 | A kind of photoelectrochemical degradation waste plant |
| CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
-
2020
- 2020-05-11 CN CN202010390584.3A patent/CN111675417B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562795A (en) * | 2004-04-07 | 2005-01-12 | 太原理工大学 | Photoelectrocatalysis and oxidation device for treating organic substance in water |
| CN1263686C (en) * | 2004-04-07 | 2006-07-12 | 太原理工大学 | Photoelectrocatalysis and oxidation device for treating organic substance in water |
| CN101555082A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院理化技术研究所 | Wastewater treatment method and device combining electrochemical degradation and photocatalysis oxidation technologies |
| CN101691262A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Optic-electronics integrated device for treating organic wastewater through catalytic oxidation |
| CN101905912A (en) * | 2010-07-08 | 2010-12-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparing organic pollutant-degrading electrode material |
| CN102157353A (en) * | 2010-12-03 | 2011-08-17 | 北京科技大学 | Method for preparing diamond substrate for high-heat-conductivity integrated circuit |
| CN103370765A (en) * | 2010-12-23 | 2013-10-23 | 六号元素有限公司 | Controlling doping of synthetic diamond material |
| CN104230067A (en) * | 2013-06-08 | 2014-12-24 | 中国科学院理化技术研究所 | Processing apparatus and method for wastewater containing organic pollutants |
| CN103643219A (en) * | 2013-11-29 | 2014-03-19 | 吉林大学 | Preparation method of boron-doped diamond film electrode taking porous titanium as matrix |
| CN104496094A (en) * | 2014-12-05 | 2015-04-08 | 无锡普睿生物环保科技有限公司 | High-risk wastewater treatment apparatus and treatment method for laboratory |
| CN106637111A (en) * | 2016-10-21 | 2017-05-10 | 中南大学 | Niobium-base boron doped diamond foam electrode and preparing method and application thereof |
| CN106430796A (en) * | 2016-10-25 | 2017-02-22 | 西安交通大学 | In-situ adsorption and electrocatalysis coupled organic wastewater treatment system and method |
| CN106986482A (en) * | 2017-05-05 | 2017-07-28 | 孝感双华应用科技开发有限公司 | A kind of photoelectrochemical degradation waste plant |
| CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960841A (en) * | 2021-02-07 | 2021-06-15 | 郑州航空工业管理学院 | Emergency water treatment method for sudden petroleum pollution of drinking water |
| CN113307335A (en) * | 2021-06-25 | 2021-08-27 | 南京理工大学 | Method for treating organic wastewater by using heterogeneous Fenton coupling tube type membrane electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111675417B (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111646632B (en) | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof | |
| CN111646611B (en) | Ultrasonic ozone coupling photoelectrocatalysis water treatment system and water treatment method | |
| CN108183251B (en) | Microbial fuel cell BCS1-MFC system for treating low C/N wastewater and wastewater treatment method thereof | |
| CN111646634B (en) | Ultrasonic coupling photoelectric Fenton activated persulfate water treatment system and water treatment method | |
| WO2019169785A1 (en) | Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system | |
| CN111675417B (en) | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method | |
| CN110156146B (en) | Biological membrane electrochemical reactor for simultaneously removing nitric acid nitrogen and trace organic matters in water | |
| WO2010135886A1 (en) | Anti-pollution electrocatalysis composite membrane and membrane reactor | |
| CN105293688B (en) | The system that nitrate nitrogen in water removal is removed in a kind of coupled biological anode electro-catalysis | |
| CN110143662B (en) | Device and method for treating electroplating wastewater of transition metal-based electrode biofuel cell | |
| CN104759272A (en) | Membrane electrode of membrane electrode low-voltage electrolysis type ozone generator and manufacturing method for positive and negative electrodes of membrane electrode low-voltage electrolysis type ozone generator | |
| CN111593316A (en) | Super-hydrophilic gradient boron-doped diamond electrode with high specific surface area and preparation method and application thereof | |
| CN106630177A (en) | Method and device for treating coking wastewater and producing hydrogen gas by microbial electrolysis cell | |
| CN111635067B (en) | Ultraviolet-assisted ultrasonic coupling electrocatalytic oxidation water treatment system and water treatment method | |
| CN111646633B (en) | Efficient energy-saving three-dimensional electrode organic water treatment system and water treatment method thereof | |
| CN111519163B (en) | Boron-doped diamond electrode with high conductivity, long service life and high specific surface area, and preparation method and application thereof | |
| CN111675396B (en) | Energy clean electro-membrane coupling water treatment system and water treatment method | |
| CN203781882U (en) | Oxidation-flocculation complex bed device for landfill leachate | |
| CN114011251B (en) | Conductive film for efficiently removing nitrate in water and preparation method thereof | |
| CN107010729B (en) | Gas-water anisotropic flow gradual-change type completely autotrophic nitrogen removal system and treatment method thereof | |
| CN111825271B (en) | Solar electricity-biology energy-saving water treatment system and water treatment method | |
| CN111370725B (en) | MFC system based on biological dynamic membrane and enhanced electricity generation method | |
| CN114196534A (en) | Carbon-based emission reduction of CO2Device and method for biologically synthesizing methane | |
| CN108383214B (en) | Photovoltaic electro-catalysis organic wastewater treatment reactor and anode preparation method thereof | |
| CN111916808A (en) | SmFCs for strengthening electrogenesis decontamination of cobaltosic oxide photocathode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230822 Address after: Room 203, 2nd Floor, Building A6, Liuhe Science and Technology Innovation Park, Nanjing Liuhe Economic Development Zone, Nanjing, Jiangsu Province, 211599 Patentee after: Nanjing Daimount Technology Co.,Ltd. Address before: 210000 No.109, building 2, No.399, Xiongzhou South Road, Longchi street, Liuhe District, Nanjing City, Jiangsu Province Patentee before: Jiangsu jingzuan Environmental Protection Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |